CN112117447A - Preparation process of composite lithium battery negative electrode material - Google Patents
Preparation process of composite lithium battery negative electrode material Download PDFInfo
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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Abstract
The invention discloses a preparation process of a composite lithium battery cathode material, which comprises the following steps: firstly, preparing the following raw materials in parts by weight: 80-100 parts of active material, 12-15 parts of carbon black and 16-20 parts of binder; and step two, mixing the raw materials, uniformly grinding, coating the paste on copper foil by using a coating method, and drying, rolling and cutting to obtain the composite lithium battery negative electrode material. According to the invention, the self-made composite material is used as the active material of the cathode, the volume expansion of the tin oxide in the battery reaction can be effectively protected by the structure of the material, the buffer effect is achieved, and the specific surface area of the composite material can be increased, so that the electrochemical performance of the battery is improved; the binder comprises two effective components of waterborne polyurethane and tragacanth, so that the green environment-friendly requirement is met, the electrochemical performance of the lithium battery is improved from multiple directions by the two effective components, and the prepared cathode material is high in electrochemical performance and good in cycle performance.
Description
Technical Field
The invention belongs to the field of lithium battery processing, and particularly relates to a preparation process of a composite lithium battery negative electrode material.
Background
Lithium ion batteries have become one of the most interesting high-performance storage batteries due to their advantages of high energy density, high working voltage, long cycle life, safety, no pollution, etc., and have been widely used in portable electronic products. The lithium ion battery mainly comprises three parts: the lithium ion battery comprises a positive electrode, a negative electrode, electrolyte and a diaphragm, so that the performance of the lithium ion battery depends on the performances of the positive electrode, the negative electrode, the electrolyte and the diaphragm to a certain extent. Compared with positive and negative electrode materials, the electrolyte and the diaphragm have much smaller influence on the performance of the battery, so that the positive and negative electrode materials with low cost, excellent cycle performance, high specific capacity and high rate performance can meet the requirements of the lithium ion power battery with low cost, high energy density, high power density and long cycle life. The cathode material is used as an important component of the lithium ion battery, and the composition and the structure of the cathode material have a decisive influence on the electrochemical performance of the lithium ion battery. However, the specific capacity of the current commercial graphite negative electrode is relatively low (372mAh/g), so that the research of a new generation of high-performance negative electrode material of the lithium ion battery becomes a development trend in the future.
Chinese patent with application number CN201110407617.1 discloses a high-safety lithium ion battery cathode material and a preparation method thereof, and the method provides Al (OH)3The sol reacts with NaOH and LiOH at the temperature of 40-90 ℃ to prepare LiAlO2Graphite and LiAlO2Mixing, adjusting the pH value, heating at 500-800 ℃, evaporating organic compounds and water in the mixture, and grinding to obtain graphite/LiAlO2Composite powder; graphite/LiAlO2Putting the composite powder into a quartz tube under an iron catalyst to prepare graphite/LiAlO2And ball milling the carbon nanotube composite material to obtain the high-safety lithium ion battery cathode material. The cathode material utilizes the electronic conductivity of the carbon nano tube, and improves the use safety on the basis of keeping higher conductivity.However, the method has the defects of complex process and high energy consumption, and the method adopts the traditional polyvinylidene fluoride as a binder, so that the van der Waals force formed between the polyvinylidene fluoride and an active substance is weak, and the method cannot meet the requirements of modern lithium ion batteries, particularly high-specific-capacity lithium ion batteries.
Disclosure of Invention
The invention aims to provide a preparation process of a composite lithium battery cathode material, wherein a self-made composite material is used as an active substance of a cathode, the structure of the substance can effectively protect the volume expansion of tin oxide in the battery reaction, the buffering effect is achieved, and the specific surface area of the composite material can be increased, so that the electrochemical performance of the battery is improved; the binder comprises two effective components of waterborne polyurethane and tragacanth, so that the requirement of environmental protection is met, and the two effective components improve the electrochemical performance of the lithium battery from multiple directions; the cathode material prepared by the invention has high electrochemical performance, good cycle performance, wide application prospect and huge market potential.
The purpose of the invention can be realized by the following technical scheme:
a preparation process of a composite lithium battery negative electrode material comprises the following steps:
firstly, preparing the following raw materials in parts by weight: 80-100 parts of active material, 12-15 parts of carbon black and 16-20 parts of binder;
and secondly, mixing the raw materials, uniformly grinding to form paste, coating the paste on copper foil by using a coating method, and drying, rolling and cutting to obtain the composite lithium battery negative electrode material.
Further, the active material is prepared by the following method:
1) dispersing graphene oxide in deionized water according to a solid-liquid ratio of 1mg:8mL, sequentially adding mercaptoethanol, stannous chloride, urea and concentrated hydrochloric acid, uniformly stirring, pouring the mixed solution into a polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into a high-pressure reaction kettle, and reacting for 8 hours at 120 ℃ to obtain composite graphene oxide;
2) adding the coated graphene oxide and the dimethyl imidazole obtained in the step into methanol, stirring and dispersing for 5-8min, adding zinc nitrate, continuously stirring for 2h at room temperature, filtering, calcining the product at 600 ℃ in a nitrogen environment for 2h, cooling, fully soaking in dilute hydrochloric acid with pH of 2 for 20-24h, taking out, washing with deionized water for 5-6 times, and drying to obtain the active material.
Further, the usage ratio of the graphene oxide, the mercaptoethanol, the stannous chloride, the urea and the concentrated hydrochloric acid in the step 1) is as follows: 1mg: 2. mu.L: 13. mu.L: 0.1g:0.1 mL.
Further, the dosage ratio of the coated graphene oxide, the dimethyl imidazole, the methanol and the zinc nitrate in the step 2) is 6mg:1.63g:100mL:0.74 g.
Further, the binder is prepared by the following method:
s1, adding polypropylene oxide glycol, 2,3,5, 6-tetramethylolpyrazine and polyethylene glycol monomethyl ether into a three-neck flask provided with a reflux condenser tube and a thermometer, firstly carrying out vacuum dehydration at 100 ℃ for 60-70min, then adding isophorone diisocyanate, heating to 90 ℃, and reacting for 2-3 h;
s2, cooling the product to below 50 ℃, adding a chain extender, reacting at 80 ℃ for 2-3h, cooling to below 50 ℃, adding dibutyltin dilaurate, heating to 70 ℃, continuing to react for 3-4h, cooling to below 50 ℃, discharging, adding deionized water for emulsification under high-speed stirring, finally adding ethylenediamine for post-expansion reaction for 30-40min, and discharging to obtain a polyurethane emulsion;
s3, washing the tragacanth with absolute ethyl alcohol for 3-4 times to remove a small amount of possible additives, fully drying, mixing the dried tragacanth with deionized water according to a solid-to-liquid ratio of 1g:45-50mL, and fully stirring until the dried tragacanth is completely dissolved to obtain a glue solution;
and S4, mixing the polyurethane emulsion and the glue solution according to the volume ratio of 1:1, and uniformly stirring to obtain the adhesive.
Further, in the step S1, the weight ratio of the polypropylene oxide glycol to the 2,3,5, 6-tetramethylolpyrazine to the polyethylene glycol monomethyl ether to the isophorone diisocyanate is 10:2-3:3-4: 16-18.
Further, in step S2, the amount of dibutyltin dilaurate added is 0.2% by mass of the system, the amount of deionized water added is 10% by mass of the system, and the amount of ethylenediamine added is 2% by mass of the system.
The invention has the beneficial effects that:
according to the invention, a self-made composite material is used as an active substance, and the active material contains graphene oxide, tin oxide, zinc oxide and other active ingredients, so that the active material has higher electrochemical performance; in addition, fine zinc oxide particles are uniformly scattered among the tin oxide sheets, so that the volume expansion of the tin oxide in the battery reaction can be effectively protected by the structural characteristics, an effective buffering effect is achieved, the specific surface area of the composite material can be increased, and the electrochemical performance of the battery is improved; after carbonization and pickling, hydrochloric acid can wash off part of the simple zinc and zinc oxide to form a plurality of microporous structures, so that the specific surface area of the composite material is increased, and in the battery material, the larger the specific surface area of the material is, the larger the contact area with ions is, the higher the electrochemical reaction activity is, so that the battery performance is stronger; in addition, during the discharging and charging process of the battery, lithium ions are continuously mixed with SnO2The reaction and volume change easily cause the change of the material structure, and the structure of the composite material can effectively buffer SnO2So that the tin oxide can still maintain a stable structure after undergoing multiple cycles, thereby continuously exerting excellent electrochemical performance;
the invention adopts a compound binder, the binder comprises polyurethane polar polymer and two components, the prepared polyurethane molecule contains more polar groups (such as-COOH, -OH and the like), and can form hydrogen bond action with the groups on the surface of an active substance, and the active substance is firmly adhered on a current collector due to the action force of the hydrogen bond, so that the radial cracking of an electrode in the process of repeated lithiation and delithiation can be prevented; and a small amount of polyurethane adhesive enables the conductive agent to be firmly fixed on the current collector, so that high specific discharge capacity and capacity retention rate can be kept; in addition, in the polyurethane polymerization process, 2,3,5, 6-tetramethylolpyrazine is added, and the substance can participate in the copolymerization reaction of polyurethane and is grafted on a polyurethane molecular chain, so that a pyrazine group is introduced on the polyurethane molecular chain and has certain conductivity, and when the polyurethane is used as one of the components of the binder, the electrochemical cycle performance and the rate capability of the electrode are improved; the molecules of the tragacanth also contain a large number of polar functional groups such as carboxyl (-COOH) and hydroxyl (-OH), and can form a large number of hydrogen bonds with the surfaces of active substance particles to generate strong interaction force, so that the volume change of the active substance in the charge and discharge process is effectively limited, and the electrochemical performance of the lithium ion battery is further improved; in addition, the molecular structure of the tragacanth has a large number of branched chains, and the structure has good wrapping property on active substance particles, so that the volume expansion of the active substance can be effectively buffered, and the electrochemical performance of the lithium battery is improved; the binder comprises two effective components of waterborne polyurethane and tragacanth, which not only meets the requirement of green environmental protection, but also improves the electrochemical performance of the lithium battery from multiple directions;
according to the invention, the self-made composite material is used as the active material of the cathode, the volume expansion of the tin oxide in the battery reaction can be effectively protected by the structure of the material, the buffer effect is achieved, and the specific surface area of the composite material can be increased, so that the electrochemical performance of the battery is improved; the binder comprises two effective components of waterborne polyurethane and tragacanth, so that the requirement of environmental protection is met, and the two effective components improve the electrochemical performance of the lithium battery from multiple directions; the cathode material prepared by the invention has high electrochemical performance, good cycle performance, wide application prospect and huge market potential.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A preparation process of a composite lithium battery negative electrode material comprises the following steps:
firstly, preparing the following raw materials in parts by weight: 80-100 parts of active material, 12-15 parts of carbon black (conductive agent) and 16-20 parts of binder;
step two, mixing the raw materials, grinding the mixture evenly to form paste, coating the paste on copper foil by using a coating method, and drying, rolling and cutting the copper foil to obtain the composite lithium battery negative electrode material;
wherein, the active material is prepared by the following method:
1) dispersing graphene oxide in deionized water according to a solid-liquid ratio of 1mg:8mL, sequentially adding mercaptoethanol, stannous chloride, urea and concentrated hydrochloric acid (mass fraction is 37%), uniformly stirring, pouring the mixed solution into a polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into a high-pressure reaction kettle, and reacting for 8 hours at 120 ℃ to obtain composite graphene oxide;
the dosage ratio of the graphene oxide, the mercaptoethanol, the stannous chloride, the urea and the concentrated hydrochloric acid is as follows: 1mg, 2 mul, 13 mul, 0.1g, 0.1 mL;
in the step, stannous chloride undergoes a hydrothermal reaction, and the generated flake tin oxide is compounded with flake graphene oxide to form composite graphene oxide;
2) adding the coated graphene oxide and the dimethyl imidazole obtained in the step into methanol, stirring and dispersing for 5-8min, adding zinc nitrate, continuously stirring for 2h at room temperature, filtering, calcining the product at 600 ℃ in a nitrogen environment for 2h, cooling, fully soaking in dilute hydrochloric acid with pH of 2 for 20-24h, taking out, washing with deionized water for 5-6 times, and drying to obtain an active material;
the dosage ratio of the coated graphene oxide to the dimethyl imidazole to the methanol to the zinc nitrate is 6mg to 1.63g to 100mL to 0.74 g;
zinc oxide nanoparticles generated by zinc nitrate are uniformly attached between the tin oxide sheets to obtain an active material; the active material contains graphene oxide, tin oxide, zinc oxide and other effective components, so that the active material has higher electrochemical performance; in addition, fine zinc oxide particles are uniformly dispersed between the tin oxide flakes, and such structural features may beThe volume expansion of the tin oxide in the battery reaction is effectively protected, an effective buffering effect is achieved, and the specific surface area of the composite material can be increased, so that the electrochemical performance of the battery is improved; after carbonization and pickling, hydrochloric acid can wash off part of the simple zinc and zinc oxide to form a plurality of microporous structures, so that the specific surface area of the composite material is increased, and in the battery material, the larger the specific surface area of the material is, the larger the contact area with ions is, the higher the electrochemical reaction activity is, so that the battery performance is stronger; in addition, during the discharging and charging process of the battery, lithium ions are continuously mixed with SnO2The reaction and volume change easily cause the change of the material structure, and the structure of the composite material can effectively buffer SnO2So that the tin oxide can still maintain a stable structure after undergoing multiple cycles, thereby continuously exerting excellent electrochemical performance;
the binder is prepared by the following method:
s1, adding polypropylene oxide glycol, 2,3,5, 6-tetramethylolpyrazine and polyethylene glycol monomethyl ether into a three-neck flask provided with a reflux condenser tube and a thermometer, firstly carrying out vacuum dehydration at 100 ℃ for 60-70min, then adding isophorone diisocyanate, heating to 90 ℃, and reacting for 2-3 h;
wherein the weight ratio of the polypropylene oxide glycol to the 2,3,5, 6-tetramethylolpyrazine to the polyethylene glycol monomethyl ether to the isophorone diisocyanate is 10:2-3:3-4: 16-18;
s2, cooling the product to below 50 ℃, adding a chain extender, reacting at 80 ℃ for 2-3h, cooling to below 50 ℃, adding dibutyltin dilaurate (the addition amount is 0.2% of the mass of the system), heating to 70 ℃, continuing to react for 3-4h, cooling to below 50 ℃, discharging, adding deionized water (the addition amount of the deionized water is 10% of the mass of the system) under high-speed stirring for emulsification, finally adding ethylenediamine (the addition amount of the ethylenediamine is 2% of the mass of the system) for post-expansion reaction for 30-40min, and discharging to obtain a polyurethane emulsion;
the prepared polyurethane molecule contains more polar groups (such as-COOH, -OH and the like), and can form hydrogen bond action with groups on the surface of an active substance, and the active substance is firmly adhered to a current collector due to the action force of the hydrogen bond, so that the electrode can be prevented from radial cracking in the process of repeated lithiation and delithiation; and a small amount of polyurethane adhesive enables the conductive agent to be firmly fixed on the current collector, so that high specific discharge capacity and capacity retention rate can be kept; in addition, in the polyurethane polymerization process, 2,3,5, 6-tetramethylolpyrazine is added, and the substance can participate in the copolymerization reaction of polyurethane and is grafted on a polyurethane molecular chain, so that a pyrazine group is introduced on the polyurethane molecular chain and has certain conductivity, and when the polyurethane is used as one of the components of the binder, the electrochemical cycle performance and the rate capability of the electrode are improved;
s3, washing the tragacanth with absolute ethyl alcohol for 3-4 times to remove a small amount of possible additives, fully drying, mixing the dried tragacanth with deionized water according to a solid-to-liquid ratio of 1g:45-50mL, and fully stirring until the dried tragacanth is completely dissolved to obtain a glue solution;
s4, mixing the polyurethane emulsion and the glue solution according to the volume ratio of 1:1, and uniformly stirring to obtain a binder;
the molecules of the tragacanth also contain a large number of polar functional groups such as carboxyl (-COOH) and hydroxyl (-OH), and can form a large number of hydrogen bonds with the surfaces of active substance particles to generate strong interaction force, so that the volume change of the active substance in the charge and discharge process is effectively limited, and further the electrochemical performance of the lithium ion battery is improved; in addition, the molecular structure of the tragacanth has a large number of branched chains, and the structure has good wrapping property on active substance particles, so that the volume expansion of the active substance can be effectively buffered, and the electrochemical performance of the lithium battery is improved; the binder comprises two effective components of waterborne polyurethane and tragacanth, not only meets the requirement of green environmental protection, but also improves the electrochemical performance of the lithium battery from multiple directions.
Example 1
A preparation process of a composite lithium battery negative electrode material comprises the following steps:
firstly, preparing the following raw materials in parts by weight: 80 parts of active material, 12 parts of carbon black and 16 parts of binder;
and secondly, mixing the raw materials, uniformly grinding to form paste, coating the paste on copper foil by using a coating method, and drying, rolling and cutting to obtain the composite lithium battery negative electrode material.
Example 2
A preparation process of a composite lithium battery negative electrode material comprises the following steps:
firstly, preparing the following raw materials in parts by weight: 90 parts of active material, 13.5 parts of carbon black and 18 parts of binder;
and secondly, mixing the raw materials, uniformly grinding to form paste, coating the paste on copper foil by using a coating method, and drying, rolling and cutting to obtain the composite lithium battery negative electrode material.
Example 3
A preparation process of a composite lithium battery negative electrode material comprises the following steps:
firstly, preparing the following raw materials in parts by weight: 100 parts of active material, 15 parts of carbon black and 20 parts of binder;
and secondly, mixing the raw materials, uniformly grinding to form paste, coating the paste on copper foil by using a coating method, and drying, rolling and cutting to obtain the composite lithium battery negative electrode material.
Comparative example 1
The active material in example 1 was replaced with tin oxide, and the remaining raw materials and preparation process were unchanged.
Comparative example 2
The binder in example 1 was replaced by a conventional polyurethane emulsion, and the remaining raw materials and preparation process were unchanged.
Comparative example 3
The adhesive in example 1 was replaced with gum tragacanth, and the rest of the raw materials and the preparation process were unchanged.
After drying the negative electrode materials prepared in examples 1 to 3 and comparative examples 1 to 3, they were transferred to glove boxes, respectively, to assemble a button cell type CR 2005: a metallic lithium plate was used as a counter electrode, a Celgard2400 thin film was used as a separator, and the electrolyte was 1mol of LiF6Dissolving in 1L of EC-DEC-DMC (volume ratio of 1:1:1),then adding 2 percent (mass fraction) of VC and 10 percent (mass fraction) of FEC as electrolyte additives, transferring the button cell from a glove box after the button cell is assembled, standing for a period of time, and carrying out electrochemical performance test and characterization:
the assembled button cells were tested for cycling stability and rate capability using a model LANDCT2001A blue test system at 30 ℃, with the test results shown in the following table:
as can be seen from the above table, the negative electrode materials prepared in examples 1 to 3 all have high cycle performance and rate capability; by combining the comparative example 1, the active substance prepared by the invention is a composite material, and the active substance is compounded with graphene oxide and nano zinc oxide to enable the active material to have higher electrochemical performance; in addition, fine zinc oxide particles are uniformly scattered among the tin oxide sheets, so that the volume expansion of the tin oxide in the battery reaction can be effectively protected by the structural characteristics, an effective buffering effect is achieved, the specific surface area of the composite material can be increased, and the electrochemical performance of the battery is improved; by combining the comparative example 2, the polyurethane prepared by the invention can not only form a strong hydrogen bond effect with an active substance, but also introduce a conducting group on a polyurethane molecular chain, so that the electrochemical performance of a lithium battery is improved; in combination with comparative example 2 and comparative example 3, it is illustrated that the binder of the present invention comprises polyurethane and tragacanth, which in combination are effective in improving the electrochemical performance of a lithium battery.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (7)
1. A preparation process of a composite lithium battery negative electrode material is characterized by comprising the following steps:
firstly, preparing the following raw materials in parts by weight: 80-100 parts of active material, 12-15 parts of carbon black and 16-20 parts of binder;
and secondly, mixing the raw materials, uniformly grinding to form paste, coating the paste on copper foil by using a coating method, and drying, rolling and cutting to obtain the composite lithium battery negative electrode material.
2. The process for preparing a negative electrode material for a composite lithium battery as claimed in claim 1, wherein the active material is prepared by the following method:
1) dispersing graphene oxide in deionized water according to a solid-liquid ratio of 1mg:8mL, sequentially adding mercaptoethanol, stannous chloride, urea and concentrated hydrochloric acid, uniformly stirring, pouring the mixed solution into a polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into a high-pressure reaction kettle, and reacting for 8 hours at 120 ℃ to obtain composite graphene oxide;
2) adding the coated graphene oxide and the dimethyl imidazole obtained in the step into methanol, stirring and dispersing for 5-8min, adding zinc nitrate, continuously stirring for 2h at room temperature, filtering, calcining the product at 600 ℃ in a nitrogen environment for 2h, cooling, fully soaking in dilute hydrochloric acid with pH of 2 for 20-24h, taking out, washing with deionized water for 5-6 times, and drying to obtain the active material.
3. The preparation process of the negative electrode material of the composite lithium battery as claimed in claim 2, wherein the usage ratio of the graphene oxide, the mercaptoethanol, the stannous chloride, the urea and the concentrated hydrochloric acid in the step 1) is as follows: 1mg: 2. mu.L: 13. mu.L: 0.1g:0.1 mL.
4. The preparation process of the negative electrode material for the composite lithium battery as claimed in claim 2, wherein the dosage ratio of the coated graphene oxide, the dimethyl imidazole, the methanol and the zinc nitrate in the step 2) is 6mg:1.63g:100mL:0.74 g.
5. The process for preparing the negative electrode material of the composite lithium battery as claimed in claim 1, wherein the binder is prepared by the following method:
s1, adding polypropylene oxide glycol, 2,3,5, 6-tetramethylolpyrazine and polyethylene glycol monomethyl ether into a three-neck flask provided with a reflux condenser tube and a thermometer, firstly carrying out vacuum dehydration at 100 ℃ for 60-70min, then adding isophorone diisocyanate, heating to 90 ℃, and reacting for 2-3 h;
s2, cooling the product to below 50 ℃, adding a chain extender, reacting at 80 ℃ for 2-3h, cooling to below 50 ℃, adding dibutyltin dilaurate, heating to 70 ℃, continuing to react for 3-4h, cooling to below 50 ℃, discharging, adding deionized water for emulsification under high-speed stirring, finally adding ethylenediamine for post-expansion reaction for 30-40min, and discharging to obtain a polyurethane emulsion;
s3, washing the tragacanth with absolute ethyl alcohol for 3-4 times to remove a small amount of possible additives, fully drying, mixing the dried tragacanth with deionized water according to a solid-to-liquid ratio of 1g:45-50mL, and fully stirring until the dried tragacanth is completely dissolved to obtain a glue solution;
and S4, mixing the polyurethane emulsion and the glue solution according to the volume ratio of 1:1, and uniformly stirring to obtain the adhesive.
6. The preparation process of the negative electrode material for the composite lithium battery as claimed in claim 5, wherein the weight ratio of the polypropylene oxide glycol, the 2,3,5, 6-tetramethylolpyrazine, the polyethylene glycol monomethyl ether and the isophorone diisocyanate in the step S1 is 10:2-3:3-4: 16-18.
7. The process of claim 5, wherein in step S2, the amount of dibutyltin dilaurate added is 0.2% by mass of the system, the amount of deionized water added is 10% by mass of the system, and the amount of ethylenediamine added is 2% by mass of the system.
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| CN114784232A (en) * | 2022-04-28 | 2022-07-22 | 安徽国洁新能源科技有限公司 | Method for manufacturing lithium ion battery cell by using nano silicon material |
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