CN114094110A - Graphite negative electrode for solid lithium ion battery - Google Patents
Graphite negative electrode for solid lithium ion battery Download PDFInfo
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- CN114094110A CN114094110A CN202210076260.1A CN202210076260A CN114094110A CN 114094110 A CN114094110 A CN 114094110A CN 202210076260 A CN202210076260 A CN 202210076260A CN 114094110 A CN114094110 A CN 114094110A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a graphite negative electrode for a solid lithium ion battery, which comprises a graphite negative electrode material, polyoxyethylene, lithium salt, a conductive agent, an aqueous binder and metal powder containing surface oxidation. The graphite negative electrode for the solid lithium ion battery comprises metal powder with oxidized surface, and the oxide layer on the surface of the metal powder does not react with water during the preparation of the negative electrode, so that the performances of the negative electrode before and after pulping are kept consistent and stable, and the quality of the negative electrode is convenient to control. In the graphite negative electrode for the solid lithium ion battery containing the metal powder with the oxidized surface, the channels containing the metal powder are built among the graphite sheet layer particles, so that the interface contact between the electrolyte layer and the graphite negative electrode in the solid lithium ion battery is improved, the rate capability of the lithium ion battery is improved, the graphite particles which do not participate in the electrode reaction originally also participate in the electrode reaction, and the capacity of the lithium ion battery is improved.
Description
Technical Field
The invention belongs to the technical field of solid lithium ion batteries, and particularly relates to a graphite cathode for a solid lithium ion battery.
Background
High energy density of lithium ion batteries is a goal pursued by battery researchers, but their safety is also receiving much attention. The solid lithium ion battery with the solid electrolyte has better safety, but the current solid lithium ion battery generally adopts a metal lithium cathode, and the solid lithium ion battery with the metal lithium cathode still has a plurality of problems which are difficult to solve in the aspects of safety and cycle life. The graphite cathode is a more reliable solution as a cathode of a lithium ion solid battery of a new generation. However, due to the special layered structure of graphite, lithium ions in the solid lithium ion battery cannot directly penetrate through the graphite sheet layers in the charging and discharging processes, and can only enter the graphite sheet layers through the side surfaces of the graphite sheet to move, so that a lot of graphite particles on the contact interface of the graphite cathode and the solid electrolyte cannot participate in the reaction, and the rate capability of the solid lithium ion battery with the graphite cathode is poor.
Disclosure of Invention
The purpose of the invention is: provided is a graphite-based negative electrode for a solid lithium ion battery, which can improve the mobility efficiency of lithium ions in the graphite negative electrode and improve the rate capability of the solid lithium ion battery.
The technical scheme of the invention is as follows:
a graphite negative electrode for a solid lithium ion battery comprises a graphite negative electrode material, polyoxyethylene, lithium salt, a conductive agent, an aqueous binder and surface oxidized metal powder.
The graphite negative electrode for the solid lithium ion battery comprises an aqueous binder, and when the graphite negative electrode is used, all components and slurry are coated on a current collector by water to prepare a pole piece. In the process, the surface oxidation layer of the metal powder with oxidized surface is not easy to react with water as a solvent, and simultaneously, the oxidation layer separates metal in the metal powder from water, so that the reaction of the metal powder and the water is basically not generated in the pulping process, the performance of the whole negative electrode before and after pulping can be kept consistent and stable, and the overall quality of the negative electrode can be conveniently controlled.
The graphite-based negative electrode for a solid lithium ion battery according to the present invention is added with a surface-oxidized metal powder, and lithium ions cyclically participate in oxidation and reduction reactions during charge and discharge of the solid lithium ion battery made from the negative electrode, and the generated metal lithium has strong reducibility, so that the metal lithium reduces the surface-oxidized metal powder to a metal powder having no oxide layer during the first charge and discharge of the lithium ion battery. Because the metal powder generated by reduction is uniformly mixed in the graphite negative electrode material and filled between the graphite sheet layer particles of the graphite negative electrode material, a channel containing the metal powder is built between two adjacent graphite sheet layer particles, and the metal lithium obtained by reduction of lithium ions in the negative electrode forms an alloy with the metal powder, so that the metal lithium becomes a channel for electron transmission between two adjacent graphite sheet layer particles, thereby increasing the electron conductivity of the negative electrode, improving the interface contact between an electrolyte layer and the graphite negative electrode in the solid lithium ion battery and improving the rate capability of the lithium ion battery. When lithium in the negative electrode is in an ionic state, a channel containing metal powder with a surface oxidation layer is built between two adjacent graphite sheet layer particles, so that lithium ions can enter the graphite particles which cannot participate in the reaction, the graphite particles which originally do not participate in the electrode reaction also participate in the electrode reaction, the defect of poor multiplying power performance caused by the fact that the lithium ions in the graphite negative electrode can only move between the sheet layers which are in butt joint is overcome, and the capacity of the lithium ion battery is improved.
Preferably, the mass percentage of the metal powder is 1-5%. The metal powder with the mass percentage of 1-5% can better build a transmission channel with good electronic conductivity in the negative electrode, the electronic conductivity is poor due to the small amount of the metal powder, and the specific capacity of the negative electrode is influenced by the excessive metal powder.
Preferably, the mass percentages of the rest substances are as follows: 1.4-3.5% of polyoxyethylene, 0.6-1.5% of lithium salt, 1-5% of conductive agent, 1-5% of aqueous binder and the balance of graphite negative electrode material.
Preferably, the surface oxidized metal powder is made by the following method: stirring and mixing metal powder and dry gas with the oxygen volume ratio concentration of 0.5-5% for 1-2 hours at the temperature of 10-50 ℃; wherein the particle size of the metal powder is 0.1-10 μm; the metal powder is at least one of zinc powder, magnesium powder, aluminum powder and tin powder.
By using the method of oxidizing oxygen in a dry state, the surface oxidized metal powder with stable performance and good consistency can be obtained, so that the prepared lithium ion battery cathode has stable performance and good consistency. The zinc powder, the magnesium powder, the aluminum powder and the tin powder are used not only because the raw materials are sufficient, but also the cost is low. The graphite cathode for the solid lithium ion battery uses zinc powder, magnesium powder, aluminum powder or tin powder with oxidized surface, and can replace expensive silver powder. The temperature is 10-50 ℃, metal powder with the grain diameter of 0.1-10 mu m is used, and oxidation is carried out in dry gas with the oxygen volume ratio concentration of 0.5-5%, so that the oxide layer on the surface of the prepared metal powder is uniform and consistent and the structure is compact, and the performance of the prepared cathode is stable.
Preferably, the surface oxidized metal powder has a particle size of 0.5 to 5 μm. The oxide layer on the surface of the metal particles with the excessively small particle size is not easy to form uniformly, so that the metal inside is easy to expose, and the metal easily reacts with water in the pulping process; metal particles with excessively large particle sizes are easily broken in the charging electrical cycle process of the battery, so that the electrical performance of the lithium ion battery is unstable.
Preferably, the graphite-based negative electrode material is at least one of natural graphite and artificial graphite.
Preferably, the conductive agent is carbon nanotubes or conductive carbon black.
Preferably, the aqueous binder is at least one of aqueous styrene-butadiene rubber emulsion, aqueous polyurethane emulsion, polytetrafluoroethylene emulsion and polyacrylic acid.
Preferably, the lithium salt is at least one of lithium perchlorate, lithium bistrifluoromethanesulfonimide, lithium bistrifluorosulfonimide and lithium difluorophosphate.
The invention has the beneficial effects that:
the graphite negative electrode for the solid lithium ion battery comprises metal powder with oxidized surface, and the oxide layer on the surface of the metal powder does not react with water during the preparation of the negative electrode, so that the performances of the negative electrode before and after pulping are kept consistent and stable, and the quality of the negative electrode is convenient to control. In the graphite negative electrode for the solid lithium ion battery containing the metal powder with the oxidized surface, the channels containing the metal powder are built among the graphite sheet layer particles, so that the interface contact between the electrolyte layer and the graphite negative electrode in the solid lithium ion battery is improved, the rate capability of the lithium ion battery is improved, the graphite particles which do not participate in the electrode reaction originally also participate in the electrode reaction, and the capacity of the lithium ion battery is improved.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
1. Preparation of graphite negative electrode for solid lithium ion battery
Step one, preparing surface oxidized metal powder:
at 25 ℃, adding D505g of 5-micron metal zinc powder is added into a passivation tank, and mixed gas of argon and oxygen is injected after the passivation tank is slowly vacuumized, wherein the volume ratio of the argon is 95%, and the volume ratio of the oxygen is 5%. And starting stirring to fully mix the metal zinc powder and the mixed gas for 1 hour to obtain the surface oxidized metal zinc powder.
Step two, pulping and pole piece coating
1.4g of polyoxyethylene and 0.6g of lithium bis (fluorosulfonyl) imide are added to 100ml of deionized water, and stirred to obtain a uniform solution, and 90g of mesocarbon microbeads are added and stirred uniformly. 1g of polytetrafluoroethylene emulsion (with solid content of 60%) is added and stirred evenly, and 1.1g of carbon nano tube is added and stirred evenly. And (4) adding the metal zinc powder with the oxidized surface obtained in the step one, and uniformly stirring. And filtering and removing bubbles to obtain the graphite cathode slurry. And coating the slurry on copper foil, drying and cutting to obtain the graphite cathode for the solid lithium ion battery.
Example 2
1. Preparation of graphite negative electrode for solid lithium ion battery
Step one, preparing surface oxidized metal powder:
at 10 ℃, adding D50Adding 1g of 0.5 mu m metal aluminum powder into a passivation tank, slowly vacuumizing, and injecting a mixed gas of argon and oxygen, wherein the proportion of argon is 98% and the proportion of oxygen is 2%. Stirring is started to allow the metal aluminum powder to be fully mixed with the mixed gas for 2 hours to obtain the product with oxidized surfaceMetal aluminum powder.
Step two, pulping and pole piece coating
3.5g of polyethylene oxide and 0.6g of lithium perchlorate are added into 100ml of deionized water and stirred to obtain a uniform solution, and 90g of artificial graphite is added and stirred uniformly. 1g of waterborne polyurethane emulsion (with solid content of 50%) is added and stirred uniformly, and 3.9g of conductive carbon black is added and stirred uniformly. And (4) adding the metal aluminum powder with the oxidized surface obtained in the step one, and stirring uniformly. And filtering and removing bubbles to obtain the graphite cathode slurry. And coating the slurry on a copper foil, and drying and slitting to obtain the solid battery cathode.
Example 3
1. Preparation of graphite negative electrode for solid lithium ion battery
Step one, preparing surface oxidized metal powder:
at 35 ℃, adding D50Adding 1.5g of 0.1 mu m metal tin powder into a passivation tank, slowly vacuumizing, and injecting a mixed gas of argon and oxygen, wherein the proportion of argon is 99%, and the proportion of oxygen is 1%. Stirring is started to fully mix the metallic zinc powder and the mixed gas for 1.5 hours, and the metallic tin powder with oxidized surface is obtained.
Step two, pulping and pole piece coating
1.4g of polyethylene oxide and 1.0g of lithium bistrifluoromethanesulfonimide are added to 100ml of deionized water, stirred to obtain a uniform solution, and 90g of natural graphite is added and stirred uniformly. 1.1g of water-based styrene-butadiene rubber emulsion (with the solid content of 50%) is added and stirred evenly, and 5g of carbon nano tube is added and stirred evenly. And (4) adding the metallic tin powder with oxidized surface obtained in the step one, and stirring uniformly. And filtering and removing bubbles to obtain the graphite cathode slurry. And coating the slurry on a copper foil, and drying and slitting to obtain the solid battery cathode.
Example 4
1. Preparation of graphite negative electrode for solid lithium ion battery
Step one, preparing surface oxidized metal powder:
at 50 ℃, adding D50Adding 1g of 10 mu m metal magnesium powder into a passivation tank, slowly vacuumizing, and injecting a mixed gas of argon and oxygen, wherein the proportion of argon is 99.5 percent, and the proportion of oxygen is 0.5 percent% of the total weight of the composition. And starting stirring to fully mix the metal aluminum powder and the mixed gas for 2 hours to obtain the metal magnesium powder with oxidized surface.
Step two, pulping and pole piece coating
100ml of deionized water was added with 1.4g of polyethylene oxide and 0.6g of lithium difluorophosphate and stirred to obtain a homogeneous solution, and 90g of artificial graphite was added and stirred to obtain a homogeneous solution. Adding 5g of polyacrylic acid, stirring uniformly, adding 2g of carbon nano tube, and stirring uniformly. Adding the surface oxidized metal magnesium powder obtained in the step one, and stirring uniformly. And filtering and removing bubbles to obtain the graphite cathode slurry. And coating the slurry on a copper foil, and drying and slitting to obtain the solid battery cathode.
Comparative example 1
3.5g of polyethylene oxide and 0.6g of lithium perchlorate are added into 100ml of deionized water and stirred to obtain a uniform solution, and 90g of artificial graphite is added and stirred uniformly. 1g of waterborne polyurethane emulsion (with solid content of 50%) is added and stirred uniformly, and 3.9g of conductive carbon black is added and stirred uniformly. And filtering and removing bubbles to obtain the graphite cathode slurry. And coating the slurry on a copper foil, and drying and slitting to obtain the solid battery cathode.
Comparative example 2
3.5g of polyethylene oxide and 0.6g of lithium perchlorate are added into 100ml of deionized water and stirred to obtain a uniform solution, and 90g of artificial graphite is added and stirred uniformly. 1g of waterborne polyurethane emulsion (with solid content of 50%) is added and stirred uniformly, and 3.9g of conductive carbon black is added and stirred uniformly; addition of D501g of 0.5 mu m metal aluminum powder is stirred uniformly. And filtering and removing bubbles to obtain the graphite cathode slurry. And coating the slurry on a copper foil, and drying and slitting to obtain the solid battery cathode.
Manufacturing a lithium ion battery:
the graphite negative electrodes for solid lithium ion batteries prepared in the above examples and comparative examples 1 and 2 were respectively prepared into solid lithium ion batteries by the following methods:
the prepared solid lithium ion battery negative electrode plate takes metal lithium as a counter electrode and takes polyethylene oxide as solid electrolyte to assemble a 2032 solid lithium ion half-battery with a negative electrode/solid electrolyte/metal lithium.
And (3) testing the battery performance:
the 2032 solid lithium-ion half-cell prepared above was subjected to 0.05C, 0.1C, 0.2C and 1C charge-discharge performance tests and 0.2C 100-cycle performance tests at 30 ℃ under a voltage of 0.05V-2.0V, and the test results are shown in Table 1.
TABLE 1
In the above examples 1, 2, 3 and 4, the scheme of the present invention was adopted, and the surface oxidized metal powder was added to the graphite-based negative electrode for the solid lithium ion battery, while the negative electrode used in the lithium ion battery prepared in comparative example 1 was not added with the surface oxidized metal powder, and the rest of the components were completely the same as those in example 2, and the metal aluminum powder added to the negative electrode used in the lithium ion battery prepared in comparative example 2 was not subjected to the surface oxidation in step one of the present invention. As can be seen from the test results in table 1, the specific charge capacities of 0.05C, 0.1C, 0.2C, and 1C of the solid lithium ion battery prepared in example 2 are all significantly greater than those of comparative example 1, and it can be seen that the specific capacity of the negative electrode can be increased by adding the surface oxidized aluminum powder. The metal lithium reduces the metal aluminum powder oxidized on the surface into the metal aluminum powder without an oxide layer in the first charge and discharge process of the lithium ion battery, and the metal aluminum powder filled among the graphite sheet layer particles builds a passage for lithium ions to enter between the adjacent graphite sheet layer particles on one hand, so that the graphite particles which can not directly participate in the reaction through the butt joint among the graphite sheet layers also participate in the electrode reaction, thereby improving the specific capacity of the negative electrode; on the other hand, an alloy of lithium and aluminum is formed between graphite sheet particles, so that the graphite sheet particles become an electron transmission channel, the interface contact resistance of an electrolyte layer and a negative electrode in the solid lithium ion battery is reduced, and the rate capability of the solid lithium ion battery is improved, which can be seen from the test results in table 1: the specific capacity reduction ratio of 1C to 0.2C of the solid lithium ion battery prepared in example 2 was only 13.52%, whereas that of 1C to 0.2C of the solid lithium ion battery prepared in comparative example 1The specific capacity reduction ratio is as high as 31.80 percent. Due to the reduction of the interface contact resistance between the electrolyte layer and the negative electrode in the solid lithium ion battery, the performance of the battery can be relatively stable after multiple charge and discharge cycles, which can be seen from the capacity retention rate result of 100 cycles after 0.2C cycle in table 1: the capacity retention rate at 100 cycles of 0.2C of the solid lithium ion battery prepared in example 2 was 91%, while the capacity retention rate at 100 cycles of 0.2C of the solid lithium ion battery prepared in comparative example 1 was only 82%. In addition, the specific charge capacities of 0.05C, 0.1C, 0.2C and 1C of the battery prepared in comparative example 2 were greatly reduced, compared to example 2; and are also lower than the lithium ion battery prepared by the negative electrode of the solid battery without the surface alumina powder in the comparative example 1. The reason is that the metal aluminum powder added in the comparative example 2 does not pass through the surface oxidation procedure of the first step of the invention, and the added 0.5 mu m metal aluminum powder is micro-nano aluminum powder with active property. Adding the metal aluminum powder into the water-containing graphite cathode slurry, and reacting the metal aluminum powder with water to generate non-conductive Al (OH)3This leads to poor conductivity of the negative electrode, which affects the electrical performance of the battery, and decreases the specific charge capacity of the negative electrode material, especially decreases more the 1C discharge capacity with a larger rate, and also deteriorates the cycle performance of the battery, as indicated by the capacity retention rate decreasing from 0.2C cycle 100 cycles to 80%. Although active micro-nano aluminum powder can be naturally oxidized in air, uncontrolled natural oxidation cannot guarantee whether the surface of the aluminum powder is completely coated with oxides or is excessively oxidized to be inactivated, and whether metallic aluminum is isolated from water during preparation of cathode slurry cannot be controlled, so that the electrical property of the cathode prepared by the method cannot be optimized in an expected manner when the cathode is applied to a lithium ion battery, and the electrical property of the cathode is deteriorated.
From the above analysis, it can be seen that the graphite negative electrode for the solid lithium ion battery of the present invention contains the metal powder with oxidized surface, so that the rate capability, the battery capacity and the cycle performance of the solid lithium ion battery prepared by the method are effectively improved.
It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the above embodiments are only some embodiments, not all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work based on the embodiments of the present invention belong to the protection scope of the present invention.
Claims (9)
1. A graphite negative electrode for a solid lithium ion battery comprises a graphite negative electrode material, polyethylene oxide, lithium salt, a conductive agent and an aqueous binder, and is characterized by comprising metal powder with oxidized surface.
2. The graphite-based negative electrode for a solid lithium ion battery according to claim 1, wherein the metal powder is contained in an amount of 1 to 5% by mass.
3. The graphite negative electrode for the solid lithium ion battery according to claim 2, wherein the mass percentages of the remaining substances are as follows: 1.4-3.5% of polyoxyethylene, 0.6-1.5% of lithium salt, 1-5% of conductive agent, 1-5% of aqueous binder and the balance of graphite negative electrode material.
4. The graphite-based negative electrode for a solid lithium ion battery according to any one of claims 1 to 3, wherein the surface-oxidized metal powder is produced by:
stirring and mixing metal powder and dry gas with the oxygen volume ratio concentration of 0.5-5% for 1-2 hours at the temperature of 10-50 ℃; wherein the particle size of the metal powder is 0.1-10 μm; the metal powder is at least one of zinc powder, magnesium powder, aluminum powder and tin powder.
5. The graphite-based negative electrode for a solid lithium ion battery according to claim 2, wherein the surface-oxidized metal powder has a particle size of 0.5 to 5 μm.
6. The graphite-based negative electrode for a solid lithium ion battery according to claim 2, wherein the graphite-based negative electrode material is at least one of natural graphite and artificial graphite.
7. The graphite-based negative electrode for a solid lithium ion battery according to claim 2, wherein the conductive agent is a carbon nanotube or conductive carbon black.
8. The graphite-based negative electrode for a solid lithium ion battery according to claim 2, wherein the aqueous binder is at least one of an aqueous styrene-butadiene rubber emulsion, an aqueous polyurethane emulsion, a polytetrafluoroethylene emulsion, and a polyacrylic acid.
9. The graphite-based negative electrode for a solid lithium ion battery according to claim 2, wherein the lithium salt is at least one of lithium perchlorate, lithium bistrifluoromethylsulfonyl imide, lithium bistrifluorosulfonimide, and lithium difluorophosphate.
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