CN110423301A - A kind of binder waterborne polymeric and preparation method thereof, aqueous binders and silicon cathode lithium ion battery - Google Patents
A kind of binder waterborne polymeric and preparation method thereof, aqueous binders and silicon cathode lithium ion battery Download PDFInfo
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- CN110423301A CN110423301A CN201910696169.8A CN201910696169A CN110423301A CN 110423301 A CN110423301 A CN 110423301A CN 201910696169 A CN201910696169 A CN 201910696169A CN 110423301 A CN110423301 A CN 110423301A
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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
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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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- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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 present invention relates to a kind of binder waterborne polymeric and preparation method thereof, aqueous binders and silicon cathode lithium ion batteries.The binder is line style with waterborne polymeric, is at room temperature solid-state；The waterborne polymeric is made of tri- kinds of structural unit A, structural unit B, structural unit C structural units；Structural unit A, structural unit B, structural unit C molar ratio be (1~20): (0.1~5): 1.Binder waterborne polymeric provided by the invention has excellent adhesion strength, toughness and mechanical strength, the volume expansion after capable of effectively inhibiting the embedding lithium of silicium cathode material containing hydroxyl isopolarity group.Meanwhile the selection of the above structural unit is also of great advantage to the dispersibility and stability of negative electrode material slurry, a kind of binder high-performance water-based polymer that waterborne polymeric is that caking property is strong, applied widely, performance is stable.
Description
Technical field
The invention belongs to lithium ion battery binder fields, and in particular to a kind of binder waterborne polymeric and its preparation
Method, aqueous binders and silicon cathode lithium ion battery.
Background technique
Currently, traditional negative electrode material in lithium ion battery is graphite-like carbon-based material, including natural graphite, artificial stone
Ink, hard carbon and soft carbon etc., but the embedding lithium capacity of such materials theory is only 372mAh/g, cannot achieve lithium ion secondary electricity of new generation
Requirement of the pond to high-energy density.Compared with graphite-like carbon-based material, the silicon not only rich content in the earth's crust, but also its theory appearance
Amount is to have now been found that highest in negative electrode material, can achieve 4200mAh/g after complete embedding lithium, and being expected to, which becomes substitution graphite, becomes
The negative electrode material of next-generation lithium ion battery.However, during embedding lithium alloyage, can not be kept away when silicon is as negative electrode material
The biggish Volumetric expansion of the generation exempted from (volume deformation is up to 300%).This causes silicon based anode material in battery charge and discharge
In the process of electricity, cathode particle surface rupture, conductive network is also destroyed, and solid electrolyte (SEI) film in interface repeats to give birth to
At eventually leading to coulombic efficiency reduces, and cycle performance is deteriorated or even active material falls off from collector, eventually leads to battery
Failure.In recent years, more and more researches show that, binder, which plays the performance of silicon based anode material, has important shadow
It rings, and the industrial application by realizing silicon cathode lithium ion battery to the optimization of binder, not only improvement is significant,
And it is low in cost.
The common binder of graphite-like carbon based negative electrodes material is styrene-butadiene emulsion (SBR) or styrene-acrylic emulsion, but due to viscous
Agent emulsion is tied to negative electrode material and does not have dispersion performance, needs to add dispersing agent sodium carboxymethylcellulose (CMC).So
In the pole piece of graphite-like carbon based negative electrodes, styrene-butadiene emulsion (SBR) or styrene-acrylic emulsion play between graphite particle, graphite particle and collection
Cementation between fluid, and CMC plays dispersion and suspension effect to graphite slurry.Due to styrene-butadiene emulsion (SBR) or
In the molecular structure of styrene-acrylic emulsion be not present a large amount of polar group, cementation power be only derive from negative electrode material and
Weaker Van der Waals force between collector, therefore adhesion strength is all lower, is not suitable for negative in the silicon with larger volume bulking effect
It is applied in the material of pole.
Authorization Notice No. is that the Chinese invention patent of CN105336960B discloses one kind for lithium ion cell electrode material
The preparation method of the ion polymer type binder waterborne polymeric of material is to carry out hydrophilic monomer, lipophilic monomer
Copolymerization prepares ion polymer type aqueous binders.The caking property of the aqueous binders, to the dispersion energy of electrode material
Power and stabilizing power need to be further increased.
Summary of the invention
The purpose of the present invention is to provide a kind of binder waterborne polymerics, to solve the bonding of existing waterborne polymeric
Property is poor, needs the problem of being further increased to the dispersibility and stabilizing power of electrode material.
Second object of the present invention is to provide a kind of preparation method of binder waterborne polymeric, existing to solve
The bad adhesion of the waterborne polymeric of method preparation, what dispersibility and stabilizing power to electrode material needed to be further increased
Problem.
Third object of the present invention is to provide a kind of aqueous binders, cannot be effective to solve existing aqueous binders
The problem of inhibiting negative electrode volume expansion.
Fourth object of the present invention is to provide a kind of silicon cathode lithium ion battery, to solve existing silicium cathode lithium ion
The problem that the internal resistance of battery is high, cycle performance is to be improved.
To achieve the above object, the technical solution of binder of the invention waterborne polymeric is:
A kind of binder waterborne polymeric, the waterborne polymeric are line style, are at room temperature solid-state；It is described aqueous poly-
Object is closed to be made of tri- kinds of structural unit A, structural unit B, structural unit C structural units；
Structural unit A are as follows:
AndMole accounting in structural unit A
At least 50%；
Structural unit B are as follows:
In any one；
Structural unit C is selected from:
In any one；
Wherein, R1For H or-CH3；M is Li, Na, K or NH4；R2For H, halogen, phenyl, cyano, C1~C18Alkyl, C1~
C18Alkoxy,-COOR3Or-CONHR3；R3For C1~C18 alkyl；
Structural unit A, structural unit B, structural unit C molar ratio be (1~20): (0.1~5): 1.
Binder waterborne polymeric provided by the invention, containing hydroxyl isopolarity group, have excellent adhesion strength,
Toughness and mechanical strength, the volume expansion after the embedding lithium of silicium cathode material can be effectively inhibited.Meanwhile the choosing of the above structural unit
Select also of great advantage to the dispersibility and stability of negative electrode material slurry, which is a kind of caking property with waterborne polymeric
By force, high-performance water-based polymer applied widely, performance is stable.
For the cementitiousness for advanced optimizing waterborne polymeric, improve dispersibility and stability to negative electrode material, preferably
, structural unit A, structural unit B, structural unit C molar ratio be 10:(0.5~3): 1.
Binder technical solution used by the preparation method of waterborne polymeric of the invention is:
A kind of preparation method of binder waterborne polymeric, comprising the following steps:
1) vinyl acetate, hydrophilic monomer, hydrophobic monomer are subjected to radical copolymerization in a solvent, polymerize
Object intermediate；
The hydrophilic monomer is selected from acrylic acid, methacrylic acid, β-propyloic acrylic ester, β-carboxyethyl methylphosphinate propylene
Acid esters, maleic acid, monomethyl maleate, maleic anhydride, itaconic acid, monomethyl itaconate；
The hydrophobic monomer be selected from ethylene, propylene, 1- butylene, vinyl chloride, styrene, α-methylstyrene, acrylonitrile,
Methacrylonitrile, N- caprolactam, C1~C18Alkyl vinyl ether, C1~C18Alkyl acrylate, C1~C18Alkyl
Methacrylate, C1~C18Alkyl acrylamide, C1~C18Alkyl methacrylamides, C1~C18Alkyl maleic acid diester,
C1~C18Alkyl maleimide；
2) by intermediate polymer in a solvent existing for the base catalyst under the conditions of carry out alcoholysis reaction to get.
The preparation method of binder waterborne polymeric provided by the invention is contained by free radical copolymerization preparation
Then the copolymer of different structure unit is reacted by alkali catalyzed alcoholysis, converts the ester group in vinyl acetate structural unit
For hydroxyl, the waterborne polymeric containing carboxylate, hydroxyl and hydrophobic group is finally obtained；The waterborne polymeric has caking property
By force, the volume expansion of cathode can be effectively relieved in feature applied widely, performance is stable, preparation process is simple, improve cell performance
Energy.
Monomer vinyl acetate (VAc) is the precursor monomer of hydroxyl in aqueous binders, and the introducing of hydroxyl can assign viscous
Tie agent adhesion strength with higher and processing performance；Carboxylic acid, acid anhydrides or carboxylate groups are introduced binder by hydrophilic monomer
Macromolecular chain in, generate electrostatic repulsion, thus the dispersion easy to accomplish to negative electrode material；Hydrophobic monomer can be in water
Hydrophobic structure unit is introduced in property binder, hydrophobic structure unit can be used as anchoring group and fit to silicium cathode material
Grain surface makes to generate volume excluding effect between particle, so that assigning negative electrode material slurry has preferable dispersion and stability.
From the aspect of the industrialization cost of combined polymerization, it is preferred that in step 1), cause used in radical copolymerization
Agent is azo and/or peroxide, and the dosage of initiator is that vinyl acetate, hydrophilic monomer, hydrophobic monomer weight are total
The 0.1-2% of sum；The temperature of copolymerization is 25-100 DEG C, polymerization reaction time 2-24h.
Further to promote reacting balance to carry out, the consistency of reaction product is improved, it is preferred that in step 1), initiator
Dosage be vinyl acetate, hydrophilic monomer, hydrophobic monomer weight summation 0.5-1%；The temperature of copolymerization is
35-80 DEG C, polymerization reaction time 4-12h.
For the industrializing implementation for simplifying alcoholysis reaction, industrialization cost is reduced, it is preferred that in step 2), the base catalysis
Agent is sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide
One of or multiple combinations, the mole of catalyst be to be tied in the mole and intermediate polymer of carboxyl in hydrophilic monomer
The summation of the mole 0.5-20% of structure unit A.
To carry out alcoholysis reaction steadily, orderly, it is preferred that in step 2), the temperature of alcoholysis reaction is 25-100 DEG C, when
Between be 1-24h.
Technical solution used by aqueous binders of the invention is:
A kind of aqueous binders, including water and binder waterborne polymeric, binder are line style, In with waterborne polymeric
It is at room temperature solid-state；The waterborne polymeric is made of tri- kinds of structural unit A, structural unit B, structural unit C structural units；
Structural unit A are as follows:
AndMole accounting in structural unit A
At least 50%；
Structural unit B are as follows:
In any one；
Structural unit C is selected from:
In any one；
Wherein, R1For H or-CH3；M is Li, Na, K or NH4；R2For H, halogen, phenyl, cyano, C1~C18Alkyl, C1~
C18Alkoxy,-COOR3Or-CONHR3；R3For C1~C18 alkyl；
Structural unit A, structural unit B, structural unit C molar ratio be (1~20): (0.1~5): 1.
Aqueous binders provided by the invention have good water-soluble and adhesive property, can easily be applied to battery
In the preparation process of cathode, the comprehensive performances such as bonds well, the dispersion for promoting negative electrode material and suspension are played, are glued with excellent
Knotting strength, toughness and mechanical strength, the volume expansion after the embedding lithium of silicium cathode material can be effectively inhibited.In use not
The dispersing agents such as CMC must separately be added, simplify negative electrode slurry system, avoid dispersion. formulation to the bad shadow of battery performance
It rings.
For the cementitiousness for advanced optimizing waterborne polymeric, improve dispersibility and stability to negative electrode material, preferably
, structural unit A, structural unit B, structural unit C molar ratio be 10:(0.5~3): 1.
For convenience of the application of binder, it is preferred that in aqueous binders, the mass content of waterborne polymeric is 1-70%.
To further increase binder application effect in cell size preparation process, it is preferred that in aqueous binders also
It is not more than 2% auxiliary agent including mass concentration.Further to improve levelability and defoaming effect, it is preferred that the auxiliary agent includes
Levelling agent and defoaming agent.
Technical solution used by silicon cathode lithium ion battery of the invention is:
A kind of silicon cathode lithium ion battery, including anode, silicium cathode, electrolyte and diaphragm, silicium cathode include collector and
Negative electrode active material layer on a current collector is set, and negative electrode active material layer includes negative electrode active material, conductive agent and aqueous poly-
Close object；The negative electrode active material includes silicon materials and graphite；The waterborne polymeric is line style, is at room temperature solid-state；Institute
Waterborne polymeric is stated to be made of tri- kinds of structural unit A, structural unit B, structural unit C structural units；
Structural unit A are as follows:
AndMole accounting in structural unit A
At least 50%；
Structural unit B are as follows:
In any one；
Structural unit C is selected from:
In any one；
Wherein, R1For H or-CH3；M is Li, Na, K or NH4；R2For H, halogen, phenyl, cyano, C1~C18Alkyl, C1~
C18Alkoxy,-COOR3Or-CONHR3；R3For C1~C18 alkyl；
Structural unit A, structural unit B, structural unit C molar ratio be (1~20): (0.1~5): 1.
Silicon cathode lithium ion battery provided by the invention, used aqueous binders have excellent adhesion strength, tough
Property and mechanical strength, the dispersibility and stability to negative electrode material are good, can effectively improve the performance of silicon cathode lithium ion battery；
Using the silicon cathode lithium ion battery of the binder, have internal resistance low, the characteristics of cycle performance and good rate capability.
For the cementitiousness for advanced optimizing waterborne polymeric, improve dispersibility and stability to negative electrode material, preferably
, structural unit A, structural unit B, structural unit C molar ratio be 10:(0.5~3): 1.
Specific embodiment
The present invention provides a kind of alternative existing negative electrode binders (such as styrene-butadiene emulsion, styrene-acrylic emulsion, polyacrylic acid)
Waterborne polymeric not only show water solubility its main feature is that the quantity of carboxyl, hydroxyl, amide isopolarity group occupies leading
Characteristic, but also have the characteristics that adhesion strength, toughness and mechanical strength are excellent.
Above-mentioned waterborne polymeric mainly passes through the radical copolymerization of vinyl acetate, hydrophilic monomer, hydrophobic monomer
It is prepared with alkali catalyzed alcoholysis.
Structural unit A, structural unit B, in structural unit C,Show the structural unit and adjacent structure list
The link position of first (or terminal groups), and refer not to any group.
Structural unit A is vinyl acetate structural unit,A mole accounting in structural unit A represents
Alcoholysis degree situation, alcoholysis degree can have the hydroxyl for accounting for quantity big absolutely 50% or more, and the higher the better for alcoholysis degree, preferably alcoholysis degree
Alcoholysis reaction is carried out 80% or more, or by target of complete alcoholysis.
Structural unit B is hydrophilic structure unit.The end group of hydrophilic structure unit is carboxylic acid, carboxylate etc., is preferably held
Base is carboxylic acid sodium, to assign the preferable slurry dispersibility of binder, adhesive force and processing performance, and then can provide respective negative
The cycle performance of piece.
Structural unit C is hydrophobic structure unit.Hydrophobic structure unit be weak or non-polar group, including H, halogen,
Phenyl, cyano, C1~C18Alkyl, C1~C18Alkoxy,-COOR3Or-CONHR3；R3For C1~C18 alkyl；It is preferred that
For H, halogen, phenyl, cyano, C1~C4Alkyl, C1~C12Alkoxy ,-COOR3Or-CONHR3；R3For C1~C12Alkyl.
Radical copolymerization is generated free radicals under initiator or other conditions with monomer of the difference containing carbon-carbon double bond
Initiated polymerization.
Hydrophilic monomer includes acrylic acid, methacrylic acid, β-propyloic acrylic ester, β-carboxyethyl methylphosphinate acrylic acid
Ester, maleic acid, monomethyl maleate, maleic anhydride, itaconic acid or monomethyl itaconate.
Hydrophobic monomer includes ethylene, propylene, 1- butylene, vinyl chloride, styrene, α-methylstyrene, acrylonitrile, methyl
Acrylonitrile, C1~C18Alkyl vinyl ether, C1~C18Alkyl acrylate, C1~C18Alkylmethacrylate, C1~C18Alkane
Base acrylamide, C1~C18Alkyl methacrylamides, C1~C18Alkyl maleic acid diester, C1~C18Alkyl maleimide.
Optimal ethylene, propylene, vinyl chloride, methoxy ethylene, dimethyl maleate.
Azo-compound, per-compound, preferably azodiisobutyronitrile may be selected in the initiator of radical copolymerization
(AIBN), azobisisoheptonitrile (AIVN) and benzoyl peroxide (BPO).Also light-initiated and gamma Rays etc., light may be selected
Arone compounds, Benzoin derivative, acyl group phosphoric-oxygenic compound etc. may be selected in the initiator of initiation.
The solvent of radical copolymerization include methanol, ethyl alcohol, propyl alcohol, n-butanol, ethylene glycol, ethyl acetate, butyl acetate,
Methyl acetate, acetonitrile, tetrahydrofuran, methylene chloride, acetone, 1,1- dichloroethanes, chloroform, butanone, benzene, toluene, chlorobenzene, second two
One of alcohol monomethyl ether, DMAC N,N' dimethyl acetamide, N- methyl pyrrole network alkanone, dimethyl sulfoxide, sulfolane, succinonitrile are more
Kind, preferably methanol, ethyl alcohol, ethyl acetate, tetrahydrofuran.
Sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, sodium methoxide, first may be selected in the base catalyst of alkaline alcoholysis reaction
The basic salts such as potassium alcoholate, lithium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide.It is preferred that sodium hydroxide, potassium hydroxide, lithium hydroxide, methanol
Sodium, lithium methoxide.
Alkali catalyzed alcoholysis reaction temperature be 25~100 DEG C, preferably 25~60 DEG C, the reaction time be 1~24 hour, preferably 1
~6 hours.The mole of base catalyst is the 0.5-20% and hydrophily list of the mole of structural unit A in intermediate polymer
The summation of the mole of carboxyl in body；The 1-10% of the mole of structural unit A and hydrophilic more preferably in intermediate polymer
The summation of the mole of carboxyl in property monomer.
Above-mentioned waterborne polymeric is dissolved in water, be added further according to actual conditions or is added without auxiliary agent, can prepare to obtain water
Property binder.
Above-mentioned aqueous binders are particularly suitable for silicon cathode lithium ion battery, and it is embedding can to effectively inhibit silicium cathode material
Volume expansion after lithium reduces the internal resistance of cell, improves cycle performance.
Silicon cathode lithium ion battery includes anode, silicium cathode, electrolyte and diaphragm, and silicium cathode includes that collector and setting exist
Negative electrode active material layer on collector, negative electrode active material layer include negative electrode active material, conductive agent and above-mentioned polymerizable aqueous
Object；The negative electrode active material includes silicon materials and graphite.It (is such as followed since the battery performance performance of single silicon materials electrode is poor
Ring, multiplying power etc.), it can only be used as added material, primarily serve the effect for improving battery energy density.Graphite remains main negative
Pole material plays the role of improving battery performance and and reduces cost；Preferably, the mass ratio of silicon materials and graphite be 1:5~
10.The silicon materials are silicon or the sub- silicon of oxidation.The part of not addressing of the above battery can refer to the prior art.
Embodiments of the present invention are described further combined with specific embodiments below.
One, the specific embodiment of the preparation method of binder waterborne polymeric of the invention is as follows:
Embodiment 1
The preparation method of the binder waterborne polymeric of the present embodiment, comprising the following steps:
1) in the high pressure resistant polymerization reaction kettle of 300mL, be added 50g vinyl acetate (VAc), 50g anhydrous methanol and
0.72g azodiisobutyronitrile (AIBN) is stirred with 200 revs/min of speed and is warming up to 70 DEG C.Oxygen is emptied by high pure nitrogen
After 1 hour, gradually 20g hydrophobic monomer ethylene and 2.1g hydrophilic monomer acrylic acid is added in (being continuously added to), has been added within 4 hours
Finish.
With the progress of polymerization reaction, system viscosity is become larger, fast when continuation polymerization reaction 5 is small after monomer finishes
Prompt drop low temperature stops polymerization reaction to room temperature.After emptying unreacted residual gas monomer, it is warming up to 60 DEG C and is evaporated under reduced pressure out
Residual monomer and solvent add 50mL methanol, and vacuum distillation is repeated 3 times, and drying obtains intermediate polymer 27g.Chemistry knot
Structure measuring and calculation shows in intermediate polymer that the molar ratio of vinyl acetate, ethylene and acrylic acid structure unit is 10:2:
1.What vinyl acetate structural unit, that is, vinyl acetate monomer was formed after polymerisation is present in intermediate polymer strand
Corresponding construction unit, ethylene unit unit, the meaning of acrylic acid structure unit are similar.
2) intermediate polymer 27g and 250g anhydrous methanol is added in 500mL reaction kettle, with 200 revs/min of speed
It stirs and is warming up to 40 DEG C, heat preservation is completely dissolved for 2 hours, obtains mixed liquor.Then by 2.35g sodium hydroxide (10% second
The mole of vinyl acetate structural unit and acrylic acid structure unit and) be dissolved in 20g anhydrous methanol, to prevent local reaction from putting
Heat is excessively violent, and the methanol solution of NaOH is gradually added dropwise in mixed liquor, and 30min is added dropwise, with the methanol of sodium hydroxide
The dropwise addition of solution, solution gradually become sticky atherosclerotic, are vigorously stirred and smash colloid, continue insulation reaction 5 hours, obtain white
Sediment.Low-boiling products and solvent are evaporated under reduced pressure out, drying obtains the product (i.e. waterborne polymeric) close to complete alcoholysis
16g。
Embodiment 2
The preparation method of the binder waterborne polymeric of the present embodiment, the preparation method with binder waterborne polymeric
The difference of embodiment 1 is: in step 1), the dosage of AIBN is 0.92g；It is gradually added 40g hydrophobic monomer propylene；Drying obtains
Obtain copolymer intermediate 30g；Chemical structure test calculation shows that, in intermediate polymer, vinyl acetate, propylene and acrylic acid
The molar ratio of corresponding construction unit is 10:2:1.
Embodiment 3
The preparation method of the binder waterborne polymeric of the present embodiment, the preparation method with binder waterborne polymeric
The difference of embodiment 1 is: in step 1), the dosage of AIBN is 1.02g；It is gradually added 50g hydrophobic monomer vinyl chloride；Drying
Obtain intermediate polymer 30g；Chemical structure test calculation shows that, in intermediate polymer, vinyl acetate, vinyl chloride and third
The molar ratio of olefin(e) acid structural unit is 10:2:1.
Embodiment 4
The preparation method of the binder waterborne polymeric of the present embodiment, the preparation method with binder waterborne polymeric
The difference of embodiment 1 is: in step 1), the dosage of AIBN is 0.56g；It is gradually added 3.38g hydrophobic monomer vinyl first
Ether；Drying obtains intermediate polymer 30g；Chemical structure test calculation shows that, in intermediate polymer, vinyl acetate, second
The molar ratio of alkenyl methyl ether and acrylic acid structure unit is 10:2:1.
Embodiment 5
The preparation method of the binder waterborne polymeric of the present embodiment, the preparation method with binder waterborne polymeric
The difference of embodiment 1 is: in step 1), the dosage of AIBN is 0.60g；It is gradually added 8.38g hydrophobic monomer maleic acid two
Methyl esters；Drying obtains intermediate polymer 35g；Chemical structure test calculation shows that, in intermediate polymer, vinyl acetate,
The molar ratio of dimethyl maleate and acrylic acid structure unit is 10:2:1.
Embodiment 6
The preparation method of the binder waterborne polymeric of the present embodiment, the preparation method with binder waterborne polymeric
The difference of embodiment 1 is: in step 1), the dosage of AIBN is 0.55g；It is gradually added 20g hydrophobic monomer ethylene and 4.2g
Hydrophilic monomer β-propyloic acrylic ester；Drying obtains intermediate polymer 30g；Chemical structure test calculation shows that, polymerization
In object intermediate, vinyl acetate, ethylene and β-propyloic acrylic ester structural unit molar ratio are 10:2:1.
Embodiment 7
The preparation method of the binder waterborne polymeric of the present embodiment, the preparation method with binder waterborne polymeric
The difference of embodiment 1 is: in step 1), the dosage of AIBN is 0.94g；It is gradually added 40g hydrophobic monomer propylene and 4.2g
Hydrophilic monomer β-propyloic acrylic ester；Drying obtains intermediate polymer 31g；Chemical structure test calculation shows that, polymerization
In object intermediate, vinyl acetate, propylene and β-propyloic acrylic ester structural unit molar ratio are 10:2:1.
Embodiment 8
The preparation method of the binder waterborne polymeric of the present embodiment, the preparation method with binder waterborne polymeric
The difference of embodiment 1 is: in step 1), the dosage of AIBN is 1.04g；Be gradually added 50g hydrophobic monomer vinyl chloride and
4.2g hydrophilic monomer β-propyloic acrylic ester；Drying obtains intermediate polymer 32g；Chemical structure test calculation shows that,
In intermediate polymer, vinyl acetate, vinyl chloride and β-propyloic acrylic ester structural unit molar ratio are 10:2:1.
Embodiment 9
The preparation method of the binder waterborne polymeric of the present embodiment, the preparation method with binder waterborne polymeric
The difference of embodiment 1 is: in step 1), the dosage of AIBN is 0.57g；It is gradually added 3.38g hydrophobic monomer vinyl first
Ether and 4.2g hydrophilic monomer β-propyloic acrylic ester；Drying obtains intermediate polymer 32g；Chemical structure test computational chart
Bright, in intermediate polymer, vinyl acetate, methoxy ethylene and β-propyloic acrylic ester structural unit molar ratio are
10:2:1。
Embodiment 10
The preparation method of the binder waterborne polymeric of the present embodiment, the preparation method with binder waterborne polymeric
The difference of embodiment 1 is: in step 1), the dosage of AIBN is 0.62g；It is gradually added 8.38g hydrophobic monomer maleic acid two
Methyl esters and 4.2g hydrophilic monomer β-propyloic acrylic ester；Drying obtains intermediate polymer 37g；Chemical structure test calculates
Show in intermediate polymer, vinyl acetate, dimethyl maleate and β-propyloic acrylic ester structural unit molar ratio
For 10:2:1.
Embodiment 11
The preparation method of the binder waterborne polymeric of the present embodiment, the preparation method with binder waterborne polymeric
The difference of embodiment 1 is: in step 1), the dosage of AIBN is 0.73g；It is gradually added 20g hydrophobic monomer ethylene and 3.37g
Hydrophilic monomer maleic acid；Drying obtains intermediate polymer 30g；Chemical structure test calculation shows that, in intermediate polymer,
The molar ratio of vinyl acetate, ethylene and maleic acid structural unit is 10:2:1.
Embodiment 12
The preparation method of the binder waterborne polymeric of the present embodiment, the preparation method with binder waterborne polymeric
The difference of embodiment 1 is: in step 1), the dosage of AIBN is 0.93g；It is gradually added 40g hydrophobic monomer propylene and 3.37g
Hydrophilic monomer maleic acid；Drying obtains intermediate polymer 30g；Chemical structure test calculation shows that, in intermediate polymer,
The molar ratio of vinyl acetate, propylene and maleic acid structural unit is 10:2:1.
Embodiment 13
The preparation method of the binder waterborne polymeric of the present embodiment, the preparation method with binder waterborne polymeric
The difference of embodiment 1 is: in step 1), the dosage of AIBN is 1.03g；Be gradually added 50g hydrophobic monomer vinyl chloride and
3.37g hydrophilic monomer maleic acid；Drying obtains intermediate polymer 32g；Chemical structure test calculation shows that, among polymer
In body, the molar ratio of vinyl acetate, vinyl chloride and maleic acid structural unit is 10:2:1.
Embodiment 14
The preparation method of the binder waterborne polymeric of the present embodiment, the preparation method with binder waterborne polymeric
The difference of embodiment 1 is: in step 1), the dosage of AIBN is 0.56g；It is gradually added 3.38g hydrophobic monomer vinyl first
Ether and 3.37g hydrophilic monomer maleic acid；Drying obtains intermediate polymer 31g；Chemical structure test calculation shows that, polymer
In intermediate, the molar ratio of vinyl acetate, methoxy ethylene and maleic acid structural unit is 10:2:1.
Embodiment 15
The preparation method of the binder waterborne polymeric of the present embodiment, the preparation method with binder waterborne polymeric
The difference of embodiment 1 is: in step 1), the dosage of AIBN is 0.61g；It is gradually added 8.38g hydrophobic monomer maleic acid two
Methyl esters and 3.37g hydrophilic monomer maleic acid；Drying obtains intermediate polymer 36g；Chemical structure test calculation shows that, polymerization
In object intermediate, the molar ratio of vinyl acetate, dimethyl maleate and maleic acid structural unit is 10:2:1.
Embodiment 16
The preparation method of the binder waterborne polymeric of the present embodiment, the preparation method with binder waterborne polymeric
The difference of embodiment 1 is: in step 1), the dosage of AIBN is 0.72g；It is gradually added 20g hydrophobic monomer ethylene and 2.85g
Hydrophilic monomer maleic anhydride；Drying obtains intermediate polymer 29g；Chemical structure test calculation shows that, intermediate polymer
In, the molar ratio of vinyl acetate, ethylene and maleic anhydride structural unit is 10:2:1.
Embodiment 17
The preparation method of the binder waterborne polymeric of the present embodiment, the preparation method with binder waterborne polymeric
The difference of embodiment 1 is: in step 1), the dosage of AIBN is 0.92g；It is gradually added 40g hydrophobic monomer propylene and 2.85g
Hydrophilic monomer maleic anhydride；Drying obtains intermediate polymer 30g；Chemical structure test calculation shows that, intermediate polymer
In, the molar ratio of vinyl acetate, propylene and maleic anhydride structural unit is 10:2:1.
Embodiment 18
The preparation method of the binder waterborne polymeric of the present embodiment, the preparation method with binder waterborne polymeric
The difference of embodiment 1 is: in step 1), the dosage of AIBN is 1.02g；Be gradually added 50g hydrophobic monomer vinyl chloride and
2.85g hydrophilic monomer maleic anhydride；Drying obtains intermediate polymer 31g；Chemical structure test calculation shows that, in polymer
In mesosome, the molar ratio of vinyl acetate, vinyl chloride and maleic anhydride structural unit is 10:2:1.
Embodiment 19
The preparation method of the binder waterborne polymeric of the present embodiment, the preparation method with binder waterborne polymeric
The difference of embodiment 1 is: the dosage of AIBN is 0.55g in step 1)；It is gradually added 3.38g hydrophobic monomer methoxy ethylene
With 2.85g hydrophilic monomer maleic anhydride；Drying obtains intermediate polymer 31g；Chemical structure test calculation shows that, polymer
In intermediate, the molar ratio of vinyl acetate, methoxy ethylene and maleic anhydride structural unit is 10:2:1.
Embodiment 20
The preparation method of the binder waterborne polymeric of the present embodiment, the preparation method with binder waterborne polymeric
The difference of embodiment 1 is: in step 1), the dosage of AIBN is 0.61g；It is gradually added 8.38g hydrophobic monomer maleic acid two
Methyl esters and 2.85g hydrophilic monomer maleic anhydride；Drying obtains intermediate polymer 36g；Chemical structure test calculation shows that, gather
It closes in object intermediate, the molar ratio of vinyl acetate, dimethyl maleate and maleic anhydride structural unit is 10:2:1.
Embodiment 21
The preparation method of the binder waterborne polymeric of the present embodiment, the preparation method with binder waterborne polymeric
The difference of embodiment 1 is: in step 1), the dosage of AIBN is 0.77g；It is gradually added 20g hydrophobic monomer ethylene and 7.77g
Hydrophilic monomer itaconic acid；Drying obtains intermediate polymer 36g；Chemical structure test calculation shows that, in intermediate polymer,
The molar ratio of vinyl acetate, ethylene and itaconic acid structural unit is 10:2:1.
Embodiment 22
The preparation method of the binder waterborne polymeric of the present embodiment, the preparation method with binder waterborne polymeric
The difference of embodiment 1 is: in step 1), the dosage of AIBN is 0.97g；It is gradually added 40g hydrophobic monomer propylene and 7.77g
Hydrophilic monomer itaconic acid；Drying obtains intermediate polymer 31g；Chemical structure test calculation shows that, in intermediate polymer,
The molar ratio of vinyl acetate, propylene and itaconic acid structural unit is 10:2:1.
Embodiment 23
The preparation method of the binder waterborne polymeric of the present embodiment, the preparation method with binder waterborne polymeric
The difference of embodiment 1 is: in step 1), the dosage of AIBN is 1.07g；Be gradually added 50g hydrophobic monomer vinyl chloride and
7.77g hydrophilic monomer itaconic acid；Drying obtains intermediate polymer 32g；Chemical structure test calculation shows that, among polymer
In body, the molar ratio of vinyl acetate, vinyl chloride and itaconic acid structural unit is 10:2:1.
Embodiment 24
The preparation method of the binder waterborne polymeric of the present embodiment, the preparation method with binder waterborne polymeric
The difference of embodiment 1 is: in step 1), the dosage of AIBN is 0.60g；It is gradually added 3.38g hydrophobic monomer vinyl first
Ether and 7.77g hydrophilic monomer itaconic acid；Drying obtains intermediate polymer 32g；Chemical structure test calculation shows that, polymer
In intermediate, the molar ratio of vinyl acetate, methoxy ethylene and itaconic acid structural unit is 10:2:1.
Embodiment 25
The preparation method of the binder waterborne polymeric of the present embodiment, the preparation method with binder waterborne polymeric
The difference of embodiment 1 is: in step 1), the dosage of AIBN is 0.65g；It is gradually added 8.38g hydrophobic monomer maleic acid two
Methyl esters and 7.77g hydrophilic monomer itaconic acid；Drying obtains intermediate polymer 32g；Chemical structure test calculation shows that, polymerization
In object intermediate, the molar ratio of vinyl acetate, dimethyl maleate and itaconic acid structural unit is 10:2:1.
Two, the specific embodiment of binder waterborne polymeric of the invention is as follows:
Embodiment 26-50
The binder waterborne polymeric of embodiment 26-50, respectively corresponds the final product of embodiment 1-25, wherein knot
The difference of structure unit A, structural unit B, structural unit C are listed in Table 1 below.
The binder waterborne polymeric of 1 embodiment of table
Three, the specific embodiment of aqueous binders of the invention is as follows:
Embodiment 51
The waterborne polymeric of embodiment 26 is dissolved in water by the aqueous binders of the present embodiment, is configured to quality solid content and is
10% aqueous binders.
Embodiment 52-75
The waterborne polymeric of embodiment 27-50 is dissolved in water respectively, is configured to matter by the aqueous binders of embodiment 52-75
Measure the aqueous binders that solid content is 10%.
In the embodiment of other aqueous binders, it should be noted that alcoholysis product obtained by step 2) is (i.e. aforementioned aqueous
Polymer) it is graininess, with excellent water solubility.When dissolving alcoholysis product with water, water can be adjusted as needed
Dosage, in embodiments above, solid content 10% can be adjusted flexibly between 1-70%, is generally advisable with 5-15%.
The auxiliary agents such as levelling agent, defoaming agent can also further be added, improve the application effect of aqueous binders, the additive amount of auxiliary agent is with little
It is advisable in 2%.
Four, the specific embodiment of silicon cathode lithium ion battery of the invention is as follows:
Embodiment 76
The silicon cathode lithium ion battery of the present embodiment, is prepared using following methods:
1) by 0.095 mass parts aoxidize sub- silicon active material (partial size between 5-10 μm, Bei Terui new energy materials share
Co., Ltd production), 0.855 mass parts graphite (average grain diameter be 10 μm, Jiangxi Zi Chen Science and Technology Ltd. production) (mass ratio
SiO:C=1:9), (parts by weight are with solid after drying for the aqueous binders of the conductive agent (SP) of 0.02 parts by weight and 0.03 parts by weight
Body content meter uses the product of embodiment 51) mixing, high speed grinding synthetic slurry is carried out, adjusts solid content after 50%, uniformly
It is coated on copper foil, after drying compacting, obtains cathode pole piece；
2) gained cathode pole piece is carried out to vacuum drying 24 hours at 100 ± 5 DEG C, is subsequently placed in the hand of dry argon atmospher
In casing, using metal lithium sheet as to electrode assembling button cell；Diaphragm is Cellgard-2400, and electrolyte is 1.2M's
LiPF6/ ethylene carbonate (EC)+fluorinated ethylene carbonate (FEC)+diethyl carbonate (DEC), volume ratio EC:FEC:DEC=
45:10:45。
Embodiment 77-100
The silicon cathode lithium ion battery of embodiment 77-100 uses the product of aqueous binders embodiment 52-75, ginseng respectively
The method for examining embodiment 76 prepares the battery of same size.
Embodiment 101-125
The silicon cathode lithium ion battery of embodiment 101-125 uses the product of aqueous binders embodiment 51-75 respectively,
And with the oxidation Asia silicon active matter in silicon (Si:5-10um, Bei Terui new energy materials limited liability company) alternative embodiment 76
The method of matter, other and embodiment 76 is consistent.
In the other embodiments of silicon cathode lithium ion battery of the invention, metal lithium sheet is replaced with into positive-active respectively
Substance is LiFePO4Positive plate, positive active material be NCM (Ni, Co, Mn) ternary material positive plate, positive electrode active material
Matter is the positive plate of NCA (Ni, Co, Al) ternary material, and corresponding silicon cathode lithium ion battery can be obtained.
Five, the explanation of comparative example
Comparative example 1-4
The silicon cathode lithium ion battery of comparative example 1-4, the difference with embodiment 76 are only that, aqueous binders are replaced respectively
It is changed to and is answered by sodium carboxymethylcellulose (CMC-Na) and butadiene-styrene rubber (SBR) according to what the ratio that mass ratio is 1:1 was mixed to get
Close binder, CMC-Na, sodium alginate (SA), polyacrylic acid (PAA).
Comparative example 5-8
The silicon cathode lithium ion battery of comparative example 5-8, the difference with embodiment 101 is only that, aqueous binders are distinguished
It replaces with and is mixed to get according to the ratio that mass ratio is 1:1 by sodium carboxymethylcellulose (CMC-Na) and butadiene-styrene rubber (SBR)
Compound binding agent, CMC-Na, sodium alginate (SA), polyacrylic acid (PAA).
Six, experimental example
It is A1-A25 by the silicon cathode lithium ion battery number consecutively in embodiment 76-100, it will be in embodiment 101-125
Silicon cathode lithium ion battery number consecutively be B1-B25, by the silicon cathode lithium ion battery number consecutively of comparative example 1-8 be C1-
Silicon cathode lithium ion battery after above-mentioned number is carried out cyclic test, cut-off electricity at 25 DEG C with 0.1C charge-discharge magnification by C8
Pressure is 0.005-1.5V (vs Li+/ Li), charge and discharge 3 circulation after test its electrochemical impedance R and gram volume, test result is shown in
Shown in table 2 and table 3.
The performance test results of the silicon cathode lithium ion battery of table 2 embodiment 76-100 and comparative example 1-4
The performance test results of the silicon cathode lithium ion battery of table 3 embodiment 101-125 and comparative example 4-8
By the result of table 2 and table 3 it is found that because of aqueous binders of the invention in cohesive force, to the dispersibility of negative electrode material
Improved comprehensively with stability etc., corresponding silicon cathode lithium ion battery shows the spy that internal resistance is low, has extended cycle life
Point.
Claims (10)
1. a kind of binder waterborne polymeric, which is characterized in that the waterborne polymeric is line style, is at room temperature solid-state；
The waterborne polymeric is made of tri- kinds of structural unit A, structural unit B, structural unit C structural units；
Structural unit A are as follows:
AndMole accounting in structural unit A is at least
It is 50%；
Structural unit B are as follows:
In any one；
Structural unit C is selected from:
In any one；
Wherein, R1For H or-CH3；M is Li, Na, K or NH4；R2For H, halogen, phenyl, cyano, C1~C18Alkyl, C1~C18Alcoxyl
Base,-COOR3Or-CONHR3；R3For C1~C18 alkyl；
Structural unit A, structural unit B, structural unit C molar ratio be (1~20): (0.1~5): 1.
2. binder waterborne polymeric as described in claim 1, which is characterized in that structural unit A, structural unit B, structure
The molar ratio of unit C is 10:(0.5~3): 1.
3. a kind of preparation method of binder waterborne polymeric as described in claim 1, which is characterized in that including following step
It is rapid:
1) vinyl acetate, hydrophilic monomer, hydrophobic monomer are subjected to radical copolymerization in a solvent, obtained in polymer
Mesosome；
The hydrophilic monomer is selected from acrylic acid, methacrylic acid, β-propyloic acrylic ester, β-carboxyethyl methylphosphinate acrylic acid
Ester, maleic acid, monomethyl maleate, maleic anhydride, itaconic acid, monomethyl itaconate；
The hydrophobic monomer is selected from ethylene, propylene, 1- butylene, vinyl chloride, styrene, α-methylstyrene, acrylonitrile, methyl
Acrylonitrile, N- caprolactam, C1~C18Alkyl vinyl ether, C1~C18Alkyl acrylate, C1~C18Alkyl methyl
Acrylate, C1~C18Alkyl acrylamide, C1~C18Alkyl methacrylamides, C1~C18Alkyl maleic acid diester, C1~
C18Alkyl maleimide；
2) by intermediate polymer in a solvent existing for the base catalyst under the conditions of carry out alcoholysis reaction to get.
4. the preparation method of binder waterborne polymeric as claimed in claim 3, which is characterized in that in step 1), freely
Initiator used in base combined polymerization is azo and/or peroxide, and the dosage of initiator is vinyl acetate, hydrophily list
The 0.1-2% of body, hydrophobic monomer weight summation；The temperature of copolymerization is 25-100 DEG C, polymerization reaction time 2-
24h。
5. the preparation method of binder waterborne polymeric as claimed in claim 4, which is characterized in that in step 1), cause
The dosage of agent be vinyl acetate, hydrophilic monomer, hydrophobic monomer weight summation 0.5-1%；The temperature of copolymerization
It is 35-80 DEG C, polymerization reaction time 4-12h.
6. the preparation method of the binder waterborne polymeric as described in any one of claim 3-5, which is characterized in that step
2) in, the base catalyst is sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, sodium methoxide, potassium methoxide, lithium methoxide, ethyl alcohol
One of sodium, potassium ethoxide, lithium ethoxide or multiple combinations, the mole of base catalyst are the mole of carboxyl in hydrophilic monomer
With the summation of the mole 0.5-20% of structural unit A in intermediate polymer；The temperature of alcoholysis reaction is 25-100 DEG C, the time
For 1-24h.
7. a kind of aqueous binders, which is characterized in that including water and binder waterborne polymeric, binder waterborne polymeric
It is at room temperature solid-state for line style；The waterborne polymeric is by tri- kinds of structural unit A, structural unit B, structural unit C structure lists
Member is constituted；
Structural unit A are as follows:
AndMole accounting in structural unit A is at least
It is 50%；
Structural unit B are as follows:
In any one；
Structural unit C is selected from:
In any one；
Wherein, R1For H or-CH3；M is Li, Na, K or NH4；R2For H, halogen, phenyl, cyano, C1~C18Alkyl, C1~C18Alcoxyl
Base,-COOR3Or-CONHR3；R3For C1~C18 alkyl；
Structural unit A, structural unit B, structural unit C molar ratio be (1~20): (0.1~5): 1.
8. aqueous binders as claimed in claim 7, which is characterized in that structural unit A, structural unit B, structural unit C
Molar ratio is 10:(0.5~3): 1.
9. a kind of silicon cathode lithium ion battery, which is characterized in that including anode, silicium cathode, electrolyte and diaphragm, silicium cathode includes
The negative electrode active material layer of collector and setting on a current collector, negative electrode active material layer includes negative electrode active material, conductive agent
And waterborne polymeric；The negative electrode active material includes silicon materials and graphite；The waterborne polymeric be line style, at room temperature for
Solid-state；The waterborne polymeric is made of tri- kinds of structural unit A, structural unit B, structural unit C structural units；
Structural unit A are as follows:
AndMole accounting in structural unit A is at least
It is 50%；
Structural unit B are as follows:
In any one；
Structural unit C is selected from:
In any one；
Wherein, R1For H or-CH3；M is Li, Na, K or NH4；R2For H, halogen, phenyl, cyano, C1~C18Alkyl, C1~C18Alcoxyl
Base,-COOR3Or-CONHR3；R3For C1~C18 alkyl；
Structural unit A, structural unit B, structural unit C molar ratio be (1~20): (0.1~5): 1.
10. silicon cathode lithium ion battery as claimed in claim 9, which is characterized in that structural unit A, structural unit B, structure
The molar ratio of unit C is 10:(0.5~3): 1.
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| CN109777328B (en) * | 2019-01-18 | 2021-03-26 | 广州天赐高新材料股份有限公司 | Lithium ion battery cathode aqueous binder, preparation method thereof and cathode material |
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Application publication date: 20191108 |