Engineering Chemistry Volume 5

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Volume 5 of Engineering Chemistry

ISSN print 2813-6527
ISSN web 2813-6535

Full text available online at https://www.scientific.net/book/engineering-chemistry-vol-5/978-3-0364-1502-4

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Table of Contents

The Effect of Sodium Acetate on Biodegradable Rice Starch-Based Solid Polymer Electrolyte for Supercapacitor

Agung Nugroho, Muchammad Syaifudin, Sylvia Ayu Pradanawati

Synthesis and Electrochemical Performance of Sodium Iron Phosphate Cathode Battery Based on Water-Chitosan Slurry

Mohammad Arrafi Azhar, Andyan Rafi Setopratama, Phahul Zhemas Zul Nehan, Revaldo Anugerah Putra Pradana, Chanifa Zulaiha Ahmad, Darminto Darminto

Corn Starch-Sodium Acetat Composite Material from Industrial Waste Fly Ash for Solid Electrolyte Polymer Ionic Conductivity in Supercapacitor Application

Irfani Faiq Erlangga, Sylvia Ayu Pradanawati, Azzah Dyah Pramata, Nur Laila Hamidah

Solid Polymer Electrolyte (SPE) from Corn Starch and Aluminum Nitrate Salt Composites for Aluminum - Ion Battery

Khoirul Anam, Sylvia Ayu Pradanawati, Azzah Dyah Pramata, Nur Laila Hamidah

Enhanced lonic Conductivity of Fluoride-Doped as Solid Electrolyte of Lithium-lon Battery

Muhammad Rial Afif, Vania Mitha Pratiwi, Lukman Noerochim

Study of Addition Metal (Ti, Zn) Dopan on The Structure of NASICON as Solid Electrolyte Batteries

Vania Mitha Pratiwi, Lukman Noerochim, Hariyati Purwaningsih, Agung Ari Wibowo, Fakhri Akbar Maulana

The Effect of Nitrogen on the Capacitive Properties of N-Doped rGO/CuCr Composites as Materials for Supercapacitors

Diah Susanti, Adzon Nugraha Rizky Pratama, Haniffudin Nurdiansah

Keywords Index

Authors Index

The original version of this eBook is available on https://www.scientific.net/book/engineering-chemistry-vol-5/978-3-0364-1502-4

Engineering Chemistry, ISSN: 2813-6535, Vol. 5, pp 1-11

doi: 10.4028/p-AuNW19

© 2024 The Author(s). Published by Trans Tech Publications Ltd, Switzerland.

Submitted:
2022-09-23

Revised:
2023-04-08

Accepted:
2023-06-14

Online:
2024-01-19

The Effect of Sodium Acetate on Biodegradable Rice Starch-Based Solid Polymer Electrolyte for Supercapacitor

The original version of this paper is available on https://www.scientific.net/EC.5.1.pdf

Agung Nugroho , Muchammad Syaifudin , and Sylvia Ayu Pradanawati

¹Chemical Engineering Department, Universitas Pertamina, Indonesia

Mechanical Engineering Department, Universitas Pertamina, Indonesia

agung.n@universitaspertamina.ac.id, chammadsyaifudin@gmail.com, sylvia.pradanawati@universitaspertamina.ac.id,

Keywords: Amorphous, ionic conductivity, rice starch, salt, sodium acetate, solid polymer electrolyte, supercapacitor

Abstract

This study examined the use of sodium acetate salt as an ionic dopant in biodegradable solid polymer electrolyte (SPE). In the solution casting method for making polymer electrolyte, rice starch is used as the host polymer and glycerol is used as the plasticizer. The characteristics of SPE film were investigated using X-Ray Diffraction (XRD), Fourier Transform Infrared (FT-IR), and Thermogravimetric Analysis (TGA). Salt enhances the amorphous structure by decreasing the crystallinity of the polymer. Alternatively, it decreases the temperature of thermal breakdown. In addition, the biodegradability of SPE was investigated using the soil burial method. Electrochemical Impedance Spectroscopy (EIS) was used to evaluate the ionic conductivity behavior and temperature dependent of SPE. The sodium acetate salt addition makes the supercapacitor's electrolyte have the highest ionic conductivity at room temperature, which is .

Introduction

The original version of this paper is available on https://www.scientific.net/EC.5.1.pdf

Supercapacitor has promising potential as energy storage system for renewable energy plant. It has the ability to store about 10-100 times more energy per unit volume than ordinary capacitors and has a faster charge transfer rate than batteries [1]. In supercapacitor, there are several problems encountered such as leaks and limited size design when using liquid electrolyte. Therefore, researchers are investigating various solid polymer electrolytes (SPE) as suitable replacements for liquid electrolytes. SPE has environmentally friendly properties because it uses natural raw materials that are non-toxic, biodegradable, and sustainable based material. Organic polymers can be generally extracted directly from biomass such as starch, cellulose, and chitosan [2]. In this study, starch will be used as the host polymer for preparing solid electrolytes because it has lower glass transition temperature than chitosan and cellulose [3]. In SPE synthesis, lower glass transition temperature is more preferred because it can make the ionic conductivity increase. This is because the movement and flexibility of polymer chains are higher in polymer matrix that have a low glass transition temperature [3].

The source of starch used in this research is derived from rice because it has the highest amylose content compared to other starches [4]. The concentration of amylose in rice starch is , and that of amylopectin is [4]. The content of amylose and amylopectin plays a role in the crystalline and amorphous structure of starch. Amylose corresponds to the amorphous structure of starch since it has a linear chain while amylopectin corresponds in the crystal structure of starch because of its branched chain. Therefore, starch with higher amylose content has more amorphous structure [5]. In SPE synthesis, starch with higher amylose content has higher ion mobility since ions from the addition of salts attack more on the amylose unit [6].

In general, solid electrolytes derived from biomass polymers have low ionic conductivity. Therefore, it requires the addition of salt as an ionic dopant to improve the ionic conductivity. Commonly, the salt used as ionic dopant is lithium (Li) salt, but this salt is dangerous and limited availability in nature. In this study, ionic dopants based on sodium salt ( Na ) were used because they are abundant in nature, cheap, and environmentally friendly and also have chemical properties similar
to lithium [7]. In addition, based on comparative studies conducted by Osman et al. [8] showed that sodium-based electrolyte systems have a higher ionic conductivity compared to lithium-based electrolyte systems at room temperature. This is due to has lower energy lattice compared to , therefore sodium-based salts are more conductive and more mobile in matrix polymer. Based on previous research written by Khanmirzaei et al. [6], it was obtained that the highest ionic conductivity of rice starch-based SPE was found in the addition of of sodium iodide ( NaI ) salts with an ionic conductivity of . In this study, further research will be studied regarding the ionic conductivity of the addition of other sodium salts, namely sodium acetate salt which is more environmentally friendly, harmless, and abundant in nature. The effect of adding sodium acetate salts will be further analyzed through XRD, FTIR, TGA, Soil Burial Test, EIS, and CV.

Experiments

The original version of this paper is available on https://www.scientific.net/EC.5.1.pdf

The solution casting technique was used to prepare SPE using 2 grams rice starch as host polymer, 20 ml distilled water with 99% purity as solvent, 1.36 ml glycerol 85% purity Merck CAS no 56-815 as plasticizer, and various concentration of anhydrous sodium acetate salt purity Merck CAS no 127-09-3 as ionic dopant. The salt variation used in this study were , , and by weight of sodium acetate salt to the weight of rice starch. Sample with no addition of salt ( ) will use as a control sample.

All samples were characterized by XRD Olympus BTX-534 to study the crystal structure, FTIR Thermo Scientific Nicolet IS5 with ATR Id7 to study the functional group, TA Instruments SDT 650 to study the temperature decomposition, Soil Burial Test to study the biodegradability, and AutoLab Electrochemical Impedance Spectroscopy (EIS) to study the resistance of SPE. EDLC performance analysis was performed by measuring specific capacitance through cyclic voltammetry using AutoLab instrument with 2 system electrodes. The EDLC was fabricate using symmetric EDLC with 2 graphite electrodes separated by the SPE.

Result and Discussion

The original version of this paper is available on https://www.scientific.net/EC.5.1.pdf

X-Ray Diffraction (XRD). Based on the result of XRD in Figure 1, there are sharp and nonwidening diffraction peaks were found at angles of , and in diffractogram of salt. In rice starch can be found diffraction peaks at angles of , and that categorized as type A crystalline and diffraction peak at angles of , and categorized as type B crystalline. Thus, the crystal structure of starch can be categorized as type C which consist of type A and type B . In crystalline type C , the XRD pattern can contain various superpositions of diffraction peaks that depend on the ratio of composition between polymorphs [9]. According to Yang et al. [10], the peak of -angle diffraction located at is identified as amylose and at as amylopectin. During the gelatinization process, the amylose chain is released, the viscosity increases, and the amorphous structure increases [11]. The difference in diffraction peaks between rice starch and pure SPE (sample 0%) is found in the presence of diffraction peaks at an angle of in rice starch, while in pure SPE sample there is no peaks at that angle of . The difference is also clearly visible at angles of , and in rice starch whose peaks widen at a sample of indicated at angles of and .

Fig. 1. X-Ray diffraction patterns of , rice salt, and SPE with variation of the salt concentration

Fig. 1. X-Ray diffraction patterns of , rice salt, and SPE with variation of the salt concentration

The addition of salt to a pure SPE sample based on Figure 1 influences the crystal structure of the sample. Changes in the crystal structure are located at angles of and which indicates the presence of diffraction peaks in pure SPE samples ( ), but these peaks are not present in SPE samples with the addition of salts. The change indicates that the addition of salt makes the crystal structure of SPE more amorphous [12]. When the amount of salt added is continuously increased, XRD diffraction does not show significant changes. To find out the most amorphous crystal structure, it is necessary to calculate the crystal size using the Debye-Scherrer equation expressed by Eq. (1).

where is the estimated crystal size ( nm ), is the wavelength of X-rays ( nm ), is full width halfmaximum (FWHM) , and is the peak angle of diffraction [13]. The FWHM value of the sample increased along with the increase in the concentration of sodium acetate salt.

Table 1. Crystal size calculation

Sample | 2θ (°) | θ (°) | FWHM (°)
0% Salt | 19.786 | 9.893 | 8.562
15% Salt | 19.829 | 9.914 | 8.729
25% Salt | 19.786 | 9.893 | 8.874
35% Salt | 19.572 | 9.786 | 10.358
45% Salt | 19.786 | 9.893 | 9.162

Based on Table 1, the highest value of FWHM is reached by the sample SPE with the addition salt. The greater the FWHM value means that the increment of the amorphous phase on the sample is due to the addition of plasticizer and salt. However, SPE samples with salt experienced a decrease in FWHM values due to crystallization. It is because the host polymer could not accommodate an excess amount of salt [14].

Fourier Transform Infrared (FTIR). Based on Fig. 2, the pure SPE spectrum, represent by a black line color, has a wide absorption band in single bond region at . The region around indicates the presence of a hydroxyl group O-H stretching. At wavenumber of 2929 and there are also peak for stretching. Meanwhile, in triple and double bond region, there is no absorption band. This suggests that the SPE do not have a functional group with a triple bond nor double bond. In addition, the peak at is associated with water function group, bending.

Fig. 2. FTIR spectrum of (a) SPE with variation of sodium salt concentration and (b) enlargement wavenumber

Fig. 2. FTIR spectrum of (a) SPE with variation of sodium salt concentration and (b) enlargement wavenumber

In the fingerprint region there are many functional groups such as bending at bending at , and several typical starch functional groups at range . That typical starch functional groups are by glycosidic bonds, , and . It is specified as C-O-C stretching at , secondary alcohol (C-O-H) stretching at , primary alcohol (C-O-H) stretching at , and glycosidic bond (C-O-C) stretching with high intensity at . In addition, there are also peak of bending groups at 924,860 , and . Figure 2 (b) shows the enlargement area of FTIR spectrum. In sections (a) at wavenumber and (b) at there are new absorption bands and the peak increase along with the addition of salt concentrations. It can be attributed to carbonyl bonds, with two peaks detected due to the presence of two resonant structures [16]. The vibration of the carbonyl group was declared by Habka et al. [17] to be an antisymmetric stretching carboxylate (COO-) group at and a carboxylate group ( ) symmetric stretching at . The presence of the COO function groups indicates the occurrence of acetyl group substitution due to starch acetylation. The substitution of acetyl groups in starch increases the resistance to retrogradation [18]. Thus, it makes the amorphous structure more stable.

Thermogravimetric Analysis (TGA). Figure 3 shows that all samples have single-step decomposition. In sample salt, the weight of the sample experienced a drastic decrease at and it is referred as the decomposition temperature.

Fig. 3. TGA Thermogram of SPE

Fig. 3. TGA Thermogram of SPE

When the sample was added with salt, the decomposition temperature shifted to a lower temperature. It occurs due to the complexity between polymers and salts which increases segmental flexibility in the polymer matrix [6]. In other words, the addition of causes a weak bond between ions and hydroxyl groups in starch polymers. Along with the increasing concentration of salt, there is no significant change in the decomposition temperature. The difference can be seen in the sample of of salts that slightly experienced weight loss at . Since the weight loss is quite drastic at , it is set to be the decomposition temperature of the sample.

Soil Burial Test. This biodegradability test focuses on analyzing the effect of salt addition on the degree of degradability of the film. The selection of the test time is determined based on the minimum time that one of the samples can be perfectly degraded. The results of the biodegradability test showed that within 28 hours the sample salt had been fully degraded while the sample of salt was still not degraded. If the testing time is extended, the sample will degrade perfectly because rice starch is an organic compound. This is because microorganisms in the soil use organic compounds as a source of nutrients for their metabolism [19].

Fig. 4. Volume loss of SPE samples within 28 hours

Fig. 4. Volume loss of SPE samples within 28 hours

The calculation of volume loss was chosen compared to weight loss because the samples that have been planted in the soil are difficult to clean. Therefore, an approach is made to the remaining area of the area and multiplied by the thickness of the sample. Based on Figure 4, it is known that the higher the salt concentration, the greater the volume lost from SPE due to biodegradation. So that the maximum biodegradability occurs at the highest salt concentration [20]. The increase in biodegradability is due to the interaction of sodium salts to the starch hydroxyl group. In addition, the reaction of acetylation also affects the biodegradability of starch. The large biodegradability of the
film results from the insertion of acetyl groups that can reduce the inter- and intramolecular interactions promoted by hydrogen bonds [21].

Electrochemical Impedance Spectroscopy (EIS). This impedance study focused on calculating the value of bulk resistance obtained through the Nyquist Plot which is a graph that presents impedance value data ( ) consisting of a real impedance ( ) and an imaginer impedance ( ). On the Nyquist plot, there is a semicircle curve at high frequency describing the process of ion transfer on SPE and a linear curve at low frequency describing the diffusion process.

Fig. 5. Nyquist plot at SPE at room temperature

Fig. 5. Nyquist plot at SPE at room temperature

Based on the Fig. 5, the semicircle obtained by the SPE sample of salt has a much larger shape than the SPE sample with the addition of salt. The larger the semicircle indicates that the process of ion diffusion is proceeding slowly due to the large resistance. In the salt addition sample, the semicircle looks very small indicating that the resistance is significantly decreased. The difference between the semicircle's initial and final intersections at the real impedance axis ( ) is expressed as bulk resistance (Rb). The ionic conductivity is calculated using Eq. (2).

where is the thickness of the sample (cm), is the surface area of the sample (cm²), is the bulk resistance , and is the ionic conductivity ( ).

Fig. 6. Temperature-dependent of Ionic Conductivity

Fig. 6. Temperature-dependent of Ionic Conductivity

Based on the Fig. 6, the resistance of the sample begins to decrease when a pure SPE sample is added with salt. The decrease in resistance is due to the presence of in the polymer which can increase the ionic conductivity. cations have a weak bond with in polymers, making will easily jump to other vacant sites to produce an ionic conduction mechanism [22]. An increase in salt concentration will make an increase in the concentration of ions in the polymer matrix so that the ionic conductivity will be increased [7]. Based on the tests that have been carried out, SPE samples with a concentration of salt have the smallest with a value of and the largest ionic conductivity with a value of . The continuous increase in salt concentration does not necessarily increase ionic conductivity as it happens in the sample of adding salt. In samples 45% of salts the ionic conductivity drops after reaching the highest value in the sample of salt. The decrease in ionic conductivity at high salt concentrations is caused by ion aggregation which causes overcrowded ions in the polymer matrix so that ion mobility decreases [23].The impedance study was also carried out at elevated temperatures to study the temperature-dependent of ionic conductivity. In Fig. 6, it can be known that an increase in temperature can increase ionic conductivity. The higher the temperature, the lower the resistance of the SPE. It is because bonds of O and Na will be more easily released at higher temperatures so that the ion movement will increase. In addition, the expansion of the film volume due to the increase in temperature makes more space for the ion to mobile so that the ionic conductivity increases [24]. The temperature-dependent of ionic conductivity was further studied using Arrhenius modeling.

From Eq. (3) can be known the relationship between activation energy to ionic conductivity. The value of the activation energy ( ) is calculated based on the linearization of the Arrhenius equation. The value of the activation energy can be obtained from the slope (gradient) of the plot ionic conductivity vs 1000/T.

Table 4. Activation energy of SPE

Sample | Slope | Ea (J/mol)
0% Salt | -7.621 | 63.357
15% Salt | -2.724 | 22.649
25% Salt | -2.703 | 22.476
35% Salt | -2.121 | 17.636
45% Salt | -2.148 | 17.861

The activation energy value indicates the quantity of energy required by the ion to be able to move on the polymer matrix. The decrease in activation energy shows that ion movement goes easier and faster. Based on Table 4, an increase in the concentration of salts plays a role in lowering activation energy.

Fig. 8. Scan Rate Test Sample (a) Salt, (b) Salt

Fig. 8. Scan Rate Test Sample (a) Salt, (b) Salt

Cyclic Voltammetry (CV). EDLC performance tests were performed with Cyclic Voltammetry (CV) to calculate specific capacitance. The shape of the curve due to the change in scan rate did not undergo significant changes with no redox reaction peak found as shown in Figure 8. It shows that the SPE with a graphite electrode can run at low or high scan rates from the range of to 100 . In this study, a scan rate of was used to determine the changes occurred when the EDLC running with 50 cycles.

Fig. 9. CV with 50 Cycles at of the SPE sample with and salt concentration

Fig. 9. CV with 50 Cycles at of the SPE sample with and salt concentration

In the Fig. 9, a curve with a green line represents the behavior of a sample of salt in 50 cycles whose area decreases slightly in the initial cycle. However, after cycle 10 the area is more stable. The decrease in the area that occurs may be caused by ion aggregation during the charge-discharge process [26]. In the initial cycle, the ions from sodium have very high mobility in the polymer matrix and after 10 cycles, ion aggregation tend to decrease thus their mobility is more stable. The calculation of the capacitance value is carried out using Eq. (4).

where is the specific capacitance ( ), is the electrode mass (gram), is the scan rate ( ), and are the initial and final potentials and is the CV area.

Table 5. Specific Capacitance of EDLC Using SPE

Sample | Area (A.V) | Scan rate (mV/s) | Specific Capacitance (F/g)
0% Salt | 1.22 × 10⁻⁶ | 10 | 0.0047
35% Salt | 6.73 × 10⁻⁶ | 10 | 0.0240

Based on the Table 5, the area of the sample is salt bigger than the sample salt. The specific capacitance is directly proportional to the area, making the specific capacitance of salt reach . In this study, the addition of salt was able to increase the specific capacitance up to 5 times. dispersed in the matrix polymer can improve the adsorption and desorption processes in the electrolyte-electrode interface during the charging and discharging process.

Fig. 11. EIS Before and After 50 Cycles Sample (a) Salt, (b) Salt

Fig. 11. EIS Before and After 50 Cycles Sample (a) Salt, (b) Salt

In the picture above, there is a Nyquist plot that shows the difference in the size of the semicircle. In the salt sample there was a significant decrease in semicircle size from to after 50 cycles. The decrease in resistance is indicated due to the influence of the ion adsorption and desorption process during charge-discharge which makes the SPE surface more conductive. Whereas in a sample of salt, the change in resistance tended to be small from to which showed that the 50 cycles did not significantly affect the mobility of ions in the polymer matrix.

Summary

The original version of this paper is available on https://www.scientific.net/EC.5.1.pdf

Synthesis SPE from rice starch makes the crystal structure of the starch turn amorphous through a gelatinization process. The addition of sodium acetate salt ( ) plays a role in improving the amorphous structure of SPE. The SPE sample with salt has the most amorphous structure. The addition of salts to the sample was evidenced by the presence of new functional groups at wavenumbers and which were identified as carboxylate functional groups antisymmetric stretching and carboxylate groups ( ) symmetric stretching. The influence of salt addition also affects decreasing the decomposition temperature and increasing the biodegradability of the sample. The effect of salt addition was seen in a significant decrease in bulk resistance of SPE samples from at salt to at salt. An increase in salt concentration indicates a decrease in resistance thus ionic conductivity becomes increased. The highest ionic conductivity is achieved by a sample of of salts with a value of . The fabrication of the EDLC is carried out with 2 graphite electrodes separated by SPE salt as a solid electrolyte. CV test results showed 5 times increase in capacitance when using SPE salt compared to SPE 0% salt.

Acknowledgment

The original version of this paper is available on https://www.scientific.net/EC.5.1.pdf

The author would like to thank the Mechanical Engineering Department and Chemical Engineering Department, Faculty of Industrial Technology, Universitas Pertamina for technical and financial support for this research.

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The original version of this paper is available on https://www.scientific.net/EC.5.1.pdf

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The original version of this eBook is available on https://www.scientific.net/book/engineering-chemistry-vol-5/978-3-0364-1502-4

Engineering Chemistry, ISSN: 2813-6535, Vol. 5, pp 13-18

doi: 10.4028/p-3BdwtU

© 2024 The Author(s). Published by Trans Tech Publications Ltd, Switzerland.

Submitted:
2022-09-30

Revised:
2023-04-28

Accepted:
2023-07-01

Online:
2024-01-19

Synthesis and Electrochemical Performance of Sodium Iron Phosphate Cathode Battery Based on Water-Chitosan Slurry

The original version of this paper is available on https://www.scientific.net/EC.5.13.pdf

Mohammad Arrafi Azhar , Andyan Rafi Setopratama , Phahul Zhemas Zul Nehan , Revaldo Anugerah Putra Pradana , Chanifa Zulaiha Ahmad , and Darminto

Physics Department, ITS Surabaya, Indonesia

Chemistry Department, ITS Surabaya, Indonesia

Materials and Metallurgical Engineering Department, ITS Surabaya, Indonesia

m.arrafi.azhar@gmail.com, rafi.nadra@gmail.com, pahul869@gmail.com, revaldoapp88@gmail.com, chanifaahmad01@gmail.com, darminto@physics.its.ac.id

Keywords: Battery, Chitosan, Electrochemical, PVDF

Abstract

The implementation of water-chitosan slurry is needed to achieve better battery, in terms of enviromentally friendly and cheapest cost. In this research, sodium-ion cathode batteries based on sodium iron phosphate and the water-chitosan slurry were successfully synthesized with the sol-gel method. The result of the X-Ray Diffraction (XRD) test confirmed the two phases of sodium iron phosphate, which are and , with the percentage weight of the phases of and , respectively. Then, this sample was examined using Scanning Electron Microscope-Energy Dispersive X-ray (SEM-EDX) test, it is known that the morphology of particles look like agglomerate thin sponges and no other elements besides , and O were found in the sample. Cyclic Voltammetry (CV) dan Electrical Impedance Spectroscopy (EIS) tests were also carried out to determine the electrochemical performance of the cathode material. The CV test was carried out to determine the specific capacity value of each sample. From the test results, it is known that sodium iron phosphate cathode with PVDF binder had a higher specific capacity value than cathode with chitosan binder, which was and , respectively. From the EIS results, it was found that sodium iron phosphate cathode with chitosan binder had better electrical conductivity and ion diffusion, with values of and respectively.

Introduction

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Batteries are components for energy storage which are able to convert chemical energy into electrical energy. One of the most popular batteries used in various electronic devices today is the lithium-ion battery. Nonetheless, lithium-ion battery technology comes with problems, which are its high cost and the limited abundance of lithium materials [1]. Hence the use of lithium materials on a large scale leads to concerns about the availability of lithium in nature. Therefore, it is necessary to search for alternative materials as a substitute for lithium. One alternative material which is suitable to be utilized as a substitute for lithium is sodium due to its properties that are almost equal to lithium. Based on the source of abundance in nature, it is safe to say that sodium is greatly abundant and can be found in seawater. Sodium also has a lower ionization potential compared to lithium, making it suitable as a candidate for new electrode materials. Consequently, today many researchers are interested in conducting studies on sodium-ion batteries either experimentally or theoretically [2].

One of the active materials for sodium-ion battery cathode that has been successfully developed is Sodium Iron Phosphate. Sodium Iron Phosphate is a polyanion-based phosphate material that possesses high voltage and good thermal stability [3]. In addition to the active cathode material, conductive (carbon-based) materials, binder materials and their solvents are necessary in making cathode material [4]. The well-known binder and solvent materials used nowadays are polyvinylidene difluoride (PVDF) and N-Methyl-2-Pyrrolidone (NMP). However, these two materials have a highly
expensive price [5]. In fact, NMP is a toxic material for the environment and has been added to the list of banned substances by the European Commission in 2018 [6]. Thus, researchers started looking for cheaper and cleaner binders and solvents. One of them is to use chitosan as a binder and water as a solvent because chitosan is the most abundant polymer in nature second to cellulose [7]. Chitosan contains amino and hydroxyl groups that are hydrophilic and soluble in water, also the presence of nitrogen increases the conductivity [8]. Chitosan with a 75% degree of deacetylation (DD) has the best conductivity than and , it is because the higher DD has a larger number of amine groups that easily protonated [7]. Based on the latest study, chitosan and PVDF have been compared by using it as a binder of battery. Chitosan binder has a higher conductivity compared to PVDF, the value of conductivity improved from to [8].

Due to the extremely high potential of the active material Sodium Iron Phosphate and chitosan as a binder, the objective of this research is to find out the effect of calcination temperature on the formation phase and to obtain the effect of chitosan binder in compared with PVDF binder on the electrochemistry test result of .

Experiments

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Sodium Iron Phosphate was synthesized using the sol-gel method. In the initial step, the researcher prepared three solutions named solution A, solution B, and solution C. Solution A is created by mixing NaCl and distilled water. Solution B was generated from and distilled water. Meanwhile, solution C was made from and distilled water. Later, the three solutions were mixed to form solution D. Solution D was dripped with ammonia solution until it reached a pH of 7 and then heated to dry. After drying, it could be ground and mashed using a mortar to produce a powder. The powder was then put into the oven at to dry. Next, the powder was calcined at for 10 hours in a free air atmosphere. The crystalline phase was confirmed using XRD (PANalytical X'Pert PRO of the PW 3040/x0 series) at angles between to . Afterwards, proceeded to the SEM (Carl Zeiss EVO MA10) testing to determine the morphology of the sample.

This research compares two cathodes which are made with PVDF binder and chitosan. Cathode with PVDF binder is created from a mixture of NFP, NMP, PVDF, and AB materials. While the cathode with chitosan binder is prepared by mixing NFP material, distilled water containing , chitosan, and AB . Both cathodes have material ratios of NFP, binder, and AB of 90:5:5, respectively [8]. Subsequently, a slurry would be obtained which was then coated on one surface of the aluminum foil which previously had been coated with copper tape on the other side. When it was deemed to be dry, the cathode was then cut into a square shape with an area of . The square cathode is then connected with cables and pipette tubes using epoxy glue.

Electron Impedance Spectroscopy (EIS) and Cyclic Voltammetry (CV) tests were conducted to determine the electrochemical performance of the cathodes. EIS testing is operated to detect the impedance values which are associated with charge transfer and conductivity in each battery cell. The curve obtained must be in the form of a Nyquist plot. Electrochemical processes taking place can be represented by equivalent circuit / (R2 + W2) which can be seen in Figure 4 where R1, R2, and W2 respectively represent ohmic, charge transfer, and Warburg resistance and Q2 represents capacitance [1]. The curve is a combination of a semicircle and a sloping line at low frequencies. While the CV test is used to determine the potential for redox reactions which occur at the cathodes [9]. The test results are in the form of a voltammogram curve that shows the relationship between voltage and current. CV testing was carried out using a tool called CorrTest Electrochemical Workstation with a scan rate of and a voltage range of . Afterwards, the reduction and oxidation peaks were determined. According to electrochemical data can have been calculated specific capacity, conductivity, and diffusion of sodium ions can be given equation [12] [13] :

Result and Discussion

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Figure 1 shows the X-Ray Diffraction (XRD) pattern of samples which have been synthesized. It is confirmed that two phases of Sodium Iron Phosphate were formed, which were and , with the percentage weight of the phases of and , respectively. is shown in , while is shown in . This represents that the Sodium Iron Phosphate has been successfully synthesized and the two phases are able to be an active material for battery cathodes as well [ 10,11 ].

Fig. 1. X-Ray Diffracion Patterns of Sodium Iron Phosphate

Fig. 1. X-Ray Diffracion Patterns of Sodium Iron Phosphate

Scanning Electron Microscopy (SEM) testing was performed to determine the morphology of the resulting sample material. The respective SEM results can be seen in Figure 2. In this figure, the morphology looks like agglomerated thin sponges with the mean of particles length of . At the same time, the Energy Dispersive X-Ray (EDX) testing was conducted to determine the composition of each element in the sample. The results of the EDX test show that the elements contained in the sample are appropriate in view of the fact that only , and O elements that appear as can be seen in Table 1.

Fig. 2. SEM Image of Sodium Iron Phosphate

Fig. 2. SEM Image of Sodium Iron Phosphate

Table 1. EDX Result of Elemental Content

Element | Percentage (%)
Na | 18.00
Fe | 10.14
P | 14.47
O | 57.39

CV testing was carried out to determine the existence of a reduction and oxidation process which afterwards would be displayed in the form of a voltammogram curve. The voltammogram curve is a curve that shows the relationship between voltage and current. In this research, CV testing was conducted using a tool called CorrTest Electrochemical Workstation with a scan rate of and a voltage range of 1.5-4 V. The CV test results from samples prepared from chitosan binder and solvent would then be compared with conventional cathode samples made from PVDF binder and NMP solvent. The results of the CV test of the two variations can be seen in Figure 3.

Fig. 3. CV Results of Sample Contain (a) and (b) Chitosan

Fig. 3. CV Results of Sample Contain (a) and (b) Chitosan

The CV results reveal that both variations have formed a cyclic curve. Nonetheless, there is no visible reduction and oxidation peaks on both curves, hence it cannot be determined whether a redox reaction occurred in these two samples. Even the CV results from these two variations had a considerable amount of noise before the smoothing process is carried out by the software. Such phenomenon can happen possibly due to the scan rate used being too high that it affects the accuracy when performing the CV test. Notwithstanding that in both samples, the anodic and cathodic peaks had not yet appeared. Nonetheless, the specific capacity is still able to be calculated using equation (1) [12].

The results of the calculation of the area of the CV graph and the specific capacity are shown in Table 2. It can be seen that the value of the specific capacity of the PVDF binder is greater than the sample using the chitosan binder, such is due to the difference in area which is generated from the CV graph. Nevertheless, by knowing the specific capacity, both samples with PVDF and chitosan binders are known to be able to store energy like the function of a battery in general.

Table 2. Calculation Results of Area and Specific Capacity

Variation | Area (V.A) | Specific Capacity (F/g) | Specific Capacity (mAh/g)
NMP + PVDF | 2.22×10⁻³ | 1.64×10⁻⁶ | 44.13
H₂O + Chitosan | 1.34×10⁻³ | 1.00×10⁻⁶ | 26.78

The EIS test was carried out using the same tool as the CV test, namely CorrTest Electrochemical Workstation. The frequency used in this test utilized a range between 0.01 Hz to . It is shown that the resulting EIS graph in Figure 4.4 has formed a Nyquist plot curve, thus the conductivity and sodium ion diffusion values of the two cathode samples can be discovered. The results of the calculation of the conductivity and diffusion of sodium ions are displayed in Table 4.

It can be seen in Table 4, the resistance (Rp) of the variation of the NMP binder sample and the PVDF solvent was lower than the sample with the variation of the chitosan binder and the solvent. However, if the conductivity is calculated by equation (2) [13], the conductivity of the sample with the variation of the chitosan binder and the solvent was greater than the variation of the
sample with the NMP binder and the PVDF solvent. As for the diffusion of sodium ions, it can be calculated using equation (3) [13].

Table 4 shows that the highest ion diffusion was found in the variation of chitosan binder and solvent. This indicates that the electron transfer that occurs on the surface of the sample particles with a variation of chitosan binder and solvent is better than the variation of PVDF binder and NMP solvent.

Fig. 4. EIS Results of Sample Contain (a) and (b) Chitosan

Fig. 4. EIS Results of Sample Contain (a) and (b) Chitosan

Table 3 Calculation Results of Sodium Ion Conductivity and Diffusion Coefficient

Variation
Rp
(Ω)
σe
(S cm⁻¹)
DNa⁺
(cm² s⁻¹)

NMP + PVDF
4.6
2.17×10⁻¹
1.31×10⁻¹¹

H₂O + Chitosan
6.3
1.58×10⁻¹
1.48×10⁻¹¹

Summary

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Sodium Iron Phosphate was successfully synthesized using the sol-gel method. From the XRD test results, two phases of Sodium Iron Phosphate material were obtained, which are and , with the percentage weight of the phases of and . CV and EIS tests were used to measure the electrochemical performance of cathode samples. From the CV results, it was discovered that the cathode sample with the PVDF binder had a higher specific capacity value than the sample with the chitosan binder, with a specific capacity of and , respectively. From the EIS results, it was found that the cathode samples using chitosan binder have better diffusion of ions but lower electrical conductivity, with values of and respectively. From the result, it represents that the battery cathodes made from water-chitosan slurry are able to be a battery cathode as well as NMP-PVDF slurry.

Acknowledgment

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This work were supported by the Indonesia Directorate General of Higher Education, Ministry of Education, Culture, Research, and Technology. The authors also acknowledge the facilities, scientific and technical support from Laboratory of Advanced Materials, Departement of Physics, Sepuluh Nopember Institute of Technology.

References

The original version of this paper is available on https://www.scientific.net/EC.5.13.pdf

S. Yadav, S. Rajoba, R. Kalubarme, V. Parale and L. Jadhav, "Solution combustion synthesis of and its electrochemical performance", Chinese Journal of Physics, vol. 69, pp. 134-142, 2021. Available: 10.1016/j.cjph.2020.11.020

D. Wang, Y. Wu, J. Lv, R. Wang and S. Xu, "Carbon encapsulated maricite NaFePO4 nanoparticles as cathode material for sodium-ion batteries", Colloids and Surfaces A: Physicochemical and Engineering Aspects, vol. 583, p. 123957, 2019. Available: 10.1016/j.colsurfa.2019.123957

C. Heubner, S. Heiden, M. Schneider and A. Michaelis, "In-situ preparation and electrochemical characterization of submicron sized cathode material for sodium-ion batteries", Electrochimica Acta, vol. 233, pp. 78-84, 2017. Available: 10.1016/j.electacta.2017.02.107

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D.L. Wood, J. D. Quass, J. Li, S. Ahmed, D. Ventola, and C. Daniel, "Technical and economic analysis of solvent-based lithium-ion electrode drying with water and NMP," Drying Technology, vol. 36, no. 2, pp. 234-244, Aug. 2017, doi: 10.1080/07373937.2017.1319855.

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M. Kuenzel et al., "Deriving Structure-Performance Relations of Chemically Modified Chitosan Binders for Sustainable High-Voltage Cathodes," Batteries & Supercaps, vol. 3, no. 2, pp. 155-164, Nov. 2019, doi: 10.1002/batt.201900140.

K. Prasanna, T. Subburaj, Y. N. Jo, W. J. Lee, and C. W. Lee, "Environment-Friendly Cathodes Using Biopolymer Chitosan with Enhanced Electrochemical Behavior for Use in Lithium Ion Batteries," ACS Applied Materials & Interfaces, vol. 7, no. 15, pp. 7884-7890, Apr. 2015, doi: 10.1021/am5084094.

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Engineering Chemistry, ISSN: 2813-6535, Vol. 5, pp 19-25

doi: 10.4028/p-Kqn5dt

© 2024 The Author(s). Published by Trans Tech Publications Ltd, Switzerland.

Submitted:
2022-09-30

Revised:
2023-07-14

Accepted:
2023-07-14

Online:
2024-01-19

Corn Starch-Sodium Acetat Composite Material from Industrial Waste Fly Ash for Solid Electrolyte Polymer Ionic Conductivity in Supercapacitor Application

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Irfani Faiq Erlangga , Sylvia Ayu Pradanawati , Azzah Dyah Pramata Nur Laila Hamidah

Department of Engineering Physics, Institut Teknologi Sepuluh Nopember

Mechanical Engineering Departement, Univesitas Pertamina, Jakarta, Indonesia 12220

Center of Advance Material, Universitas Pertamina, Jakarta 12220 Indonesia

Department of Materials and Metalurgical Engineering, Institut Teknologi Sepuluh Nopember

*Correspondence author

fairfanifaiq@gmail.com, sylvia.pradanawati@universitaspertamina.ac.id, azzah.pramata@outlook.com nurlaila@its.ac.id,

Keywords: solid polymer electrolyte; spe; fly ash; ionic conductivity; clean energy technology

Abstract

Solid polymer electrolyte (SPE) is a safer alternative to use than liquid electrolytes. This research focuses on the highest conductivity with fly ash filler in solid polymer electrolyte (SPE) based on corn starch, using the solution casting method. The crystallinity and interaction between fly ash and ions of solid polymer electrolyte were seen by X-ray Diffraction (XRD), then Fourier Transform Infra-Red (FTIR), showing a shift in functional groups due to the interaction of in fly ash and ions, and surface morphology forms was observed by Scanning Electron Microscopy (SEM). Ionic conductivity was analyzed by Electrochemical impedance Spectrometry (EIS). solid polymer electrolyte with fly ash showed the highest ionic conductivity , at room temperature with addition fly ash . the highest conductivity result was corresponding with amorphous peak with same concetration on XRD. SPE based on corn starch with Fly ash filler has potential to be used as a solid polymer electrolyte in supercapacitors.

Introduction

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The supercapacitor design is almost the same as the ordinary capacitor design which consists of a pair of electrodes filled with electrolyte and separated by a dielectric material as an insulator. In general, electrolytes are in the form of liquids, but the use of liquid electrolytes has drawbacks including being less practical, leaking easily and easily corroding [1]. Therefore, to overcome this problem Solid Polymer Electrolyte (SPE) as an alternative electrolyte in supercapacitors. SPE can overcome some of the problems inherent in liquid electrolytes, namely, it is safer than liquid electrolytes, electrode systems that have non-flammable electrolytes, better storage capacity and in terms of safety, will not leak as in liquid electrolytes [2].

Starch easily ionizes in water and forms a thin film easily. When compared to corn starch, arrowroot starch, potato starch, they have good morphology and form a flexible film that produces high ionic conductivity [3]. Therefore, solid polymer electrolytes are prepared by dissolving inorganic salts such as potassium acetate and sodium acetate in a polymer matrix. In the research of F.F. Awang (2020) added to SPE corn starch, and got an increase from to with . Therefore, in this study, sodium acetate was used as a salt solution in the polymer because it is an abundant natural earth element and is widely used [8,9]. Supercapacitors are one of the energy storage devices that can use solid electrolytes, but the lower ionic conductivity of liquid polymer electrolytes and poor accessibility to ions in the device limit their wide application in the electronics industry [13]. Therefore, to increase the ionic conductivity in several previous studies, fillers such as , and fly ash were added [2,14] it was found that the highest conductivity was obtained by the addition of fly ash.In the study of Ni'mah Y,L, et al, the maximum ion
conductivity was at with PEO-Na polymer and fly ash, then research by Wardhani A,S,S, obtained a maximum ionic conductivity of at with PEO and fly ash . This is because the excess in Fly Ash is rich in a mixture of oxides containing silicon , iron , and aluminum . Fly Ash is a waste from coal combustion in conventional power plants so it is cheap and easy to obtain. So in this study it is hoped that the use of fly ash as a filler on solid polymer corn starch and sodium acetate can increase the SPE ion conductivity in the supercapacitor and is friendly to the environment.

Materials and Methods

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A.Experiment

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The manufacture of SPE in this study was carried out by the solution casting method [2,4], Fly ash was added as a filler referring to the journal in the manufacture of electrolyte polymers which made the ionic conductivity of the spe more better [1,2]. The homogeneous solution is heated to evaporate the solution and make a solid electrolyte polymer. Heating using the oven for 8-12 hours at a temperature of . Synthesis of solid electrolyte polymer using Corn Starch as polymer, Sodium Acetate as salt, Glyserol , Aquades and using fly ash with variations of , , and as filler.

B. Materials Characterization And Electrochemical Test

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The synthesized SPE samples were then characterized using an X-ray diffractometer (XRD). X-ray diffraction measurements were carried out at an angle of and used a wavelength of filter, 40 kV and 100 mA . All samples were analyzed in the range of . FTIR Thermo Scientific Nicolet iS10 to Identification of functional groups, ionic interactions with polymers, salt and flyash. SEM (Scanning Electron Microscope) type Type FEI Inspect S50, analysis was carried out to determine the surface morphology of the solid polymer electrolyte (SPE). Image images are captured at various magnifications of and .

C. Electrochemical Test

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Electrochemical Impedance Spectroscopy (EIS) test to Measurement of resistance and capacitance using type CS Series 5 Electrochemical Workstation. Conductivity value is observed with a frequency range of ( ).

Fig. 4.1 Equivalent circuit from of EIS test on SPE [16].

Fig. 4. 1 Equivalent circuit from of EIS test on SPE [16].

The measurement results is in the form of a Nyquist plot between the imaginary impedance ( ") and the real impedance ( ) which shows the capacitance and resistance value of the material and resulting semicircle graph [16]. The equivalent circuit obtained from this SPE is as shown in Figure 4.1.

From result test can determine the ionic conductivity of the SPE sample according to equation 1.1. Where the ionic conductivity ( ) is calculated in units of , I is the thickness of the SPE sheet in centimeters, Rb is the resistance in Ohms, and A is the cross-sectional area.

Result and Discussion

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Solid polymer electrolytes (SPE) generally use natural polymers such as corn starch as a home or host, and salts as ionic dopants such as the use of sodium acetate . The performance of the solid polymer electrolyte (SPE) is based on higher value of ionic conductivity. in this case the ion in sodium acetate and and other element in fly ash is very important for higher ionic conductivity. The greater the number of ions in the polymer, under the same ion mobility conditions, the conductivity also tends to increase.

A. Solid Polymer Electrolyte (SPE) Synthesis Results

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The results of the synthesis will be in the form of SPE film sheets like the results of previous solid polymer synthesis experiments .

Fig. 4.2 Solid electrolyte polymer (SPE)

Fig. 4. 2 Solid electrolyte polymer (SPE)

The results of the SPE film sheet in Figure 4.2 with different variations of fly ash. It can be seen that the variation without using fly ash has a transparent white color and a smoother surface. fly ash variation which has a contrast apperance with brown color and a rougher surface than non varian fly ash, the higher the flyash concentration added it have darker color and the rougher surface [2].

B. XRD Analysis

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XRD characterization aims to identify the pattern of crystalline and amorphous microstructures that occur in the synthesis of solid electrolyte polymers. The diffraction pattern of the addition of corn starch, and fly ash samples.

Fig. 4.3 Comparison of XRD pattern of SPE

Fig. 4. 3 Comparison of XRD pattern of SPE

The results of the XRD pattern show that the increase of amount fly ash increases, the diffraction peaks gradually decrease and there is new identical peak at with increase of amount fly ash from content in fly ash (green color symbol). The results figure 4.3, its seen how to corn starch as host polymer at peak (red color symbol) and sodium acetat produces an amorphous SPE [11] at peak (yellow color symbol) , and . The addition of filler fly ash and show XRD pattern and with there no fly ash addition ( ) have more sharp amorphous peak.

The result indicates that fly ash can be reduces crystallinity of entirety XRD pattern but show a new peaks but still more amorphous than without addition of fly ash and XRD peaks are increasingly sloping down accordance with amorphous structure . The decrease in crystallinity of the spe to amorphous makes the solid polymer properties change to be more electrolyte and higher ionic conductivity. The amorphous polymer electrolyte matrix facilitates the mobility of ions in the matrix, with an increase in the mobility of ions in the matrix, charge transfer increases so that the Solid Polymer Electrolyte becomes more conductive [2,12].

C.FTIR Analysis

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Change in the frequency of the strain or bending vibration of a particular bond of the SPE sample can be characterized by FTIR and local interactions of the polymer with the salt and fly ash. The peak intensity, peak shift associated with the presence of salt and the emergence of new bonds due to the presence of fly ash in the polymer.

Fig. 4.4 FTIR Spectrum Result of SPE

Fig. 4. 4 FTIR Spectrum Result of SPE

The FTIR spectrum without fly ash and with various concentrations of fly ash filler obtained by FTIR spectrophotometer in the range of can be observed in Fig. 4.4. Infrared spectra of corn starch polymer and without fly ash filler identified characteristic peaks at , group. After adding Fly Ash with various variations, the peaks in the wave number are identified. Fly ash peaks can usually be observed in the wavelength range of and the activation of fly ash creates vibrations that make the peaks sharper [2].

D. Morphological Analysis

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SEM (Scanning Electron Microscope) analysis was carried out to determine the surface morphology of the solid polymer electrolyte (SPE)

Fig. 4.5 Surface Morfology of SPE with 15,000x magnification

Fig. 4. 5 Surface Morfology of SPE with 15,000x magnification

In sample solid polymer electrolyte with the addition of fly ash and show membrane looks rough, textured and hollow be arranged randomly (irregularly), while the bond between the polymer chains are well arranged. It can be seen that the three components of the raw material react to form, which and pull the polymer chains to form pores in the spe film, figure 4.5. In addition, larger pore size will also contribute to higher ion penetration through the system for ion conduction. Therefore, it is clear that the number of voids or pores formed causes the porosity of the SPE film to increase. This makes that the higher conductivity value is influenced by the porosity of the SPE film [8,9].

E. Electrochemical Analysis

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The most important thing about solid polymer electrolyte (SPE) is the conductivity value. To determine the conductivity value, it is necessary to know the value of the bulk resistance ( Rb ). To analyze the Electrochemical Impedance Spectroscopy (EIS) test, and use the CS Studio 5 software. The conductivity value is observed with a frequency range of . From the results of a quarter circle nyquist plot at low frequencies on the real Z axis, it shows that there is a change in the conductivity of the added fly ash concentration figure 4.6

Fig. 4.6. Nyquist Plot SPE at Room Temperature

Fig. 4. 6. Nyquist Plot SPE at Room Temperature

In addition to confirming the value of bulk resistance ( Rb ) obtained from the results of electrochemical semicircle fit fittings, the equivalent circuit, Figure 4.1 explains how the SPE is assembled. A battery based on the equivalent circuit in Figure 4.6, it can be seen that the bulk resistance (Rb) is the SPE resistance value between the capacitance units. The conductivity value is
influenced by the bulk resistance and the thickness of the sample. the lower the bulk resistance, the greater the conductivity and the thicker the sample, the higher the ion conductivity.

The results Table 4.1 of the Ionic Conductivity based on Equivalent circuit from EIS test determine the ionic conductivity of the SPE sample according to equation 1.1. Table 4.1 shows, have the highest Ionic conductivity of and lowest bulk resistance ( Rb ) to. The conductivity reuslt are related to the amorphicity properties of the starch host, also reported by previous experiment.

Table 1. Ionic Conductivity Value (S.cm ) for Each Sample

Sample
t
(cm)
Rb
(Ω)
σ
(S/cm)

CS - CH₃COONa
0,22 x10⁻¹
256.7632
8,56 x 10⁻⁵

CS - CH₃COONa + FA 10%
0,32 x10⁻¹
127.4762
2,51 x 10⁻⁴

CS - CH₃COONa + FA 20%
0,22 x10⁻¹
147.4804
1,49 x 10⁻⁴

Conclusion

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Based on the results of research analysis on SPE samples, it can be concluded as follows: The addition of fly ash filler can affect the characteristics of the SPE show from EIS analysis of addition of fly ash have more higher ionic conductivity with it consist From the XRD results, it is known that the addition of Fly Ash to SPE can reduce the level of crystallinity and turn it into a more amorphous one, and identical peak at with increase of amount fly ash. Then from the results of the ftir there is a minor shift of the functional group due to the presence of salt, The results of the SEM also shows that the surface structure is more larger area with cracks existence with addition of fly ash indicate more ion store in SPE and higher ionic conductivity.

Acknowledgement

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The authors gratefully acknowledgement financial support from the Institut Teknologi Sepuluh Nopember for this work, under project scheme of the Publication Writing and IPR Incentive Program (PPHKI).

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The original version of this paper is available on https://www.scientific.net/EC.5.19.pdf

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Ni'mah, Y. L., Taufik, M. F., Maezah, A., & Kurniawan, F. (2018). Increasing the ionic conductivity of solid state polymer electrolyte using fly ash as a filler. Malaysian Journal of Fundamental and Applied Sciences, 14(4), 443-447.

Amran, N. N. A., Manan, N. S. A., & Kadir, M. F. Z. (2016). The effect of LiCF 3 SO 3 on the complexation with potato starch-chitosan blend polymer electrolytes. Ionics, 22(9), 1647-1658.

Awang, F. F., Kamarudin, K. H., & Hassan, M. F. (2020). Employing an Electrochemical Impedance Spectroscopy Technique to Estimate the Ion Transport Parameters in Corn Starch Based Solid Polymer Electrolyte. International Journal of Advanced Research in Engineering Innovation, 2(3), 78-88.

Awang, F. F., Hassan, M. F., & Kamarudin, K. H. (2021). Corn starch doped with sodium iodate as solid polymer electrolytes for energy storage applications.

Ramesh, S., Shanti, R., & Morris, E. (2012). Exerted influence of deep eutectic solvent concentration in the room temperature ionic conductivity and thermal behavior of corn starch based polymer electrolytes. Journal of Molecular Liquids, 166, 40-43.

Ramesh, S., Shanti, R., & Morris, E. (2012). Studies on the plasticization efficiency of deep eutectic solvent in suppressing the crystallinity of corn starch based polymer electrolytes. Carbohydrate polymers, 87(1), 701-706.

Kumar, M. S., & Rao, M. C. (2019). Effect of Al 2 O 3 on structural and dielectric properties of PVP-CH3COONa based solid polymer electrolyte films for energy storage devices. Heliyon, 5(10), e02727.

Kumar, M. S., & Rao, M. C. (2018). Dielectric studies on PVP-CH3COONa based solid polymer electrolytes. Materials Today: Proceedings, 5(13), 26405-26410.

Kasturi, P. R., Ramasamy, H., Meyrick, D., Lee, Y. S., & Selvan, R. K. (2019). Preparation of starch-based porous carbon electrode and biopolymer electrolyte for all solid-state electric double layer capacitor. Journal of colloid and interface science, 554, 142-156.

Alvarez-Ramirez, J., Vazquez-Arenas, J., García-Hernández, A., & Vernon-Carter, E. J. (2019). Improving the mechanical performance of green starch/glycerol/Li+ conductive films through cross-linking with . Solid state ionics, 332, 1-9.

Abdullah, A. M., Aziz, S. B., Brza, M. A., Saeed, S. R., Al-Asbahi, B. A., Sadiq, N. M., ... & Murad, A. R. (2022). Glycerol as an efficient plasticizer to increase the DC conductivity and improve the ion transport parameters in biopolymer based electrolytes: XRD, FTIR and EIS studies. Arabian Journal of Chemistry, 15(6), 103791.

Verma, M. L., Minakshi, M., & Singh, N. K. (2014). Synthesis and characterization of solid polymer electrolyte based on activated carbon for solid state capacitor. Electrochimica Acta, 137, 497-503.

Hwang, M., San Jeong, J., Lee, J. C., Yu, S., Jung, H. S., Cho, B. S., & Kim, K. Y. (2021). Composite solid polymer electrolyte with silica filler for structural supercapacitor applications. Korean Journal of Chemical Engineering, 38(2), 454-460.

Alvarez-Ramirez, J., Vazquez-Arenas, J., García-Hernández, A., & Vernon-Carter, E. J. (2019). Improving the mechanical performance of green starch/glycerol/Li+ conductive films through cross-linking with . Solid state ionics, 332, 1-9.

Abdul Halim, S. I., Chan, C. H., & Apotheker, J. (2021). Basics of teaching electrochemical impedance spectroscopy of electrolytes for ion-rechargeable batteries-part 1: a good practice on estimation of bulk resistance of solid polymer electrolytes. Chemistry Teacher International, 3(2), 105-115.

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Engineering Chemistry, ISSN: 2813-6535, Vol. 5, pp 27-35

doi: 10.4028/p-2wZJJR

© 2024 The Author(s). Published by Trans Tech Publications Ltd, Switzerland.

Submitted:
2022-10-01

Revised:
2023-06-16

Accepted:
2023-06-18

Online:
2024-01-19

Solid Polymer Electrolyte (SPE) from Corn Starch and Aluminum Nitrate Salt Composites for Aluminum - Ion Battery

The original version of this paper is available on https://www.scientific.net/EC.5.27.pdf

Khoirul Anam , Sylvia Ayu Pradanawati , Azzah Dyah Pramata Nur Laila Hamidah

¹Department of Engineering Physics, Institut Teknologi Sepuluh Nopember, Kampus ITS Sukolilo, Surabaya 60111, Indonesia

Department of Mechanical Engineering, Universitas Pertamina, Jakarta 12220 Indonesia

Center of Advanced Materials, Universitas Pertamina, Jakarta 12220 Indonesia

Department of Materials and Metalurgical Engineering, Institut Teknologi Sepuluh Nopember, Kampus ITS Sukolilo, Surabaya 60111, Indonesia

khoirulanam.206009@mhs.its.ac.id,

Corresponding authors: sylvia.pradanawati@universitaspertamina.ac.id, azzah@its.ac.id nurlaila@its.ac.id,

Keywords: Aluminum-ion battery, Solid Polymer Electrolyte, corn starch, ionic conductivity, and Amorphous

Abstract

The increasing of need for portable electrical energy makes the demand for rechargeable batteries high. Aluminum-ion battery with Solid Polymer Electrolyte (SPE) produced from the natural polymer corn starch with salt additive has the potential to be developed. The flexibility and resilience of SPE are enhanced by glycerol ( ). Throughing gelatinization of the linear monomer chains to become amorphous, the space for the ions in it is more free so that the ionic conductivity is high. By means of solution casting, heating temperature of for 9 hours found SPE with a strong structure. With the same concentration CS-Al has a higher conductivity with than CS-Na whose value is . This is due to the SPE CS-Al show more amorphous structure which allow more flexible ionic segmental motion. This is in accordance with XRD resulting which shows that the addition of aluminum nitrate salt is more amorphous than sodium acetate; the shift in peak pattern is also greater due to cation intercalation with corn starch. FTIR is the result found that nitrate fixed by corn starch, indicated a change in the hydroxyl group of corn starch amylopectin. SEM photo of result also showed aluminum nitrate salt ion more easily in overcoming than sodium acetate. The indicate of SPE was more homogeneous because corn starch was already intercalated. They are combined to and ions. With this value it can be an appropriate reference for developing SPE on Aluminum-ion batteries with aluminum nitrate salts have higher performance and environment friendly.

1. Introduction

The original version of this paper is available on https://www.scientific.net/EC.5.27.pdf

The development of the battery is started from a primary battery (non-rechargeable) with a small ability to store electrical energy and then developed into a secondary battery (rechargeable). Currently, the most of the secondary batteries on the market are based on lithium ion. This happens because lithium-based batteries can store and provide considerable energy and also power [1]. In addition, lithium metal has electropositive properties, thus providing a high energy density [2]. In fact, the abundance of lithium in nature is very limited, and the waste lithium-ion batteries are included in B3 (Toxic and Hazardous Materials) waste [3]. So, there is an urgent needs to find alternative battery technologies that it can be ballance costs and performance with environment friendly .

Aluminum is a metal with a fairly high abundance in the earth's crust ( ), has a gravimetric energy density of and volumetric capacity times higher than [4] so that aluminum is an ideal element for rechargeable batteries [5]. The differentiate with the lithium, there are other metals such as sodium [6], potassium [7], magnesium
[8] and aluminum [9]. It can be used for reversible intercalation or deintercalation processes. The differentiate between to sodium and potassium, aluminum has a smaller ion size, higher theoretical capacity and is less reactive, making it easier to handle. [10].

Starch is a renewable, inexpensive polysaccharide polymer, and contains a lot of -OH chemical particles so that it is open to the possibility of modification and the ability to melt processes in the presence of plasticizers [11]. The Corn starch which consists of long chains of starch molecules and when heated in a dissolved state will cause the solution to thicken. This condition is due to the reaction of water absorption or the gelatinize process into corn starch. This starch has many advantages over synthetic plastics which are generally single-use applications with superior mechanical and electrical characteristics [12], It can be produced at low cost, there are abundant and renewable raw materials with good biocompatibility [13] [14] [15]. In addition, other properties of corn starch are solubility and high recrystallization stability from the amorphous phase [16].

The most natural polymers are such as starch exhibit relatively low ionic conductivity [17]. To increase the conductivity, several attempts have been made such as by mixing the polymer to produce [18], plasticization to produce [19], the addition of ceramics produced and the addition of NaCl salt resulted . Based on the research results, the concentration and type of salt also affect the ionic conductivity of the polymer. The higher is the salt concentration, the lower the degree of dissociation [22].

The relationship between aluminum and corn starch to be used as a battery making material is that the aluminum as an ion-producing metal with a hollow structure, while corn starch using as a space holder or as a polymer matrix whose ionic conductivity can be increased by adding salt. By being formed as a positive and negative electrode of aluminum metal, ionic conductivity will occur between the two poles when connected to a conductive polymer material so that a rechargeable battery system can be produced [10]. Conditioning the polymer electrolyte in the solid state is the right choice compared to the liquid or gel form. This is because in the solid state of the material in addition to its main properties of high ionic conductivity, other desirable properties are to have good electrochemical stability, flexibility, leakage free so that it is safe to use, and has a long life cycle [23].

2. Research Description

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2.1 SPE Synthesis

Making SPE by solution casting, aluminum nitrate is put in 50 ml of in a beaker while stirring at 1200 rpm for 15 minutes to dissolve optimally, then 1.75 ml of glycerol or 2.198 grams and 2.5 grams of corn starch were added. This process was continued while the solution and it is still stirred, 10 minutes later the beaker in covering with plastic wrap and put in a water bath and hot plate magnetic stirrer with a temperature of and 1200 rpm for 1 hour until homogeneous. The liquid was removed to be cooled while being stirred again for 10 minutes and poured into a petri dish. Furthermore, it is evaporated to increase the viscosity of the solution by placing it in an oven at for 9 hours until the liquid forms a solid so that SPE sheets are produced from corn starch. Show in Figure 1.

Fig. 1. SPE synthesis process of SPE in the laboratory

Fig. 1. SPE synthesis process of SPE in the laboratory

This process is also for sodium acetate salt , accordance with research that has been carried out the optimal concentration for sodium-based SPE is at [24]. So in this research were 3 test samples, SPE of cornstarch without salt (CS) as baseline, SPE aluminum nitrate (CSAl ) and SPE sodium acetate (CS-Na).

The use of aluminum nitrate salt SPE material in the aluminum-ion battery system is according to the following scheme in Figure 2

Fig. 2. SPE Coin cell design for Aluminum-ion Battery

Fig. 2. SPE Coin cell design for Aluminum-ion Battery

The cathode contains aluminum foil because it is ionically and electrically conductive. The anode negative electrode is used graphite foil, because it is able to store and release ion charges well, has a long usage cycle rate, is easy to process, and safe to use. SPE as a solid electrolyte besides functioning as a conductor of aluminum ions from the anode to the cathode and on the contrary with its solid form also functions as a separator to prevent short circuits and contacts between the cathode and anode. This SPE separator is ionic conductive but not electrical conductive.

2.2 Characterization of SPE Materials

Electrochemical Impedance Spectroscopy (EIS) was chosen over the Four Point Probe (FPP) because EIS produces more comprehensive data, can analyze electrochemical kinetic parameters related to the electrical elements of resistance (R), capacitance (C) and induction (L) of an electrode to AC potential signal at low amplitude ( ) over a very wide frequency range, whereas FPP is limited to measuring its resistivity only. Identify the phase and its crystal structure by looking at the graph between the diffraction angle (20) and the intensity using an X'pert PRO PANalytical type XRD measuring instrument which has an X-ray diffract to meter of radiation with a wavelength of in the range of . The scan rate is with an angle of from an X-ray source with a wavelength of 532 nm . The Identification of functional groups, ionic interactions
with polymers based on the level of vibrational energy and rotation of the bonds using FTIR Thermo Scientific Nicolet iS10 type. The surface topography and sample size were generated by the SEM Type FEI Inspect S50 test, which is a three-dimensional photo of the sample surface.

2.3 Measurement of Electrical Conductivity of SPE Material Materials

Measurement of resistance and capacitance are properties of SPE using EIS type CS Series Electrochemical Workstation. The performing is at a frequency of 0.001 Hz to 100.000 Hz . Electrical conductivity is calculated using the equation:

With is SPE conductivity ( ), 1 is the thickness ( cm ), A is the area and Rs is the membrane resistance as measured by EIS using the 2 probe DC method following Debye's response, as shown in Figure 3 below :

Fig. 3. (a) SPE depiction scheme with 2 blocking electrodes (b) Equivalent Circuit Model located between 2 blocking electrodes [25]

Fig. 3. (a) SPE depiction scheme with 2 blocking electrodes (b) Equivalent Circuit Model located between 2 blocking electrodes [25]

The measurement results is in the form of a Nyquist plot between the imaginary impedance ( ) and the real impedance ( ) which shows the capacitance and resistance value of the material. The equivalent circuit obtained from this SPE is as shown in Figure 4 below:

Fig. 4. Equivalent Circuit Material SPE Corn Starch.

Fig. 4. Equivalent Circuit Material SPE Corn Starch.

The impedance value is obtained by fitting curve with the resulting imperfect semicircle graph so that CPE, and components are used to simulate the conductivity of the 2 probes used.

2.4 Results and Discussion

SPE data from research as shown in figure 5 below (a) CS (b) CS-Al (c) CS-Na

Fig. 5. SPE material synthesis results

Fig. 5. SPE material synthesis results

The results of the diffraction pattern test of the cornstarch sample without aluminum nitrate salt showed 4 peaks in the diffraction pattern and with the addition of aluminum nitrate salt there were 3 peaks. This shows the lower crystallinity of the material (more amorphous). The amorphous peak is described as a broad and continuous peak [26].

Fig. 6. Corn Starch SPE Diffractogram.

Fig. 6. Corn Starch SPE Diffractogram.

Figure 6 shows the initial condition of pure corn starch contained 4 peaks which were quite large after SPE formed with the addition of glycerol, the structure became they were more amorphous as indicated by the more gentle slope of the XRD spectrum, with the addition of salt there was a decrease in peak and shift. In the CS-Al found 4 peaks at and indicating type A corn starch [27]. At a concentration of , only 3 peaks were found at and , without the formation of new peaks and only experienced a shift, indicating a change to type B starch crystals [28]. The heated starch polymer causes a lot of water to be adsorbed, the hydrogen bonds between starch polymers weaken so that water is absorbed, making the size of the starch molecules increase. Heating to a temperature of 80 oC gelatinization reaches its optimum some of the amylose begins to loosen so that the molecular chain structure becomes more open, amylose crystals expand up to from containing 4 water molecules to 36 molecules per unit crystal cell, monolithic crystal type becomes hexagonal, the double helix chain becomes stranded parallel, so that a new crystal type polymorphy is formed from type A to type B [29]. The number of peaks in salt was less than the baseline CS-Na which still found 4 peaks at , and . The less number of peaks formed indicates that SPE with the addition of aluminum nitrate is more amorphous than sodium acetate. The shift and the gentler slope of this peak is due to the insertion of ions from into the corn starch crystals.

Based on the identification of functional groups, the results of the FTIR showed the presence of bonded alkane group in the wavelength range of , describing the content of corn starch as amylose hydrocarbon compound

Fig. 7. Spectrum of FTIR SPE Corn Starch.

Fig. 7. Spectrum of FTIR SPE Corn Starch.

Figure 7 shows a clear difference in the appearance of the absorption peak, at the wavelength of at CS-Al more widens than CS-Na, indicates the amilopectin more higher than amylose. Amylose is compactly arranged in the crystalline region while amylopectin is arranged in the amorphous region. Amorphous structure is formed because the fixation of nitrate compounds by corn starch. The nitrate ions are produced by aluminum nitrate compounds which dissociate into ions and ions. It can be indicated CS-Al more amorphous than CS-Na.

Based on the SEM test image at Figure 8, it appears that at pure CS there are still white lumps which are the remnants of corn starch which are not all dissolved and undergo gelatinization, but after adding 15% aluminum nitrate salt (CS-Al), gelatinization and SPE homogenization are faster. This process have result a brighter structure indicating SPE already intercalated with aluminum nitrate salt ions. But there are also some in small amounts that have not been dissolved. In addition, cracks were found in the sample, this increases the contact surface area so that it can accommodate more ions . While in the CS-Na, in finding that there were wrinkles on the surface which indicated the smaller the contact surface so that it accommodated fewer ions than aluminum nitrate

Fig. 8. SEM test results of SPE Corn Starch with a magnification of 15,000 X and measuring scale

Fig. 8. SEM test results of SPE Corn Starch with a magnification of 15,000 X and measuring scale

Nyquist plot as a resulted EIS test of sample has show in almost the same impedance curve response forming a semicircular pattern.

Fig. 9. Plot Results of Corn Starch SPE Nyquist

Fig. 9. Plot Results of Corn Starch SPE Nyquist

Figure 9 shows at a pure CS, it has a large semi-circle size which indicates a large impedance, after the addition of 15% aluminum nitrate salt, the semicircle tends to decrease drastically which means the conductivity is high. Compared to addition sodium acetate salt at the same concentration, is still smaller than aluminum nitrate. It meaning the conductivity SPE CS-Al more higher than CSNa.

Based on the curve fitting of the Nquist plot graph pattern above, it was found the value Rs to determines the conductivity of this SPE, with values such as the following table:

Table 1. Results measurements SPE materials from equivalent circuit method

No | Concentration | l (cm) | A (cm²) | Rs (Ω) | σ (S/cm)
1 | CS-Al 0% | 0,32 x10⁻¹ | 1 | 3620 | 8,84 x10⁻⁶
2 | CS-Al 15% | 0,36 x10⁻¹ | 1 | 730 | 4,93 x 10⁻⁵
3 | CS-Na 15% | 0,22 x10⁻¹ | 1 | 753,6 | 2,92 x 10⁻⁵

Use equation 1, it appears that the conductivity of is much greater than that of with a value is almost twice of .

3. Summary

The original version of this paper is available on https://www.scientific.net/EC.5.27.pdf

The synthesys of SPE had made from corn starch can be done by solution casting technique by heating in an oven for 9 hours at a temperature of . This structure becomes stronger supported by the addition of glycerol. It was found that the conductivity value of CS-Al was greater than that of CS- Na whose value was . This is due to the SPE CS-Al show more amorphous structure which allow more flexible ionic segmental motion. This is also supported by XRD results which show that the addition of aluminum nitrate salt is more amorphous than sodium acetate, the shift in peak pattern is also greater due to the intercalation of cations into corn starch. The results of FTIR found that there was fixation of nitrate compounds by corn starch, indicated a change in the hydroxyl group of corn starch amylopectin. The results of the SEM photos also shows that the surface structure is brighter and there are cracks that make the touch surface area larger so that the energy storage has a larger capacity. This makes it a good reference for developing SPE on Aluminum-ion batteries with aluminum nitrate salts.

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The original version of this paper is available on https://www.scientific.net/EC.5.27.pdf

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The original version of this eBook is available on https://www.scientific.net/book/engineering-chemistry-vol-5/978-3-0364-1502-4

Engineering Chemistry, ISSN: 2813-6535, Vol. 5, pp 37-42

doi: 10.4028/p-FrjE6w

© 2024 The Author(s). Published by Trans Tech Publications Ltd, Switzerland.

Submitted:
2022-10-28

Revised:
2023-06-04

Accepted:
2023-06-14

Online:
2024-01-19

Enhanced lonic Conductivity of Fluoride-Doped as Solid Electrolyte of Lithium-lon Battery

The original version of this paper is available on https://www.scientific.net/EC.5.37.pdf

Muhammad Rizal Afif , Vania Mitha Pratiwi , Lukman Noerochim

1Department of Materials and Metallurgical Engineering, Sepuluh Nopember Institute of Technology, Surabaya 60111, Indonesia

Department of Materials and Metallurgical Engineering, Sepuluh Nopember Institute of Technology, Surabaya 60111, Indonesia

Department of Materials and Metallurgical Engineering, Sepuluh Nopember Institute of Technology, Surabaya 60111, Indonesia

rizalapip@gmail.com, vaniamithapratiwi@gmail.com,

Abstract

In this study, (LTP) was synthesized by the addition of lithium fluoride (LiF) of , and . A wet solid-state reaction method is applied by mixing , and into a ball mill, then calcined at for 12 hr . XRD pattern of Fluoride-doped LTP is indexed and found in two phases. First is the Nasicon phase with rhombohedral structure, and second, the Olivine phase with orthorhombic structure at the addition of and of LiF. The higher LiF decreases the cell volume while the crystallite size, particle size, and material density increase. The morphology of the Fluoride-doped LTP is increasingly homogeneous and more rectangle-shape. LTP 2, adding of LiF, has high ionic conductivity at as a promising candidate material for solid-electrolyte of lithium-ion battery.

Introduction

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Nowadays, batteries are one of the most widely used energy storage technology. Lithium-ion batteries are widely used in portable electronic devices and electric vehicles. Unfortunately, lithiumion battery is hampered by their flammable electrolyte solution component . It is a significant problem regarding the safety of using this type of lithium battery.

Current technological developments lead to the use of lithium-ion batteries with all components in a solid state . In particular, using solid electrolytes can improve the performance and safety of lithium-ion batteries. Ceramic oxide electrolyte is a material that has the potential as a solid electrolyte because of its high chemical stability in the environment . Solid electrolyte type NASICON is a promising candidate because of its high ionic conductivity, stability, and low cost, especially .

However, using ceramic oxide electrolytes has drawbacks in high resistivity directly proportional to the interface between the electrolyte and the electrodes and lack of electrochemical stability . Many studies have been conducted to improve the performance of . Partial substitution of with trivalent elements and with trivalent elements has been shown to increase the lithium concentration in the solid phase . However, high electrolyte density is only obtained at hightemperature sintering for several hours. Various sintering methods have been developed to increase the density and reduce the possibility of lithium loss in the high-temperature process . This sintering method is challenging to perform and increases the cost of solid electrolyte preparation.

Another strategy is adding molten material to the solid electrolyte, which will reduce the loss of lithium and affect its density . Lithium Fluoride (LiF) salt can be selected to be mixed in the manufacture of solid electrolytes because it has properties as a densifying agent . Therefore, in this study, variations in the addition of melted Lithium Fluoride (LiF) were carried out, which could improve the performance of solid electrolytes of the type of NASICON LiTi .

Experimental Procedures

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Materials Preparation

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was synthesized using the solid-state reaction method. First, , and are mixed by using a ball mill with methanol as solvent. The ball-to-powder ratio is , and the ball mill speed is 400 rpm for 10 hours. Then, the precursor mixture was calcined at a temperature of for 12 hours. The as-prepared powder is ground using a mortar. Before forming into pellets, powder was mixed with LiF with variations of , and wt., and then formed pellets were formed using a press with a pressure of 25 MPa . The pellets were sintered to stabilize the phase at a temperature of for 12 hours.

Electrochemical characterization

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In this study, to determine the phase formed in the sample, XRD testing was carried out using the PAN Analytical instrument with an angle range of with a wavelength of . For samples without the addition of LiF , prior to the XRD test, the sample was ground in the form of grinding it first using a mortar to obtain a homogeneous size. Meanwhile, samples with the addition of LiF were tested in the form of pellets. The SEM Inspect S50 machine with an energy of 20 kV was used to observe the morphological sample. Specimen preparation was carried out by grinding using a mortar and then coating the surface using AuPd to prevent charging when using SEM. The electronic conductivity test uses the EIS method with the Corrtest type CS350 Potentiostat. EIS measurements use a small AC signal of 20 mV and a DC bias voltage of more than 3 V to produce a curve that can form a semi-circular arc pattern on the Nyquist Plot graph.

Results and Discussion

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The XRD characterization results showed the peak match between the synthesized material with ICDD No. 00-35-0754, as shown in Fig. 1. From these results, it is also seen that other phases appear at of , indicating that the material has a high degree of crystallinity. XRD pattern shows that the diffraction peak of the sample is relatively narrow, indicating the high crystallinity of the sample. The fitting results of the XRD show the addition of LiF , causing the intensity of the peak to increase and the width of the peak to be narrower. It indicates an increase in the material's crystallinity, affecting the conductivity of the sample.

The XRD pattern also shows the formation of Nasicon phase with rhombohedral crystal structure in all samples. However, several peaks with low intensity are not in accordance with ICDD No. 00-35-0754. The diffraction peaks formed at angles of , and were identified as the peaks of (ICDD 00-038-1468) and (ICDD 01-083-2243) compounds. and compounds appeared in all samples. Based on research by Kee et al. , the impurities in the LTP sample are formed from the decomposition reaction of . It is due to the transition of into the gas phase at temperatures above with following reaction

Fig. 1. XRD pattern of pure LTP, LTP 0, LTP 1, and LTP 2

Fig. 1. XRD pattern of pure LTP, LTP 0, LTP 1, and LTP 2

Samples with the addition of LiF showed the emergence of another phase, namely the Olivine phase, which has an orthorhombic crystal structure. The formation of the was induced by the addition of LiF which reacted with and impurities. The appearance of impurities in can be avoided using the active precursor synthesized at temperatures below . At this temperature, the active precursors of can be formed without the appearance of and . XRD data were also analyzed quantitatively by manual calculations and the Rietveld method using Rietica software. Analysis in the form of relative weight fraction, lattice parameter values, and crystal size. Table 1 shows the results of the phase composition formed in each sample.

Table 1. Percentage of Phase Composition

Sample | LiTi₂(PO₄)₃ (%) | LiTiPO₅ (%)
LTP 0 | 100 | -
LTP 1 | 89.85 | 10.15
LTP 2 | 74.37 | 25.63

Table 1 shows the percentage composition of the phase with Nasicon structure formed in all LTP samples, while the secondary phase in the form of Olivine phase was formed in samples with LiF . The lattice parameters obtained from Rietveld's analysis are shown in Table 2. The lattice parameter of shows of 8.5129, c of 20.878, and cell volume of . The increased addition of LiF decreased the size of the lattice parameters and cell volume. The decrease in cell volume indicates that there is an exchange of oxygen ions with fluoride ion where the atomic radius of fluoride is smaller than the atomic radius of oxygen .

Table 2. Comparison of lattice parameters and cell volume of

Sample
a (Å)
b(Å)
c(Å)
V (Å³)

ICDD
00-35-0754
8.513
8.513
20.878
1310.31

LTP 0
8.513
8.513
20.875
1310.053

LTP 1
8.514
8.514
20.856
1309.109

LTP 2
8.511
8.511
20.850
1307.817

The crystal size calculation was carried out using the Debye Scherrer equation, with the results shown in Table 3. The pure LTP obtained a crystal size of 75.06 nm . In general, the addition of LiF will reduce the crystal size. With the addition of LiF of , there was an increase in particle size, reaching 97.42 nm , then at the addition of , it increased to 108.93 nm . This increase in crystal size will improve the mobility of lithium ions while increasing ionic conductivity .

Table 3. Crystallite size .

Sample | Crystallite size(nm)
LTP 0 | 75.06
LTP 1 | 97.42
LTP 2 | 108.93

The surface morphology of the samples can be seen from the SEM characterization results in Fig. 2. All samples showed a poor rectangular particle shape with varying particle sizes. Adding LiF resulted in the size of the particle shape getting bigger and closer to a perfect rectangle. In pure obtained particles with a size of . The addition of resulted in an increase in particle size to . Meanwhile, the particle size of the sample with the addition of was . In the LTP 2 sample, the addition of LiF has the particle size much more homogeneous than the other samples. SEM characterization also shows the porosity of the sample. All samples showed the presence of porosity. The greater the addition of LiF, the less visible porosity. It shows that adding LiF will help the particle enlargement process, reducing the grain boundaries so that the amount of porosity decreases. This condition will affect the conductivity of the material. The less porosity will increase the ionic conductivity of the material . The reduced amount of porosity was confirmed by increasing the density of . The increase in material density is shown in Table 4.

Fig. 2. SEM images of (a)LTP 0, (b) LTP 1, and (c) LTP 2

Fig. 2. SEM images of (a)LTP 0, (b) LTP 1, and (c) LTP 2

Table 4. Density of

Sample | Density (gr cm⁻³)
LTP 0 | 0.768
LTP 1 | 0.776
LTP 2 | 0.779

Measurement of the impedance of the LTP solid electrolyte sample using Electrochemical Impedance Spectroscopy (EIS). The frequency range used is . Characteristics of EIS curve consist of a semicircle arc pattern (semicircle) and straight lines. Semicircle in EIS is related to the electrolyte resistance (Re) and charge transfer resistance (Rct). While the straight line indicates the diffusion/intercalation-de-intercalation process of lithium. The EIS test was carried out using a pellet-shaped sample with silver paste coated on both sides. The Nyquist curve plot of the EIS test results can be seen in Fig. 3. It can be seen that all samples have a single semicircle curve with different diameters. The size of the semicircle diameter shows the impedance value, the larger the diameter, the higher the impedance value, and vice versa. LTP 0 seems to have the smallest semicircle. Meanwhile, LTP 2 shows the largest semicircle diameter, indicating a large sample's
impedance value. However, it should be noted that the main property of solid electrolyte to be obtained from the EIS test is electrolyte conductivity because the increase in the size of the semicircle indicates a large change in the grain boundary impedance which is a charge transfer resistance. The value of the EIS test results is shown in Table 5.

Fig. 3. Nyquist Plot of

Fig. 3. Nyquist Plot of

The addition of LiF showed the value of the electrical conductivity and total conductivity decreased. However, the total conductivity value does not indicate that this material is suitable for use as a solid electrolyte. As for electrical conductivity, adding LiF affects the material have better electrical conductivity as a solid electrolyte. Because the characteristics required by solid electrolytes are to have good ion conduction ability but low electron conduction ability to avoid short circuit in their application. This is in accordance with a study conducted by Kunshina , on the high-frequency Nyquist curve associated with lithium ion transfer characterized by the value of electrolyte resistance and low frequency indicating grain boundary properties characterized by electronic resistance. Adding LiF enhances the solid electrolyte by increasing the ionic conductivity and decreasing the electrical conductivity.

Table 4. Conductivity of

Sample | Density (gr cm⁻³)
LTP 0 | 0.768
LTP 1 | 0.776
LTP 2 | 0.779

It can be seen that LTP 2 has the highest ionic conductivity of but has the lowest electrical conductivity of .

Conclusion

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The solid electrolyte synthesis of lithium titanium phosphate using the solid-state reaction method was successfully carried out. It is found two phases formed in the sample, namely Nasicon phase with a rhombohedral structure and a secondary phase in the form of Olivine phase ( ) with an orthorhombic structure. The formation of single phase Nasicon occurred at a concentration of . There is a second phase for the concentration of LiF of and , namely Olivine . The greater the concentration of LiF added, the increased percentage of the secondary phase formed. At the same time, the crystal size, particle size, and density of the material get bigger. The morphology of the resulting material looks
more homogeneous and is getting closer to a perfect rectangular shape, indicating an increasing crystallinity. Adding LiF improves solid electrolyte performance . The best performance value was obtained in the LTP 2, the addition of LiF of , which has an ionic conductivity of but had a low electron conductivity of . It is due to phase and morphological changes after the addition of LiF .

References

The original version of this paper is available on https://www.scientific.net/EC.5.37.pdf

Xiong, L. et al. LiF assisted synthesis of solid electrolyte with enhanced ionic conductivity. Solid State Ionics 309, 22-26 (2017).

Oh, G., Hirayama, M., Kwon, O., Suzuki, K. & Kanno, R. Bulk-Type All Solid-State Batteries with 5 V Class Cathode and Solid Electrolyte. Chem. Mater. 28, 2634-2640 (2016).

Tatsumisago, M., Takano, R., Tadanaga, K. & Hayashi, A. Preparation of glass-ceramic electrolytes for all-oxide lithium batteries. J. Power Sources 270, 603-607 (2014).

Liang, Y., Peng, C., Kamiike, Y., Kuroda, K. & Okido, M. Gallium doped NASICON type thin-film grown on graphite anode as solid electrolyte for all solid state lithium batteries. J. Alloys Compd. 775, 1147-1155 (2019).

Inaguma, Y. et al. Effect of lithium isotopes on the phase transition in NASICON-type lithiumion conductor . Solid State Ionics 321, 29-33 (2018).

Xu, X. et al. The preparation and lithium mobility of zinc based NASICON-type solid electrolyte . Ceram. Int. 40, 3819-3822 (2014).

Kosova, N. V, Devyatkina, E. T., Stepanov, A. P. & Buzlukov, A. L. Lithium conductivity and lithium diffusion in NASICON-type ; 0.3 prepared by mechanical activation. Ionics (Kiel). 14, 303-311 (2008).

Chen, K., Shen, Y., Zhang, Y., Lin, Y. & Nan, C.-W. High capacity and cyclic performance in a three-dimensional composite electrode filled with inorganic solid electrolyte. J. Power Sources 249, 306-310 (2014).

Kwatek, K. & Nowiński, J. L. The lithium-ion-conducting ceramic composite based on with addition of LiF. Ionics (Kiel). 25, 41-50 (2019).

Kee, Y., Dimov, N., Minami, K. & Okada, S. Orthorhombic Lithium Titanium Phosphate as an Anode Material for Li-ion Rechargeable Battery. Electrochim. Acta 174, 516-520 (2015).

Kwatek, K. & Nowiński, J. L. Electrical properties of and solid electrolytes containing ionic liquid. Solid State Ionics 302, 54-60 (2017).

Banyamin, Z. Y., Kelly, P. J., West, G. & Boardman, J. Electrical and Optical Properties of Fluorine Doped Tin Oxide Thin Films Prepared by Magnetron Sputtering. Coatings vol. 4 732746 (2014).

Yu, C. et al. Revealing the relation between the structure, Li-ion conductivity and solid-state battery performance of the argyrodite Li6PS5Br solid electrolyte. J. Mater. Chem. A 5, 2117821188 (2017).

Aono, H., Sugimoto, E., Sadaoka, Y., Imanaka, N. & Adachi, G. Ionic Conductivity of Solid Electrolytes Based on Lithium Titanium Phosphate. J. Electrochem. Soc. 137, 1023-1027 (1990).

Kunshina, G. B., Bocharova, I. V & Ivanenko, V. I. Preparation of the solid electrolyte with high ionic conductivity. Inorg. Mater. Appl. Res. 8, 238-244 (2017).

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Engineering Chemistry, ISSN: 2813-6535, Vol. 5, pp 43-48

doi: 10.4028/p-n3dhJR

© 2024 The Author(s). Published by Trans Tech Publications Ltd, Switzerland.

Submitted:
2023-03-28

Revised:
2023-06-08

Accepted:
2023-06-14

Online:
2024-01-19

Study of Addition Metal (Ti, Zn) Dopan on The Structure of NASICON as Solid Electrolyte Batteries

The original version of this paper is available on https://www.scientific.net/EC.5.43.pdf

Vania Mitha Pratiwi , Lukman Noerochiem , Hariyati Purwaningsih , Agung Ari Wibowo , Fakhri Akbar Maulana

1Department of Materials and Metallurgical Engineering, Faculty of Industrial Technology, and Systems Engineering, Institut Teknologi Sepuluh Nopember (ITS), Surabaya

Department of Chemical Engineering, Politeknik Negeri Malang, JI. Soekarno Hatta No. 9, Malang, 65141, Indonesia

Department of Metallurgical and Materials Engineering,University of Indonesia, Kampus UI, Depok, Indonesia

vaniamitha@mat-eng.its.ac.id, lukman@mat-eng.its.ac.id, chariyati@mat-eng.its.ac.id,

Keywords: NASICON, doping metal, titanium, zinc, ionic conductivity

Abstract

This study aims to analysized the effect of addition doped metal (Ti and Zn) on NASICON structure to morphology, materials structure, and electrochemical performance especially ionic conductivity properties. NASICON is a sodium super ionic conductor that it could be as solid electrolyte batteries. One of the problems that exist in the secondary battery is the low working temperature of the electrolyte, which makes it easy to explode when exposed to free air. The common electrolyte in liquid phase, so NASICON as replacement alternative. The synthesis method used is the solid-state reaction method by mixing sodium carbonate, silicon dioxide, zirconium oxide, ammonium dihydrogen phosphate, doped metal (titanium oxide and zinc oxide) and some anhydrous ethanol into a planetary ball mill, dried then calcined. Then the material is pressed to produce pellets and the sintered. The doping used varies from 0 to of titanium and zinc. XRD results showed that all variations in titanium doped had found rhombohedral and monoclinic. whereas in zinc doping also have those phase. The highest ionic conductivity is on Zinc Addition

Introduction

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As is common knowledge, daily-used electronic devices include backup batteries that can be recharged. Due to its high energy density, lengthy lifespans, and performance as free memory, lithium-ion batteries are typically utilized as energy storage [1]. However, LIB also has safety drawbacks because the electrolyte employed is a liquid electrolyte that explodes when it comes into contact with air. As a result, NASICON is an alternative since it is a solid electrolyte [2], is extensively distributed in nature, and also has nearly the same properties as lithium, allowing it to be employed as a battery material with a big capacity [3].

The NASICON type of solid electrolyte, which uses sodium ions instead of lithium ions as charge carriers, is the type that is frequently utilized. The structure, one of the well-known NASICON kinds, has the benefit of being a stable crystal structure[4]. In order to transmit ions when used in a battery, ions in the NASICON type must pass through a bottlenecklike barrier when employed as a Solid State Electrolyte (SSE). By adding the necessary substituents as doping to the NASICON structure, it is a standard practice to increase the bottleneck size, hence increasing the ionic conductivity [2].

NVP (type-NASICON) has undergone structural modification by doping or replacement to enhance the electrochemical performance and energy density. Previous studies found that substituting , and Cr improved the electrical conductivity or ion diffusivity, which showed promise for enhancing the electrochemical characteristics. In sodium diffusion channels, for instance, dopant ion substitution can reduce the average bond length or raise the unit cell volume [5]. In addition, research has also been carried out on the addition of doping magnesium by with an ionic
conductivity value of [3], Cerium with the addition of and that the total ionic conductivity value of the sample , and N 5 respectively, namely ; ; and [6], while Yanli Ruan et al. obtained the conductivity value from the NASICON sample with dopant in the form of ytria which has a bulk conductivity value of , while the total conductivity is [7].

Vania Mitha Pratiwi et al. investigated the use of titanium oxide as a dopant for the NASICON sample in 2019. The use of titanium varies from to . The optimum value for the variation of the addition of in the ionic conductivity test was . Danchen et al. obtained conductivity values ranging from 0.1 to 0.4 at room temperature , namely , , and . Total conductivity, as is well known, is an inherent electrochemical property that is primarily influenced by the geometry of the bottleneck [9]. The effect of adding zinc oxide and titanium oxide to the NASICON structure was investigated in this study. The cation is expected to be replaced by zinc and titanium.

Experimental Procedure

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Solid-state reaction technique was used to create the solid electrolyte Na 3 Zr 2 Si 2 PO 12 . To begin, combine ethanol with , and the dopan ( ) in a ball mill. and ZnO are added in amounts ranging from to mole fraction. Ball milling is done for 12 hours at 400 rpm , followed by 12 hours of drying at . Then, it is calcined for 12 hours at at a heating rate of per minute. A mortar is then used to crush the powder. An X-ray diffraction tester (X'pert PRO PANalytical) and scanning electron microscopy were used to characterize each variant (FEI Inspect S50).

Preparation of Solid Electrolyte Pellets: A mold with a 10 mm diameter circle was used to produce a pellet out of the weighted NASICON sample. NASICON powder was compressed for 7 minutes. In an alumina crucible, the pellets are sintered for 12 hours at a temperature of and a heating rate of min-1 to stabilize their phase. To determine the ionic conductivity value, all materials were evaluated using an electrochemical impedance spectroscopy tester (CorrTest CS310)

Result and Discussion

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To determine the crystalline phase, the samples that were obtained were examined using an X-ray diffraction tester. In accordance with JCPDF Nos. 01-084-1200 ; and 01-087-0617 , respectively, the dominant structures of the produced NASICON on titanium doping were monoclinic at 0 , and and rombhohedral at . as with Ti doping According to JCPDF No. 01-084-1200 and 01-087-0617, respectively, the structure of the produced NASICON on zinc doping was rhombohedral at ; and and monoclinic at 0 and . It was discovered that the NASICON crystal structure changed from monoclinic to rhombohedral as a result of the addition of doping material. The aberrations in the crystal structure are the cause of these modifications. The calculation of the XRD diffraction pattern also provides information about the increase in lattice parameters. Monoclinic , and , are impurities that have been discovered.

Fig. 1. X-Ray Diffraction Pattern of NASICON doped Ti at variation

Fig. 1. X-Ray Diffraction Pattern of NASICON doped Ti at variation

Fig. 2. X-Ray Diffraction Pattern of NASICON doped Zn at variation

Fig. 2. X-Ray Diffraction Pattern of NASICON doped Zn at variation

Fig. 3. SEM images of Titanium doped NASICON after sintering with 10000x magnification a) , b) , c) , d) , e) f)

Fig. 3. SEM images of Titanium doped NASICON after sintering with 10000x magnification a) , b) , c) , d) , e) f)

Fig.4. SEM images of Zinc doped NASICON after sintering with 10000x magnification
a) , b) , c) , d) , e) f)

Fig.4. SEM images of Zinc doped NASICON after sintering with 10000x magnification a) , b) , c) , d) , e) f)

In Figure 3, the micro-graph images provided by SEM testing of titanium doped NASICON with variation of mol percentages. The morphology of pellet after sintering which contain 1,3 , and mol has an indicate of good densification owing to less void compared to the other sample. That Figure (Figure 4) shown the morphology powder after calcination, which , and mol contain of zinc doping is very good at densification and less void so particle that look dense

Fig. 5. Result of EIS tester for (a) Titanium doped NASICON (b) Zinc doped NASICON at 0-5% mol addition.

Fig. 5. Result of EIS tester for (a) Titanium doped NASICON (b) Zinc doped NASICON at 0-5% mol addition.

Fig. 6. The conductivity value (a) Titanium doped NASICON (b) Zinc doped NASICON at mol addition.

Fig. 6. The conductivity value (a) Titanium doped NASICON (b) Zinc doped NASICON at mol addition.

The Nyquist curves of titanium and zinc doped NASICON at addition are shown in Figure 5. Samples of electrolyte were sintered for 12 hours at . The sample's total conductivities were calculated by fitting the pattern's data to the data on the CorrTest CS310. Total ion conductivity increases up to a doping concentration of 0.02 as can be observed, but it subsequently declines as the concentration of zinc doping increases. However, there are anomalous data for titanium doping. The NASICON lattice characteristics rise with increasing Ti and Zn doping concentration, as discussed in the XRD analysis, which expands the lithium-ion transmission channels and improves ion conductivity [1].

Grain resistance and grain boundary resistance make to the total resistance for the NASICON electrolyte. Grain resistance and grain boundary resistance exhibit responses in the high- and midfrequency ranges, respectively. The blocking effect of the electrode ions is shown in the lowfrequency region by slanted straight lines. The results of EIS testing for samples with various doping content values are shown in Figure 4.a. All samples initially had a semicircular response, but the addition of doping caused a shift in frequency to the right or to a lower frequency.

As is well known, the geometry of the bottleneck has a significant impact on the total conductivity, which is an inherent electrochemical feature. There are two parts to the impact of various dopants on bulk conductivity. First and foremost, while the dopant level in the valence state drops, bulk conductivity rises. This means that the higher conductivity is a result of the dopant's lower valence state. The sodium ions and dopants will be less attracted to one another due to the low valence cations that are present at the zirconium sites. It requires less energy for the sodium ions to diffuse around the zirconium ions because there is less electrostatic connection between them. As a result, the doped NASICON ceramics exhibit an improvement in overall conductivity. Additionally, the and doped NASICON ceramics create oxygen vacancies and zirconium vacancies to preserve charge neutrality. ions can move via openings and voids. The ions are allowed to migrate into the empty space, increasing the bulk conductivity [9].

In addition, Figure 6 displays the titanium and zinc doping's ionic conductivity values for all variations. Figure 5 shows that a 2 %mole addition of zinc has a smaller semicircle and lower impedances, which indicates a higher conductivity. The value, , is higher than that found in earlier studies [4]. The conductivity of the generated sample ions changes as a result of variations in the crystal structure. There will be more sodium ions in one crystal unit due to an increase in sodium ion sites caused by the electrostatic interaction between sodium ions and the octahedral structure of the crystal diminishing. The ionic conductivity increases with the number of charge carrier ions.

Conclusion

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A solid electrolyte of the titanium and zinc-doped NASICON type was successfully synthesized in this study. The crystal structure created in the NASICON sample is known to be rhombohedral, which will later transform into monoclinic depending on the quantity of doping used. The NASICON sample appears to have a compact structure with a reasonably adequate degree of densification as dopant concentrations increase. This influences the sample's ionic conductivity, with increased densification directly enhancing ionic conductivity by decreasing grain resistance and grain boundaries. For and doping, the greatest ionic conductivity is and , respectively. The NASICON solid-type electrolyte's high conductivity value has the potential to replace liquid-based electrolytes, lowering the risk of a battery explosion.

References

The original version of this paper is available on https://www.scientific.net/EC.5.43.pdf

Qiaohui Wang, Lei Liu, Bojie Zhao, Lei Zhang, Xiao Xiao, Hao Yan, Guoli Xu, Lei Ma, and Yong Liu,"Transport and Characteristics of Te-doped NASICON Solid Electrolyte ", Electrochimica Acta 399 , 2021, pp. 139367. Available: https://doi.org/10.1016/j.electacta.2021.139369

Blomgren, George E. 2017. "The Development and Future of Lithium Ion Batteries." Journal of The Electrochemical Society 164 (1), 2016: 5019-5025.

Vania Mitha Pratiwi, Lukman Noerochiem, Widyastuti, Hariyati Purwaningsih, Diah Susanti, Fakhri Akbar Maulana, "The Effect Of Magnesium Doping On The Structure And Conductivity Of NASICON As Solid Electrolyte," 2021. AIP Conference Proceedings 2384, 050007 (2021);

Ong, Balachandran Radhakrishnan & Shyue Ping. 2016. "Aqueous Stability of Alkali Superionic Conductors from First-Principles Calculations." Frontiers in Energy Research 4: 16-28, 2016.

Jun Lee, Sohyun Park, Young Park, Jinju Song, Balaji Sambandam, Vinod Mathew, JangYeon Hwang, Jaekook Kim., "Chromium doping into NASICON-structured cathode for high-power Na-ion batteries," Volume 422, 15 October 2021, 130052, Available:

Bingxing Xie, Danyu Jiang, Jian Wu, Tao Feng, Jinfeng Xia, & Hongqiang Nian. 2016. "Effect of substituting Ce for Zr on the electrical properties of NASICON materials." Journal of Physics and Chemistry of Solids 88: 104-108. 2016.

Yanli Ruan, Shidong Song, Jingjing Liu, Ping Liu, Bowen Cheng, Xiangyun Song, & Vincent Battaglia. 2017. "Improved structural stability and ionic conductivity of solid electrolyte by rare earth metal substitutions." Ceramics International 43 (10): 7810-7815.2017. Available:

Pratiwi, Vania Mitha, et al. "Characterization of NASICON Structure Prepared with Titanium Dioxide Doping for NOx Gas Sensor Application." Materials Science Forum. Vol. 964. Trans Tech Publications Ltd., 2019. Available : . 964.168

Dan Chen, Fa Luo, Wancheng Zhou, Dongmei Zhu. 2018. "Influence of and doped solid electrolyte on its conductivity." Journal of Alloys and Compounds. Volume 757, 15 August 2018, Pages 348-355. Available:

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Engineering Chemistry, ISSN: 2813-6535, Vol. 5, pp 49-56

doi: 10.4028/p-i1dZ9Z

© 2024 The Author(s). Published by Trans Tech Publications Ltd, Switzerland.

Submitted:
2023-03-31

Revised:
2023-07-06

Accepted:
2023-07-14

Online:
2024-01-19

The Effect of Nitrogen on the Capacitive Properties of N-Doped rGO/CuCr Composites as Materials for Supercapacitors

The original version of this paper is available on https://www.scientific.net/EC.5.49.pdf

Diah Susanti , Adzon Nugraha Rizky Pratama and Haniffudin Nurdiansah

Materials and Metallurgical Engineering Department, Institut Teknologi Sepuluh Nopember (ITS), Surabaya, Indonesia

*Corresponding author email: santiche@mat-eng.its.ac.id, adzonnrp@gmail.com,

Keywords: Hydrothermal, Specific Capacitance, N-Doped rGO/CuCr2O4 composite, Hybrid Supercapacitor

Abstract

A hybrid supercapacitor is an energy storage device that combines the properties of EDLCs and pseudocapacitors. In this research, the goal was to analyze the effect of hydrothermal temperature on the structure, morphology, and capacitive properties of the N-Doped reduced graphene oxide/Copper Chromite (N-Doped ) composite, which was being investigated as a potential material for hybrid supercapacitor electrodes. The method used was hydrothermal, with temperature variations of , and . The structure and morphology of the composites were analyzed using Scanning Electron Microscope (SEM) and Energy Dispersive X-Ray Analysis (EDX), X-Ray Diffractometer (XRD), and Fourier Transform Infrared Spectrometer (FTIR). Meanwhile, the capacitance and conductivity values of N-doped were measured using Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS) tests. The results of the XRD tests showed that an increase in temperature led to a greater value, indicating the presence of more substituted nitrogen atoms. This was supported by the results from EDX, which showed that the sample with a hydrothermal temperature of had the largest percentage of nitrogen. Nitrogen is important in increasing the conductivity of the material. The FTIR results revealed a covalent bond between Carbon (C) and Nitrogen (N). Meanwhile, the results of the CV test, performed at a scan rate of and a potential window of , showed that the specific capacitance values were , and for the samples with hydrothermal temperatures of , and , respectively. The EIS test measured the conductivity values of the samples, which were 0.123 , 0.518 , and for the samples with hydrothermal temperatures of , and , respectively. Thus, the specific capacitance values were influenced by the electrical conductivity of the materials and the nitrogen doping content in the electrode composite material.

Introduction

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Indonesia is working with the United Nations as part of the global effort to achieve the goals outlined in the Sustainable Development Goals (SDGs) framework. As part of this effort, the country is transitioning from fossil fuels to renewable energy sources for electricity generation, and reliable energy storage solutions are needed. Electrochemical supercapacitors are a promising option for energy storage.

Supercapacitors are among the top electrical energy storage technologies, offering advantages such as fast charging times, long life cycles, environmental sustainability, and high-temperature operation. There are three main types of supercapacitors: Electrochemical Double-Layer Capacitors (EDLCs), pseudocapacitors, and hybrid supercapacitors [1]. The capacitance of EDLCs can be increased by using materials with high surface areas, such as graphene [2], while the capacitance of pseudocapacitors can be boosted by combining carbon with pseudocapacitive materials, such as metal oxides.

Graphene is a crystalline form of carbon with a diamond-like crystal structure [3]. It boasts impressive physical properties, including a tensile strength of 130.5 GPa , Young's modulus of 1.0 TPa [4], low density ( ), a high specific area (up to ), intrinsic mobility (up to ), and thermal conductivity (up to ) [5].

A hybrid supercapacitor electrode with optimal capacitance can be achieved by combining the properties of EDLCs and pseudocapacitors. is a metal oxide commonly used in pseudocapacitor electrodes due to its capacitive properties, cyclic stability, and high-power density [6]. By combining rGO and , a hybrid supercapacitor can be produced. Nitrogen doping of reduced graphene oxide (rGO) can effectively enhance its electronic properties by introducing an additional free electron into the carbon structure of rGO. This process not only alters the chemical composition but also influences the capacitive properties of N -doped rGO [7]. Therefore, this research aimed to examine the impact of hydrothermal temperature on the structure, morphology, and capacitive properties of the N -doped composite material as a hybrid supercapacitor.

Experiments

The original version of this paper is available on https://www.scientific.net/EC.5.49.pdf

The synthesis process of was carried out by dissolving , and using distilled water and stirring for 30 minutes to achieve homogeneity. The resulting precipitate was filtered using filter paper and dried at for 12 hours. Calcination was then performed at a temperature of for 2 hours to obtain powder.
rGO was synthesized via a modified Hummer method. 2 g of graphite powder was stirred into 80 ml of solution at an ice bath temperature for 4 hours. After 4 hours of stirring, , and were gradually and alternately added to the solution. The stirring was continued at for 20 hours outside the ice bath and then 200 ml of distilled water was gradually added and stirred for another hour until the solution became homogeneous.
The remaining content in the solution was removed by adding of 20 ml of and stirring for 30 minutes. The solution was then centrifuged for 1 hour at 2500 rpm and the precipitate was washed with to remove the remaining metal ions. The washing process was repeated until the pH was neutral.
Nitrogen doping on rGO was performed using and 2 mL of were mixed with 50 mL of distilled water in a 100 mL beaker glass. The mixture was ultra-sonicated for 30 minutes to facilitate the entry of and into the interlayer area of rGO. The mixture was then placed into a stainless-steel autoclave and hydrothermally treated in a furnace with temperature variations of , and for 4 hours each, followed by drying for 12 hours.
The N-doped rGO/CuCr2 composite was synthesized using the sol-gel method. N-doped rGO and were ultrasonicated separately for 2 hours each, then mixed in a 95:5 ratio of N -doped rGO to and stirred at 500 rpm for 2 hours. The resulting precipitate was washed with distilled water until the pH was neutral and dried at for 12 hours. This process resulted in the formation of an N-doped composite.
A solution of N -doped composite and distilled water at a ratio of 1 mg of N -doped composite: 1 mL of distilled water was deposited on Nickel foam using ultrasonic for 90 minutes to form a working electrode of hybrid supercapacitor. The samples were dried at for 12 hours, compressed, and weighed to measure the mass of the N -doped composite deposited on the Nickel Foam surface. The prepared electrodes were then tested using Cyclic Voltammetry (CV) instrument and Electrochemical Impedance Spectroscopy (EIS) with 1M electrolyte solution.
The materials characterizations performed in this study included X-ray Diffraction (XRD), Fourier Transform Infra-Red (FTIR), Energy Dispersive X-Ray Analysis (EDX), Cyclic Voltammetry (CV), and Electrochemical Impedance Spectroscopy (EIS). Electrochemical measurements, specifically cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), were conducted using a three-electrode setup. The setup included the composite sample as the working
electrode, a graphite rod as the counter electrode, and a standard calomel electrode (SCE) as the reference electrode. CV measurements were performed within a potential window of at scan rates of , and . On the other hand, EIS tests were conducted at frequencies ranging from 0.1 to with an AC amplitude of 10 mV and a DC potential of 0 V . For ease in the designation, the composite treated at was labeled as , at was labeled as N-rGO140, and at was labeled as N-rGO160, and the electrodes were labeled as E120, E140, and E160.

Result and Discussion

The original version of this paper is available on https://www.scientific.net/EC.5.49.pdf

Fig. 1. X-Ray Diffraction pattern of N-rGO/CuCr2 composite material compared to standard XRD patterns of materials.

Fig. 1. X-Ray Diffraction pattern of N-rGO/CuCr2 composite material compared to standard XRD patterns of materials.

Fig. 1 displays the XRD pattern of the composite material. The peaks corresponding to N-rGO marked with solid circles can be seen at and (JCPDF No 41-1487) [8]. The XRD pattern displayed similarities to that of graphite; however, it exhibited an amorphous structure characterized by low intensities and broadened peaks. The XRD peaks of , marked with diamond symbols, indicate a tetragonal structure (JCPDS No 88-0110) [9]. Additionally, the XRD pattern reveals the presence of as an impurity (JCPDS No 01-072-2355) [10]. Using Bragg's Law, the of rGO, N-rGO120, N-rGO140, and N-rGO160 were , and 3.73 nm , respectively. Therefore, the increased as the hydrothermal temperature was raised, suggesting that more nitrogen atoms were incorporated into the carbon atom lattice arrangement at higher temperatures. As the lattice spacing expanded further at higher temperatures, more dopants could penetrate the material structure.

The crystallite sizes of rGO, N-rGO120, N-rGO140, and N-rGO160 were determined using the Debbye-Scherrer formula and found to be , and , respectively. While the values were not significantly different, the crystallite sizes appeared to decrease slightly with increasing temperature.

Fig. 2. FTIR result of composite material

Fig. 2. FTIR result of composite material

Fig. 2 illustrates the results of the FTIR analysis performed on the N-rGO/CuCr2O4 composite material. The absorption peaks at 550 and are associated with the and vibrations of , respectively, which has been previously reported [11]. Furthermore, other IR peaks were detected at , and , representing the , and bonds, respectively. The presence of and peaks indicated Nitrogen doping in rGO, while the and peaks suggested the presence of rGO bonds.

Fig. 3 depicts the N-rGO/CuCr composite deposited on the surface of a nickel foam. The composite material effectively filled the pores of the nickel foam, promoting the smooth flow of electrons and ions.

Fig. 3. N-rGO/ was deposited on Ni foam

Fig. 3. N-rGO/ was deposited on Ni foam

Fig. 4. Cyclic Voltammetry (CV) diagrams of N-rGO120, N-rGO140, and N-rGO160.

Fig. 4. Cyclic Voltammetry (CV) diagrams of N-rGO120, N-rGO140, and N-rGO160.

Figure 4 presents the CV curves normalized as specific capacitance ( ) vs. potential (V) at different scan rates of , and . As the scan rate increased, the CV curves and specific capacitances decreased. This decrease can be attributed to the fact that a slower scan rate allows more charges, in the form of electrons and ions, to be stored and released from less accessible sites within the hybrid supercapacitor electrode, leading to higher specific capacitances. All the CV diagrams exhibit almost symmetrical curves at the y -axis ( 0 Ampere current) and nearly horizontal rectangular shapes, indicating nearly ideal electrochemical supercapacitor behaviours.

Table 1 displays the specific capacitances, specific energy densities, and specific power densities of the electrodes at various scan rates. The electrode labelled as E160 exhibited the highest specific capacitances and specific energy densities, followed by samples E140 and E120. Interestingly, the specific power density values showed an inverse relationship to the specific energy density values. As the specific energy densities increased, the supercapacitor required more time to charge and discharge, resulting in lower power densities. It is important to note that power density is determined by dividing energy density by time.

The highest specific capacities at scan rate of were , and 99.5 for samples E 160 , E 140 , and E 120 respectively. The specific capacitances of E 160 ranged from to at scan rates ranging from to . Similarly, the specific capacitances of E140 ranged from to , while those of E120 ranged from to . It is worth noting that these values were found to be lower than those reported by Sarkar, et.al (2020) for supercapacitors made from the same composite material of . Specifically, the specific capacitances at a scan rate of and potential window of -0.2 V to 0.4 V were reported as and for the composition ratios of 90:10, 95:5, and 98:2 respectively. However, our values were higher than those reported by Angelika, et.al (2022) who reported the highest specific capacitance of for the same composite material at scan rate of and potential window of [13].

Table 1. Specific Capacitance, Specific Energy Density, and Specific Power Density of The Samples based on the CV measurements

Sample
Scan rate
(mVs⁻¹)
Cs (Fg⁻¹)
Specific Energy
Density, W (Whkg⁻¹)
Specific Power
Density, P (Wkg⁻¹)

E120
5
99.5
8.8
99.8

10
83.4
7.3
164.8

25
59.7
5.3
298.4

50
38.4
3.4
384.2

100
29.4
2.6
587.8

E140
5
196.2
17.4
196.8

10
168.5
14.9
336.9

25
124.4
11.1
622.1

50
82.9
7.4
829.3

100
55.7
4.9
1113.5

E160
5
221.6
19.7
222.3

10
192.7
17.1
385.4

25
135.5
12
677.5

50
89.1
7.9
891.4

100
55.1
4.9
1101.5

Table 2 displays the based on XRD measurement, nitrogen content based on EDX, electrical conductivity based on EIS measurement, and specific capacitance based on EIS measurement. The EDX analysis results indicate that the N-rGO120 sample contained nitrogen, while the N-rGO140 and N-rGO160 samples contained and nitrogen, respectively. These findings suggest that as the hydrothermal temperature increased, the nitrogen content in the composite material also increased. The higher temperature during the hydrothermal process likely provided more energy for the decomposition of nitrogen from and facilitated its insertion into the carbon lattice, leading to the increased nitrogen content in the composite material. This trend confirmed the XRD results written above, which indicated that as the temperature increased, the of carbon increased from , to 3.73 nm , suggesting the insertion of more nitrogen into the carbon lattice. As the consequences, the electrical conductivities also increased from , to . The specific capacitance values were seemed to be determined by the electrical conductivities as shown from the CV measurements, in which the E160 showed the highest specific capacitances.

In table 2, the specific capacitance calculated based on EIS measurement at 0.1 Hz showed in-line trend with the results from CV measurement. The values of , and resulted from samples , and E 160 , respectively, were comparable to those from CV measurements at .

Table 2. , nitrogen content based on EDX, electrical conductivity based on EIS measurement, and specific capacitance based on EIS measurement

Sample | dspacing (nm) (XRD) | Nitrogen Content (%) (EDX) | Conductivity (Sm⁻¹) (EIS) | Specific Capacitance (Fg⁻¹) (EIS)
E120 | 3.59 | 11.74 | 0.123 | 33.6
E140 | 3.61 | 12.9 | 0.518 | 115.4
E160 | 3.73 | 14.88 | 0.549 | 116.2

Summary

The original version of this paper is available on https://www.scientific.net/EC.5.49.pdf

In conclusion, this study found that increasing the hydrothermal temperature led to a reduction in rGO, decreased the crystal size, and increased the value, indicating successful nitrogen substitution. This was confirmed by the EDX test, which showed the highest nitrogen content of in the sample treated at a hydrothermal temperature of . The results of the CV and EIS tests showed that the hybrid supercapacitor electrode ( ) combined the characteristics of EDLC and pseudocapacitors, confirming the successful formation of the hybrid supercapacitor electrode. The highest capacitance value observed in the E160 sample was at scan rate due to the highest conductivity value of .

Acknowledgment

The original version of this paper is available on https://www.scientific.net/EC.5.49.pdf

This work was financially supported by the Directorate of Research and Community Service (DRPM), Sepuluh Nopember Institute of Technology (ITS). The authors also acknowledge the facilities, scientific and technical support from Materials Chemistry Laboratory, Corrosion, and Material Failure Laboratory, and Materials Characterization Division, Department of Materials and Metallurgical Engineering - ITS.

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The original version of this paper is available on https://www.scientific.net/EC.5.49.pdf

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Keywords Index

A

Aluminum-ion Battery Solid Polymer Electrolyte (SPE) from Corn Starch and Aluminum Nitrate Salt Composites for Aluminum - Ion Battery

Amorphous The Effect of Sodium Acetate on Biodegradable Rice Starch-Based Solid Polymer Electrolyte for Supercapacitor

And Amorphous Solid Polymer Electrolyte (SPE) from Corn Starch and Aluminum Nitrate Salt Composites for Aluminum - Ion Battery

B

Battery Synthesis and Electrochemical Performance of Sodium Iron Phosphate Cathode Battery Based on Water-Chitosan Slurry

C

Chitosan Synthesis and Electrochemical Performance of Sodium Iron Phosphate Cathode Battery Based on Water-Chitosan Slurry

Corn Starch Solid Polymer Electrolyte (SPE) from Corn Starch and Aluminum Nitrate Salt Composites for Aluminum - Ion Battery

D

Doping Metal Study of Addition Metal (Ti, Zn) Dopan on The Structure of NASICON as Solid Electrolyte Batteries

E

Electrochemical Synthesis and Electrochemical Performance of Sodium Iron Phosphate Cathode Battery Based on Water-Chitosan Slurry

H

Hybrid Supercapacitor The Effect of Nitrogen on the Capacitive Properties of N-Doped rGO/CuCr Composites as Materials for Supercapacitors

Hydrothermal The Effect of Nitrogen on the Capacitive Properties of N-Doped rGO/CuCr Composites as Materials for Supercapacitors

I

Ionic Conductivity The Effect of Sodium Acetate on Biodegradable Rice Starch-Based Solid Polymer Electrolyte for Supercapacitor; Solid Polymer Electrolyte (SPE) from Corn Starch and Aluminum Nitrate Salt Composites for Aluminum - Ion Battery; Study of Addition Metal (Ti, Zn) Dopan on The Structure of NASICON as Solid Electrolyte Batteries

N

N-doped Rgo/cucr2o4 Composite The Effect of Nitrogen on the Capacitive Properties of N-Doped rGO/CuCr Composites as Materials for Supercapacitors

Nasicon Study of Addition Metal (Ti, Zn) Dopan on The Structure of NASICON as Solid Electrolyte Batteries

P

Pvdf Synthesis and Electrochemical Performance of Sodium Iron Phosphate Cathode Battery Based on Water-Chitosan Slurry

R

Rice Starch The Effect of Sodium Acetate on Biodegradable Rice Starch-Based Solid Polymer Electrolyte for Supercapacitor

S

Salt The Effect of Sodium Acetate on Biodegradable Rice Starch-Based Solid Polymer Electrolyte for Supercapacitor

Sodium Acetate The Effect of Sodium Acetate on Biodegradable Rice Starch-Based Solid Polymer Electrolyte for Supercapacitor

Solid Polymer Electrolyte The Effect of Sodium Acetate on Biodegradable Rice Starch-Based Solid Polymer Electrolyte for Supercapacitor; Solid Polymer Electrolyte (SPE) from Corn Starch and Aluminum Nitrate Salt Composites for Aluminum - Ion Battery

Solid Polymer Electrolyte; Spe; Fly Ash; Ionic Conductivity; Clean Energy Technology Corn Starch-Sodium Acetat Composite Material from Industrial Waste Fly Ash for Solid Electrolyte Polymer Ionic Conductivity in Supercapacitor Application

Specific Capacitance The Effect of Nitrogen on the Capacitive Properties of N-Doped rGO/CuCr Composites as Materials for Supercapacitors

Supercapacitor The Effect of Sodium Acetate on Biodegradable Rice Starch-Based Solid Polymer Electrolyte for Supercapacitor

T

Titanium Study of Addition Metal (Ti, Zn) Dopan on The Structure of NASICON as Solid Electrolyte Batteries

Z

Zinc Study of Addition Metal (Ti, Zn) Dopan on The Structure of NASICON as Solid Electrolyte Batteries

Authors Index

A

Afif, M. Enhanced lonic Conductivity of Fluoride-Doped

Ahmad, C. Synthesis and Electrochemical Performance of Sodium Iron Phosphate Cathode Battery Based on Water-Chitosan Slurry

Anam, K. Solid Polymer Electrolyte (SPE) from Corn Starch and Aluminum Nitrate Salt Composites for Aluminum - Ion Battery

Azhar, M. Synthesis and Electrochemical Performance of Sodium Iron Phosphate Cathode Battery Based on Water-Chitosan Slurry

D

Darminto, D. Synthesis and Electrochemical Performance of Sodium Iron Phosphate Cathode Battery Based on Water-Chitosan Slurry

E

Erlangga, I. Corn Starch-Sodium Acetat Composite Material from Industrial Waste Fly Ash for Solid Electrolyte Polymer Ionic Conductivity in Supercapacitor Application

H

Hamidah, N. Corn Starch-Sodium Acetat Composite Material from Industrial Waste Fly Ash for Solid Electrolyte Polymer Ionic Conductivity in Supercapacitor Application; Solid Polymer Electrolyte (SPE) from Corn Starch and Aluminum Nitrate Salt Composites for Aluminum - Ion Battery

M

Maulana, F. Study of Addition Metal (Ti, Zn) Dopan on The Structure of NASICON as Solid Electrolyte Batteries

N

Nehan, P. Synthesis and Electrochemical Performance of Sodium Iron Phosphate Cathode Battery Based on Water-Chitosan Slurry

Noerochim, L. Enhanced lonic Conductivity of Fluoride-Doped ; Study of Addition Metal (Ti, Zn) Dopan on The Structure of NASICON as Solid Electrolyte Batteries

Nugroho, A. The Effect of Sodium Acetate on Biodegradable Rice Starch-Based Solid Polymer Electrolyte for Supercapacitor

Nurdiansah, H. The Effect of Nitrogen on the Capacitive Properties of N-Doped rGO/CuCr Composites as Materials for Supercapacitors

P

Pradana, R. Synthesis and Electrochemical Performance of Sodium Iron Phosphate Cathode Battery Based on Water-Chitosan Slurry

Pradanawati, S. The Effect of Sodium Acetate on Biodegradable Rice Starch-Based Solid Polymer Electrolyte for Supercapacitor; Corn Starch-Sodium Acetat Composite Material from Industrial Waste Fly Ash for Solid Electrolyte Polymer Ionic Conductivity in Supercapacitor Application; Solid Polymer Electrolyte (SPE) from Corn Starch and Aluminum Nitrate Salt Composites for Aluminum - Ion Battery

Pramata, A. Corn Starch-Sodium Acetat Composite Material from Industrial Waste Fly Ash for Solid Electrolyte Polymer Ionic Conductivity in Supercapacitor Application; Solid Polymer Electrolyte (SPE) from Corn Starch and Aluminum Nitrate Salt Composites for Aluminum - Ion Battery

Pratama, A. The Effect of Nitrogen on the Capacitive Properties of N-Doped rGO/CuCr Composites as Materials for Supercapacitors

Pratiwi, V. Enhanced lonic Conductivity of Fluoride-Doped ; Study of Addition Metal (Ti, Zn) Dopan on The Structure of NASICON as Solid Electrolyte Batteries

Purwaningsih, H. Study of Addition Metal (Ti, Zn) Dopan on The Structure of NASICON as Solid Electrolyte Batteries

S

Setopratama, A. Synthesis and Electrochemical Performance of Sodium Iron Phosphate Cathode Battery Based on Water-Chitosan Slurry

Susanti, D. The Effect of Nitrogen on the Capacitive Properties of N-Doped rGO/CuCr Composites as Materials for Supercapacitors

Syaifudin, M. The Effect of Sodium Acetate on Biodegradable Rice Starch-Based Solid Polymer Electrolyte for Supercapacitor

W

Wibowo, A. Study of Addition Metal (Ti, Zn) Dopan on The Structure of NASICON as Solid Electrolyte Batteries