CN104538635B - High-performance binder for silicon materials for lithium ion batteries and preparation method thereof - Google Patents
High-performance binder for silicon materials for lithium ion batteries and preparation method thereof Download PDFInfo
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- CN104538635B CN104538635B CN201410761021.5A CN201410761021A CN104538635B CN 104538635 B CN104538635 B CN 104538635B CN 201410761021 A CN201410761021 A CN 201410761021A CN 104538635 B CN104538635 B CN 104538635B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- 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
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a high-performance binder for silicon materials for lithium ion batteries, which is a polyacrylonitrile copolymer, a polymeric monomer of the copolymer comprises acrylonitrile, also comprises a second monomer and/or a third monomer; and the second monomer is a monobutyl itaconate monomer, and the third monomer is selected from a mixture of one or more of an itaconic acid, sodium allylsulfonate, acrylamide, amino, a pyridyl or acylamino monomer, n-butyl acrylate or methyl acrylate. The invention also provides a preparation method of the binder. Compared with existing binders, the binder disclosed by the invention has better binding power, can effectively improve the expansion of silicon materials in the processes of charging and discharging, and can improve the performance of a silicon electrode in the process of cycling. Meanwhile, the binder is simple in preparation method, low in cost and good in repeatability, and can achieve the practical need of mass production.
Description
Technical field
The invention belongs to technical field of lithium ion and in particular to a kind of lithium ion battery silicon negative electrode binder and its
Preparation method.
Background technology
Still based on graphite material, it has reached on capacity utilization lithium ion battery negative material substantially at this stage
Theoretical value (372mA h/g).In order to meet the requirement of wireless telecommunications system of future generation, hybrid electric vehicle it would be desirable to significantly carry
The energy density of high-lithium ion battery, power density.Silicium cathode had both had the specific capacity (quality exceeding ten times than traditional Carbon anode
Specific capacity is：4200mA·h/g；Volume and capacity ratio is：9786mA·h/cm3), but also with a relatively low electric discharge position
(averagely de- lithium current potential in 0.4V about), and element silicon in the rich reserves in the earth's crust, (content in the earth's crust is only second to
Oxygen), environmentally friendly, chemical property is more stable, is widely used in semi-conductor industry.
In electrode mixed process with slurry, high molecular polymer is as binding agent：Polymer molecule segment can adsorb
On different active material particles, active substance therefore " is bridged " together, and then is wound around, is wrapped to form by bonding agent molecule
Fixing network structure.When solvent volatilizees, active material particle is fixed, and plays the effect of bonding.As can be seen here, glue
Knot agent is to prepare one of necessary material of battery core.But using silicon grain as electrode active material, traditional binding agent PVDF is (poly-
Vinylidene) numerous with stripping electrode etc. asking of can not improving that silicon grain causes because of volumetric expansion in cyclic process very well
Topic.Polyacrylonitrile strand is difficult to freely rotatable in general and forms spiral helicine three-dimensional conformation.Make silicon materials class
Electrode active material has more sufficient space reply volumetric expansion.
In sum, high-performance adhesive can not be ignored to improving the development as lithium ion battery negative for the silicon, high-performance
Binding agent should become one of the main contents optimizing battery core, the exploitation of new binding agent also will become electrokinetic cell and have to
One of problem solving.
Content of the invention
It is an object of the invention to：A kind of lithium ion battery silicium cathode binding agent and electrode slurry are provided.Relatively existing
For having binding agent, performance in cyclic process for the silicon electrode can be improved.
The above-mentioned purpose of the present invention is achieved through the following technical solutions：
There is provided a kind of lithium ion battery silicium cathode binding agent, it is polyacrylonitrile copolymer, wherein, polymerized monomer removes third
Second comonomer and/or Third monomer is also included outside alkene nitrile；Described second comonomer is monobutyl itaconate monomer, the described 3rd
Monomer is selected from appointing in itaconic acid, sodium allylsulfonate, acrylamide, amino, pyridine radicals or amide groups monomer, n-butyl acrylate
Anticipate one or more mixture.
In currently preferred binding agent, described Third monomer is n-butyl acrylate or acrylic acid methyl ester.；Most preferably
N-butyl acrylate.
In currently preferred binding agent, in described polymerized monomer, second comonomer and acrylonitrile weight are than for 1～10:
99～90, Third monomer and acrylonitrile weight are than for 1～5:99～95.
In currently preferred binding agent, described polyacrylonitrile copolymer is that described monomer passes through emulsion polymerization
Obtain, described emulsion polymerization is under inert gas shielding, add initiator, breast in emulsion polymerization container
Agent, monomer and solvent, the weight of initiator and monomer is than for 1:999～1:9, preferably 1～2:180～250, solvent adding amount
1.5～10 times (preferably 5～10 times) for monomer mass, emulsifying agent addition is the 0.1%～1% of monomer gross mass；With 150
The rotating speed stirring of～250r/min, in the range of 25～160 DEG C, preferably 60～120 DEG C, polymerization time controls controlling reaction temperature
Between 2～24h.
The present invention also provides a kind of method preparing lithium ion battery silicium cathode binding agent, comprises the following steps：
Under inert gas shielding, add initiator, emulsifying agent, monomer and solvent in emulsion polymerization container, draw
Send out the weight of agent and monomer ratio for 1:999～1:9 (preferably 1～2:180～250), solvent adding amount be monomer mass 1.5～
10 (preferably 5～10 times), emulsifying agent addition is the 0.1%～1% of monomer gross mass；Stirred with the rotating speed of 150～250r/min
Mix, in the range of 25～160 DEG C, preferably 60 DEG C～120 DEG C, polymerization time controls between 2～24h controlling reaction temperature；Institute
The monomer stated also includes second comonomer and/or Third monomer in addition to acrylonitrile；Described second comonomer is monobutyl itaconate list
Body, described Third monomer is selected from itaconic acid, acrylic acid methyl ester., sodium allylsulfonate, acrylamide, amino, pyridine radicals or amide
Any one in base monomer, n-butyl acrylate or two or more mixture.
In currently preferred preparation method, described Third monomer is n-butyl acrylate or acrylic acid methyl ester.；Optimum
Select n-butyl acrylate.
In currently preferred preparation method, in described polymerized monomer, second comonomer and acrylonitrile weight than for 1～
10:99～90, Third monomer and acrylonitrile weight are than for 1～5:99～95.
In currently preferred preparation method, the preferred azo of described initiator, organic peroxide class, oxidoreduction
At least one of system apoplexy due to endogenous wind；Further preferably azo isobutyronitrile, Ammonium persulfate. or potassium peroxydisulfate
In currently preferred preparation method, the oil-in-water such as described emulsifying agent preferred Co-458, OP-10 or tween 80
Type emulsifying agent..
In currently preferred preparation method, the preferred dimethyl sulfoxide of described solvent, dimethyl acetylamide, dimethyl methyl
One of amide or water；Preferably dimethyl sulfoxide or water.
In currently preferred preparation method, described reaction temperature controls at 60～120 DEG C.
The modified polyacrylonitrile copolymer molecular weight M of the present invention>30,000g/mol, intrinsic viscosity>0.5dL/g.
Binding agent of the present invention is the PAN modified by specific process, due to adding more in its building-up process
The initiator of volume, and have selected more suitable monomer, there is higher molecular weight, improve the microcosmic group of strand
Become so that the polyacrylonitrile copolymer of synthesis is easier cyclisation so that it is born as lithium ion battery silicon in preoxidation process
During the binding agent of pole, be more applicable for improving between powder granule and collector by heat treatment, powder granule and powder body
Cohesive force between grain is additionally it is possible to alleviate silicon materials as volumetric expansion causing in battery charge and discharge process during active substance etc.
Problem.And, the modified binding agent crossed of the present invention has preferable electric conductivity, can reduce the internal resistance of overall pole piece；So that
Obtain lithium ion battery and there is outstanding chemical property.
In a word, the binding agent of the present invention can solve the problem that silicon materials apply the many skills in the presence of lithium ion cell electrode
Art problem, makes silicon materials can apply to the broader field of lithium ion battery (such as active substance：Electric automobile, extrahigh energy
Amount battery, field of batteries of distinct temperature environmental applications etc.), compared with traditional industrialization binding agent PVDF, have on the whole
More obvious advantage.
Meanwhile, the present invention provides a kind of lithium ion battery negative, comprises active material, conductive agent, dispersant, also comprises
State the binding agent of emulsion polymerization synthesis, and modified through Overheating Treatment；Described Binder Composition account for negative pole gross mass 1%～
10%, active material, the mixed active material material composition of conductive agent account for the 85%～98.5% of negative pole gross mass, and dispersant becomes
Divide and account for the 0.5%～5% of negative pole gross mass.
Wherein said mixed active material material includes amorphous silicon grain, amorphous silicon rod, crystal silicon particle, crystalline silicon nanometer
Line, Si-SiOxGranule, silicon alloy powder, graphite, hard carbon, soft carbon, carbonaceous mesophase spherules, acetylene black, white carbon black, Super-P, KS-
6th, at least two in CNT, Graphene, fullerene etc..
Described dispersant is paid the utmost attention to using polyvinyl alcohol, cetyl ammonium bromide, dodecylbenzene sodium sulfonate, silane
One or more of coupling agent (KH550, KH560, KH570, KH620, A-151, A-171).
The invention also discloses, the polyacrylonitrile that emulsion polymerization is synthesized is used for lithium ion battery negative and bears as silicon materials
The binding agent of pole is prepared into battery cathode the method to electrode modification.
Key step is as follows：
1) preparation of polyacrylonitrile binding agent：
In the flask equipped with mechanical agitator, it is filled with inert gas shielding, and carries thermometer, control reaction solution temperature
Degree.Sequentially add initiator, surfactant, additive, monomer and solvent by different proportion in flask, control rotating speed to exist
200r/min is heated to uniform temperature, takes out after reaction 2～24h.Obtaining main component after washing and filtering is multiple is polyacrylonitrile
Polymeric powder, as lithium ion battery silicon materials binding agent.
2) preparation of electrode slurry and lithium ion battery silicon materials negative plate：
By conductive agent and the mixing of silicon materials active substance high-speed stirred；Meanwhile, by 1) in the polyacrylonitrile macromolecule that obtains
Powder is dissolved in one of DMF, DMSO, DMAc, NMP, THF organic solvent and obtains polyacrylonitrile solution；By mix
Conductive agent and silicon materials active substance mixed-powder and dispersant (polyvinyl alcohol, cetyl ammonium bromide, detergent alkylate sulphur
Sour sodium, silane coupler (one or more of KH550, KH560, KH570, KH620, A-151, A-171) press certain matter
Amount ratio is added in polyacrylonitrile solution, keeps solid content ＞ 30%, and strong agitation 24h obtains uniform electrode slurry.
By above-mentioned electrode slurry after homogenate, being coated on Copper Foil, electrode is made to solidify with the temperature less than 80 DEG C；Solidification
After the completion of electrode is placed in 120 DEG C of vacuum drying ovens, directly application is prepared into the lithium ion battery of material to keep more than 12h
Negative plate.
3) method of modifying of silicon materials negative plate：
Then the Copper Foil being coated with mixed active material is 2) the middle anode plate for lithium ionic cell prepared, it is placed in body of heater
In, in air atmosphere, at a temperature of 280～800 DEG C, keep 0.1～60min, then take out and obtain a kind of lithium ion battery silicon
Material is with polyacrylonitrile for the modified electrode piece of main component binding agent.
Brief description
Fig. 1 is the scanning electron microscope diagram piece of the electrode slice of the embodiment of the present invention 3 preparation.
Specific embodiment
With reference to the accompanying drawings and examples the present invention is described in further detail, but not as a limitation of the invention.
Embodiment 1：
Prepare a kind of lithium ion battery silicon materials binding agent of the present invention, preparation method is as follows：
Equipped with mechanical agitator, N2Add successively by different proportion in the 250mL four-hole boiling flask of protection device and thermometer
Enter monobutyl itaconate (accounting for the 5% of monomer mass), azo isobutyronitrile (accounting for the 0.5% of monomer mass), n-butyl acrylate (account for
The 2% of acrylonitrile monemer quality), polyoxyethylene nonylphenol ether 10 (accounting for the 0.5% of monomer mass) and acrylonitrile monemer and water is (for monomer matter
9 times of amount), it is heated to 110 DEG C, takes out after reaction 24h, deionized water wash obtains main component after filtering repeatedly be polypropylene
The polymeric powder of nitrile, as lithium ion battery silicon materials binding agent I, its molecular weight is about 280 000.
Embodiment 2：
Prepare a kind of lithium ion battery silicon materials binding agent of the present invention, preparation method is as follows：
Equipped with mechanical agitator, N2Add successively by different proportion in the 250mL four-hole boiling flask of protection device and thermometer
Enter monobutyl itaconate (accounting for the 8% of monomer mass), azo isobutyronitrile (accounting for the 0.5% of monomer mass), n-butyl acrylate (account for
The 2% of monomer mass), polyoxyethylene nonylphenol ether 10 (accounting for the 0.5% of monomer mass) and acrylonitrile monemer (accounting for the 90% of monomer mass)
With water (for 9 times of monomer mass), it is heated to 85 DEG C, take out after reaction 24h, it is poly- for obtaining main component after washing and filtering is multiple
The polymeric powder of acrylonitrile, as lithium ion battery silicon materials binding agent II, its molecular weight is about 354 000.
Embodiment 3：
The present embodiment selects high-purity crystal silicon (Wt%=99.9%) material of a diameter of～100nm and particle diameter to be～1 μm
Super P, 3 μm of MCMBs and MWCNTs are conductive agent (Super P：MCMB：MWCNTs w/w=60:35:5)、
The binding agent I that embodiment 1 preparation is used is as the binder material preparing electrode.
Prepare high-purity crystal silicon electrode according to following steps：
1) by mass percentage, weigh 50% silicon class active material, 20% material with carbon element conductive agent mixing is uniformly dispersed；
2) by mass percentage, weigh 30% embodiment 1 preparation binding agent I as binding agent powder body, be dissolved in suitable
In the NMP of amount, it is uniformly dispersed, stirs into vitreosol shape；
3) by step 1) powder body that obtains is added to step 2) in the colloidal sol shape material that obtains, control solid content 40%,
It is stirred vigorously, be mixing uniformly to form slurry；
4) by step 3) in gained silicon electrode slurry, be coated directly onto on 10 μm of Copper Foils that (coating thickness is with film applicator
60μm).Electrode is made to solidify with 50 DEG C of temperature, the vacuum finally Copper Foil being loaded with nano-silicon active substance being positioned over 120 DEG C is dried
Keep 12h in case, take out after being cooled to room temperature.
According to following steps modification high-purity crystal silicon electrode：
During the Copper Foil being covered with silicon active substance is lain against outside body of heater, treat that furnace temperature rises to 700 DEG C, nano-silicon activity will be loaded with
The foil section of material is quickly pulled in stove.At 700 DEG C, in the environment of nitrogen buffer gas, flow is 2m3/ h, heat treatment 30s
Afterwards, the partly rapid pull-out annealing of nano-silicon active substance Copper Foil will be loaded with, obtain the electrode of modification, that is, lithium ion battery is used
Silicon materials negative pole.
Using embodiment 3 silicon electrode as negative electrode for lithium ion battery, test result is shown in Table 1, scanning electron microscopy
Fig. 1 is shown in by mirror picture.
Embodiment 4：
The present embodiment selects high-purity crystal silicon (Wt%=99.9%) material of a diameter of～100nm and particle diameter to be～1 μm
Super P, 3 μm of MCMBs and MWCNTs are conductive agent (Super P：MCMB：MWCNTs w/w=60:35:5)、
The binding agent I that embodiment 1 preparation is used is as the binder material preparing electrode.
Prepare high-purity crystal silicon electrode according to following steps：
1) by mass percentage, weigh 50% silicon class active material, 20% material with carbon element conductive agent mixing is uniformly dispersed；
2) by mass percentage, weigh 30% embodiment 1 preparation binding agent I as binding agent powder body, be dissolved in suitable
In the NMP of amount, it is uniformly dispersed, stirs into vitreosol shape；
3) by step 1) powder body that obtains is added to step 2) in the colloidal sol shape material that obtains, control solid content 40%,
It is stirred vigorously, be mixing uniformly to form slurry；
4) by step 3) in gained silicon electrode slurry, be coated directly onto on 10 μm of Copper Foils that (coating thickness is with film applicator
60μm).Electrode is made to solidify with 50 DEG C of temperature, the vacuum finally Copper Foil being loaded with nano-silicon active substance being positioned over 120 DEG C is dried
Keep 12h in case, take out after being cooled to room temperature.
According to following steps modification high-purity crystal silicon electrode：
During the Copper Foil being covered with silicon active substance is lain against outside body of heater, treat that furnace temperature rises to 300 DEG C, nano-silicon activity will be loaded with
The foil section of material is quickly pulled in stove.At 300 DEG C, dry air is in the environment of carrier gas, and flow is 2m3/ h, heat treatment
After 20min, the partly rapid pull-out annealing of nano-silicon active substance Copper Foil will be loaded with, obtain the electrode of modification, i.e. lithium ion
Battery silicon materials negative pole.
Using embodiment 4 silicon electrode as negative electrode for lithium ion battery, test result is shown in Table 1.
Embodiment 5：
The present embodiment selects high-purity crystal silicon (Wt%=99.9%) material of a diameter of～100nm and particle diameter to be～1 μm
Super P, 3 μm of MCMBs and MWCNTs are conductive agent (Super P：MCMB：MWCNTs w/w=60:35:5)、
The binding agent II that embodiment 2 preparation is used is as the binder material preparing electrode.
Prepare high-purity crystal silicon electrode according to following steps：
1) by mass percentage, weigh 50% silicon class active material, 20% material with carbon element conductive agent mixing is uniformly dispersed；
2) by mass percentage, weigh 30% embodiment 2 preparation binding agent II as binding agent powder body, be dissolved in suitable
In the NMP of amount, it is uniformly dispersed, stirs into vitreosol shape；
3) by step 1) powder body that obtains is added to step 2) in the colloidal sol shape material that obtains, control solid content 35%,
It is stirred vigorously, be mixing uniformly to form slurry；
4) by step 3) in gained silicon electrode slurry, be coated directly onto on 10 μm of Copper Foils that (coating thickness is with film applicator
60μm).Electrode is made to solidify with 50 DEG C of temperature, the vacuum finally Copper Foil being loaded with nano-silicon active substance being positioned over 120 DEG C is dried
Keep 12h in case, take out after being cooled to room temperature.
According to following steps modification high-purity crystal silicon electrode：
During the Copper Foil being covered with silicon active substance is lain against outside body of heater, treat that furnace temperature rises to 700 DEG C, nano-silicon activity will be loaded with
The foil section of material is quickly pulled in stove.At 700 DEG C, in the environment of nitrogen buffer gas, flow is 2m3/ h, heat treatment 30S
Afterwards, the partly rapid pull-out annealing of nano-silicon active substance Copper Foil will be loaded with, obtain the electrode of modification, that is, lithium ion battery is used
Silicon materials negative pole.
Using embodiment 5 silicon electrode as negative electrode for lithium ion battery, test result is shown in Table 1.
Embodiment 6：
The present embodiment selects high-purity crystal silicon (Wt%=99.9%) material of a diameter of～100nm and particle diameter to be～1 μm
Super P, 3 μm of MCMBs and MWCNTs are conductive agent (Super P：MCMB：MWCNTs w/w=60:35:5)、
The binding agent II that embodiment 2 preparation is used is as the binder material preparing electrode.
Prepare high-purity crystal silicon electrode according to following steps：
1) by mass percentage, weigh 50% silicon class active material, 20% material with carbon element conductive agent mixing is uniformly dispersed；
2) by mass percentage, weigh 30% embodiment 2 preparation binding agent II as binding agent powder body, be dissolved in suitable
In the NMP of amount, it is uniformly dispersed, stirs into vitreosol shape；
3) by step 1) powder body that obtains is added to step 2) in the colloidal sol shape material that obtains, control solid content 35%,
It is stirred vigorously, be mixing uniformly to form slurry；
4) by step 3) in gained silicon electrode slurry, be coated directly onto on 10 μm of Copper Foils that (coating thickness is with film applicator
60μm).Electrode is made to solidify with 50 DEG C of temperature, the vacuum finally Copper Foil being loaded with nano-silicon active substance being positioned over 120 DEG C is dried
Keep 12h in case, take out after being cooled to room temperature.
According to following steps modification high-purity crystal silicon electrode：
During the Copper Foil being covered with silicon active substance is lain against outside body of heater, treat that furnace temperature rises to 300 DEG C, nano-silicon activity will be loaded with
The foil section of material is quickly pulled in stove.At 300 DEG C, dry air is in the environment of carrier gas, and flow is 2m3/ h, heat treatment
After 20min, the partly rapid pull-out annealing of nano-silicon active substance Copper Foil will be loaded with, obtain the electrode of modification, i.e. lithium ion
Battery silicon materials negative pole.
Using embodiment 6 silicon electrode as negative electrode for lithium ion battery, test result is shown in Table 1.
Embodiment 7
Prepare a kind of lithium ion battery silicon materials binding agent of the present invention, preparation method is as follows：
Equipped with mechanical agitator, N2Add successively by different proportion in the 250mL four-hole boiling flask of protection device and thermometer
Enter monobutyl itaconate (accounting for the 8% of monomer mass), azo isobutyronitrile (accounting for the 0.2% of monomer mass), n-butyl acrylate (account for
The 2% of monomer mass), polyoxyethylene nonylphenol ether 10 (accounting for the 0.2% of monomer mass) and acrylonitrile monemer (accounting for the 90% of monomer mass)
With water (for 9 times of monomer mass), it is heated to 85 DEG C, take out after reaction 24h, it is poly- for obtaining main component after washing and filtering is multiple
The polymeric powder of acrylonitrile, as lithium ion battery silicon materials binding agent III, its molecular weight is about 250 000.
Embodiment 8
Prepare a kind of lithium ion battery silicon materials binding agent of the present invention, preparation method is as follows：
Equipped with mechanical agitator, N2Add successively by different proportion in the 250mL four-hole boiling flask of protection device and thermometer
Enter acrylic acid methyl ester. (accounting for the 8% of monomer mass), azo isobutyronitrile (accounting for the 0.5% of monomer mass), n-butyl acrylate (account for list
The 2% of weight), polyoxyethylene nonylphenol ether 10 (accounting for the 0.2% of monomer mass) and acrylonitrile monemer (accounting for the 90% of monomer mass) and
Water (for 9 times of monomer mass), is heated to 85 DEG C, takes out after reaction 24h, and obtaining main component after washing and filtering is multiple is poly- third
The polymeric powder of alkene nitrile, as lithium ion battery silicon materials binding agent IV, its molecular weight is about 223 000.
Embodiment 9
Prepare a kind of lithium ion battery silicon materials binding agent of the present invention, preparation method is as follows：
Equipped with mechanical agitator, N2Add successively by different proportion in the 250mL four-hole boiling flask of protection device and thermometer
Enter monobutyl itaconate (accounting for the 8% of monomer mass), Ammonium persulfate. (accounting for the 0.5% of monomer mass), n-butyl acrylate (account for list
The 2% of weight), polyoxyethylene nonylphenol ether 10 (accounting for the 0.2% of monomer mass) and acrylonitrile monemer (accounting for the 90% of monomer mass) and
Water (for 9 times of monomer mass), is heated to 85 DEG C, takes out after reaction 24h, and obtaining main component after washing and filtering is multiple is poly- third
The polymeric powder of alkene nitrile, as lithium ion battery silicon materials binding agent V, its molecular weight is about 310000.
Embodiment 10：
The present embodiment selects high-purity crystal silicon (Wt%=99.9%) material of a diameter of～100nm and particle diameter to be～1 μm
Super P, 3 μm of MCMBs and MWCNTs are conductive agent (Super P：MCMB：MWCNTs w/w=60:35:5)、
The binding agent III that embodiment 7 preparation is used is as the binder material preparing electrode.
Prepare high-purity crystal silicon electrode according to following steps：
1) by mass percentage, weigh 50% silicon class active material, 20% material with carbon element conductive agent mixing is uniformly dispersed；
2) by mass percentage, weigh 30% embodiment 7 preparation binding agent III as binding agent powder body, be dissolved in
In appropriate NMP, it is uniformly dispersed, stir into vitreosol shape；
3) by step 1) powder body that obtains is added to step 2) in the colloidal sol shape material that obtains, control solid content 40%,
It is stirred vigorously, be mixing uniformly to form slurry；
4) by step 3) in gained silicon electrode slurry, be coated directly onto on 10 μm of Copper Foils that (coating thickness is with film applicator
60μm).Electrode is made to solidify with 50 DEG C of temperature, the vacuum finally Copper Foil being loaded with nano-silicon active substance being positioned over 120 DEG C is dried
Keep 12h in case, take out after being cooled to room temperature.
According to following steps modification high-purity crystal silicon electrode：
During the Copper Foil being covered with silicon active substance is lain against outside body of heater, treat that furnace temperature rises to 700 DEG C, nano-silicon activity will be loaded with
The foil section of material is quickly pulled in stove.At 700 DEG C, in the environment of nitrogen buffer gas, flow is 2m3/ h, heat treatment 30s
Afterwards, the partly rapid pull-out annealing of nano-silicon active substance Copper Foil will be loaded with, obtain the electrode of modification, that is, lithium ion battery is used
Silicon materials negative pole.
Embodiment 11
According to the modified high-purity crystal silicon electrode of method preparation of embodiment 10, simply binding agent therein is using embodiment 8
The binding agent IV of preparation, remaining method is all identical, obtains the lithium ion battery silicon materials negative pole of modification.
Embodiment 12
According to the modified high-purity crystal silicon electrode of method preparation of embodiment 10, simply binding agent therein is using embodiment 9
The binding agent V of preparation, remaining method is all identical, obtains the lithium ion battery silicon materials negative pole of modification.
Comparative example 1：
It is～30nm that the present embodiment selects high-purity crystal silicon (Wt%=99.9%) material of a diameter of～100nm and particle diameter
Conductive agent mixed powder (white carbon black：Acetylene black w/w=1:And MWCNTs accounts for the 2% of white carbon black acetylene black mixed powder, and gather inclined fluorine 1)
Ethylene (PVDF) (M=150 000) is as the binder material preparing electrode.
Prepare high-purity crystal silicon electrode according to following steps：
1) by mass percentage, weigh 50% silicon class active material, 20% material with carbon element conductive agent mixing is uniformly dispersed；
2) by mass percentage, weigh 30% Kynoar as binding agent powder body, be dissolved in appropriate NMP,
It is uniformly dispersed, stir into vitreosol shape；
3) by step 1) powder body that obtains is added to step 2) in the colloidal sol shape material that obtains, control solid content 40%,
It is stirred vigorously, be mixing uniformly to form slurry；
4) by step 3) in gained silicon electrode slurry, be coated directly onto on 10 μm of Copper Foils that (coating thickness is with film applicator
60μm).So that electrode is solidified with 50 DEG C of temperature, finally the Copper Foil being loaded with nano-silicon active substance is positioned over 80 DEG C of vacuum drying oven
Middle holding 12h, takes out after being cooled to room temperature.
According to following steps modification high-purity crystal silicon electrode：
The Copper Foil being covered with silicon active substance is lain against outside body of heater, treats that furnace temperature rises to 400 DEG C, nano-silicon active matter will be loaded with
The foil section of matter is quickly pulled in stove.It is passed through N at 400 DEG C2Protection, flow is 0.3m3/ h, after heat treatment 5min, will be loaded with and receive
The partly rapid pull-out annealing of rice silicon active substance Copper Foil, has obtained the electrode of modification, i.e. lithium ion battery silicon materials negative pole.
Using comparative example 1 silicon electrode as negative electrode for lithium ion battery, test result is shown in Table 1.
Experimental example 1.
This experiment using embodiment of the present invention 3-6,10-12 and comparative example 1 preparation silicon electrode as negative plate, with lithium metal
As to electrode, using Cathay's Huarong LB-315 electrolyte, (composition is piece：LiPF6EC/DMC/EMC=1:1:1 (V/V/V)),
Celgard2300 barrier film, is assembled in glove box using 2032 button cells, and uses Wuhan Lan electricity Electronics Co., Ltd.
CT2001A cell tester carries out the test of battery performance to battery, and (using the charge and discharge system of constant current charge-discharge, electric current sets
It is set to 100mA/g, blanking voltage is set to 0.01～1.2V vs Li+/Li)
The hypovolemic of modified battery is tested using cell tester (CT2001A type, Wuhan Lan electricity Electronics Co., Ltd.)
Can and cycle performance, employ in embodiment 3-6,10-12 the silicon electrode of modified PAN as negative electrode for lithium ion battery, its
Specific capacity is more than 800mAh/g, and after circulating 100 times, capability retention is more than 90%, illustrates that the modified PAN of the present invention can be lithium
The silicon materials negative pole of ion battery brings significant performance improvement.
Table 1：The lithium ion battery of embodiment 3～6,10-12 and comparative example 1 electrochemical property test of silicon materials negative pole
Result
Claims (7)
1. a kind of lithium ion battery silicium cathode binding agent, it is polyacrylonitrile copolymer, described polyacrylonitrile copolymer bag
Include acrylonitrile, second comonomer and/or Third monomer；It is characterized in that：
Described second comonomer is monobutyl itaconate monomer, and described Third monomer is selected from itaconic acid, sodium allylsulfonate, propylene
Any one in amide, n-butyl acrylate, acrylic acid methyl ester. or two or more mixture；
Described polyacrylonitrile copolymer is prepared from by following methods：Described monomer is obtained by emulsion polymerization
, described emulsion polymerization is under inert gas shielding, adds initiator, emulsifying in emulsion polymerization container
Agent, monomer and solvent, the weight of initiator and monomer is than for 1:999～1:9, solvent adding amount is the 1.5～10 of monomer mass
Times, emulsifying agent addition is the 0.1%～1% of monomer gross mass；With the rotating speed stirring of 150～250r/min, control reaction temperature
In the range of 25～160 DEG C, polymerization time controls between 2～24h degree；
Described initiator is azo isobutyronitrile, described emulsifying agent is one of Co-458, OP-10 or tween80, described
Solvent be one of toluene, o-Dimethylbenzene, hexane, normal hexane or water.
2. binding agent according to claim 1 it is characterised in that：Described Third monomer is n-butyl acrylate.
3. binding agent according to claim 1 it is characterised in that：In described polymerized monomer, second comonomer and acrylonitrile
Weight is than for 1～10:99～90, Third monomer and acrylonitrile weight are than for 1～5:99～95.
4. a kind of method of preparing lithium ion battery silicium cathode binding agent, comprises the following steps：
Under inert gas shielding, add initiator, emulsifying agent, monomer and solvent, initiator in emulsion polymerization container
With the weight of total monomer than for 1:9～999, solvent adding amount is 1.5-10 times of monomer gross mass, and emulsifying agent addition is single
The 0.1%～1% of body gross mass；With the stirring of the rotating speed of 150～250r/min, controlling reaction temperature in the range of 25～160 DEG C,
Polymerization time controls between 2～24h；Described monomer includes acrylonitrile, second comonomer and/or Third monomer；
Described second comonomer is monobutyl itaconate monomer, and described Third monomer is selected from itaconic acid, sodium allylsulfonate, propylene
Any one in amide, n-butyl acrylate, acrylic acid methyl ester. or two or more mixture.
5. method according to claim 4, comprises the following steps：Under inert gas shielding, hold to emulsion polymerization
Initiator, emulsifying agent, monomer and solvent is added, the weight of initiator and total monomer ratio is for 1～2 in device:180～250, solvent adds
Enter 5～10 times that amount is monomer gross mass, emulsifying agent addition is the 0.1%～1% of monomer gross mass；With 150～250r/
The rotating speed stirring of min, in the range of 60～120 DEG C, polymerization time controls between 2～24h controlling reaction temperature.
6. method according to claim 4 it is characterised in that：Described Third monomer is n-butyl acrylate.
7. method according to claim 4 it is characterised in that：Described initiator is selected from azo isobutyronitrile.
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| CN106220779B (en) * | 2016-08-17 | 2018-08-31 | 四川茵地乐科技有限公司 | Acrylonitrile copolymer binder and its application in lithium ion battery |
| KR102583192B1 (en) * | 2016-10-13 | 2023-09-27 | 테슬라, 인크. | Large battery anode containing silicon particles |
| CN108461691B (en) * | 2018-02-08 | 2019-05-10 | 深圳锂硫科技有限公司 | A kind of lithium-sulfur cell diaphragm and preparation method thereof |
| US20220204857A1 (en) * | 2019-03-29 | 2022-06-30 | Toyo Ink Sc Holdings Co., Ltd. | Dispersant, dispersed material, resin composition, mixture slurry, electrode film, and non-aqueous electrolyte secondary battery |
| JP6743954B1 (en) * | 2019-05-10 | 2020-08-19 | 東洋インキＳｃホールディングス株式会社 | Conductive material dispersion and use thereof |
| CN111816870B (en) * | 2019-04-10 | 2022-03-29 | 惠州市赛能电池有限公司 | Lithium battery negative electrode binder and preparation method and application thereof |
| CN112436105A (en) * | 2019-08-24 | 2021-03-02 | 深圳格林德能源集团有限公司 | Pre-lithiation negative pole piece and preparation method thereof |
| WO2021253302A1 (en) * | 2020-06-17 | 2021-12-23 | Guangdong Haozhi Technology Co. Limited | Conductive composition for secondary battery |
| WO2021253674A1 (en) * | 2020-06-17 | 2021-12-23 | Guangdong Haozhi Technology Co. Limited | Binder composition for secondary battery |
| CN114142039B (en) * | 2021-11-29 | 2023-11-28 | 珠海冠宇电池股份有限公司 | Adhesive and lithium ion battery comprising same |
| CN114566649B (en) * | 2022-02-24 | 2024-01-23 | 东莞赣锋电子有限公司 | High-areal-density negative plate and preparation method thereof |
| CN114736632A (en) * | 2022-04-29 | 2022-07-12 | 瑞固新能(上海)材料科技有限公司 | Acrylonitrile binder powder and preparation method thereof |
| CN117645852B (en) * | 2024-01-29 | 2024-04-05 | 中国科学院长春应用化学研究所 | Oily adhesive system and application thereof |
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