CN117417474A - Negative electrode additive for lithium battery - Google Patents
Negative electrode additive for lithium battery Download PDFInfo
- Publication number
- CN117417474A CN117417474A CN202311367374.2A CN202311367374A CN117417474A CN 117417474 A CN117417474 A CN 117417474A CN 202311367374 A CN202311367374 A CN 202311367374A CN 117417474 A CN117417474 A CN 117417474A
- Authority
- CN
- China
- Prior art keywords
- negative electrode
- lithium ion
- acrylate
- ion battery
- methacrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000654 additive Substances 0.000 title claims abstract description 78
- 230000000996 additive effect Effects 0.000 title claims abstract description 76
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title description 26
- 229910052744 lithium Inorganic materials 0.000 title description 26
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 67
- -1 alkyl acrylic acid Chemical compound 0.000 claims abstract description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 26
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 25
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 25
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 25
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 25
- 239000000839 emulsion Substances 0.000 claims abstract description 24
- 239000002174 Styrene-butadiene Substances 0.000 claims abstract description 21
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011115 styrene butadiene Substances 0.000 claims abstract description 21
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 21
- 239000011267 electrode slurry Substances 0.000 claims abstract description 18
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 78
- 239000008367 deionised water Substances 0.000 claims description 75
- 229910021641 deionized water Inorganic materials 0.000 claims description 75
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 29
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- 238000006243 chemical reaction Methods 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 13
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 10
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- 239000004641 Diallyl-phthalate Substances 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 6
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- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 6
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 6
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
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- 239000003513 alkali Substances 0.000 claims description 4
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- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 claims description 4
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 claims description 4
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
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- 230000035484 reaction time Effects 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 4
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 3
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 3
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- 239000007800 oxidant agent Substances 0.000 claims description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 3
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- IPCRTSDORDQHRO-DUXPYHPUSA-N (e)-3-methoxyprop-2-enenitrile Chemical compound CO\C=C\C#N IPCRTSDORDQHRO-DUXPYHPUSA-N 0.000 claims description 2
- LFSHREXVLSTLFB-UHFFFAOYSA-N 1-cyanoethenyl acetate Chemical compound CC(=O)OC(=C)C#N LFSHREXVLSTLFB-UHFFFAOYSA-N 0.000 claims description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
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- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000010350 erythorbic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229940026239 isoascorbic acid Drugs 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lithium ion battery negative electrode additive, which is prepared by emulsion polymerization reaction of alkyl acrylic acid, alkyl acrylic ester, vinyl derivatives, emulsifying agent, initiator and cross-linking agent. The negative electrode slurry prepared by compounding carboxymethyl cellulose and styrene-butadiene emulsion has higher cohesive force and lower viscosity, and is suitable for preparing a negative electrode plate in a dispersed graphite material. When the negative electrode slurry prepared by the negative electrode additive is used for manufacturing a negative electrode plate, the viscosity of the negative electrode plate is similar to that of the traditional negative electrode slurry, so that the negative electrode plate can be adapted to the current industrial equipment and matched process, and the processing performance of the negative electrode plate is further improved due to the higher adhesive force.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a lithium battery negative electrode additive.
Background
The lithium ion battery has wide market space, and has the advantages of high working voltage, long cycle life, low self-discharge rate, no memory effect and the like. The current widely-used cathode binder is carboxymethyl cellulose and styrene-butadiene emulsion, has the advantages of low cost and wide sources, but cannot meet the requirements of the market on low addition amount and high binding force of the cathode binder due to the limitation of material performance. At present, the alternative material of carboxymethyl cellulose and styrene-butadiene emulsion in the market is PAA products (polyacrylate), but most PAA products have the problems of strong thickening capacity, high glass transition temperature and brittleness of the manufactured pole pieces, so that the PAA products are unsuitable for processes and equipment when the pole pieces are manufactured by running water in factories. Based on the above, the invention develops a lithium battery negative electrode additive which is mainly applied to a lithium battery negative electrode, is compounded with carboxymethyl cellulose and styrene-butadiene emulsion, improves the binding force, does not increase the viscosity of negative electrode slurry as much as possible, and can be suitable for industrial production.
Disclosure of Invention
Therefore, the invention aims to provide the lithium ion battery negative electrode additive which has mild synthesis conditions, low raw material price, wide sources, low energy consumption and easy industrial production, and the negative electrode slurry prepared by compounding the carboxymethyl cellulose and the styrene-butadiene emulsion has higher cohesive force and lower viscosity, and is suitable for preparing the negative electrode plate from a dispersed graphite material. When the negative electrode slurry prepared by the negative electrode additive is used for manufacturing a negative electrode plate, the viscosity of the negative electrode plate is similar to that of the traditional negative electrode slurry, so that the negative electrode plate can be adapted to the current industrial equipment and matched process, and the processing performance of the negative electrode plate is further improved due to the higher adhesive force.
The invention adopts the following specific technical scheme:
the lithium ion battery negative electrode additive is obtained by emulsion polymerization reaction of raw materials including alkyl acrylic acid, alkyl acrylic ester, vinyl derivatives, emulsifying agent, initiator and cross-linking agent, and comprises the following raw materials in percentage by mass:
25 to 40wt% of alkyl acrylic acid;
4 to 37wt% of alkyl acrylate;
22 to 54wt% of vinyl derivative;
0.5 to 2.5 weight percent of emulsifying agent;
0.05 to 0.25 weight percent of initiator;
0.05 to 0.2wt% of a cross-linking agent.
Preferably, the amount of alkyl acrylic acid in the comonomer is 27 to 40wt%.
More preferably, the amount of alkyl acrylic acid in the comonomer is 30 to 40wt%.
Preferably, the alkyl acrylate is used in the comonomer in an amount of 25 to 37wt%.
More preferably, the alkyl acrylate is used in the comonomer in an amount of 25 to 35wt%.
Preferably, the vinyl derivative is used in an amount of 32wt% to 48wt%.
More preferably, the vinyl derivative is used in an amount of 35wt% to 45wt%.
Preferably, the cross-linking agent is used in an amount of 0.08wt% to 0.2wt%.
More preferably, the crosslinking agent is used in an amount of 0.1wt% to 0.2wt%.
Preferably, the emulsifier is used in an amount of 1wt% to 2.5wt%.
More preferably, the emulsifier is used in an amount of 1.5wt% to 2.5wt%.
Preferably, the initiator is used in an amount of 0.1wt% to 0.25wt%.
More preferably, the initiator is used in an amount of 0.15wt% to 0.25wt%.
Further, the solvent used in the emulsion polymerization reaction of the raw materials is deionized water, and the mass ratio of the deionized water to the sum of the raw materials is 100: 15-20.
Further, the emulsion polymerization reaction comprises the following steps:
(1) Sequentially adding alkyl acrylic acid, alkyl acrylic ester, vinyl derivative, emulsifier, cross-linking agent and deionized water into a reaction container, stirring, installing a condensing tube, introducing nitrogen, and heating to a reaction temperature;
(2) After the temperature is stable, completely dissolving the initiator in a certain amount of deionized water, injecting the deionized water into a reaction container, wherein the reaction time is 90-120 min, and heating to the heat preservation temperature for 60-90 min;
(3) Cooling to room temperature, filtering with 150-200 mesh sieve, adding alkali liquor for neutralization, and adjusting pH to 6-8.
Further, in the step (1), the stirring speed is 150-300RPM, and nitrogen is introduced for 15-60min.
Further, the reaction temperature in the step (1) is 60 to 85 ℃, preferably 65 to 85 ℃, and more preferably 65 to 80 ℃.
Preferably, the reaction time of the step (2) is 100 to 120min, more preferably 110 to 120min.
Preferably, the temperature of the heat preservation in the step (2) is 65-90 ℃, and more preferably, the temperature of the heat preservation is 70-90 ℃.
Further, the alkali liquor in the step (3) is sodium hydroxide or lithium hydroxide.
Further, the alkyl acrylic acid is at least one of acrylic acid or methacrylic acid.
Further, the alkyl acrylate is one or more of methyl acrylate, ethyl acrylate, N-butyl acrylate, N-pentyl acrylate, isopentyl acrylate, methyl methacrylate, ethyl methacrylate, N-butyl methacrylate, N-pentyl methacrylate, isopentyl methacrylate, N-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylamide, methacrylamide, methylolacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, allyl polyether, N-bisallyl dodecyl diamine, octadecyl polyethylene glycol acrylate, octadecyl polyethylene glycol methacrylate, polyethylene glycol methoxy acrylate, vinyl methacrylate, alkoxyphenol acrylate, isodecyl methacrylate.
Further, the vinyl derivative is one or more of styrene, alpha-methylstyrene, acrylonitrile, methacrylonitrile, 2-acetoxyacrylonitrile, 3-methoxy acrylonitrile, 2, 3-dimethyl acrylonitrile, 3- (benzenesulfonyl) acrylonitrile, ethylene acetate, ethylene diethyl ester, N-vinyl pyrrolidone, vinyl pyridine, vinyl imidazole, vinyl propionate and vinyl butyrate.
Further, the emulsifier is one or more of an anionic surfactant, a nonionic surfactant and a reactive emulsifier; the anionic surfactants include, but are not limited to, sulfate salts of higher alcohols, alkylbenzene sulfonate, alkyldiphenyl ether disulfonate, aliphatic sulfonates, aliphatic carboxylates, sulfate salts of nonionic surfactants; the nonionic surfactant includes, but is not limited to, polyethylene glycol alkyl ester type, alkylphenyl ether type, alkyl ether type; the reactive emulsifier includes, but is not limited to, sodium methallyl sulfonate, sodium allyl sulfonate, sodium p-styrene sulfonate.
Further, the initiator is a free radical polymerization initiator, and the free radical polymerization initiator comprises a water-soluble polymerization initiator and a redox reaction polymerization initiator; the water-soluble polymerization initiator includes, but is not limited to, potassium persulfate, sodium persulfate, ammonium persulfate; the redox polymerization initiator includes an oxidizing agent including but not limited to potassium persulfate, sodium persulfate, ammonium persulfate, benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, dicumyl hydroperoxide, and a reducing agent including but not limited to isoascorbic acid, ferrous ion salts, sodium sulfite, sodium bisulfite.
Further, the cross-linking agent is one or more of divinylbenzene, diallyl phthalate, trimethylolpropane triacrylate, trimethylolpropane tri (meth) acrylate, triethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, divinyl glycol, diallyl itaconate, diallyl maleate, pentaerythritol triacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, ethoxylated bisphenol A dimethacrylate BPA30 EODMA.
Further, the molecular weight of the lithium ion battery negative electrode additive is 50000-600000, and Tg is 45-150 ℃.
Correspondingly, the invention also provides lithium ion battery negative electrode slurry which is formed by mixing the lithium ion battery negative electrode additive, carboxymethyl cellulose and butylbenzene emulsion.
Correspondingly, the invention also provides a lithium ion battery negative plate, which comprises the following components in percentage by mass: graphite: conductive carbon: negative electrode additive for lithium ion battery: carboxymethyl cellulose: styrene-butadiene emulsion = 95.75:1.5:1.5:0.5:0.75.
the invention further provides a preparation method of the lithium ion battery negative plate, which comprises the following steps: adding deionized water into a stirring tank, adding carboxymethyl cellulose into the stirring tank for dissolution, adding a lithium ion battery negative electrode additive and conductive carbon, dispersing at a high speed for a certain time, adding graphite, and continuing dispersing at a high speed; and after the fineness of the negative electrode slurry is tested to be qualified, regulating the mixture to be stirred at a low speed, adding the styrene-butadiene emulsion, defoaming, coating the mixture on a copper foil, and drying to obtain the negative electrode plate of the lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
in the design of the traditional PAA products, in order to improve the cohesive force of the products, the dosage of hydrophilic polar functional group-containing monomers or the molecular weight (up to 150W) can be improved as much as possible so as to improve the interfacial cohesive force and cohesive force of the products, but the thickening capacity of the products can be obviously improved, and the prepared negative electrode slurry is higher in viscosity, so that the coating performance of the slurry is influenced. The lithium battery negative electrode additive is a PAA product with low thickening and high peeling strength, adopts hydrophilic polar functional group monomers (alkyl acrylic acid and alkyl acrylic acid ester) and vinyl derivatives to carry out compound polymerization, and can form bonds with a current collector in a lithium ion battery to provide binding force, wherein the hydrophilic polar functional group monomers (alkyl acrylic acid and alkyl acrylic acid ester) ensure the wetting and graphite dispersing capacity of the product, and the vinyl derivatives reduce the affinity with water so as to achieve the purpose of reducing the viscosity, cooperate with each other, reduce the affinity with water to reduce the viscosity while ensuring enough polar functional groups to provide peeling force, and simultaneously use a small amount of cross-linking agents and more initiators to ensure that the molecular weight of the lithium battery negative electrode additive is in a proper range (the molecular weight of the lithium battery negative electrode additive is 50000-600000), thereby ensuring that the viscosity reaches the requirement and ensuring that the viscosity of the lithium battery negative electrode additive is not obviously improved. When the lithium battery negative electrode additive is compounded with carboxymethyl cellulose and styrene-butadiene emulsion and applied to a lithium battery negative electrode, the adhesive force is improved, and meanwhile, the viscosity of the negative electrode slurry is hardly improved. And, because of its higher binding power and lower viscosity, its use amount is smaller than that of a general negative electrode binder.
And, from the test, it is known that:
(1) The additive for the lithium ion battery cathode is prepared by the steps of preparing the cathode slurry, wherein the additive amount of the cathode slurry is 1.5%, the additive amount of carboxymethyl cellulose is 0.5%, the additive amount of styrene-butadiene emulsion is 0.75%, the total additive amount is 2.75%, the viscosity of the cathode slurry is 4000-8000 mPa.s, and the viscosity of the cathode slurry is close to that of the cathode slurry of which the 2% of styrene-butadiene emulsion is compounded by 1.5% of carboxymethyl cellulose, but the total additive amount of the cathode slurry of which the total additive is compounded by carboxymethyl cellulose is 3.5%, so that the use amount of the total additive can be reduced; meanwhile, the lithium ion battery negative electrode additive has good peel strength, when the total addition amount is 2.75%, the peel strength of a pole piece manufactured by the negative electrode slurry is more than 20N/m, and compared with the carboxymethyl cellulose compound styrene-butadiene emulsion, the peel strength is only 15N/m. Compared with similar PAA products, the viscosity of the PAA products is very high at the same addition amount, and the PAA products are more than 10000 mPa.s, and the peel strength is only about 16N/m. Therefore, the lithium ion battery negative electrode additive has the advantages of low thickening and high peeling strength;
(2) The pole piece prepared by compounding the lithium ion battery negative electrode additive and the carboxymethyl cellulose and the styrene-butadiene emulsion has the internal resistance of 28.2mΩ and the DCR of 47.2mΩ after chemical composition test. The discharge capacity retention rate at low temperature of-20 ℃ was 77.2%. The discharge capacity retention rate was 91.3% when stored at 60℃for 7 days. The 1C, 2C, 3C and 4C have good multiplying power performance. After the material is circulated for 450 circles at normal temperature, the discharge capacity retention rate is more than 99.57%, and after the material is circulated for 350 circles at 55 ℃, the discharge capacity retention rate is more than 81.65%. From the results, the lithium ion battery negative electrode additive provided by the invention has good electrochemical performance.
Detailed Description
In order to describe the technical content, constructional features, achieved objects and effects of the technical solution in detail, the following description is made in detail with reference to specific embodiments.
Example 1
The embodiment provides a lithium ion battery negative electrode additive, and the preparation method comprises the following steps: adding 0.5g of sodium dodecyl sulfate, 0.5g of dodecylphenol polyoxyethylene ether, 1g of sodium p-styrenesulfonate, 6g of n-amyl acrylate, 46g of methacrylic acid, 40g of acrylonitrile, 28g of 2-acrylamido-2-methylpropanesulfonic acid, 0.24g of diallyl phthalate and 660g of deionized water into a 1L five-neck flask, starting stirring at 250RPM, introducing nitrogen for 30min, and heating to 65 ℃; 5g of deionized water is used for dissolving 0.15g of ammonium persulfate, 5g of deionized water is used for dissolving 0.1g of sodium sulfite, and the mixture is sequentially added into a 1L five-neck flask as an initiator, and after the reaction is started for 120min, the temperature is raised to 70 ℃ and the temperature is kept for 60min. Cooling, discharging, adding NaOH solution for neutralization, adjusting pH to 6-8, and adjusting the solid content of the product to 10% by using deionized water to obtain the lithium battery additive.
Example 2
The embodiment provides a lithium ion battery negative electrode additive, and the preparation method comprises the following steps: adding 0.5g of sodium dodecyl sulfate, 0.5g of dodecylphenol polyoxyethylene ether, 1g of sodium p-styrenesulfonate, 6g of n-amyl methacrylate, 46g of acrylic acid, 40g of methacrylonitrile, 28g of 2-acrylamido-2-methylpropanesulfonic acid, 0.24g of diallyl phthalate and 660g of deionized water into a 1L five-neck flask, starting stirring at 250RPM, introducing nitrogen for 30min, and heating to 65 ℃; 5g of deionized water is used for dissolving 0.15g of ammonium persulfate, 5g of deionized water is used for dissolving 0.1g of sodium sulfite, and the mixture is sequentially added into a 1L five-neck flask as an initiator, and after the reaction is started for 110min, the temperature is raised to 70 ℃ and the temperature is kept for 90min. Cooling, discharging, adding NaOH solution for neutralization, adjusting pH to 6-8, and adjusting the solid content of the product to 10% by using deionized water to obtain the lithium battery additive.
Example 3
The embodiment provides a lithium ion battery negative electrode additive, and the preparation method comprises the following steps: adding 0.5g of sodium dodecyl sulfate, 0.5g of dodecylphenol polyoxyethylene ether, 1g of sodium p-styrenesulfonate, 6g of hydroxypropyl acrylate, 46g of methacrylic acid, 40g of styrene, 28g of 2-acrylamido-2-methylpropanesulfonic acid, 0.24g of diallyl maleate and 660g of deionized water into a 1L five-neck flask, starting stirring at 200RPM, introducing nitrogen for 35min, and heating to 65 ℃; 5g of deionized water is used for dissolving 0.15g of ammonium persulfate, 5g of deionized water is used for dissolving 0.1g of sodium sulfite, and the mixture is sequentially added into a 1L five-neck flask as an initiator, and after the reaction is started for 120min, the temperature is raised to 85 ℃ and the temperature is kept for 90min. Cooling, discharging, adding NaOH solution for neutralization, adjusting pH to 6-8, and adjusting the solid content of the product to 10% by using deionized water to obtain the lithium battery additive.
Example 4
The embodiment provides a lithium ion battery negative electrode additive, and the preparation method comprises the following steps: adding 0.5g of sodium dodecyl sulfate, 0.5g of dodecylphenol polyoxyethylene ether, 1g of sodium p-styrenesulfonate, 6g of ethylene acetate, 46g of acrylic acid, 40g of vinyl propionate, 28g of 2-acrylamido-2-methylpropanesulfonic acid, 0.24g of diallyl maleate and 660g of deionized water into a 1L five-neck flask, starting stirring at a rotating speed of 200RPM, introducing nitrogen for 35min, and heating to 65 ℃; 5g of deionized water is used for dissolving 0.15g of ammonium persulfate, 5g of deionized water is used for dissolving 0.1g of sodium sulfite, and the mixture is sequentially added into a 1L five-neck flask as an initiator, and after the reaction is started for 110min, the temperature is raised to 85 ℃ and the temperature is kept for 60min. Cooling, discharging, adding NaOH solution for neutralization, adjusting pH to 6-8, and adjusting the solid content of the product to 10% by using deionized water to obtain the lithium battery additive.
Example 5
The embodiment provides a lithium ion battery negative electrode additive, and the preparation method comprises the following steps: adding 0.5g of sodium dodecyl sulfate, 0.5g of dodecylphenol polyoxyethylene ether, 1g of sodium p-styrenesulfonate, 6g of n-amyl acrylate, 46g of methacrylic acid, 40g of acrylonitrile, 28g of 2-acrylamido-2-methylpropanesulfonic acid, 0.24g of triethylene glycol di (methyl) acrylate and 660g of deionized water into a 1L five-neck flask, starting stirring at a rotating speed of 200RPM, introducing nitrogen for 30min, and heating to 65 ℃; 5g of deionized water is used for dissolving 0.15g of ammonium persulfate, 5g of deionized water is used for dissolving 0.1g of sodium sulfite, and the mixture is sequentially added into a 1L five-neck flask as an initiator, and after the reaction is started for 120min, the temperature is raised to 70 ℃ and the temperature is kept for 60min. Cooling, discharging, adding NaOH solution for neutralization, adjusting pH to 6-8, and adjusting the solid content of the product to 10% by using deionized water to obtain the lithium battery additive.
Example 6
The embodiment provides a lithium ion battery negative electrode additive, and the preparation method comprises the following steps: adding 0.5g of sodium dodecyl sulfate, 0.5g of dodecylphenol polyoxyethylene ether, 1g of sodium p-styrenesulfonate, 6g of n-amyl acrylate, 46g of acrylic acid, 40g of acrylonitrile, 28g N-vinyl pyrrolidone, 0.24g of triethylene glycol di (methyl) acrylate and 660g of deionized water into a 1L five-neck flask, starting stirring at a rotating speed of 150RPM, introducing nitrogen for 40min, and heating to 65 ℃; 5g of deionized water is used for dissolving 0.15g of ammonium persulfate, 5g of deionized water is used for dissolving 0.1g of sodium sulfite, and the mixture is sequentially added into a 1L five-neck flask as an initiator, and after the reaction is started for 110min, the temperature is raised to 85 ℃ and the temperature is kept for 90min. Cooling, discharging, adding NaOH solution for neutralization, adjusting pH to 6-8, and adjusting the solid content of the product to 10% by using deionized water to obtain the lithium battery additive.
Example 7
The embodiment provides a lithium ion battery negative electrode additive, and the preparation method comprises the following steps: adding 0.5g of sodium dodecyl sulfate, 0.5g of dodecylphenol polyoxyethylene ether, 1g of sodium p-styrenesulfonate, 6g of n-amyl acrylate, 46g of methacrylic acid, 40g of acrylonitrile, 28g of ethylene acetate, 0.24g of diallyl phthalate and 660g of deionized water into a 1L five-neck flask, starting stirring, introducing nitrogen for 30min at the rotating speed of 200RPM, and heating to 65 ℃; 5g of deionized water is used for dissolving 0.15g of ammonium persulfate, 5g of deionized water is used for dissolving 0.1g of sodium sulfite, and the mixture is sequentially added into a 1L five-neck flask as an initiator, and after the reaction is started for 120min, the temperature is raised to 85 ℃ and the temperature is kept for 90min. Cooling, discharging, adding NaOH solution for neutralization, adjusting pH to 6-8, and adjusting the solid content of the product to 10% by using deionized water to obtain the lithium battery additive.
Example 8
The embodiment provides a lithium ion battery negative electrode additive, and the preparation method comprises the following steps: adding 0.5g of sodium dodecyl sulfate, 0.5g of dodecylphenol polyoxyethylene ether, 1g of sodium p-styrenesulfonate, 6g of n-hexyl methacrylate, 46g of acrylic acid, 40g of methylolacrylamide, 28g of 3- (benzenesulfonyl) acrylonitrile, 0.24g of pentaerythritol triacrylate and 660g of deionized water into a 1L five-neck flask, starting stirring at 200RPM, introducing nitrogen for 40min, and heating to 65 ℃; 5g of deionized water is used for dissolving 0.15g of ammonium persulfate, 5g of deionized water is used for dissolving 0.1g of sodium sulfite, and the mixture is sequentially added into a 1L five-neck flask as an initiator, and after the reaction is started for 110min, the temperature is raised to 70 ℃ and the temperature is kept for 90min. Cooling, discharging, adding NaOH solution for neutralization, adjusting pH to 6-8, and adjusting the solid content of the product to 10% by using deionized water to obtain the lithium battery additive.
Example 9
The embodiment provides a lithium ion battery negative electrode additive, and the preparation method comprises the following steps: adding 0.5g of sodium dodecyl sulfate, 0.5g of dodecylphenol polyoxyethylene ether, 1g of sodium p-styrenesulfonate, 6g of n-amyl acrylate, 46g of acrylic acid, 40g of methacrylonitrile, 28g of 3- (benzenesulfonyl) acrylonitrile, 0.24g of pentaerythritol triacrylate and 660g of deionized water into a 1L five-neck flask, starting stirring at 250RPM, introducing nitrogen for 30min, and heating to 65 ℃; 5g of deionized water is used for dissolving 0.15g of ammonium persulfate, 5g of deionized water is used for dissolving 0.1g of sodium sulfite, and the mixture is sequentially added into a 1L five-neck flask as an initiator, and after the reaction is started for 120min, the temperature is raised to 70 ℃ and the temperature is kept for 90min. Cooling, discharging, adding NaOH solution for neutralization, adjusting pH to 6-8, and adjusting the solid content of the product to 10% by using deionized water to obtain the lithium battery additive.
Example 10
The embodiment provides a lithium ion battery negative electrode additive, and the preparation method comprises the following steps: adding 0.5g of sodium dodecyl sulfate, 0.5g of dodecylphenol polyoxyethylene ether, 1.5g of sodium p-styrenesulfonate, 12g of n-amyl acrylate, 40g of acrylic acid, 30g of acrylonitrile, 38g N-vinylpyrrolidone, 0.24g of triethylene glycol di (methyl) acrylate and 660g of deionized water into a 1L five-neck flask, starting stirring at 250RPM, introducing nitrogen for 30min, and heating to 65 ℃; 5g of deionized water is used for dissolving 0.15g of ammonium persulfate, 5g of deionized water is used for dissolving 0.1g of sodium sulfite, and the mixture is sequentially added into a 1L five-neck flask as an initiator, and after the reaction is started for 120min, the temperature is raised to 85 ℃ and the temperature is kept for 90min. Cooling, discharging, adding NaOH solution for neutralization, adjusting pH to 6-8, and adjusting the solid content of the product to 10% by using deionized water to obtain the lithium battery additive.
Example 11
The embodiment provides a lithium ion battery negative electrode additive, and the preparation method comprises the following steps: adding 0.5g of sodium dodecyl sulfate, 0.5g of dodecylphenol polyoxyethylene ether, 1.5g of sodium p-styrenesulfonate, 12g of n-amyl acrylate, 40g of acrylic acid, 35g of acrylonitrile, 33g of vinylimidazole, 0.24g of diallyl phthalate and 660g of deionized water into a 1L five-neck flask, starting stirring, introducing nitrogen for 30min at the rotating speed of 250RPM, and heating to 65 ℃; 5g of deionized water is used for dissolving 0.15g of ammonium persulfate, 5g of deionized water is used for dissolving 0.1g of sodium sulfite, and the mixture is sequentially added into a 1L five-neck flask as an initiator, and after the reaction is started for 120min, the temperature is raised to 85 ℃ and the temperature is kept for 60min. Cooling, discharging, adding NaOH solution for neutralization, adjusting pH to 6-8, and adjusting the solid content of the product to 10% by using deionized water to obtain the lithium battery additive.
Example 12
The embodiment provides a lithium ion battery negative electrode additive, and the preparation method comprises the following steps: adding 0.5g of sodium dodecyl sulfate, 0.5g of dodecylphenol polyoxyethylene ether, 1.5g of sodium p-styrenesulfonate, 6g of n-hexyl methacrylate, 46g of acrylic acid, 30g of methylolacrylamide, 38g of 3- (benzenesulfonyl) acrylonitrile, 0.24g of tripropylene glycol diacrylate and 660g of deionized water into a 1L five-neck flask, starting stirring at a rotating speed of 250RPM, introducing nitrogen for 30min, and heating to 65 ℃; 5g of deionized water is used for dissolving 0.15g of ammonium persulfate, 5g of deionized water is used for dissolving 0.1g of sodium sulfite, and the mixture is sequentially added into a 1L five-neck flask as an initiator, and after the reaction is started for 120min, the temperature is raised to 85 ℃ and the temperature is kept for 90min. Cooling, discharging, adding NaOH solution for neutralization, adjusting pH to 6-8, and adjusting the solid content of the product to 10% by using deionized water to obtain the lithium battery additive.
Example 13
The embodiment provides a lithium ion battery negative electrode additive, and the preparation method comprises the following steps: adding 0.5g of sodium dodecyl sulfate, 0.5g of dodecylphenol polyoxyethylene ether, 1.5g of sodium p-styrenesulfonate, 12g of n-amyl acrylate, 40g of acrylic acid, 40g of methacrylonitrile, 28g of 3- (benzenesulfonyl) acrylonitrile, 0.24g of divinylbenzene and 660g of deionized water into a 1L five-neck flask, starting stirring at 250RPM, introducing nitrogen for 30min, and heating to 65 ℃; 5g of deionized water is used for dissolving 0.15g of ammonium persulfate, 5g of deionized water is used for dissolving 0.1g of sodium sulfite, and the mixture is sequentially added into a 1L five-neck flask as an initiator, and after the reaction is started for 120min, the temperature is raised to 85 ℃ and the temperature is kept for 90min. Cooling, discharging, adding NaOH solution for neutralization, adjusting pH to 6-8, and adjusting the solid content of the product to 10% by using deionized water to obtain the lithium battery additive.
Comparative example 1
Carboxymethyl cellulose and butylbenzene emulsion
Comparative example 2
Negative electrode additive: commercial product LA136D
Comparative example 3
Negative electrode additive: commercial product 288C
Comparative example 4
The preparation method of the lithium ion battery negative electrode additive comprises the following steps: adding 0.5g of sodium dodecyl sulfate, 0.5g of dodecylphenol polyoxyethylene ether, 1.5g of sodium p-styrenesulfonate, 12g of n-amyl acrylate, 40g of acrylic acid, 40g of methacrylamide, 28g of methyl acrylate, 0.24g of pentaerythritol triacrylate and 660g of deionized water into a 1L five-neck flask, starting stirring, introducing nitrogen for 30min at the rotating speed of 250RPM, and heating to 65 ℃; 5g of deionized water is used for dissolving 0.15g of ammonium persulfate, 5g of deionized water is used for dissolving 0.1g of sodium sulfite, and the mixture is sequentially added into a 1L five-neck flask as an initiator, and after the reaction is started for 120min, the temperature is raised to 85 ℃ and the temperature is kept for 90min. Cooling, discharging, adding NaOH solution for neutralization, adjusting pH to 6-8, and adjusting the solid content of the product to 10% by using deionized water to obtain the lithium battery additive.
Comparative example 5
The preparation method of the lithium ion battery negative electrode additive comprises the following steps: adding 0.5g of sodium dodecyl sulfate, 0.5g of dodecylphenol polyoxyethylene ether, 1.5g of sodium p-styrenesulfonate, 12g of n-amyl acrylate, 40g of acrylic acid, 40g of methacrylonitrile, 28g of methylol acrylamide, 2.4g of pentaerythritol triacrylate and 660g of deionized water into a 1L five-neck flask, starting stirring, introducing nitrogen for 30min at the rotating speed of 250RPM, and heating to 65 ℃; 5g of deionized water is used for dissolving 0.75g of ammonium persulfate, 5g of deionized water is used for dissolving 0.5g of sodium sulfite, and the mixture is sequentially added into a 1L five-neck flask as an initiator, and after the reaction is started for 120min, the temperature is raised to 85 ℃ and the temperature is kept for 90min. Cooling, discharging, adding NaOH solution for neutralization, adjusting pH to 6-8, and adjusting the solid content of the product to 10% by using deionized water to obtain the lithium battery additive.
Application examples:
the negative electrode additive synthesized in the above examples 1-13 is mixed with active material graphite and conductive agent, and then added with styrene-butadiene emulsion and carboxymethyl cellulose to prepare a pole piece, and finally assembled into a soft-package battery, and the specific method is as follows:
the formula combination is as follows: graphite: conductive carbon: negative electrode additives synthesized in examples 1 to 13: carboxymethyl cellulose: styrene-butadiene emulsion: =95.75: 1.5:1.5:0.5:0.75.
adding deionized water into a stirring tank, adding carboxymethyl cellulose into the solution, respectively adding the negative electrode additive and conductive carbon synthesized in the examples 1-13, dispersing at a high speed of 1000rpm for 2 hours, adding graphite, continuing dispersing at a high speed for 2 hours, adjusting to 300rpm after the fineness of the negative electrode slurry is qualified, stirring at a low speed, adding styrene-butadiene emulsion, defoaming for 30 minutes, coating the mixture on a copper foil, and drying to obtain the negative electrode plate of the lithium ion battery.
Comparative examples were applied:
comparative example 1 was applied, the formulation combination was: graphite: conductive carbon: carboxymethyl cellulose: styrene-butadiene emulsion=95: 1.5:1.5:2.
adding deionized water into a stirring tank, adding carboxymethyl cellulose into the solution, adding conductive carbon, dispersing at a high speed of 1000rpm for 2 hours, adding graphite, continuing dispersing at a high speed for 2 hours, testing the qualified fineness of the negative electrode slurry, adjusting to 300rpm, stirring at a low speed, adding styrene-butadiene emulsion, defoaming for 30 minutes, coating the mixture on a copper foil, and drying to obtain the silicon-carbon negative electrode plate of the lithium ion battery.
Comparative examples 2 to 5 were used, and the specific application method is as follows:
the formula combination is as follows: graphite: conductive carbon: negative electrode additives of comparative examples 2 to 5: carboxymethyl cellulose: styrene-butadiene emulsion: =95.75: 1.5:1.5:0.5:0.75.
adding deionized water into a stirring tank, adding carboxymethyl cellulose into the solution, respectively adding the negative electrode additive and conductive carbon of comparative examples 2-5, dispersing for 2 hours at a high speed of 1000rpm, adding graphite, continuing dispersing for 2 hours at a high speed, adjusting to 300rpm after the fineness of the negative electrode slurry is qualified, stirring at a low speed, adding styrene-butadiene emulsion, defoaming for 30 minutes, coating the mixture on a copper foil, and drying to obtain the negative electrode plate of the lithium ion battery.
The formula of the paired positive electrode plate of the negative electrode plate is as follows: NCM (nickel cobalt manganese 811): conductive carbon: PVDF 5130=96.75: 2:1.25, the separator used was PP.
The soft package lithium ion battery is assembled according to the negative pole piece and the positive pole piece to carry out constant current charge and discharge test, the electrolyte is a TINA electrolyte, the brand is TC-E8630N3, the charge termination voltage is 2.7-4.2V, the charge and discharge multiplying power is 1C, and the cut-off current is 100mA.
Application examples and application comparative examples the results of the performance test of the assembled negative electrode tab are shown in table 1 below.
TABLE 1 negative electrode plate Performance test results
Peel force test method: the negative electrode sheets of examples and comparative examples were tested for 180 ° peel force using a universal tensile tester, and the peel force test was made using a sample 2cm wide and about 5cm long, with a pull rate of 2mm/s and a peel force in N/m.
The surface density testing method comprises the following steps: the negative electrode slurries of examples and comparative examples were coated on copper foil, and the load amount on the copper foil per unit area was controlled by adjusting the gap of the coater, and the dried pole piece was tested for flexibility using curl test, and with reference to national standard GB1731-2020, it was checked whether the pole piece was qualified or not, and the minimum diameter shaft rod required to pass was a steel rod of r=1 mm.
For a specific method of curl test, reference is made to national standard GB1731-2020:1. cutting the pole piece into 1 x 8cm sample strips; 2. testing, namely tightly pressing a sample strip on a shaft rod, bending a pole piece outwards by 180 degrees, taking out and observing 2-3 seconds; 3. and observing whether the surface of the sample strip has cracks and flaking or not by using a 4-time magnifying glass, wherein the shaft rod with the smallest diameter passes through the surface of the sample strip to be flexible.
Examples 1, 2, 7 and comparative examples 1, 2,3 were selected from the examples and comparative examples, and the electrochemical properties of the assembled lithium ion batteries were tested as follows:
TABLE 2 chemical composition of the test results
| Sequence number | First discharge capacity (mAh) | First discharge efficiency | Internal resistance (mΩ) | Voltage (V) | DCR value (mΩ) |
| Example 1 | 2316.7 | 89.6％ | 28.2 | 4.2 | 47.2 |
| Example 2 | 2334.9 | 89.8％ | 29.3 | 4.2 | 48.9 |
| Example 7 | 2336.6 | 90.6％ | 29.2 | 4.2 | 49.5 |
| Comparative example 1 | 2272.3 | 90.5％ | 30.3 | 4.2 | 48.2 |
| Comparative example 2 | 2307.1 | 88.0％ | 28.8 | 4.2 | 49.0 |
| Comparative example 3 | 2287.2 | 89.7％ | 30.1 | 4.2 | 50.6 |
The assembled lithium ion battery is subjected to low-temperature discharge performance test, and the specific method comprises the following steps: and (3) standing until the temperature of the lithium ion battery reaches 25+/-2 ℃, testing the capacity of the lithium ion battery, recording the capacity as the capacity before storage, discharging the lithium ion battery at a constant current of 0.5 ℃ to a voltage of 2.75V, placing the lithium ion battery into a constant temperature box at-20 ℃ for standing for 300min, charging the lithium ion battery at a constant current of 0.5 ℃ to a voltage of 4.25V, testing the capacity of the lithium ion battery at the moment, and testing the capacity as the low-temperature discharge capacity, wherein the test result is shown in the table 3 below.
TABLE 3 Low temperature discharge Performance test
| Sequence number | Discharge rate&Temperature (C)&℃) | Discharge vesselRate of retention of quantity |
| Example 1 | 0.5C&-20℃ | 77.2％ |
| Example 2 | 0.5C&-20℃ | 72.9％ |
| Example 7 | 0.5C&-20℃ | 72.1％ |
| Comparative example 1 | 0.5C&-20℃ | 70.3％ |
| Comparative example 2 | 0.5C&-20℃ | 73.3％ |
| Comparative example 3 | 0.5C&-20℃ | 71.7％ |
The assembled lithium ion battery is subjected to high-temperature storage performance test, and the specific method comprises the following steps: and standing until the temperature of the lithium ion battery reaches 25+/-2 ℃, testing the capacity, internal resistance, voltage, DCR and other data of the lithium ion battery, placing the lithium ion battery in a 60 ℃ oven, standing for 7 days, testing the data, calculating the change rate, and testing the result shown in the table 4 below.
TABLE 4 high temperature storage Properties
The assembled lithium ion battery was subjected to discharge rate performance test, and the test results are shown in table 5 below.
TABLE 5 rate capability
| Sequence number | Temperature (. Degree. C.) | 1C/0.5C | 2C/0.5C | 3C/0.5C | 4C/0.5C |
| Example 1 | 25℃ | 97.58％ | 95.14％ | 91.10％ | 85.90％ |
| Example 2 | 25℃ | 97.44％ | 95.09％ | 90.95％ | 85.08％ |
| Example 7 | 25℃ | 97.55％ | 95.33％ | 90.80％ | 85.54％ |
| Comparative example 1 | 25℃ | 97.63％ | 95.06％ | 90.26％ | 83.53％ |
| Comparative example 2 | 25℃ | 97.63％ | 94.59％ | 90.26％ | 84.80％ |
| Comparative example 3 | 25℃ | 97.74％ | 94.78％ | 90.11％ | 83.59％ |
The assembled lithium ion battery was subjected to a normal temperature 25 ℃ and high temperature 55 ℃ cycle charge-discharge test, the charge-discharge rate was 1C/1C, wherein 3 batteries were tested at normal temperature cycle and 2 batteries were tested at high temperature cycle, and the test results are shown in table 6 below.
TABLE 6 cycle test at normal temperature and high temperature 55 DEG C
While the embodiments have been described above, other variations and modifications will occur to those skilled in the art once the basic inventive concepts are known, and it is therefore intended that the foregoing description be regarded as illustrative rather than limiting, and that it is intended that all such modifications and variations be regarded as being included within the scope of the invention, whether they are to be regarded as equivalent structures or equivalent processes using the teachings of this invention, or whether they are directed to or directed to other relevant technology.
Claims (10)
1. The lithium ion battery negative electrode additive is characterized by being prepared by emulsion polymerization reaction of alkyl acrylic acid, alkyl acrylic ester, vinyl derivatives, emulsifying agents, initiating agents and crosslinking agents serving as raw materials, wherein the raw materials comprise, by mass:
25 to 40wt% of alkyl acrylic acid;
4 to 37wt% of alkyl acrylate;
22 to 54wt% of vinyl derivative;
0.5 to 2.5 weight percent of emulsifying agent;
0.05 to 0.25 weight percent of initiator;
0.05 to 0.2 weight percent of cross-linking agent.
2. The lithium ion battery negative electrode additive according to claim 1, wherein the solvent used in the emulsion polymerization reaction of the raw materials is deionized water, and the mass ratio of the deionized water to the sum of the raw materials is 100: 15-20.
3. The negative electrode additive for lithium ion batteries according to claim 2, wherein said emulsion polymerization reaction comprises the steps of:
(1) Sequentially adding alkyl acrylic acid, alkyl acrylic ester, vinyl derivative, emulsifier, cross-linking agent and deionized water into a reaction container, stirring, installing a condensing tube in the reaction container, introducing nitrogen, and heating to a reaction temperature;
(2) After the temperature is stable, completely dissolving the initiator in a certain amount of deionized water, injecting the deionized water into a reaction container, wherein the reaction time is 90-120 min, and heating to the heat preservation temperature for 60-90 min;
(3) Cooling to room temperature, filtering with 150-200 mesh sieve, adding alkali liquor for neutralization, and adjusting pH to 6-8.
4. A lithium ion battery negative electrode additive according to claim 3, wherein,
in the step (1), the stirring rotating speed is 150-300RPM, and nitrogen is introduced for 15-60min; and/or the number of the groups of groups,
the reaction temperature in the step (1) is 60-85 ℃, preferably 65-85 ℃, more preferably 65-80 ℃; and/or the number of the groups of groups,
the reaction time of the step (2) is 100-120 min, preferably 110-120 min; and/or the number of the groups of groups,
the heat preservation temperature in the step (2) is 65-90 ℃, and more preferably, the heat preservation temperature is 70-90 ℃; and/or the number of the groups of groups,
the alkali liquor in the step (3) is sodium hydroxide or lithium hydroxide.
5. The negative electrode additive for lithium ion batteries according to any one of claims 1 to 4, wherein said alkyl acrylic acid is at least one of acrylic acid or methacrylic acid; and/or
The alkyl acrylate is one or more of methyl acrylate, ethyl acrylate, N-butyl acrylate, N-pentyl acrylate, isopentyl acrylate, methyl methacrylate, ethyl methacrylate, N-butyl methacrylate, N-pentyl methacrylate, isopentyl methacrylate, N-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylamide, methacrylamide, methylolacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, allyl polyether, N-bisallyl dodecyl alcohol acrylate, octadecyl polyethylene glycol methacrylate, polyethylene glycol methoxy acrylate, vinyl methacrylate, alkoxyphenol acrylate and isodecyl methacrylate; and/or
The vinyl derivative is one or more of styrene, alpha-methyl styrene, acrylonitrile, methacrylonitrile, 2-acetoxy acrylonitrile, 3-methoxy acrylonitrile, 2, 3-dimethyl acrylonitrile, 3- (benzenesulfonyl) acrylonitrile, ethylene acetate, ethylene diethyl ester, N-vinyl pyrrolidone, vinyl pyridine, vinyl imidazole, vinyl propionate and vinyl butyrate.
6. The negative electrode additive for lithium ion batteries according to any one of claims 1 to 4, wherein the emulsifier is one or more of an anionic surfactant, a nonionic surfactant and a reactive emulsifier; the anionic surfactants include, but are not limited to, sulfate salts of higher alcohols, alkylbenzene sulfonate, alkyldiphenyl ether disulfonate, aliphatic sulfonates, aliphatic carboxylates, sulfate salts of nonionic surfactants; the nonionic surfactant includes, but is not limited to, polyethylene glycol alkyl ester type, alkylphenyl ether type, alkyl ether type; the reactive emulsifier includes, but is not limited to, one or more of sodium methallyl sulfonate, sodium allyl sulfonate, sodium p-styrene sulfonate; and/or
The initiator is a free radical polymerization initiator, and the free radical polymerization initiator comprises a water-soluble polymerization initiator and a redox reaction polymerization initiator; the water-soluble polymerization initiator includes, but is not limited to, potassium persulfate, sodium persulfate, ammonium persulfate; the redox polymerization initiator comprises an oxidant and a reducing agent, wherein the oxidant comprises one or more of potassium persulfate, sodium persulfate, ammonium persulfate, benzoyl peroxide, tert-butyl hydroperoxide, acetyl peroxide and dicumyl hydroperoxide; and/or
The cross-linking agent is one or more of divinylbenzene, diallyl phthalate, trimethylolpropane triacrylate, trimethylolpropane tri (meth) acrylate, triethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, divinyl glycol, diallyl itaconate, diallyl maleate, pentaerythritol triacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate and ethoxylated bisphenol A dimethacrylate BPA30 EODMA.
7. The negative electrode additive for lithium ion batteries according to any one of claims 1 to 4, wherein the molecular weight of the negative electrode additive for lithium ion batteries is 50000 to 600000 and tg is 45 to 150 ℃.
8. A lithium ion battery negative electrode slurry, which is characterized by being prepared by mixing the lithium ion battery negative electrode additive, carboxymethyl cellulose and butylbenzene emulsion according to any one of claims 1-4.
9. The lithium ion battery negative plate is characterized by comprising the following components in percentage by mass: graphite: conductive carbon: a lithium ion battery negative electrode additive according to any one of claims 1-4: carboxymethyl cellulose: styrene-butadiene emulsion = 95.75:1.5:1.5:0.5:0.75.
10. the method for preparing the lithium ion battery negative plate according to claim 9, comprising the following steps: adding deionized water into a stirring tank, adding carboxymethyl cellulose into the stirring tank for dissolution, adding a lithium ion battery negative electrode additive and conductive carbon, dispersing at a high speed, adding graphite, and continuing dispersing at a high speed; and after the fineness of the negative electrode slurry is tested to be qualified, regulating the mixture to be stirred at a low speed, adding the styrene-butadiene emulsion, defoaming, coating the mixture on a copper foil, and drying to obtain the negative electrode plate of the lithium ion battery.
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| CN117777904B (en) * | 2024-02-27 | 2024-05-28 | 湖南高瑞电源材料有限公司 | Positive electrode fluorine-free binder material, and preparation method and application thereof |
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