Anode material and electrolyte using biomass as raw material, all-solid-battery including the same, and manufacturing methods thereof

Abstract

The present invention provides an all-solid-state battery using rice bran and rice starch as materials. More specifically, the invention provides an all-solid-state battery comprising a negative electrode material composed of activated carbon and silicon particles prepared by heat-treating rice bran in a nitrogen and oxygen atmosphere, respectively; a binder prepared by first crosslinking rice starch with a polyol and then secondarily crosslinking it with an organic acid; and a solid electrolyte in which the binder is combined with a lithium salt. The present invention aims to provide a battery with high energy density and excellent charge / discharge characteristics, while reducing the manufacturing cost of the all-solid-state battery by utilizing such renewable resources and overcoming the stability and environmental pollution issues of existing batteries.

Description

Technology Field

[0001] The present invention relates to a cathode material and an electrolyte using biomass, and an all-solid-state battery comprising the same. Background Technology

[0002] Lithium-ion batteries are widely used in various applications, such as portable electronic devices, electric vehicles, and energy storage systems, due to their high energy density and excellent charge / discharge characteristics. However, conventional lithium-ion batteries are based on liquid electrolytes, raising safety concerns regarding potential leakage, fire, and explosion risks. To overcome these limitations, all-solid-state batteries are emerging and are attracting particular attention as next-generation energy storage devices capable of providing high stability and performance.

[0003] The anode material and binder, which are key components of all-solid-state batteries, are major factors determining the battery's performance and stability. Graphite, conventionally used as an anode material, has limitations in energy density and charge / discharge speed, leading to research on silicon-based anode materials to replace it. While silicon possesses high theoretical capacity, it presents a problem where battery performance degrades due to volume expansion during the charging and discharging process.

[0004] Furthermore, the core components of conventional all-solid-state batteries have a high potential for generating toxic compounds due to the use of organic materials. For example, polymer electrolytes have low biodegradability, potentially causing long-term plastic-related problems upon disposal, while sulfide-based electrolytes can release toxic gases by reacting with air and moisture.

[0005] Therefore, research and development is ongoing to reduce concerns regarding environmental pollution while maintaining or improving the performance of these key components. As part of this research and development, there is a demand for the development of biomass-based cathode materials with unique characteristics and binder materials that complement them. Prior art literature

[0006] Japanese Published Patent No. 2022-169131 (Nov. 09, 2022) Korean Registered Patent Publication No. 10-1527644 (June 03, 2015) The problem to be solved

[0007] To solve the above-mentioned problems, the present invention aims to provide a cathode material and an electrolyte using biomass, and an all-solid-state battery containing the same. means of solving the problem

[0008] To solve the above-mentioned problems, the present invention provides an all-solid-state battery comprising: a negative electrode material made of rice bran; and a binder made of rice starch.

[0009] The above cathode material may include activated carbon particles and silicon particles.

[0010] The above cathode material may contain 70 to 90 weight percent of the above activated carbon particles.

[0011] The above cathode material may contain 10 to 30 weight percent of the silicon particles.

[0012] The above binder may be rice starch cross-linked with glycerol and organic acid.

[0013] The above organic acid may be one or more selected from oxalic acid, malonic acid, and succinic acid.

[0014] The above all-solid-state battery may include a negative electrode comprising the above negative electrode material; and the above binder.

[0015] The above all-solid-state battery may comprise an electrolyte comprising the binder; and a lithium salt.

[0016] The above all-solid-state battery may be capable of operating at a charge / discharge rate of 0.2 to 5.0 C.

[0017] In addition, the present invention provides a method for manufacturing the above-mentioned all-solid-state battery.

[0018] The above manufacturing method may be characterized by forming a cathode material by heat-treating rice bran, wherein activated carbon is formed by heat-treating the rice bran in a nitrogen atmosphere, and silica is formed by heat-treating the rice bran in an oxygen atmosphere.

[0019] The above binder may be formed through a step of first cross-linking rice starch with glycerol; and a step of secondarily cross-linking the rice starch, which has completed the first cross-linking, with an organic acid. Effects of the invention

[0020] The biomass-based cathode material and electrolyte according to the present invention, and the all-solid-state battery including the same, provide an all-solid-state battery comprising a cathode material manufactured from rice bran and a rice starch-based crosslinking binder, thereby effectively resolving safety issues and adverse environmental effects occurring in conventional batteries.

[0021] Furthermore, the all-solid-state battery of the present invention provides high energy density and excellent charge / discharge characteristics, and enables eco-friendly and cost-effective production by utilizing biomass in the manufacturing process. In addition, due to the excellent mechanical strength and thermal stability of the rice starch binder, the durability of the battery is enhanced, and the environmental impact upon disposal can be minimized. Brief explanation of the drawing

[0022] FIG. 1 is a schematic diagram showing the manufacturing process of a cathode material according to the present invention. FIG. 2 is a schematic diagram showing the manufacturing process of a binder according to the present invention. FIG. 3 is a schematic diagram showing the process of manufacturing an anode, a cathode, and an electrolyte using a binder according to the present invention. Figure 4 shows a Scanning Electron Microscope (SEM) image and X-ray Diffraction (XRD) measurement results of a cathode material according to the present invention. Figure 5 shows photographs of the ion conductivity and flammability test results according to the organic acid used in the electrolyte. Figure 6 shows the results of measuring the rate capability characteristics of half paper. Figure 7 shows the results of the Electrochemical Impedance Spectroscopy (EIS) and rate capability measurements of the complete paper. Specific details for implementing the invention

[0023] The cathode material and electrolyte utilizing biomass according to the present invention, and an all-solid-state battery including the same, will be described in detail below. The drawings presented below are provided as examples to ensure that the concept of the present invention is sufficiently conveyed to those skilled in the art. Accordingly, the present invention is not limited to the drawings presented below and may be embodied in other forms, and the drawings presented below may be exaggerated to clarify the concept of the present invention. In this case, unless otherwise defined, technical and scientific terms used in the present invention have the meaning commonly understood by those skilled in the art to which this invention pertains, and descriptions of known functions and configurations that could unnecessarily obscure the essence of the present invention are omitted in the following description and attached drawings.

[0024] To solve the above-mentioned problems, the present invention provides an all-solid-state battery comprising: a negative electrode material made of rice bran; and a binder made of rice starch.

[0025] The all-solid-state battery of the present invention comprises a positive electrode; a negative electrode; and an electrolyte; wherein the negative electrode may comprise a negative electrode material; a binder; a conductive material; and a current collector.

[0026] The above cathode material is made from rice bran and may include activated carbon particles and silicon particles.

[0027] The above-mentioned activated carbon particles are produced by heat-treating rice bran in a nitrogen atmosphere and possess a highly porous structure, capable of effectively storing and releasing lithium ions. Furthermore, although the above-mentioned activated carbon particles exhibit a greater volume change than graphite, which is the most widely used conventional anode material, their porous structure results in superior high-speed charge / discharge characteristics, leading to significantly fewer lithium plating issues. Additionally, by combining the above-mentioned activated carbon particles with the above-mentioned silicon particles, high stability can be provided even during high-speed charge / discharge. The above-mentioned activated carbon particles may account for 70 to 90 weight percent of the total weight of the anode material. Preferably, they should account for 75 to 85 weight percent. By combining them with the above-mentioned silicon particles within this range, the electrochemical performance of the all-solid-state battery can be significantly improved.

[0028] The above-mentioned activated carbon particles are manufactured according to the manufacturing method described below, having a specific surface area of ​​1,000 to 1,500 m² 2 g -1 And, the residual carbon content may be 80% or more.

[0029] The silicon particles mentioned above are produced by heat-treating rice bran in an oxygen atmosphere and may be manufactured to have a diameter of tens to hundreds of nanometers. Although the silicon particles are the most promising anode material capable of storing and releasing a large amount of lithium ions, they have a major disadvantage of instability due to their extremely large volume changes, which can cause the silicon anode particles to break and even lead to volume changes in the entire cell. However, the silicon particles according to the present invention are less sensitive to volume changes by having a diameter of tens to hundreds of nanometers, and when combined with the binder, they can stably maintain the structure of the anode despite volume expansion. The anode material may contain 10 to 30 weight percent of the silicon particles. In this case, it is preferable to have 15 to 25 weight percent. By including the silicon particles within this range, the electrochemical performance of the all-solid-state battery can be significantly improved. The silica particles are manufactured according to the manufacturing method described below, and may have an average particle size of 50 to 150 nm.

[0030] The binder may be obtained by cross-linking rice starch with glycerol and organic acid. The binder according to the present invention may be included in an anode, a cathode, and an electrolyte. The binder may be applied to the anode and cathode to replace conventional electrode binders such as PVDF (Polyvinylidene fluoride) and PHFP (polyhexafluoropropylene). The raw material of the binder is rice starch, a natural polymer recovered from rice bran and rice, which consists mainly of amylose and amylopectin. The present invention is characterized by first cross-linking the rice starch with glycerol to impart flexibility and mechanical strength, and second cross-linking it with organic acid to form ester bonds, thereby forming a three-dimensional structure. The binder prepared in this manner is manufactured from rice starch and organic acid, and has the advantage of being more biodegradable and environmentally friendly than existing synthetic polymer binders. In addition, it provides strong mechanical strength compared to PVDF and offers flexibility capable of accommodating the volume expansion of the silicon particles.

[0031] The above organic acid may be one or more selected from oxalic acid, malonic acid, and succinic acid. However, since it is a necessary condition for the organic acid to have two or more carboxylic acid functional groups to form a three-dimensional structure through crosslinking, citric acid, tartaric acid, maleic acid, fumaric acid, lactic acid, or gluconic acid may be additionally considered as the organic acid. These organic acids form a three-dimensional structure by reacting with the hydroxyl groups (-OH) of the starch molecule to form ester bonds. At this time, since the simpler the stereochemical structure of the organic acid, the lower the likelihood of adverse effects on ionic conductivity, it is preferable to select from oxalic acid, malonic acid, and succinic acid. Furthermore, more preferably, when using succinic acid, which has weak intrinsic acidity and ethylene functional groups between the carboxylic acid functional groups, it is possible to manufacture a binder with the most excellent ionic conductivity, high flexibility, and superior mechanical strength by minimizing structural damage to the starch. The binder formed in this way can firmly bind particles within the electrode and has excellent ability to withstand volume expansion due to the flexibility derived from its three-dimensional structure.

[0032] The above conductive material is a material intended to improve the electronic conductivity of the cathode or anode material, and may include carbon black, graphite, carbon nanotubes, or metal-based conductive materials. In addition to the materials provided as examples above, the conductive material may be a material commonly used in the industry, and preferably, carbon black is used because its particles are very small, which can effectively connect the materials of the electrode, and it is inexpensive.

[0033] The above current collector is a component that transmits electrons generated from the cathode or anode material, and may use copper for the cathode and aluminum for the anode. The shape of the above current collector may be, for example, a metal foil or a mesh.

[0034] The above-described all-solid-state battery may comprise an electrolyte comprising the binder and a lithium salt. The electrolyte may be provided in a solid state in which the lithium salt is bonded to the binder. Due to the characteristics of the binder, the electrolyte exhibits excellent thermal and mechanical stability and excellent structural flexibility through organic acid crosslinking. Additionally, the lithium salt is uniformly dispersed in a starch-based binder matrix, 1.0 × 10⁻⁶ -4 Up to 1.0×10 -3 S cm -1 It can exhibit excellent ionic conductivity. The electrolyte can eliminate the risk of leakage associated with conventional liquid electrolytes, and since it is biomass-based, it can minimize environmental impact upon disposal. Furthermore, the ionic conductivity of the electrolyte can be further enhanced as the intermediate chain within the C0–C2 range of the organic acid becomes longer. For example, in the case of oxalic acid without an intermediate chain, the ionic conductivity is 4.50 to 4.70 × 10⁻⁶. -5 mS cm -1 , in the case of malonic acid with a C1 intermediate chain, the ionic conductivity is 5.70 to 5.80 × 10⁻⁶ -5 mS cm -1 , in the case of succinic acid with a C2 intermediate chain, the ionic conductivity is 6.20 to 6.30 × 10⁻⁶. -5 mS cm -1 It can appear as.

[0035] The above lithium salt may be used without limitation as long as it is widely used in the industry. However, preferably, LiTFSI, LiFSI, LiPF6, LiDFOB, LiBOB, and LiNO3 may be used, and more preferably, when LiTFSI or LiFSI is selected, performance such as the ionic conductivity and high voltage stability of the electrolyte can be maximized.

[0036] The above anode may comprise an anode material; a binder; a conductive material; and a current collector.

[0037] The above cathode material is LFP (LiFePO4), LCO (LiCoO2), LMO (LiMn2O4), LNO (LiNiO2), or LNCM (LiNi x Co y Mn z It may be any one selected from O2, x+y+z=1). Alternatively, it may be a cathode material that is conventionally available in the industry. However, although the anode material according to the present invention can provide very high energy density, its stability is relatively low, so it can exhibit the strongest synergistic effect when combined with LFP. LFP is a cathode material with an olivine structure, with a maximum voltage of about 3.2 to 3.4 V and a theoretical capacity of about 170 mAh / g. LFP has the advantages of excellent thermal and chemical stability, a very long lifespan, very low raw material costs due to the use of iron and phosphorus, and low toxicity, making it environmentally friendly.

[0038] Since the binder and conductive material used in the anode above are the same as those in the case of the cathode described above, a redundant explanation is omitted.

[0039] The current collector used for the anode above may be in the form of a metal foil or mesh made of aluminum, as described in the case of the cathode.

[0040] The specific capacity of the all-solid-state battery manufactured as described above is 115 to 125 mAh g at a rate of 0.05 C. -1 , 105 to 115 mAh g at a rate of 0.1 C -1 , 80 to 90 mAh g at a rate of 0.2C -1 , 35 to 45 mAh g at a rate of 0.5 C -1 It can be expressed as such. However, the standard for specific capacity according to this rate limit applies to the case of a complete battery using an LFP anode, which is the theoretical capacity of the LFP anode (170 mAh g -1When expressed as a relative capacity compared to ), it corresponds to 67.6 to 73.5% at a rate of 0.05C, 61.7 to 67.6% at a rate of 0.1C, 47.0 to 52.9% at a rate of 0.2C, and 20.5 to 26.5% at a rate of 0.5C.

[0041] In addition, the present invention provides a method for manufacturing the above-mentioned all-solid-state battery.

[0042] The above manufacturing method may be characterized by forming a cathode material by heat-treating rice bran, wherein activated carbon particles are formed by heat-treating the rice bran in a nitrogen atmosphere, and silica particles are formed by heat-treating the rice bran in an oxygen atmosphere.

[0043] More specifically, the rice bran may be heat-treated at 400 to 600°C for 1 to 4 hours in a nitrogen atmosphere to form the activated carbon particles, and the rice bran may be heat-treated at 700 to 900°C for 3 to 5 hours in an oxygen atmosphere to form the silica particles. The cathode material according to the present invention may be a mixture of activated carbon particles and silica particles manufactured by separate paths as described above.

[0044] When forming the above activated carbon particles, the particles recovered immediately after heat treatment may contain some silica particles. Therefore, high-purity activated carbon particles can be obtained by reacting and washing with an aqueous NaOH solution to remove them along with the solvent in the form of Na2SiO3. Since these reaction conditions are commonly used chemical reactions, a detailed description is omitted.

[0045] In addition, when forming the silicon particles mentioned above, the particles recovered immediately after heat treatment are silica (SiO2), which can be reduced to silicon by removing oxygen through reaction with magnesium. At this time, reduction with magnesium is carried out in an inert gas (argon, nitrogen) atmosphere or 1.0 × 10⁻⁶ -3Particles mixed with silicon and MgO can be recovered by heat treatment for 2 to 5 hours in a vacuum of less than torr. To remove the MgO and unreacted Mg, HCl or HNO3 is added and reacted, then washed 3 to 5 times with distilled water, and dried at 60 to 80°C to obtain pure silicon particles.

[0046] The above binder may be formed through a step of first cross-linking rice starch with glycerol; and a step of secondarily cross-linking the rice starch, which has completed the first cross-linking, with an organic acid.

[0047] More specifically, the primary crosslinking may be carried out by mixing 35 to 100 parts by weight of glycerol with 100 parts by weight of rice starch and reacting at 80 to 100°C for 30 to 60 minutes. At this time, by adding LiOH to provide alkaline conditions, the pH can be adjusted to a weak alkaline state of 9.0 to 11.0, thereby further activating the hydroxyl groups and promoting the crosslinking reaction. At this time, the primary crosslinking can be carried out smoothly when the concentration of LiOH is adjusted to 0.1 to 0.5 M.

[0048] In addition, secondary crosslinking may be performed by mixing 15 to 33 parts by weight of an organic acid with 100 parts by weight of rice starch and reacting at 80 to 100°C for 30 to 90 minutes to form a three-dimensional crosslinked structure. At this time, by adding HNO3 to provide oxidation conditions, the pH, which was adjusted to a weak alkaline state due to the addition of LiOH, can be adjusted back to a neutral state. At this time, secondary crosslinking can be performed smoothly when the concentration of HNO3 is adjusted to 0.01 to 0.1 M.

[0049] Hereinafter, the cathode material and electrolyte using biomass according to the present invention, and an all-solid-state battery including the same, will be described in more detail through examples. However, the following examples are merely for reference to explain the present invention in detail, and the present invention is not limited thereto and can be implemented in various forms.

[0050] Furthermore, unless otherwise defined, all technical and scientific terms have the same meaning as generally understood by one of the art to which the present invention pertains. The terms used in the description herein are merely for the purpose of effectively describing specific embodiments and are not intended to limit the present invention. Additionally, the units of additives not specifically stated in the specification may be in weight percent.

[0051] [Manufacture of Activated Carbon Particles]

[0052] Activated carbon was recovered by heat-treating rice bran at 500°C for 2 hours in a nitrogen atmosphere. The activated carbon was mixed with a 1M NaOH aqueous solution, the temperature was maintained at 90°C for 1 hour to remove silica, and the activated carbon particles were dried at 80°C for 8 hours.

[0053] [Silicon Particle Manufacturing]

[0054] Silica was recovered by heat-treating rice bran at 800°C for 4 hours in an oxygen atmosphere. Subsequently, silica and Mg powder were mixed in a molar ratio of 1:2.2 and reacted at 800°C for 3 hours to form a powder mixed with silicon and MgO. After removing the MgO by washing the mixed powder with distilled water, the silicon particles were dried at 80°C for 8 hours.

[0055] [Binder 1st Bridging]

[0056] 100 parts by weight of rice starch and 17 parts by weight (about 20% by weight) of glycerol were mixed and added to distilled water. The mixed material was reacted at 90°C for 60 minutes to recover the mixture in which the first crosslinking was completed.

[0057] [Binder 2nd Bridging]

[0058] Next, oxalic acid, malonic acid, and succinic acid were prepared separately and mixed at 10% by weight relative to the mixture in which the first crosslinking was completed. The mixture was reacted at 100°C for 1 hour to recover the crosslinked binder.

[0059] [Cathode Manufacturing]

[0060] A cathode material was prepared by weighing and mixing activated carbon particles and silicon particles in a weight ratio of 8:2, and a cathode slurry was prepared by mixing the cathode material, a binder, and carbon black in a weight ratio of 8:1:1. Subsequently, the cathode slurry was applied to a copper current collector, dried at 80°C for 12 hours, and the dried electrode was rolled to 15 MPa to produce a cathode.

[0061] [Anode Manufacturing]

[0062] An anode slurry was prepared by mixing LFP, a binder, and a conductive material in a weight ratio of 8:1:1 as the anode material. Subsequently, the anode slurry was applied to an aluminum current collector, dried at 80°C for 12 hours, and the dried electrode was rolled to 15 MPa to produce an anode.

[0063] [Electrolyte Manufacturing]

[0064] 30 wt% of LiTFSI (Lithium bis(trifluoromethanesulfonyl)imide) relative to the weight of the binder was mixed, and the mixture was drop-cast onto a PTFE (polytetrafluoroethylene) film to prepare an electrolyte.

[0065] [Reverse Battery Manufacturing]

[0066] The lithium metal foil and the cathode, anode, and electrolyte prepared as described above were cut to fit the specifications of a CR2032 cell, and a lithium-cathode half-cell and a lithium-anode half-cell were manufactured, respectively.

[0067] [Complete Paper Manufacturing]

[0068] An all-solid-state battery was manufactured by cutting the cathode, anode, and electrolyte prepared as described above to fit the specifications of a CR2032 cell.

[0069] The types of organic acids used in the manufacture of the binder are as shown in Table 1 below.

[0070] division Organic acid used Example 1 oxalic acid Example 2 Malonic acid Example 3 Succinic acid

[0071] [Comparative Example]

[0072] As described above, the cathode, anode, half-cell, and full-cell were manufactured, using PVDF (polyvinylidenefluoride) as the binder.

[0073] [Characteristic Evaluation Method]

[0074] A. Structural Analysis of Rice Bran-Based Cathode Materials

[0075] SEM (Scanning Electron Microscope) images and XRD (X-ray Diffraction) data of activated carbon and silicon produced from rice bran are shown in Figure 4.

[0076] In the case of the activated carbon, it was confirmed that a porous structure was well formed. Referring to the XRD measurement results, it was found that the amorphousness was higher compared to general activated carbon, and it was synthesized with very high purity and almost no impurities.

[0077] In the case of silicon, it was confirmed that it has a porous structure and that the particle size is 10 to 40 nm. In addition, from the XRD measurement results, it was confirmed that silicon has a crystalline structure and contains a very small amount of impurities.

[0078] From the structural analysis above, it was confirmed that a cathode material can be manufactured using rice bran as a raw material.

[0079] B. Evaluation of Electrolyte Properties

[0080] Figure 5 shows the results of ion conductivity and flammability tests on electrolyte specimens according to the type of organic acid used.

[0081] The ionic conductivity of the electrolyte is approximately 4.66 × 10⁻⁶ in the case of oxalic acid. -5 mS cm -1 , in the case of malonic acid 5.75×10 -5 mS cm -1 , in the case of succinic acid 6.23×10 -5 mS cm -1 As shown, it was confirmed that the longer the intermediate chain (C0~C2) of an organic acid having two carboxylic acid functional groups, the more positively it affects ion conductivity.

[0082] In addition, when an electrolyte specimen prepared using succinic acid was ignited with a torch to test whether it ignited or spread, it was confirmed that although scorched areas were present, the fire did not spread and was extinguished. In other words, it can be confirmed that the electrolyte according to the present invention is non-flammable.

[0083] C. Half-cell performance evaluation

[0084] Figure 6 shows the results of the performance evaluation of the half-paper. At this time, the starch binder was evaluated based on Example 3 using succinic acid.

[0085] In the case of the example using a PVDF binder, a circuit short circuit was observed in which the cathode was damaged due to excessive volume fluctuation of silicon after two charge-discharge cycles at 0.2C. On the other hand, in the case of Example 3 using a starch binder, it was confirmed that the performance was maintained stably despite the volume fluctuation of silicon.

[0086] Meanwhile, in the case of the anode, no significant performance difference was observed between the PVDF binder and the starch binder.

[0087] D. Complete Performance Evaluation

[0088] Figure 7 shows a photograph of a 2032-type coin cell, interface resistance, and charge / discharge operation results.

[0089] Electrochemical Impedance Spectroscopy (EIS) measurements following the formation process (SEI formation and stabilization) confirmed that the interfacial resistance was somewhat higher than usual. This is attributed to the high contact resistance resulting from the low impregnation at the electrode-electrolyte interface inherent in the all-solid-state electrolyte.

[0090] Accordingly, the battery showed stable operation at a low current density of 0.05 to 0.2 C during charging and discharging, but it was confirmed that the battery was overloaded due to high interfacial resistance at a high current density of 0.5 to 1.0 C.

[0091] Although the present invention has been described above through specific details and limited embodiments, this is provided merely to aid in the overall understanding of the invention, and the invention is not limited to the above embodiments. Those skilled in the art can make various modifications and variations from this description.

[0092] Accordingly, the scope of the present invention is not limited to the described embodiments, and all things equivalent to or having equivalent variations to the claims set forth below, as well as the claims set forth below, shall be considered to fall within the scope of the concept of the present invention.

Claims

Claim 1 An all-solid-state battery comprising a negative electrode; a positive electrode; and an electrolyte located between the negative electrode and the positive electrode, wherein the negative electrode comprises a negative electrode material comprising activated carbon particles and silicon particles produced by heat treatment of rice bran and a binder cross-linked with rice starch with glycerol and an organic acid, and the electrolyte comprises a binder cross-linked with rice starch with glycerol and an organic acid and a lithium salt. Claim 2 delete Claim 3 A solid-state battery according to claim 1, wherein the cathode material comprises 70 to 90 weight percent of the activated carbon particles. Claim 4 A solid-state battery according to claim 1, wherein the negative electrode material comprises 10 to 30 weight percent of the silicon particles. Claim 5 delete Claim 6 In claim 1, the organic acid is one or more selected from oxalic acid, malonic acid, and succinic acid in a solid-state battery. Claim 7 delete Claim 8 delete Claim 9 A method for manufacturing an all-solid-state battery according to any one of claims 1, 3, 4 and 6. Claim 10 A method for manufacturing an all-solid-state battery according to claim 9, wherein a negative electrode material is formed by heat-treating rice bran, wherein activated carbon is formed by heat-treating the rice bran in a nitrogen atmosphere, and silica is formed by heat-treating the rice bran in an oxygen atmosphere. Claim 11 A method for manufacturing an all-solid-state battery according to claim 9, characterized in that the binder is formed through the steps of: a first crosslinking of rice starch with glycerol; and a second crosslinking of the rice starch, which has completed the first crosslinking, with an organic acid.

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