CN110534699B - Preparation method of lithium ion battery negative plate - Google Patents
Preparation method of lithium ion battery negative plate Download PDFInfo
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- CN110534699B CN110534699B CN201910776951.0A CN201910776951A CN110534699B CN 110534699 B CN110534699 B CN 110534699B CN 201910776951 A CN201910776951 A CN 201910776951A CN 110534699 B CN110534699 B CN 110534699B
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- 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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- 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
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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
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- 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
- H01M4/139—Processes of manufacture
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- 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
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- 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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- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the field of lithium ion batteries, in particular to a lithium ion battery negative plate which comprises the following raw materials in parts by weight: 70-75 parts of silicon dioxide aerogel, 70-75 parts of graphene, 1-2.5 parts of binder, 0.5-1 part of conductive agent, 0-1 part of dispersant, 0.5-1 part of thickening agent and 150 parts of water 145 and organic solvent. According to the invention, the negative plate of the lithium ion battery is prepared by adopting the nitrogen-doped graphene and the modified polyimide resin, and the nitrogen-doped graphene and the modified polyimide resin have a synergistic effect, so that the volume expansion of the negative material can be effectively inhibited in the lithium intercalation and deintercalation process, and the cycle is stabilized, thereby improving the comprehensive performance of the lithium ion battery. Meanwhile, the lithium ion battery negative plate prepared by the invention has the advantages of large specific surface area, high specific capacitance and high flexibility, and the surface of the obtained negative plate is smooth and has weak rough feeling after being coated on the surface of the negative plate and cured by adopting a special process, so that the diaphragm can be effectively prevented from being pierced, and the service life of the battery is prolonged.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a lithium ion battery negative plate and a preparation method thereof.
Background
In recent years, the rapid development of portable electronic devices, electric tools, and electric vehicles has made higher demands on the performance of lithium ion batteries, and thus, the research on a new generation of lithium ion batteries with high specific capacity and long cycle life has been activated. The lithium ion battery is mainly composed of electrolyte, a diaphragm, positive and negative electrode materials, has the characteristics of high specific energy density, high voltage, long service life, no memory effect, small self-discharge and the like, and is a portable battery which is most widely applied at present.
Compared with the carbon-based anode material which is commercially used at present, the silicon anode material has higher specific capacity and energy density, and is considered as a potential next-generation lithium ion battery anode material. However, in practical use, the silicon negative electrode material generates drastic volume change in the process of lithium intercalation and deintercalation, which causes material pulverization, coating peeling from the surface of a current collector, and repeated cracking and generation of a solid electrolyte phase interface film, and the material has low cycling stability and short battery life. The problem of volume expansion of the silicon cathode material in the actual use process is solved by adopting three methods: the first is to improve the silicon material itself, to reduce the particle size of the silicon material itself to make it nano-sized or to compound the silicon material with other materials; the second is to modify the electrolyte and the binder; and the third is to improve the electrode current collector and the electrode structure.
The improvement of the silicon material is an effective method for solving the volume expansion of the silicon cathode material, but the improved silicon cathode material has poor cycle performance; the volume expansion problem of the silicon negative electrode material can be improved to a certain extent by improving the electrolyte, the binder, the electrode current collector and the electrode structure, but the expansion problem of the silicon is not solved essentially. Therefore, the invention aims to solve the problems that the silicon negative electrode material generates violent volume change in the process of lithium insertion and extraction, which causes material pulverization, coating peeling from the surface of a current collector and repeated cracking and generation of a solid electrolyte phase interface film, thereby causing low cycling stability of the material and short service life of a battery.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides a lithium ion battery negative electrode sheet, which comprises the following raw materials, by weight: 70-75 parts of silicon dioxide aerogel, 70-75 parts of graphene, 1-2.5 parts of binder, 0.5-1 part of conductive agent, 0-1 part of dispersant, 0.5-1 part of thickening agent and 150 parts of water 145 and organic solvent.
As a preferred technical solution, the graphene is nitrogen-doped graphene.
As a preferred technical scheme, the preparation method of the nitrogen-doped graphene comprises the following steps:
a) carrying out ultrasonic dispersion on graphene in deionized water to obtain uniform dispersion liquid;
b) adding a nitrogen dopant into the dispersion liquid obtained in the step a), and uniformly mixing to obtain a mixture;
c) placing the mixture obtained in the step b) in an autoclave with a polytetrafluoroethylene lining, reacting for 2-3h at 85-90 ℃, then heating to 210-250 ℃, and reacting for 10-12h to finally obtain the nitrogen-doped graphene.
As a preferred technical solution, the mass ratio of the graphene to the nitrogen dopant is 1: (0.2-0.8).
As a preferred technical solution, in the step b), the nitrogen dopant is a mixture of triethanolamine and guanidine carbonate.
As a preferable technical scheme, the mass ratio of the triethanolamine to the guanidine carbonate is 1: (0.5-2).
As a preferable technical solution, the binder is a modified polyimide resin.
As a preferred technical solution, the preparation method of the modified polyimide resin is as follows:
1) dissolving a diamine derivative containing carboxyl in an N, N-dimethylacetamide solvent, and adding an aromatic dibasic anhydride monomer for reaction to obtain a polyamic acid solution;
2) adding a dehydrating agent and a catalyst into the polyamic acid solution obtained in the step 1) to react for 5-10h, and finally obtaining the modified polyimide resin.
As a preferable embodiment, in step 1), the diamine derivative containing a carboxyl group is 3, 4-diamino-2-naphthoic acid.
The second aspect of the invention provides a preparation method of a lithium ion battery negative plate, which comprises the following steps:
i) adding silicon dioxide aerogel and graphene into water, stirring uniformly, sequentially adding a binder, a conductive agent, a dispersing agent and a thickening agent, dispersing uniformly, grinding, and sieving to obtain negative electrode slurry;
ii) coating the negative electrode slurry obtained in the step i) on the surface of a negative electrode current collector in a coating oven, then carrying out cold pressing and rolling, and then baking under the vacuum-pumping condition to obtain the negative electrode plate.
Has the advantages that: according to the invention, the negative plate of the lithium ion battery is prepared by adopting the nitrogen-doped graphene and the modified polyimide resin, and the nitrogen-doped graphene and the modified polyimide resin have a synergistic effect, so that the volume expansion of the negative material can be effectively inhibited in the lithium intercalation and deintercalation process, and the cycle is stabilized, thereby improving the comprehensive performance of the lithium ion battery. Meanwhile, the lithium ion battery negative plate prepared by the invention has the advantages of large specific surface area, high specific capacitance and high flexibility, and the surface of the obtained negative plate is smooth and has weak rough feeling after being coated on the surface of the negative plate and cured by adopting a special process, so that the diaphragm can be effectively prevented from being pierced, and the service life of the battery is prolonged.
Detailed Description
The technical features of the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, and the scope of protection is not limited thereto.
The words "preferred", "more preferred", and the like, in the present invention refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the expression of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
The invention provides a lithium ion battery negative plate, which comprises the following raw materials in parts by weight: 70-75 parts of silicon dioxide aerogel, 70-75 parts of graphene, 1-2.5 parts of binder, 0.5-1 part of conductive agent, 0-1 part of dispersant, 0.5-1 part of thickening agent and 150 parts of water 145 and organic solvent.
In a preferred embodiment, the composition comprises the following raw materials in parts by weight: 73 parts of silicon dioxide aerogel, 73 parts of graphene, 2 parts of binder, 0.8 part of conductive agent, 0.5 part of dispersing agent, 0.6 part of thickening agent and 147 parts of water.
< silica aerogel >
The silica aerogel of the invention is also called as 'blue smoke' or 'solid smoke', and has a nano-porous structure (2-100 nm), low density and low dielectric constant (1.1E &)2.5), low thermal conductivity (0.013-0.025 w/m.k), high porosity (65% -99%), and high specific surface area (300-1000 m)2The material has the characteristics of/g), shows unique properties in aspects of mechanics, acoustics, thermology, optics and the like, and is widely applied to the fields of aerospace, petrochemical industry, electric power, ships, new energy automobiles, lithium batteries, heat pipelines, building heat preservation and cold insulation, LNG cold chains and the like.
The silica aerogel of the present invention is not particularly limited, and can be various silica aerogels conventionally used in the art, and can be prepared, for example, silica aerogels that can be prepared include, but are not limited to, silica aerogels prepared by a sol-gel method; commercially available silica aerogels, for example, include, but are not limited to, silica aerogels available from Jiangxi Anderson high and New technology, Inc.
< graphene >
The Graphene (Graphene) is prepared from sp carbon atoms2The hybrid tracks form a hexagonal honeycomb lattice two-dimensional carbon nanomaterial.
The graphene is not particularly limited, and can be various conventionally used graphene, and can be prepared, for example, the graphene which can be prepared includes but is not limited to a graphene prepared by a mechanical stripping method, a redox method, an orientation epitaxy method, a silicon carbide epitaxy method, a hermer method and a chemical vapor deposition method; commercially available graphene may also be obtained, for example, commercially available graphene includes, but is not limited to, graphene purchased from Nanjing Xiapong nanomaterial science and technology, Inc.
In one embodiment, the graphene is nitrogen-doped graphene, and the preparation method comprises the following steps:
a) carrying out ultrasonic dispersion on graphene in deionized water to obtain uniform dispersion liquid;
b) adding a nitrogen dopant into the dispersion liquid obtained in the step a), and uniformly mixing to obtain a mixture;
c) placing the mixture obtained in the step b) in an autoclave with a polytetrafluoroethylene lining, reacting for 2-3h at 85-90 ℃, then heating to 210-250 ℃, and reacting for 10-12h to finally obtain the nitrogen-doped graphene.
In a preferred embodiment, the preparation method of the nitrogen-doped graphene comprises the following steps:
a) carrying out ultrasonic dispersion on graphene (with the model of XF001W) in deionized water to obtain uniform dispersion liquid;
b) adding a nitrogen dopant into the dispersion liquid obtained in the step a), and uniformly mixing to obtain a mixture;
c) placing the mixture obtained in the step b) in an autoclave with a polytetrafluoroethylene lining, reacting for 2 hours at 90 ℃, then heating to 220 ℃, and reacting for 10 hours to finally obtain the nitrogen-doped graphene.
In one embodiment, the mass ratio of the graphene to the nitrogen dopant is 1: (0.2-0.8).
In a preferred embodiment, the mass ratio of the graphene to the nitrogen dopant is 1: 0.5.
in one embodiment, the mass ratio of the graphene to the deionized water is 1: 1.
(Nitrogen dopant)
The nitrogen dopant is an additive rich in nitrogen source, and can introduce a nitrogen atom-containing structure into a material.
The nitrogen doping agent is selected from one or a combination of more of urea, melamine, ammonia water, triethanolamine, hydrazine hydrate, guanethidine, pyrrole, aniline, guanidine carbonate, guanidine phosphate, guanidine hydrochloride and urea phosphate.
In one embodiment, the nitrogen dopant is a mixture of triethanolamine (CAS:102-71-6) and guanidine carbonate (CAS: 593-85-1).
In a preferred embodiment, the mass ratio of triethanolamine to guanidine carbonate is 1: (0.5-2).
In a more preferred embodiment, the weight ratio of triethanolamine to guanidine carbonate is 1: 1.
nitrogen dopant is added to introduce nitrogen heteroatom into graphene, so that specific capacitance of the cathode material is improved. Because the specific capacitance of the cathode material is smaller, nitrogen heteroatom is introduced into the cathode material, so that the specific capacitance of the cathode material is improved.
The applicant has unexpectedly found that when graphene is modified with two nitrogen dopants, triethanolamine and guanidine carbonate, the cycling stability of the lithium ion battery is further improved, and the applicant speculates that the possible reasons are: on one hand, after triethanolamine and guanidine carbonate are added in the hydrothermal reaction, thermal decomposition and radical reaction can be acted together, and the introduced nitrogen finally exists in four different forms of pyridine nitrogen, pyrrole nitrogen, quaternary nitrogen and graphite nitrogen; on the other hand, triethanolamine and guanidine carbonate interact to generate more defect sites on the surface of the graphene, so that more uniform curls and folds are generated on the surface of the graphene. Therefore, the introduced nitrogen has better bonding strength on the negative electrode material, and can promote the insertion and the desorption of lithium ions in the lithium intercalation and deintercalation (i.e., charge and discharge) process.
< Binder >
The adhesive of the invention ensures the adhesive strength between the abrasive and the matrix.
The binder is selected from one or more of styrene butadiene rubber, carboxymethyl cellulose, polyvinylidene fluoride, polyimide, acrylic resin and butyraldehyde resin.
In one embodiment, the binder is a modified polyimide resin and is prepared by the following steps:
1) dissolving a diamine derivative containing carboxyl in an N, N-dimethylacetamide solvent, and adding an aromatic dibasic anhydride monomer for reaction to obtain a polyamic acid solution;
2) adding a dehydrating agent and a catalyst into the polyamic acid solution obtained in the step 1) to react for 5-10h, and finally obtaining the modified polyimide resin.
In a preferred embodiment, the modified polyimide resin is prepared as follows:
1) dissolving a diamine derivative containing carboxyl in an N, N-dimethylacetamide solvent, and adding pyromellitic dianhydride to react to obtain a polyamic acid solution;
2) adding a dehydrating agent, acetic anhydride and a catalyst, namely triethylamine, into the polyamic acid solution obtained in the step 1) to react for 7 hours, and finally obtaining the modified polyimide resin.
In a more preferred embodiment, the molar ratio of the carboxyl group-containing diamine derivative, N-dimethylacetamide, pyromellitic dianhydride, acetic anhydride, and triethylamine is 1: 5: 1: 2: 2.
(diamine derivative containing carboxyl group)
In one embodiment, examples of the carboxyl group-containing diamine derivative include, but are not limited to: 4, 6-diamino-1, 3-benzenedicarboxylic acid (CAS:13324-94-2), 2, 5-diamino-4-methylbenzoic acid (CAS:13066-80-3), 2, 3-diaminobenzoic acid (CAS:603-81-6), 2, 4-diaminobenzoic acid (CAS:611-03-0), 2, 5-diaminobenzoic acid (CAS:610-74-2), 2, 6-diaminobenzoic acid (CAS:102000-59-9), 3, 4-diaminobenzoic acid (CAS:619-05-6), 3, 5-diaminobenzoic acid (CAS:535-87-5), 3, 4-diamino-2-naphthoic acid (CAS:612806-13-0), 2, 6-diamino-1-naphthoic acid (CAS:46390-04-9), 3, 4-diamino-1-naphthoic acid (CAS: 675877-59-5).
In a preferred embodiment, the carboxyl group-containing diamine derivative is 3, 4-diamino-2-naphthoic acid (CAS: 612806-13-0).
This application has strengthened being connected between negative electrode material and the mass flow body through adding polyimide. Because the compatibility of the polyimide is poor, the compatibility of the polyimide is improved and the connection between the negative electrode material and the current collector is enhanced by modifying the polyimide by adopting the diamine derivative containing carboxyl.
The applicant has surprisingly found that when the carboxyl group-containing diamine derivative is 3, 4-diamino-2-naphthoic acid, the cycling stability of the lithium ion battery is further improved, and supposedly by the applicant that the possible reasons are: on one hand, the modified polyimide resin can form a composite conductive elastic inhibition layer with graphene and silicon dioxide aerogel through acting force; on the other hand, the active groups on the modified polyimide resin relieve the stress effect of volume irregularity of each point on an SEI film caused by lithium deposition on the surface of the negative electrode, so that the cycle stability of the lithium ion battery is improved.
In one embodiment, the mass ratio of the binder to the graphene is 1: (30-70).
In a preferred embodiment, the mass ratio of the binder to the graphene is 1: (32-45).
In a more preferred embodiment, the mass ratio of the binder to the graphene is 1: 36.5.
the applicant has surprisingly found that when the mass ratio of binder to graphene is 1: (30-70), the lithium ion battery has good cycling stability, which is probably because the modified polyimide resin can play a good synergistic role with the nitrogen-doped graphene, the thickening agent and the like in the system, on one hand, the modified polyimide resin can interact with the nitrogen-doped graphene to generate a composite conductive elastic inhibiting layer to inhibit the volume expansion of the negative electrode material; on the other hand, four different nitrogens, namely pyridine nitrogen, pyrrole nitrogen, quaternary nitrogen and graphite nitrogen in the nitrogen-doped graphene can interact with different components and groups in a system simultaneously, so that the uniform deposition of metal lithium on the surface of the negative electrode is realized, and the cycle stability of the lithium ion battery is improved. When the mass ratio of the binder to the graphene is 1: at 36.5, the lithium ion battery has the best cycle stability. When the mass ratio of the binder to the graphene is less than 1: at 70 hours, the modified polyimide resin and the nitrogen-doped graphene, the thickening agent and the like in the system cannot play a good synergistic effect, the volume expansion of the negative electrode material is severe, and the cycle stability of the lithium ion battery is poor; when the mass ratio of the binder to the graphene is more than 1: at 30 hours, the modified polyimide resin and the nitrogen-doped graphene, the thickener and the like in the system cannot play a good synergistic effect, the metal lithium deposition on the surface of the negative electrode is uneven, and the cycle stability of the lithium ion battery is poor.
< conductive agent >
The conductive agent is used for ensuring that the electrode has good charge and discharge performance, a certain amount of conductive substances are usually added during the manufacture of the pole piece, and the effect of collecting micro-current is achieved among active substances and between the active substances and a current collector, so that the movement rate of electrons accelerated by the contact resistance of the electrode is reduced, and meanwhile, the migration rate of lithium ions in the electrode material can be effectively improved, and the charge and discharge efficiency of the electrode is improved.
In one embodiment, the conductive agent is selected from one or more of artificial graphite, natural graphite, graphene, ketjen black, carbon nanotubes, carbon fibers, acetylene black, carbon black, and conductive polymers.
In a preferred embodiment, the conductive agent is carbon nanotubes or acetylene black.
In a more preferred embodiment, the conductive agent is acetylene black (CAS: 1333-86-4), available from Shanghai Noita chemical Co., Ltd.
< dispersant >
The Dispersant (Dispersant) of the invention is a surfactant which has two opposite properties of lipophilicity and hydrophilcity in a molecule.
In one embodiment, the dispersant is selected from one or a combination of carboxymethylcellulose, hydroxyethylcellulose, kelgel (from CPKelco), gemmate (from japan sumitomo pharmaceuticals limited), pectin, alginic acid, guar gum, locust bean gum, gum arabic, dextrin, aldose, sorbitol, lactose, rice starch, polysaccharides and monosaccharides of sucrose, sodium cholate, gelatin, polyvinyl alcohol, sodium dodecylbenzenesulfonate, NDZ201, KH550, KH 570.
In a preferred embodiment, the dispersing agent is carboxymethyl cellulose, gelatin, and a water-soluble polysaccharide.
In a more preferred embodiment, the dispersant is carboxymethyl cellulose (CAS: 9000-11-7), available from Lowan Biotechnology Inc., Changzhou.
< thickening agent >
The thickening agent is a rheological additive, can thicken the coating, prevents sagging phenomenon in construction, and can endow the coating with excellent mechanical property and storage stability. The additive is a very important class of additives for aqueous coatings with low viscosity.
In one embodiment, the thickener is selected from one or more of inorganic thickeners, cellulose ethers, natural polymers, synthetic polymers, and complex organic metal compounds.
Examples of inorganic thickeners include, but are not limited to: fumed silica, sodium bentonite, organic bentonite, diatomite, attapulgite, molecular sieve and silica gel.
Examples of cellulose ethers include, but are not limited to: methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, hydroxyethyl cellulose.
Examples of natural macromolecules include, but are not limited to: starch, gelatin, sodium alginate, casein, guar gum, chitosan, gum arabic, xanthan gum, soybean protein gum, natural rubber, lanolin, and agar.
Examples of synthetic macromolecules include, but are not limited to: polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, modified paraffin resin, carbomer resin, polyacrylic acid, sodium polyacrylate, polyacrylate copolymer emulsion, butadiene rubber, styrene-butadiene rubber, polyurethane, modified polyurea, low-molecular polyethylene wax, polycarboxylic acid and polyethylene oxide.
As examples of the complex type organometallic compounds, there are included, but not limited to: amino alcohol complex phthalate.
In a preferred embodiment, the thickener is gelatin (CAS: 9000-70-8), available from Shandong Fengtai Biotech Co., Ltd.
The second aspect of the invention provides a preparation method of a lithium ion battery negative plate, which comprises the following steps:
i) adding silicon dioxide aerogel and graphene into water, stirring uniformly, sequentially adding a binder, a conductive agent, a dispersing agent and a thickening agent, dispersing uniformly, grinding, and sieving to obtain negative electrode slurry;
ii) coating the negative electrode slurry obtained in the step i) on the surface of a negative electrode current collector in a coating oven, then carrying out cold pressing and rolling, and then baking under the vacuum-pumping condition to obtain the negative electrode plate.
Examples
Example 1
Embodiment 1 provides a lithium ion battery negative electrode sheet, which comprises the following raw materials in parts by weight: 73 parts of silicon dioxide aerogel, 73 parts of graphene, 2 parts of binder, 0.8 part of conductive agent, 0.5 part of dispersing agent, 0.6 part of thickening agent and 147 parts of water;
the silicon dioxide aerogel is purchased from Jiangxi Andde high and new technology, Inc.;
the preparation method of the nitrogen-doped graphene comprises the following steps:
a) carrying out ultrasonic dispersion on graphene in deionized water to obtain uniform dispersion liquid;
b) adding a nitrogen dopant into the dispersion liquid obtained in the step a), and uniformly mixing to obtain a mixture;
c) placing the mixture obtained in the step b) in an autoclave with a polytetrafluoroethylene lining, reacting for 2 hours at 90 ℃, then heating to 220 ℃, and reacting for 10 hours to finally obtain nitrogen-doped graphene;
the mass ratio of the graphene to the nitrogen dopant is 1: 0.5;
the mass ratio of the graphene to the deionized water is 1: 1;
the graphene in the step a) is purchased from Nanjing Xiancheng nanomaterial science and technology Limited and has the model of XF 001W;
the nitrogen dopant in the step b) is a mixture of triethanolamine and guanidine carbonate, and the mass ratio of the triethanolamine to the guanidine carbonate is 1: 1;
the binder is modified polyimide resin, and the preparation method comprises the following steps:
1) dissolving a diamine derivative containing carboxyl in an N, N-dimethylacetamide solvent, and adding pyromellitic dianhydride to react to obtain a polyamic acid solution;
2) adding a dehydrating agent, acetic anhydride and a catalyst, namely triethylamine, into the polyamic acid solution obtained in the step 1) to react for 7 hours, and finally preparing modified polyimide resin;
the molar ratio of the diamine derivative containing carboxyl, N-dimethylacetamide, pyromellitic dianhydride, acetic anhydride and triethylamine is 1: 5: 1: 2: 2;
the diamine derivative containing a carboxyl group in step 1) is 3, 4-diamino-2-naphthoic acid (CAS: 612806-13-0);
the conductive agent is acetylene black (CAS: 1333-86-4) which is purchased from Shanghai Nuotai chemical Co., Ltd;
the dispersant is carboxymethyl cellulose (CAS: 9000-11-7) available from Holly Biotech, Inc., Changzhou;
the thickener is gelatin (CAS: 9000-70-8) and is purchased from Shandong Fengtai Biotechnology Co., Ltd;
the preparation method of the lithium ion battery negative plate comprises the following steps:
i) adding silicon dioxide aerogel and graphene into water, stirring uniformly, sequentially adding a binder, a conductive agent, a dispersing agent and a thickening agent, dispersing uniformly, grinding, and sieving to obtain negative electrode slurry;
ii) coating the negative electrode slurry obtained in the step i) on the surface of a negative electrode current collector in a coating oven, then carrying out cold pressing and rolling, and then baking under the vacuum-pumping condition to obtain the negative electrode plate.
Example 2
Embodiment 2 provides a lithium ion battery negative electrode sheet, which comprises the following raw materials in parts by weight: 75 parts of silicon dioxide aerogel, 75 parts of graphene, 2.5 parts of binder, 1 part of conductive agent, 1 part of dispersing agent, 1 part of thickening agent and 150 parts of water;
the silicon dioxide aerogel is purchased from Jiangxi Andde high and new technology, Inc.;
the preparation method of the nitrogen-doped graphene comprises the following steps:
a) carrying out ultrasonic dispersion on graphene in deionized water to obtain uniform dispersion liquid;
b) adding a nitrogen dopant into the dispersion liquid obtained in the step a), and uniformly mixing to obtain a mixture;
c) placing the mixture obtained in the step b) in an autoclave with a polytetrafluoroethylene lining, reacting for 2 hours at 90 ℃, then heating to 220 ℃, and reacting for 10 hours to finally obtain nitrogen-doped graphene;
the mass ratio of the graphene to the nitrogen dopant is 1: 0.8;
the mass ratio of the graphene to the deionized water is 1: 1;
the graphene in the step a) is purchased from Nanjing Xiancheng nanomaterial science and technology Limited and has the model of XF 001W;
the nitrogen dopant in the step b) is a mixture of triethanolamine and guanidine carbonate, and the mass ratio of the triethanolamine to the guanidine carbonate is 1: 2;
the preparation method of the adhesive is the same as that of example 1, and the adhesive is modified polyimide resin;
the conductive agent is acetylene black (CAS: 1333-86-4) which is purchased from Shanghai Nuotai chemical Co., Ltd;
the dispersant is carboxymethyl cellulose (CAS: 9000-11-7) available from Holly Biotech, Inc., Changzhou;
the thickener is gelatin (CAS: 9000-70-8) and is purchased from Shandong Fengtai Biotechnology Co., Ltd;
the preparation method of the lithium ion battery negative plate is the same as that of example 1.
Example 3
Embodiment 3 provides a lithium ion battery negative electrode sheet, which comprises the following raw materials in parts by weight: 70 parts of silicon dioxide aerogel, 70 parts of graphene, 1 part of binder, 0.5 part of conductive agent, 0 part of dispersing agent, 0.5 part of thickening agent and 145 parts of water;
the silicon dioxide aerogel is purchased from Jiangxi Andde high and new technology, Inc.;
the preparation method of the nitrogen-doped graphene comprises the following steps:
a) carrying out ultrasonic dispersion on graphene in deionized water to obtain uniform dispersion liquid;
b) adding a nitrogen dopant into the dispersion liquid obtained in the step a), and uniformly mixing to obtain a mixture;
c) placing the mixture obtained in the step b) in an autoclave with a polytetrafluoroethylene lining, reacting for 2 hours at 90 ℃, then heating to 220 ℃, and reacting for 10 hours to finally obtain nitrogen-doped graphene;
the mass ratio of the graphene to the nitrogen dopant is 1: 0.2;
the mass ratio of the graphene to the deionized water is 1: 1;
the graphene in the step a) is purchased from Nanjing Xiancheng nanomaterial science and technology Limited and has the model of XF 001W;
the nitrogen dopant in the step b) is a mixture of triethanolamine and guanidine carbonate, and the mass ratio of the triethanolamine to the guanidine carbonate is 1: 0.5;
the preparation method of the adhesive is the same as that of example 1, and the adhesive is modified polyimide resin;
the conductive agent is acetylene black (CAS: 1333-86-4) which is purchased from Shanghai Nuotai chemical Co., Ltd;
the dispersant is carboxymethyl cellulose (CAS: 9000-11-7) available from Holly Biotech, Inc., Changzhou;
the thickener is gelatin (CAS: 9000-70-8) and is purchased from Shandong Fengtai Biotechnology Co., Ltd;
the preparation method of the lithium ion battery negative plate is the same as that of example 1.
Example 4
Embodiment 4 provides a lithium ion battery negative electrode sheet and a method for manufacturing the lithium ion battery negative electrode sheet, and the specific implementation manner of the method is the same as that in embodiment 1, except that the mass ratio of graphene to nitrogen dopant is replaced by 1: 0.05.
example 5
Embodiment 5 provides a lithium ion battery negative electrode sheet and a method for manufacturing the lithium ion battery negative electrode sheet, and the specific implementation manner of the method is the same as that of embodiment 1, except that the mass ratio of the graphene to the nitrogen dopant is replaced by 1: 1.5.
example 6
Embodiment 6 provides a lithium ion battery negative electrode sheet and a preparation method of the lithium ion battery negative electrode sheet, and the specific implementation manner of the lithium ion battery negative electrode sheet is the same as that in embodiment 1, except that XF001W is used instead of the nitrogen-doped graphene.
Example 7
Embodiment 7 provides a lithium ion battery negative electrode sheet and a method for manufacturing the lithium ion battery negative electrode sheet, and the specific implementation manner of the method is the same as that in embodiment 1, except that the nitrogen dopant is replaced by hydrazine hydrate.
Example 8
Embodiment 8 provides a lithium ion battery negative electrode sheet and a preparation method of the lithium ion battery negative electrode sheet, and the specific implementation manner of the preparation method is the same as that in embodiment 1, except that the nitrogen dopant is replaced by triethanolamine.
Example 9
Embodiment 9 provides a lithium ion battery negative electrode sheet and a method for manufacturing the lithium ion battery negative electrode sheet, and the specific implementation manner of the lithium ion battery negative electrode sheet is the same as that in embodiment 1, except that the nitrogen dopant is replaced by guanidine carbonate.
Example 10
Embodiment 10 provides a lithium ion battery negative electrode sheet and a method for manufacturing the lithium ion battery negative electrode sheet, and the specific implementation manner of the lithium ion battery negative electrode sheet is the same as that in embodiment 1, except that the nitrogen dopant is replaced by triethanolamine and melamine.
Example 11
Example 11 provides a lithium ion battery negative electrode sheet and a method for manufacturing a lithium ion battery negative electrode sheet, and a specific embodiment of the method is the same as example 1, except that guanidine carbonate and urea are substituted for the nitrogen dopant.
Example 12
Embodiment 12 provides a lithium ion battery negative electrode sheet and a method for manufacturing the lithium ion battery negative electrode sheet, and the specific implementation manner of the lithium ion battery negative electrode sheet is the same as that of embodiment 1, except that the mass ratio of triethanolamine to guanidine carbonate is replaced by 1: 0.2.
example 13
Embodiment 13 provides a lithium ion battery negative electrode sheet and a method for manufacturing the lithium ion battery negative electrode sheet, and the specific implementation manner of the lithium ion battery negative electrode sheet is the same as that of embodiment 1, except that the mass ratio of triethanolamine to guanidine carbonate is replaced by 1: 5.
example 14
Example 14 provides a lithium ion battery negative electrode sheet and a method for manufacturing the lithium ion battery negative electrode sheet, and the specific implementation manner is the same as example 1, except that the content of the binder is replaced with 3.5 parts.
Example 15
Example 15 provides a negative electrode sheet for a lithium ion battery, and a method for manufacturing the negative electrode sheet for the lithium ion battery, which is the same as example 1 except that the binder is replaced by styrene butadiene rubber (CAS: 9003-55-8), which is purchased from hills marbled ltd, yueyang.
Example 16
Example 16 provides a lithium ion battery negative electrode sheet and a method for manufacturing a lithium ion battery negative electrode sheet, which are the same as in example 1, except that the carboxyl-containing diamine derivative is replaced with 3, 4-diaminobenzoic acid.
Performance evaluation:
preparing a lithium ion battery positive plate: 94 parts by weight of positive electrode active material LiCoO2Uniformly mixing 2 parts by weight of conductive carbon SP as a conductive agent and 4 parts by weight of PVDF as a binder in N, N-dimethylacetamide as a solvent to prepare anode slurry; and uniformly coating the positive electrode slurry on a positive electrode current collector aluminum foil, drying, cold-pressing to a bulk density of 4g/cc, and slicing to obtain the lithium ion battery positive plate.
Preparing the lithium ion battery electrolyte: 50 parts by weight of Ethylene Carbonate (EC), 45 parts by weight of ethylmethyl carbonate (DEC) and 5 parts by weight of fluoroethylene carbonate (FEC) were thoroughly mixed to uniformity to obtain lithium hexafluorophosphate (LiPF)6) As solute, making into lithium ion batteryHydrolyzed solution, LiPF6The concentration of (2) is 1 mol/L.
Preparing a lithium ion battery: winding and packaging the lithium ion battery negative plate obtained in the embodiment 1-16, the lithium ion battery positive plate and a Polyethylene (PE) isolating membrane to prepare a lithium ion battery cell with the thickness of 4mm, the width of 35mm and the length of 80 mm; vacuum baking at 80 deg.C for 14h, injecting lithium ion battery electrolyte and standing for 25 h; charging to 4.5V at 35 ℃ by using a constant current of 0.1C, then charging to 0.05C by using a constant voltage of 4.5V, then discharging to 3.0V by using a constant current of 0.5C, repeating the charging and discharging for 2 times, and finally charging the lithium ion battery to 3.5V by using a constant current of 0.5C to complete capacity grading, thus obtaining the lithium ion battery.
1. Expansion rate of negative plate after capacity grading
The expansion rate of the negative plate after capacity grading is calculated according to the following formula:
and (3) after capacity separation, the expansion rate (%) of the negative plate is [ (thickness of the negative plate after capacity separation-thickness of the negative current collector)/(thickness of the negative plate after cold pressing-thickness of the negative current collector) -1] × 100%, wherein the thickness of the negative plate is measured by a spiral micrometer.
2. Battery capacity retention rate test: and setting the charging and discharging voltage range to be 0-3V, carrying out cycle test at the current density of 0.5C, and recording the discharging capacity of each cycle.
The capacity retention of the lithium ion battery is calculated according to the following formula:
the N-cycle capacity retention ratio (%) [ nth-cycle discharge capacity/first discharge capacity ] × 100%.
3. Post cycle battery expansion ratio
The post-cycle cell expansion rate was calculated according to the following formula:
and (3) the battery expansion rate after circulation (thickness of the battery after circulation-thickness of the battery after capacity grading)/thickness of the battery after capacity grading) is multiplied by 100%, wherein the thickness of the battery is tested by a height gauge, and the expansion rate level of the battery represents the expansion rate level of positive and negative pole pieces forming the battery.
The lithium ion battery performance test results of the lithium ion battery negative electrode sheets obtained in examples 1 to 16 are shown in table 1.
Table 1 lithium ion battery performance test results of the lithium ion battery negative electrode sheets obtained in examples 1 to 16
As can be seen from the performance test results of the lithium ion battery in Table 1, the lithium ion battery negative plate provided by the invention overcomes the volume expansion of the negative material in the lithium intercalation and deintercalation process, and has the advantages of small negative expansion rate, good cycle performance and excellent comprehensive performance.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (2)
1. The lithium ion battery negative plate is characterized by comprising the following raw materials in parts by weight: 70-75 parts of silicon dioxide aerogel, 70-75 parts of graphene, 1-2.5 parts of binder, 0.5-1 part of conductive agent, 0-1 part of dispersant, 0.5-1 part of thickener and 150 parts of water 145 and organic solvent;
the graphene is nitrogen-doped graphene;
the preparation method of the nitrogen-doped graphene comprises the following steps:
a) carrying out ultrasonic treatment on graphene in water to obtain a dispersion liquid;
b) adding a nitrogen dopant into the dispersion liquid obtained in the step a) to obtain a mixture;
c) placing the mixture obtained in the step b) in a high-pressure kettle, reacting for 2-3h at 85-90 ℃, then heating to 250 ℃ for reaction for 10-12h, and finally obtaining the nitrogen-doped graphene;
the mass ratio of the graphene to the nitrogen dopant is 1: (0.2-0.8);
in the step b), the nitrogen dopant is a mixture of triethanolamine and guanidine carbonate;
the mass ratio of the triethanolamine to the guanidine carbonate is 1: (0.5-2);
the binder is modified polyimide resin;
the preparation method of the modified polyimide resin comprises the following steps:
1) dissolving a diamine derivative containing carboxyl in an N, N-dimethylacetamide solvent, and adding an aromatic dibasic anhydride monomer for reaction to obtain a polyamic acid solution;
2) adding a dehydrating agent and a catalyst into the polyamic acid solution obtained in the step 1) to react for 5-10h, and finally preparing modified polyimide resin;
in the step 1), the diamine derivative containing carboxyl is 3, 4-diamino-2-naphthoic acid.
2. The preparation method of the lithium ion battery negative electrode sheet according to claim 1, characterized by comprising the following steps:
i) adding silicon dioxide aerogel and graphene into water, adding a binder, a conductive agent, a dispersing agent and a thickening agent, grinding and sieving to obtain negative electrode slurry;
ii) coating the negative electrode slurry obtained in the step i) on the surface of a negative electrode current collector in a coating oven, then carrying out cold pressing and rolling, and then baking under the vacuum-pumping condition to obtain the negative electrode plate.
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