CN104538635A - 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 PDF

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Publication number
CN104538635A
CN104538635A CN201410761021.5A CN201410761021A CN104538635A CN 104538635 A CN104538635 A CN 104538635A CN 201410761021 A CN201410761021 A CN 201410761021A CN 104538635 A CN104538635 A CN 104538635A
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monomer
silicon
binding agent
lithium ion
initator
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CN201410761021.5A
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CN104538635B (en
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侯豪情
王�琦
赵丹
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JIANGXI XIANCAI NANOFIBERS TECHNOLOGY Co Ltd
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JIANGXI XIANCAI NANOFIBERS TECHNOLOGY Co Ltd
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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
    • 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
    • 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
    • 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
    • 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

A kind of lithium ion battery silicon materials high-performance adhesive and preparation method thereof
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of lithium ion battery silicon negative electrode binder, and preparation method thereof.
Background technology
Present stage, lithium ion battery negative material was still based on graphite material, and it has substantially reached theoretical value (372mAh/g) on capacity utilization.In order to the requirement of satisfied wireless telecommunications system of future generation, hybrid electric vehicle, we need the energy density, the power density that significantly improve lithium ion battery.Silicium cathode had both had and exceeds the specific capacity of ten times than conventional carbon negative pole (specific discharge capacity is: 4200mAh/g; Volume and capacity ratio is: 9786mAh/cm 3), possess again a relatively low electric discharge position (average de-lithium current potential is at about 0.4V), and the rich reserves of element silicon in the earth's crust (content in the earth's crust is only second to oxygen), environmentally friendly, chemical property is more stable, has been widely used in semi-conductor industry.
In electrode mixed process with slurry, high molecular polymer is as binding agent: polymer molecule segment can be adsorbed on different active material particles, active material therefore by " bridge joint " together, and then bonded agent molecule be wound around, be wrapped to form fixing network configuration.When solvent evaporates, active material particle is fixed, and plays the effect of bonding.As can be seen here, binding agent is one of necessary material of preparation battery core.But using silicon grain as electrode active material, traditional binding agent PVDF (Kynoar) can not improve that silicon grain causes because of volumetric expansion in cyclic process very well with the great number of issues such as stripping electrode.Polyacrylonitrile strand is difficult to freely rotate and form spiral helicine three-dimensional conformation in the ordinary course of things.Silicon materials class electrode active material is made to have more sufficient space reply volumetric expansion.
In sum, high-performance adhesive can not be ignored improving the development of silicon as lithium ion battery negative, high performance binding agent should become one of the main contents optimizing battery core, and the exploitation of novel binding agent also will become one of problem that electrokinetic cell must solve.
Summary of the invention
The object of the invention is to: a kind of lithium ion battery silicium cathode binding agent and electrode slurry are provided.Relatively existing binding agent, can improve the performance of silicon electrode in cyclic process.
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, and wherein, polymerization single polymerization monomer also comprises second comonomer and/or Third monomer except acrylonitrile; Described second comonomer is monobutyl itaconate monomer, and described Third monomer is selected from any one or two or more mixtures in itaconic acid, sodium allylsulfonate, acrylamide, amino, pyridine radicals or amide groups monomer, n-butyl acrylate.
In the preferred binding agent of the present invention, described Third monomer is n-butyl acrylate or methyl acrylate; Most preferably n-butyl acrylate.
In the preferred binding agent of the present invention, in described polymerization single polymerization monomer, second comonomer and acrylonitrile weight ratio are 1 ~ 10:99 ~ 90, and Third monomer and acrylonitrile weight ratio are 1 ~ 5:99 ~ 95.
In the preferred binding agent of the present invention, described polyacrylonitrile copolymer is that described monomer is obtained by emulsion polymerization, described emulsion polymerization is under inert gas shielding, initator, emulsifying agent, monomer and solvent is added in emulsion polymerization container, the weight ratio of initator and monomer is 1:999 ~ 1:9, preferably 1 ~ 2:180 ~ 250, solvent adding amount is 1.5 ~ 10 times (preferably 5 ~ 10 times) of monomer mass, and emulsifying agent addition is 0.1% ~ 1% of monomer gross mass; Stir with the rotating speed of 150 ~ 250r/min, control reaction temperature within the scope of 25 ~ 160 DEG C, preferably 60 ~ 120 DEG C, polymerization time controls 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, initator, emulsifying agent, monomer and solvent is added in emulsion polymerization container, the weight ratio of initator and monomer is 1:999 ~ 1:9 (preferably 1 ~ 2:180 ~ 250), solvent adding amount is 1.5 ~ 10 (preferably 5 ~ 10 times) of monomer mass, and emulsifying agent addition is 0.1% ~ 1% of monomer gross mass; Stir with the rotating speed of 150 ~ 250r/min, control reaction temperature within the scope of 25 ~ 160 DEG C, preferably 60 DEG C ~ 120 DEG C, polymerization time controls between 2 ~ 24h; Described monomer also comprises second comonomer and/or Third monomer except acrylonitrile; Described second comonomer is monobutyl itaconate monomer, and described Third monomer is selected from any one or two or more mixtures in itaconic acid, methyl acrylate, sodium allylsulfonate, acrylamide, amino, pyridine radicals or amide groups monomer, n-butyl acrylate.
In the preferred preparation method of the present invention, described Third monomer is n-butyl acrylate or methyl acrylate; Most preferably n-butyl acrylate.
In the preferred preparation method of the present invention, in described polymerization single polymerization monomer, second comonomer and acrylonitrile weight ratio are 1 ~ 10:99 ~ 90, and Third monomer and acrylonitrile weight ratio are 1 ~ 5:99 ~ 95.
In the preferred preparation method of the present invention, at least one in the preferred azo of described initator, organic peroxide class, redox system class; Preferred azo isobutyronitrile, ammonium persulfate or potassium peroxydisulfate further
In the preferred preparation method of the present invention, the oil-in-water emulsifiers such as preferred Co-458, OP-10 or the tween 80 of described emulsifying agent.。
In the preferred preparation method of the present invention, the one in the preferred dimethyl sulfoxide (DMSO) of described solvent, dimethylacetylamide, dimethyl formamide or water; Preferred dimethyl sulfoxide (DMSO) or water.
In the preferred preparation method of the present invention, described reaction temperature controls at 60 ~ 120 DEG C.
The polyacrylonitrile copolymer molecular weight M>30 that the present invention is modified, 000g/mol, inherent viscosity >0.5dL/g.
Binding agent of the present invention is the PAN by specific process modification, owing to adding the initator of more in its building-up process, and have selected more suitable monomer, there is higher molecular weight, improve the microcosmic composition of strand, make polyacrylonitrile copolymer easier cyclisation in preoxidation process of synthesizing, when making its binding agent as lithium ion battery silicium cathode, be more applicable for and improve between powder granule and collector by heat treatment, cohesive force between powder granule and powder granule, silicon materials can also be alleviated as problems such as the volumetric expansions caused in battery charge and discharge process during active material.And the binding agent of modification of the present invention has good conductivity, can reduce the internal resistance of overall pole piece; Thus make lithium ion battery have outstanding chemical property.
In a word, binding agent of the present invention can solve silicon materials and be applied in many technical problems existing in lithium ion cell electrode, silicon materials are made to be applied to the more wide field of lithium ion battery (as: field of batteries etc. of electric automobile, superenergy battery, distinct temperature environmental applications) as active matter mass-energy, compared with traditional industrialization binding agent PVDF, there is comparatively significantly advantage on the whole.
Meanwhile, the invention provides a kind of lithium ion battery negative, comprise active material, conductive agent, dispersant, also comprise the binding agent of above-mentioned emulsion polymerization synthesis, and through Overheating Treatment modification; Described Binder Composition accounts for 1% ~ 10% of negative pole gross mass, and the mixed active material material composition of active material, conductive agent accounts for 85% ~ 98.5% of negative pole gross mass, and dispersion. formulation accounts for 0.5% ~ 5% of negative pole gross mass.
Wherein said mixed active material material comprises amorphous silicon particle, amorphous silicon rod, crystal silicon particle, crystalline silicon nano wire, Si-SiO xat least two kinds in particle, silicon alloy powder, graphite, hard carbon, soft carbon, carbonaceous mesophase spherules, acetylene black, carbon black, Super-P, KS-6, carbon nano-tube, Graphene, fullerene etc.
Described dispersant pays the utmost attention to one or more in use polyvinyl alcohol, cetyl ammonium bromide, neopelex, silane coupler (KH550, KH560, KH570, KH620, A-151, A-171).
The invention also discloses, the polyacrylonitrile that emulsion polymerisation is synthesized is used for lithium ion battery negative and is prepared into battery cathode and method to electrode modification as the binding agent of silicon materials negative pole.
Key step is as follows:
1) preparation of polyacrylonitrile binding agent:
In the flask that mechanical agitator is housed, fill with inert gas shielding, and with thermometer, control reaction solution temperature.In flask, add initator, surfactant, additive, monomer and solvent successively by different proportion, control rotating speed and be heated to uniform temperature at 200r/min, take out after reaction 2 ~ 24h.Washing and filtering repeatedly obtains the polymeric powder that main component is polyacrylonitrile afterwards, as the agent of lithium ion battery silicon material binding.
2) preparation of electrode slurry and lithium ion battery silicon materials negative plate:
By conductive agent and the mixing of silicon materials active material high-speed stirred; Meanwhile, by 1) in the polyacrylonitrile polymeric powder that obtains be dissolved in DMF, DMSO, DMAc, NMP, THF a kind of organic solvent in obtain polyacrylonitrile solution; By the conductive agent mixed and silicon materials active material mixed-powder and dispersant, (polyvinyl alcohol, cetyl ammonium bromide, neopelex, silane coupler (in KH550, KH560, KH570, KH620, A-151, A-171 one or more) join in polyacrylonitrile solution by certain mass ratio, solid content > 30%, strong agitation 24h is kept to obtain uniform electrode slurry.
By above-mentioned electrode slurry through homogenate, be coated on after on Copper Foil, by the temperature lower than 80 DEG C, electrode is solidified; Electrode is placed in 120 DEG C of vacuum drying ovens after having solidified, keeps more than 12h directly to apply the anode plate for lithium ionic cell being prepared into material.
3) method of modifying of silicon materials negative plate:
Then the Copper Foil that is 2 will being coated with mixed active material) in the anode plate for lithium ionic cell of preparation, be placed in body of heater, in air atmosphere, at 280 ~ 800 DEG C of temperature, keep 0.1 ~ 60min, then take out and obtain the modified electrode sheet that a kind of lithium ion battery silicon materials take polyacrylonitrile as main component binding agent.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram sheet of electrode slice prepared by the embodiment of the present invention 3.
Embodiment
Below in conjunction with 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:
Mechanical agitator is being housed, N 2monobutyl itaconate (accounting for 5% of monomer mass) is added successively by different proportion in the 250mL four-hole boiling flask of protective device and thermometer, azo isobutyronitrile (accounting for 0.5% of monomer mass), n-butyl acrylate (accounting for 2% of acrylonitrile monemer quality), polyoxyethylene nonylphenol ether 10 (accounting for 0.5% of monomer mass) and acrylonitrile monemer and water (9 times for monomer mass), be heated to 110 DEG C, take out after reaction 24h, deionized water washing and filtering repeatedly obtains the polymeric powder that main component is polyacrylonitrile afterwards, as lithium ion battery silicon material 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:
Mechanical agitator is being housed, N 2monobutyl itaconate (accounting for 8% of monomer mass) is added successively by different proportion in the 250mL four-hole boiling flask of protective device and thermometer, azo isobutyronitrile (accounting for 0.5% of monomer mass), n-butyl acrylate (accounting for 2% of monomer mass), polyoxyethylene nonylphenol ether 10 (accounting for 0.5% of monomer mass) and acrylonitrile monemer (accounting for 90% of monomer mass) and water (9 times for monomer mass), be heated to 85 DEG C, take out after reaction 24h, washing and filtering repeatedly obtains the polymeric powder that main component is polyacrylonitrile afterwards, as lithium ion battery silicon material binding agent II, its molecular weight is about 354 000.
Embodiment 3:
The present embodiment select diameter be ~ high-purity crystal silicon (Wt%=99.9%) material of 100nm and particle diameter be ~ 1 μm of Super P, 3 μm of MCMB and MWCNTs are conductive agent (Super P:MCMB:MWCNTs w/w=60:35:5), the binding agent I that uses embodiment 1 to prepare is as the binder material preparing electrode.
High-purity crystal silicon electrode is prepared according to following steps:
1) by mass percentage, take the silicon class active material of 50%, the material with carbon element conductive agent mixing of 20% is uniformly dispersed;
2) by mass percentage, binding agent I prepared by the embodiment 1 taking 30%, as binding agent powder, is dissolved in appropriate NMP, is uniformly dispersed, stir into vitreosol shape;
3) by step 1) powder that obtains joins step 2) in the colloidal sol shape material that obtains, control solid content 40%, vigorous stirring, forms slurry after stirring;
4) by step 3) in the silicon electrode slurry of gained, be directly coated on (coating thickness is 60 μm) on 10 μm of Copper Foils with film applicator.With 50 DEG C of temperature, electrode is solidified, finally the Copper Foil being loaded with nano-silicon active material is positioned in the vacuum drying oven of 120 DEG C and keeps 12h, take 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 material is lain against in outside body of heater, treat that furnace temperature rises to 700 DEG C, the Copper Foil part being loaded with nano-silicon active material is drawn in rapidly in stove.At 700 DEG C, in the environment of nitrogen buffer gas, flow is 2m 3/ h, after heat treatment 30s, pulls out annealing rapidly by the part being loaded with nano-silicon active material Copper Foil, obtains the electrode of modification, be i.e. lithium ion battery silicon materials negative pole.
Adopt embodiment 3 silicon electrode as negative electrode for lithium ion battery, test result is in table 1, and scanning electron microscope diagram sheet is shown in Fig. 1.
Embodiment 4:
The present embodiment select diameter be ~ high-purity crystal silicon (Wt%=99.9%) material of 100nm and particle diameter be ~ 1 μm of Super P, 3 μm of MCMB and MWCNTs are conductive agent (Super P:MCMB:MWCNTs w/w=60:35:5), the binding agent I that uses embodiment 1 to prepare is as the binder material preparing electrode.
High-purity crystal silicon electrode is prepared according to following steps:
1) by mass percentage, take the silicon class active material of 50%, the material with carbon element conductive agent mixing of 20% is uniformly dispersed;
2) by mass percentage, binding agent I prepared by the embodiment 1 taking 30%, as binding agent powder, is dissolved in appropriate NMP, is uniformly dispersed, stir into vitreosol shape;
3) by step 1) powder that obtains joins step 2) in the colloidal sol shape material that obtains, control solid content 40%, vigorous stirring, forms slurry after stirring;
4) by step 3) in the silicon electrode slurry of gained, be directly coated on (coating thickness is 60 μm) on 10 μm of Copper Foils with film applicator.With 50 DEG C of temperature, electrode is solidified, finally the Copper Foil being loaded with nano-silicon active material is positioned in the vacuum drying oven of 120 DEG C and keeps 12h, take 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 material is lain against in outside body of heater, treat that furnace temperature rises to 300 DEG C, the Copper Foil part being loaded with nano-silicon active material is drawn in rapidly in stove.At 300 DEG C, dry air is in the environment of carrier gas, and flow is 2m 3/ h, after heat treatment 20min, pulls out annealing rapidly by the part being loaded with nano-silicon active material Copper Foil, obtains the electrode of modification, be i.e. lithium ion battery silicon materials negative pole.
Adopt embodiment 4 silicon electrode as negative electrode for lithium ion battery, test result is in table 1.
Embodiment 5:
The present embodiment select diameter be ~ high-purity crystal silicon (Wt%=99.9%) material of 100nm and particle diameter be ~ 1 μm of Super P, 3 μm of MCMB and MWCNTs are conductive agent (Super P:MCMB:MWCNTs w/w=60:35:5), the binding agent II that uses embodiment 2 to prepare is as the binder material preparing electrode.
High-purity crystal silicon electrode is prepared according to following steps:
1) by mass percentage, take the silicon class active material of 50%, the material with carbon element conductive agent mixing of 20% is uniformly dispersed;
2) by mass percentage, binding agent II prepared by the embodiment 2 taking 30%, as binding agent powder, is dissolved in appropriate NMP, is uniformly dispersed, stir into vitreosol shape;
3) by step 1) powder that obtains joins step 2) in the colloidal sol shape material that obtains, control solid content 35%, vigorous stirring, forms slurry after stirring;
4) by step 3) in the silicon electrode slurry of gained, be directly coated on (coating thickness is 60 μm) on 10 μm of Copper Foils with film applicator.With 50 DEG C of temperature, electrode is solidified, finally the Copper Foil being loaded with nano-silicon active material is positioned in the vacuum drying oven of 120 DEG C and keeps 12h, take 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 material is lain against in outside body of heater, treat that furnace temperature rises to 700 DEG C, the Copper Foil part being loaded with nano-silicon active material is drawn in rapidly in stove.At 700 DEG C, in the environment of nitrogen buffer gas, flow is 2m 3/ h, after heat treatment 30S, pulls out annealing rapidly by the part being loaded with nano-silicon active material Copper Foil, obtains the electrode of modification, be i.e. lithium ion battery silicon materials negative pole.
Adopt embodiment 5 silicon electrode as negative electrode for lithium ion battery, test result is in table 1.
Embodiment 6:
The present embodiment select diameter be ~ high-purity crystal silicon (Wt%=99.9%) material of 100nm and particle diameter be ~ 1 μm of Super P, 3 μm of MCMB and MWCNTs are conductive agent (Super P:MCMB:MWCNTs w/w=60:35:5), the binding agent II that uses embodiment 2 to prepare is as the binder material preparing electrode.
High-purity crystal silicon electrode is prepared according to following steps:
1) by mass percentage, take the silicon class active material of 50%, the material with carbon element conductive agent mixing of 20% is uniformly dispersed;
2) by mass percentage, binding agent II prepared by the embodiment 2 taking 30%, as binding agent powder, is dissolved in appropriate NMP, is uniformly dispersed, stir into vitreosol shape;
3) by step 1) powder that obtains joins step 2) in the colloidal sol shape material that obtains, control solid content 35%, vigorous stirring, forms slurry after stirring;
4) by step 3) in the silicon electrode slurry of gained, be directly coated on (coating thickness is 60 μm) on 10 μm of Copper Foils with film applicator.With 50 DEG C of temperature, electrode is solidified, finally the Copper Foil being loaded with nano-silicon active material is positioned in the vacuum drying oven of 120 DEG C and keeps 12h, take 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 material is lain against in outside body of heater, treat that furnace temperature rises to 300 DEG C, the Copper Foil part being loaded with nano-silicon active material is drawn in rapidly in stove.At 300 DEG C, dry air is in the environment of carrier gas, and flow is 2m 3/ h, after heat treatment 20min, pulls out annealing rapidly by the part being loaded with nano-silicon active material Copper Foil, obtains the electrode of modification, be i.e. lithium ion battery silicon materials negative pole.
Adopt embodiment 6 silicon electrode as negative electrode for lithium ion battery, test result is 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:
Mechanical agitator is being housed, N 2monobutyl itaconate (accounting for 8% of monomer mass) is added successively by different proportion in the 250mL four-hole boiling flask of protective device and thermometer, azo isobutyronitrile (accounting for 0.2% of monomer mass), n-butyl acrylate (accounting for 2% of monomer mass), polyoxyethylene nonylphenol ether 10 (accounting for 0.2% of monomer mass) and acrylonitrile monemer (accounting for 90% of monomer mass) and water (9 times for monomer mass), be heated to 85 DEG C, take out after reaction 24h, washing and filtering repeatedly obtains the polymeric powder that main component is polyacrylonitrile afterwards, as lithium ion battery silicon material 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:
Mechanical agitator is being housed, N 2methyl acrylate (accounting for 8% of monomer mass) is added successively by different proportion in the 250mL four-hole boiling flask of protective device and thermometer, azo isobutyronitrile (accounting for 0.5% of monomer mass), n-butyl acrylate (accounting for 2% of monomer mass), polyoxyethylene nonylphenol ether 10 (accounting for 0.2% of monomer mass) and acrylonitrile monemer (accounting for 90% of monomer mass) and water (9 times for monomer mass), be heated to 85 DEG C, take out after reaction 24h, washing and filtering repeatedly obtains the polymeric powder that main component is polyacrylonitrile afterwards, as lithium ion battery silicon material 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:
Mechanical agitator is being housed, N 2monobutyl itaconate (accounting for 8% of monomer mass) is added successively by different proportion in the 250mL four-hole boiling flask of protective device and thermometer, ammonium persulfate (accounting for 0.5% of monomer mass), n-butyl acrylate (accounting for 2% of monomer mass), polyoxyethylene nonylphenol ether 10 (accounting for 0.2% of monomer mass) and acrylonitrile monemer (accounting for 90% of monomer mass) and water (9 times for monomer mass), be heated to 85 DEG C, take out after reaction 24h, washing and filtering repeatedly obtains the polymeric powder that main component is polyacrylonitrile afterwards, as lithium ion battery silicon material binding agent V, its molecular weight is about 310000.
Embodiment 10:
The present embodiment select diameter be ~ high-purity crystal silicon (Wt%=99.9%) material of 100nm and particle diameter be ~ 1 μm of Super P, 3 μm of MCMB and MWCNTs are conductive agent (Super P:MCMB:MWCNTs w/w=60:35:5), the binding agent III that uses embodiment 7 to prepare is as the binder material preparing electrode.
High-purity crystal silicon electrode is prepared according to following steps:
1) by mass percentage, take the silicon class active material of 50%, the material with carbon element conductive agent mixing of 20% is uniformly dispersed;
2) by mass percentage, binding agent III prepared by the embodiment 7 taking 30%, as binding agent powder, is dissolved in appropriate NMP, is uniformly dispersed, stir into vitreosol shape;
3) by step 1) powder that obtains joins step 2) in the colloidal sol shape material that obtains, control solid content 40%, vigorous stirring, forms slurry after stirring;
4) by step 3) in the silicon electrode slurry of gained, be directly coated on (coating thickness is 60 μm) on 10 μm of Copper Foils with film applicator.With 50 DEG C of temperature, electrode is solidified, finally the Copper Foil being loaded with nano-silicon active material is positioned in the vacuum drying oven of 120 DEG C and keeps 12h, take 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 material is lain against in outside body of heater, treat that furnace temperature rises to 700 DEG C, the Copper Foil part being loaded with nano-silicon active material is drawn in rapidly in stove.At 700 DEG C, in the environment of nitrogen buffer gas, flow is 2m 3/ h, after heat treatment 30s, pulls out annealing rapidly by the part being loaded with nano-silicon active material Copper Foil, obtains the electrode of modification, be i.e. lithium ion battery silicon materials negative pole.
Embodiment 11
Prepare modification high-purity crystal silicon electrode according to the method for embodiment 10, be the binding agent IV that binding agent wherein adopts embodiment 8 to prepare, all the other methods are all identical, obtain the lithium ion battery silicon materials negative pole of modification.
Embodiment 12
Prepare modification high-purity crystal silicon electrode according to the method for embodiment 10, be the binding agent V that binding agent wherein adopts embodiment 9 to prepare, all the other methods are all identical, obtain the lithium ion battery silicon materials negative pole of modification.
Comparative example 1:
The present embodiment select diameter be ~ high-purity crystal silicon (Wt%=99.9%) material of 100nm and particle diameter be ~ the conductive agent mixed powder (carbon black: acetylene black w/w=1:1) of 30nm and MWCNTs account for 2% of carbon black acetylene black mixed powder, and Kynoar (PVDF) (M=150 000) is as the binder material preparing electrode.
High-purity crystal silicon electrode is prepared according to following steps:
1) by mass percentage, take the silicon class active material of 50%, the material with carbon element conductive agent mixing of 20% is uniformly dispersed;
2) by mass percentage, take the Kynoar of 30% as binding agent powder, be dissolved in appropriate NMP, be uniformly dispersed, stir into vitreosol shape;
3) by step 1) powder that obtains joins step 2) in the colloidal sol shape material that obtains, control solid content 40%, vigorous stirring, forms slurry after stirring;
4) by step 3) in the silicon electrode slurry of gained, be directly coated on (coating thickness is 60 μm) on 10 μm of Copper Foils with film applicator.With 50 DEG C of temperature, electrode is solidified, finally the Copper Foil being loaded with nano-silicon active material is positioned in the vacuum drying oven of 80 DEG C and keeps 12h, take 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 material is lain against outside body of heater, treats that furnace temperature rises to 400 DEG C, the Copper Foil part being loaded with nano-silicon active material is drawn in rapidly in stove.N is passed at 400 DEG C 2protection, flow is 0.3m 3/ h, after heat treatment 5min, pulls out annealing rapidly by the part being loaded with nano-silicon active material Copper Foil, obtains the electrode of modification, be i.e. lithium ion battery silicon materials negative pole.
Adopt comparative example 1 silicon electrode as negative electrode for lithium ion battery, test result is in table 1.
Experimental example 1.
This experiment is using the silicon electrode of embodiment of the present invention 3-6,10-12 and comparative example 1 preparation as negative plate, and using metal lithium sheet as to electrode, (composition is: LiPF to adopt Cathay Huarong LB-315 electrolyte 6eC/DMC/EMC=1:1:1 (V/V/V)), Celgard2300 barrier film, 2032 button cells are used to assemble in glove box, and use Wuhan Lan electricity Electronics Co., Ltd. CT2001A cell tester (to adopt the charge and discharge system of constant current charge-discharge to the test that battery carries out battery performance, electric current is set to 100mA/g, and cut-ff voltage is set to 0.01 ~ 1.2V vs Li +/ Li)
Adopt cell tester (CT2001A type, Wuhan Lan electricity Electronics Co., Ltd.) test volumetric properties and the cycle performance of modified battery, the silicon electrode employing modification PAN in embodiment 3-6,10-12 as negative electrode for lithium ion battery, its specific capacity is greater than 800mAh/g, circulate after 100 times, capability retention is greater than 90%, illustrates that modification PAN of the present invention can bring significant performance improvement for the silicon materials negative pole of lithium ion battery.
Table 1: the lithium ion battery of embodiment 3 ~ 6,10-12 and the comparative example 1 electrochemical property test result of silicon materials negative pole

Claims (10)

1. a lithium ion battery silicium cathode binding agent, it is polyacrylonitrile copolymer, it is characterized in that: the polymerization single polymerization monomer of described copolymer also comprises second comonomer and/or Third monomer except acrylonitrile; Described second comonomer is monobutyl itaconate monomer, and described Third monomer is selected from any one or two or more mixtures in itaconic acid, sodium allylsulfonate, acrylamide, amino, pyridine radicals or amide groups monomer, n-butyl acrylate, methyl acrylate.
2. binding agent according to claim 1, is characterized in that: described Third monomer is n-butyl acrylate.
3. binding agent according to claim 1, is characterized in that: in described polymerization single polymerization monomer, and second comonomer and acrylonitrile weight ratio are 1 ~ 10:99 ~ 90, and Third monomer and acrylonitrile weight ratio are 1 ~ 5:99 ~ 95.
4. binding agent according to claim 1, it is characterized in that: described polyacrylonitrile copolymer is that described monomer is obtained by emulsion polymerization, described emulsion polymerization is under inert gas shielding, initator, emulsifying agent, monomer and solvent is added in emulsion polymerization container, the weight ratio of initator and monomer is 1:999 ~ 1:9, solvent adding amount is 1.5 ~ 10 times of monomer mass, and emulsifying agent addition is 0.1% ~ 1% of monomer gross mass; Stir with the rotating speed of 150 ~ 250r/min, control reaction temperature within the scope of 25 ~ 160 DEG C, polymerization time controls between 2 ~ 24h.
5. a method for preparing lithium ion battery silicium cathode binding agent, comprises the following steps:
Under inert gas shielding, initator, emulsifying agent, monomer and solvent is added in emulsion polymerization container, the weight ratio of initator and total monomer is 1 ~ 2:180 ~ 250, and solvent adding amount is 5 ~ 10 times of monomer gross mass, and emulsifying agent addition is 0.1% ~ 1% of monomer gross mass; Stir with the rotating speed of 150 ~ 250r/min, control reaction temperature within the scope of 60 ~ 120 DEG C, polymerization time controls between 2 ~ 24h; Described monomer also comprises second comonomer and/or Third monomer except acrylonitrile; Described second comonomer is monobutyl itaconate, and described Third monomer is selected from any one or two or more mixtures in n-butyl acrylate, methyl acrylate, itaconic acid, sodium allylsulfonate, acrylamide, amino, pyridine radicals or amide groups monomer.
6. method according to claim 5, comprises the following steps:
Under inert gas shielding, initator, emulsifying agent, monomer and solvent is added in emulsion polymerization container, the weight ratio of initator and total monomer is 1:9 ~ 999, and solvent adding amount is 1.5-10 times of monomer gross mass, and emulsifying agent addition is 0.1% ~ 1% of monomer gross mass; Stir with the rotating speed of 150 ~ 250r/min, control reaction temperature within the scope of 25 ~ 160 DEG C, polymerization time controls between 2 ~ 24h; Described monomer also comprises second comonomer and/or Third monomer except acrylonitrile; Described second comonomer is monobutyl itaconate, and described Third monomer is selected from any one or two or more mixtures in n-butyl acrylate, methyl acrylate, itaconic acid, sodium allylsulfonate, acrylamide, amino, pyridine radicals or amide groups monomer.
7. the method described in claim 5 or 6 any one, is characterized in that: described Third monomer is n-butyl acrylate.
8. the method described in claim 5 or 6 any one, is characterized in that: described initator is selected from azo isobutyronitrile, ammonium persulfate or potassium peroxydisulfate.
9. the method described in claim 5 or 6 any one, is characterized in that: described solvent is selected from the one in toluene, ortho-xylene, hexane, n-hexane or water.
10. the method described in claim 5 or 6 any one; Described solvent is toluene or water.
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