CN109994703A - Battery electrode binder, electrode and lithium ion battery - Google Patents
Battery electrode binder, electrode and lithium ion battery Download PDFInfo
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- CN109994703A CN109994703A CN201811643720.4A CN201811643720A CN109994703A CN 109994703 A CN109994703 A CN 109994703A CN 201811643720 A CN201811643720 A CN 201811643720A CN 109994703 A CN109994703 A CN 109994703A
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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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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- 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
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Abstract
The invention discloses battery electrode binder, electrode and lithium ion batteries, belong to lithium ion cell electrode bonding and electrode fabrication field.The battery electrode binder includes rigid polymer and monomer, soft polymer and monomer, additive, and the additive can excite rigid polymer and monomer, soft polymer and the polymerization of monomer interpenetrating.The present invention solves that battery electrode binder is expensive, electrode cycle performance difference and the low problem of electrode surface energy density.
Description
Technical field
The invention belongs to lithium ion cell electrode bonding and electrode fabrication fields.More particularly to one kind by soft or hard polymerization
Object forms the high viscoplasticity binder of interpenetrating polymer, and the electrode and lithium ion battery of application binder preparation.
Background technique
In numerous electrochmical power sources, lithium ion battery has energy density high, has extended cycle life, and preparation cost is low and environment
The features such as good compatibility, is the most commonly used portable energy-storing power supply, is widely used in smart phone and small-sized electric tool etc.
Portable device.In future, with the popularization of electric car and popularizing for smart grid, lithium ion battery is as scale energy storage list
The best competitor of member, will be faced with application upgrade, towards higher energy density, longer cycle life, and it is lower
Manufacturing cost development.Currently, improving battery energy density and reducing cost method the most direct using height ratio capacity
Active material and raising electrode pastes load capacity.Such as: lithium ion battery negative material is based on graphite, but its limited theory
Specific capacity is not able to satisfy the following requirement to lithium ion battery energy density.Replacer of the silicon as graphite cathode material, has
Theoretical specific capacity (4200mAh/g vs.372mAh/g) of ten times higher than graphite cathode material.It is common to prepare lithium using silicon materials
Ion battery cathode will greatly improve the energy density and power-performance of lithium ion battery.However, preparing lithium electricity with silicon materials
Cathode is still faced with critical problem, and silicon serious volume expansion in charge and discharge process shrinks, will destroy electrode structure, lead
Pole dusting is sent a telegraph, causes electrode cycle performance poor, it is difficult to practical application.
In existing patent, some methods for solving silicon electrode cycle performance are had already appeared, it is multiple to be broadly divided into silicon substrate
The application of condensation material constructed with high viscoplasticity binder.In the constructing of silicon based composite material, silicon materials particle surface cladding
Foreign peoples's material, meanwhile, structural modification is carried out on silica-base material, such as: carbon or metal oxide realize that preparation silicon substrate is compound
Material.These covering materials can limit the volume expansion of silicon, promote its cycle performance, such as Chinese patent application
CN104254490A, CN103618074A.Such methods cause silicon based composite material preparation cost to be promoted.Further, since cladding
Material does not have lithium storage function, causes the specific capacity of silicon based composite material relatively low, it is difficult to really significantly improve lithium cell negative pole
Energy density.
Another method is to use high viscoplasticity binder, and the mechanical strength in intensifier electrode improves the cyclicity of electrode
Can, such as Chinese patent CN104934609A, CN104877593A, CN103762367A.It is used multiple in above-mentioned patent
Binder is closed merely by simply mechanical mixture, effectively coherent network can not be formed, although silicon electrode cycle performance has
It is promoted, but is to test to complete under active material low-load amount.The energy area density of silicon electrode is less than 5mAh/cm2, very
To the energy area density of insufficient graphite cathode at present.Under high load capacity, above-mentioned binder is difficult to ensure cycle performance.From now
Some results of study see that silicon electrode needs a kind of high viscoelastic binder, guarantee the integrality of silicon electrode.Hardness guarantees electrode
Integrality, but suitable elastic material is needed to maintain microcosmic local link simultaneously.
Summary of the invention
It is an object of the invention to: for the low problem of existing lithium ion cell electrode poor circulation, face energy density,
The present invention provides a kind of battery electrode binders, are able to carry out interpenetrating polymerization, interpenetratingpolymernetworks are formed, using the binder
The electrode of preparation has good cycle performance and high face specific capacity, combines with lithium ion cell positive, the lithium-ion electric of assembling
The energy density in pond is high.
To achieve the above object, the present invention adopts the following technical scheme:
Battery electrode binder, the battery electrode binder include rigid polymer and monomer, soft polymer and
Monomer, additive, the additive can excite rigid polymer and monomer, soft polymer and the polymerization of monomer interpenetrating.
Wherein, the rigid polymer and monomer, soft polymer and monomer and additive may be dissolved in water or
In person's organic solvent.
Wherein, the rigid polymer is selected from the polymeric material with hardening characteristics, including epoxy resin, acrylic acid
Resinoid, poly furfuryl alcohol, polyester resin, phenolic resin, amino resins and polyaniline.
Wherein, the soft polymer is selected from the elastomer with deformation recovery capability, including polyacrylate material
Material, polyamines material, butadiene-styrene rubber, polyvinyl alcohol, butadiene rubber, isoprene rubber, EP rubbers, butyl rubber, neoprene
And nitrile rubber.
Wherein, the additive is selected from catalyst or initiator, wherein the catalyst can provide Bronsted acid to be urged
Change.
Wherein, the catalyst is selected from one of formic acid, acetic acid, oxalic acid, hydrochloric acid, sulfuric acid or nitric acid or a variety of.
Wherein, the initiator is to provide free radical, causes the compound of free radical polymerization or copolyreaction, and energy
The addition reaction for promoting rigid polymer or soft polymer, reach be cross-linked with each other and interpenetrating polymerization purpose.
Wherein, the initiator is selected from organic peroxide evocating agent, inorganic peroxide initiator, azo and causes
Agent, redox initiator.
Wherein, the initiator is selected from dibenzoyl peroxide, potassium peroxydisulfate, ammonium persulfate, azodiisobutyronitrile, peroxide
Change one of hydrogen/ferrous sulfate.
Wherein, the weight ratio between the rigid polymer or monomer, soft polymer or monomer and additive is
3:1-3:0.3。
A kind of electrode liquid phase slurry, including electrode active material and suitable solvent further include that above-mentioned battery electrode is viscous
Tie agent.
Wherein, the electrode active material is selected from positive electrode active materials or negative electrode active material.
Wherein, the solvent is selected from aqueous solvent or organic solvent；Wherein, the organic solvent is selected from N- crassitude
Ketone, tetrahydrofuran, n,N-Dimethylformamide, dimethyl sulfoxide, one of hexamethylene, acetone, isopropanol, ethyl alcohol, furfural
Or its several mixture.
Wherein, the electrode liquid phase slurry further includes conductive agent.
A kind of electrode, including electrode current collecting body further include the electrode pastes formed by above-mentioned electrode liquid phase slurry.
A kind of preparation method of such as above-mentioned electrode, including following preparation step:
Step 1), by rigid polymer or monomer, soft polymer or monomer, with suitable proportion dispersing and dissolving in
In solvent, and additive is added, stirs 10-300 minutes, form uniform colloidal solution；
Step 2), in above-mentioned uniform colloidal solution, electrode active material and conductive agent is added, is mixed 1-60 points
Clock obtains uniform electrode pastes；
Wherein, the additional amount of the electrode active material is the 60%-90% of electrode pastes gross mass, the conductive agent
Additional amount is the 5%-20% of electrode pastes gross mass, and the dosage of the uniform colloidal solution is the 5%- of electrode pastes gross mass
20%；
The electrode obtained lotion is coated with or sprays on electrode current collecting body by step 3), and heating temperature is 60-150 DEG C, is added
The hot time is 30-120 minutes, promotes additive to play the function of its catalytic polymerization by heating process.
Wherein, in step 1), the solution temperature is selected from 30-60 DEG C.
Wherein, in step 1), the glass transition temperature of the binder is 100-140 DEG C.
Wherein, in step 2), the speed when stirring is selected from 100-6000 revs/min, and mixing time is selected from 1-30 points
Clock.
Wherein, in step 3), the heating temperature is selected from 100-140 DEG C.
Wherein, in step 3), the molecular weight ranges of the resinous polymer obtained after catalytic polymerization are 1000-20000, and heat is steady
Determining temperature is 0-400 DEG C.
Wherein, in step 3), it is described spraying be electrode pastes are sprayed on electrode current collecting body it is two-sided on, injection rate 2-
1000mg/(min·m2)。
A kind of lithium ion battery includes above-mentioned electrode.
Relative to the electrode of lithium cell technology of preparing announced at present, binder of the invention makes the cycle performance of electrode
And face specific capacity is guaranteed.The binder can be with various positive electrode active materials in the prior art and negative electrode active material one
It rises and prepares electrode liquid phase slurry, so that positive plate or negative electrode tab and lithium ion battery are further prepared, the lithium-ion electric of preparation
Pond all has good performance.It is following by taking silicon materials as an example, be described in detail beneficial effects of the present invention:
(1) interpenetrating polymer-binder of the invention is applied to the negative electrode of lithium ion battery of silica-base material, efficiently solves
The bad problem of traditional silicon based electrode cycle performance.It is 90% that binder, which makes the 100 of silicon based electrode to enclose circulation volume conservation rate,
500 circle circulation volume conservation rates are 80%.The cycle performance of above-mentioned silicon based electrode can match in excellence or beauty current graphite cathode, be entirely capable of
Enough it is applied in lithium ion battery.
(2) silicon-based anode prepared with interpenetrating polymer-binder of the present invention, face specific capacity are up to 10mAh/cm2, it is existing
Peak in issued patents.High load amount silicon based electrode maintains good charging and discharging capacity in cyclic process.Currently, with
High load amount silicon based electrode collocation lithium ion battery tertiary cathode, the energy density of full battery are fully achieved up to 400Wh/kg
Second stage target in country " 2025 manufacture " planning.
(3) preparation process of use interpenetrating polymer-binder of the invention, electrode slurry and pole piece is relative to traditional
Method also has improvement effect, and effect is: the liquid monomer and numerous electrode materials have good wetability.Excellent profit
The moist mixing efficiency that material and liquid phase can be improved reduces mixing time, avoids adding the materials such as other surfactants,
Technical guarantee is provided quickly to close cream technique.Relative to the technology for preparing electrode announced, only in the slurry mixing paste stage, just
The incorporation time of a few hours is needed, binder of the invention has huge jump.
(4) rigid polymer is solid at room temperature, and shows certain hardness and brittleness, as interpenetrating cohesive bond
Skeleton inside agent makes it have the volume change of certain mechanical strength reply silicon based composite material, is silicon based composite material
Certain limit space is set, will not influence the integrality of whole silicon based electrode.Pass through nano-indenter test technology and electrolyte
Immersion test shows to be added in viscoid after rigid polymer, and mechanical strength gets a promotion, and illustrates that its resistance becomes energy and adds
By force.Meanwhile rigid polymer has good chemical stability and thermal stability: acidproof, alkaline-resisting, corrosion-resistant, insoluble in having
Solvent system and not by characteristics such as thermal decomposition temperature height, is also dissolved into interpenetrating polymer-binder, copes with it preferably
Complex environment in lithium ion battery.
(5) soft polymer is solid at room temperature, but shows high elasticity, and there is significantly deformation to restore energy
Power.Soft polymer is conducive to alleviate microcosmic local swelling stress, and the deformation scale of stability of composite materials guarantees the machine of electrode
Tool integrality.The shortcomings that being faced with brittleness due to rigid polymer, soft polymer alleviate silica-base material volume change to hard
The mechanical shock of matter polymer.Meanwhile by studies have shown that soft polymer is added in binder to silicon based composite material surface
The formation of SEI film has good facilitation.The elasticity as possessed by soft polymer, so that being glued in charge and discharge process
Property body and silica-base material surface form good contact environment, be not easy to the surface that electrolyte permeates silica-base material repeatedly, will not
The growth for causing SEI film, promotes the stability on silica-base material surface, and the coulombic efficiency for being conducive to electrode is promoted.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Fig. 1 is with the cycle performance figure of the silicon based electrode of the binder preparation in embodiment 1 and comparative example 1.
Fig. 2 is with the cycle performance figure of the silicon based electrode of the binder preparation in embodiment 2 and comparative example 2-3.
Fig. 3 is with the cycle performance figure of the silicon based electrode of the binder preparation in embodiment 3.
Fig. 4 is with the silicon pole piece microscopic appearance photo of embodiment 3.
Fig. 5-6 is the knot for the nano-indenter test that the silicon pole piece prepared with embodiment 3 and comparative example 2-3 carries out 2000 μ N
Fruit.
Specific embodiment
Embodiment below facilitates a better understanding of the present invention, but does not limit the present invention.Experiment in following embodiments
Method is unless otherwise specified conventional method.Test material as used in the following examples is unless otherwise specified city
It sells.Quantitative test in following embodiment, is respectively provided with three repeated experiments, and results are averaged.
Binder of the invention includes rigid polymer and monomer, soft polymer and monomer, additive, wherein
Additive is the catalyst or initiator for exciting rigid polymer, soft polymer and the polymerization of their monomer interpenetrating.
Rigid polymer can be used as the frame structure of electrode interior, and the mechanical strength of intensifier electrode keeps the complete of electrode
Whole property.Soft polymer alleviates microcosmic local swelling stress, maintains intergranular contact and transmitting.The presence of additive can
Excite rigid polymer, soft polymer and the polymerization of their monomer interpenetrating.By between polymer, between polymer and monomer,
Or the interpenetrating polymerization process between monomer and monomer, promote soft polymer and rigid polymer to form interpenetratingpolymernetworks,
Form high viscoelastic binder.Meanwhile the synthesis of interpenetrating polymer-binder and the preparation journey of electrode slice are completed at the same time, so that viscous
Knot agent and active material, conductive agent form good binding force between metal collector.
Rigid polymer, soft polymer and their monomers and additive are soluble in water or organic solvent,
Its mixed solution has good wetability in surface of active material.This is conducive to attachment of the binder on active material, adds
The binding force of strong binder and active material.
Rigid polymer is selected from the polymeric material with hardening characteristics, including epoxy resin, acrylic resin, gathers
Furfuryl alcohol, polyester resin, phenolic resin, amino resins and polyaniline compound.
Hardening characteristics refer to the polymer formed after monomer polymerization mechanical strength with higher, show in extension test
R type curve out, polymer deformability are poor.
Soft polymer is selected from the elastomer with deformation recovery capability, including polyacrylate material, polyamines
Material, butadiene-styrene rubber, polyvinyl alcohol, butadiene rubber, isoprene rubber, EP rubbers, butyl rubber, neoprene and butyronitrile rubber
Glue.
Requirement to the number-average molecular weight and weight average molecular weight of rigid polymer and soft polymer are as follows: 100-20000.
The weight ratio of rigid polymer or monomer, soft polymer or monomer, additive three needs to meet following
Relationship: 3:1-3:0.3, at this point, can be realized the preparation of the high face capacity electrode of silicon-based active material.The more excellent weight ratio model of three
It encloses are as follows: rigid polymer or monomer: soft polymer or monomer: additive=3:1-2:0.3, the optimum weight percent of three
Are as follows: rigid polymer or monomer: soft polymer or monomer: additive=3:1:0.3.
Catalyst is to provide the catalyst system of Bronsted acid, one in formic acid, acetic acid, oxalic acid, hydrochloric acid, sulfuric acid or nitric acid
Kind is a variety of.
Initiator is to provide free radical, causes the compound of free radical polymerization or copolyreaction, and promotes rigid polymeric
The addition reaction of object or soft polymer, reach be cross-linked with each other and interpenetrating polymerization purpose.Wherein, including organic peroxide draws
Send out agent, inorganic peroxide initiator, azo-initiator, redox initiator.Initiator can be selected from diphenyl peroxide
Formyl, potassium peroxydisulfate, ammonium persulfate, azodiisobutyronitrile, one of hydrogen peroxide/sulfuric acid ferrous iron.
Electrode liquid phase slurry according to one embodiment, including electrode active material and suitable solvent, further include on
The binder stated.
Electrode active material is selected from positive electrode active materials or negative electrode active material.
Anode, negative electrode active material be all not particularly limited, can choose the common positive electrode active materials of related fields and
Negative electrode active material.The unrestricted example of positive electrode active materials includes class containing lithium metal oxide, phosphoric acid salt, fluoride
Class, sulfenyl material；The unrestricted example of negative electrode active material includes graphite, carbon materials, metal oxide-type, silicon substrate
Material, tin-based material.For example silicon based composite material includes but is not limited to Si-C composite material, silicon metal oxide composite material, silicon
Alloy composite materials, wherein the mass content of silicon in the composite is 1~85wt.%.For example metal oxide includes but not
It is limited to iron oxide, lithium titanate, copper oxide etc. is considered as all and is able to carry out removal lithium embedded, stores up the metal oxide of lithium.Such as phosphate
Including LiFePO4, lithium manganese phosphate, phosphoric acid vanadium lithium.For example containing lithium metal oxide includes cobalt acid lithium, LiMn2O4.
Solvent is selected from aqueous solvent or organic solvent, and wherein organic solvent is selected from N-Methyl pyrrolidone, tetrahydrofuran, N, N-
Dimethylformamide, dimethyl sulfoxide, one of hexamethylene, acetone, isopropanol, ethyl alcohol, furfural.
Electrode liquid phase slurry further includes conductive agent, and any conductive agent commonly used in lithium battery can be used, conductive agent
Example includes carbons substance such as carbon black, acetylene black, Ketjen black and carbon fiber (such as gas-phase growth of carbon fibre), and metal substance is such as
Copper, nickel, aluminium and silver metal powder and metallic fiber；Such as poly- sub- benzene derivative of conducting polymer and its mixture.Conductive agent
Dosage can carry out adjusting appropriate.
Electrode according to one embodiment, the electrode cream formed including electrode current collecting body and above-mentioned electrode liquid phase slurry
Body.The electrode obtained lotion is coated with or is sprayed on electrode current collecting body surface, heated solidification, biomass monomer material is handed in situ
Connection polymerization.
The thickness of negative current collector is typically about 3 μm to about 100 μm.Collector is unrestricted, if it be it is conductive and
Will not cause chemical change to lithium battery, the example of collector include copper, stainless steel, nickel, titanium, sintering carbon, have carbon, nickel,
The copper or stainless steel, aluminium-cadmium alloy etc. on titanium or the processed surface of silver.Alternatively, can be formed by the surface in collector small
Binding force that is coarse and increasing negative electrode active material, and collector can have any one of following different shape, such as
Film, piece, foil, net, cellular, foam-like and nonwoven shape.
Plus plate current-collecting body with a thickness of about 3 μm to about 100 μm, and be not particularly limited, as long as collector have it is highly conductive
Property is without causing chemical change to lithium battery.The example of collector include stainless steel, aluminium, nickel, titanium, sintering carbon or have
Carbon, nickel, titanium or silver process the aluminium or stainless steel on surface.Alternatively, can be by and collection liquid surface forms small coarse
Increase the adhesion strength of positive active material, collector can have any one of following different shape, as film, piece, foil,
Net, cellular, foam-like and nonwoven shape.
The preparation method of electrode includes the following steps:
Step 1) prepares binder: rigid polymer or monomer, soft polymer or monomer and additive, will be hard
Matter polymer or monomer, soft polymer or monomer with suitable proportion dispersing and dissolving in solvent, and add addition
Agent stirs 10-300 minutes, forms uniform colloidal solution；
The weight ratio of the rigid polymer or monomer, soft polymer or monomer, additive three needs to meet
Following relationship: 3:1-3:0.3；
The dosage of the solvent requires to disperse rigid polymer or monomer, soft polymer or monomer and add
Add agent material, it is therefore an objective to solute can be completely dissolved, and uniform colloidal solution can be stirred into.
The solution temperature is selected from 30-60 DEG C, within this temperature range, has and can speed up solvent dissolution solute process but
Reduce the effect of solvent volatilization.
The glass transition temperature of the binder is 100-140 DEG C.If glass transition temperature is excessively high, pole piece is easily led to
It is hard, crisp, i.e., there is edge decarburization when many stripeds, cut-parts after easily occurring cracking phenomena, cold pressing in coating process in binder
And in winding process the phenomenon that the picking of pole piece bending place, poor processability, to seriously restrict its application in the battery.
Step 2), in above-mentioned uniform colloidal solution, electrode active material and conductive agent is added.By high-speed homogenization machine one
It is mixed 1-60 minutes under fixed mixing speed, obtains uniform electrode pastes；
The additional amount of the electrode active material is the 60%-90% of electrode pastes gross mass, the addition of the conductive agent
Amount is the 5%-20% of electrode pastes gross mass, and the dosage of uniform colloidal solution is the 5%-20% of electrode pastes gross mass.
The mixing speed be selected from 100-6000 revs/min, mixing time can be selected from 1-30 minute, the mixing speed with
Under mixing time, it will be able to obtain uniform electrode pastes.
The electrode obtained lotion is coated with or sprays on electrode current collecting body by step 3), and heating temperature is 60-150 DEG C, is added
The hot time is 30-120 minutes, promotes additive to play the function of its catalytic polymerization, obtained resin polymerization by heating process
The molecular weight ranges of object are 1000-20000, and thermal stable temperature is 0-400 DEG C.
Preferred 100-140 DEG C of the heating temperature, within this temperature range, can preferably guarantee monomer polymerization at polymerization
Object mechanical performance.
It is described spraying be electrode pastes are sprayed on electrode current collecting body it is two-sided on, injection rate be 2-1000mg/ (min
m2)。
Lithium ion battery according to one embodiment includes above-mentioned electrode.
The preparation of lithium ion battery is known, therefore no longer describes its details herein.
Each embodiment will be described in further detail with reference to following embodiment and comparative example.Following embodiment is only illustrative mesh
The range for being not intended to limit embodiment.
Embodiment 1
The preparation of silicon-based anode piece
Step 1), rigid polymer or monomer, soft polymer or monomer are dispersed molten with the proportion of mass ratio 1:1
Solution adds the additive of 10wt.% mass fraction in solvent, stirs 30 minutes, forms uniform colloidal solution.
Step 2), in above-mentioned uniform colloidal solution, be added silicon-based active substance and electrodes conduct agent, binder and conductive
Total dosage of agent is the 40% of electrode pastes gross mass, and the additional amount of conductive agent is 20%, by high-speed homogenization machine 2500
It is mixed 10 minutes under rev/min mixing speed, obtains uniform electrode pastes.
The electrode obtained lotion is coated with or sprays on electrode current collecting body by step 3), promotes to add by heating process
Agent plays the function of its catalytic polymerization, and heating temperature is 140 DEG C, and heating time is 60 minutes.
In the present embodiment, it is 14000 poly furfuryl alcohol (PFA) that rigid polymer, which selects weight average molecular weight,；
It is 16000 polyvinyl alcohol (PVA) that soft polymer, which selects weight average molecular weight,；
Additive selects oxalic acid；
Solvent selects water；
Conductive black is selected in electrodes conduct agent.
After measured, the mass fraction that content of the binder generated in negative electrode tab is about 20%.
Comparative example 1
Using Kynoar (PVdF) bonding system mixing paste, the quality proportioning of binder and active material is referring to embodiment
Each component quality condition in 1.
1. the PVdF binder of the mass fraction of 20wt.% to be dissolved in 10 milliliters of organic solvent N- hydroxymethyl pyrrolidine
In ketone, silicon based composite material is added, stirs 10 hours.
2. uniformly mixed lotion is coated in metal collector, vacuum drying, the preparation of silicon based electrode piece is completed.
The comparison result of embodiment 1 and comparative example 1 is shown in Fig. 1.
Fig. 1 is with the cycle performance figure of the silicon based electrode of the binder preparation in embodiment 1 and comparative example 1.
Chemical property by comparing above-mentioned different binder silicon based electrode pieces can be seen that viscous in embodiment 1
The silicon based electrode of knot agent preparation shows preferable cyclical stability.
Embodiment 2
The preparation of silicon-based anode piece
Step 1), soft polymer or monomer, rigid polymer or monomer are 1:2 proportion with mass ratio, disperse molten
Solution adds the additive of 10wt.% mass fraction in solvent, stirs 30 minutes, forms uniform colloidal solution.
Step 2), in above-mentioned uniform colloidal solution, be added silicon-based active material and electrodes conduct agent, binder and conductive
Total dosage of agent is the 40% of electrode pastes gross mass, and the additional amount of conductive agent is 20%, by high-speed homogenization machine 2500
It is mixed 10 minutes under rev/min mixing speed, obtains uniform electrode pastes；
The electrode obtained lotion is coated with or sprays on electrode current collecting body by step 3), promotes to add by heating process
Agent plays the function of its catalytic polymerization, and heating temperature is 140 DEG C, and heating time is 60 minutes.
In the present embodiment, it is 14000 poly furfuryl alcohol that rigid polymer, which selects weight average molecular weight,；
It is 16000 polyvinyl alcohol that soft polymer, which selects weight average molecular weight,；
Additive selects oxalic acid；
Solvent selects water；
Conductive black is selected in electrodes conduct agent.
After measured, the mass fraction that content of the binder generated in negative electrode tab is about 20%.
Comparative example 2
Using only PVA bonding system mixing paste, the quality proportioning of binder and active material is referring to each component in embodiment 2
Quality condition.
Comparative example 3
Using only poly furfuryl alcohol bonding system mixing paste, the quality proportioning of binder and active material is referring to each in embodiment 2
Constituent mass situation.
Fig. 2 is with the cycle performance figure of the silicon based electrode of the binder preparation in embodiment 2 and comparative example 2-3.
Compared to embodiment 1, the cycle performance of silicon based electrode is further increased in embodiment 2.Meanwhile passing through comparative example 2
In sample find out that silicon-based active material cannot effectively be bonded by being only applicable in PVA binder, since PVA is as a kind of elastomer,
Belong to soft polymer.Therefore, lack the binder of rigid polymer in the application of silicon materials, frame structure can not be established,
Maintain the mechanical strength of electrode.Although the elasticity of electrode reaches maximum value, the chemical stability and heating power of soft polymer
It learns stability and is not so good as rigid polymer, therefore the cycle performance of silicon based electrode is difficult to ensure.
Found out by the sample in comparison 3, cannot effectively bond silicon-based active material using only rigid polymer binder
Material.Although rigid polymer has good hardness, the frame of electrode interior can be used as, its brittleness deficiency stable silicon material
The volume expansion of material, leads to rigid polymer cracking dusting, and electrode cycle performance is bad.In rigid polymer, it is added a small amount of
Soft polymer, the stress of electrode interior will be alleviated, promotes the cycle performance of electrode, in embodiment 2.
Embodiment 3
The preparation of silicon-based anode piece
Step 1), soft polymer or monomer, rigid polymer or monomer are 1:3 proportion with mass ratio, disperse molten
It is dissolved in solvent, adds the additive of 10wt.% mass fraction, stir 30 minutes, form uniform colloidal solution.
Step 2), in above-mentioned uniform colloidal solution, be added silicon-based active substance and electrodes conduct agent, binder and conductive
Total dosage of agent is the 40% of electrode pastes gross mass, and the additional amount of conductive agent is 20%, by high-speed homogenization machine 2500
It is mixed 10 minutes under rev/min mixing speed, obtains uniform electrode pastes.
The electrode obtained lotion is coated with or sprays on electrode current collecting body by step 3), promotes to add by heating process
Agent plays the function of its catalytic polymerization, and heating temperature is 140 DEG C, and heating time is 60 minutes.
In the present embodiment, it is 14000 poly furfuryl alcohol that rigid polymer, which selects weight average molecular weight,；
It is 16000 polyvinyl alcohol that soft polymer, which selects weight average molecular weight,；
Additive selects oxalic acid；
Solvent selects water；
Conductive black is selected in electrodes conduct agent.
After measured, the mass fraction that content of the binder generated in negative electrode tab is about 20%.
Fig. 3 is with the cycle performance figure of the silicon based electrode of the binder preparation in embodiment 3.
Found out by the sample in example 3, after optimization, the cycle performance of Gao Zailiang silicon electrode is further increased, and says
The ratio of the bright soft or hard polymer of optimization can promote the cycle performance of silicon electrode indirectly.
Illustrated by embodiment 1-3 and comparative example 1-3, the sticky volume grid being polymerize using soft or hard interpenetrating, rigid polymeric
Object and soft polymer act synergistically, and can be good at the cycle performance for stablizing silicon materials.It, should compared to existing bonding technology
Face specific capacity is greatly improved in sticky volume grid, and stablizes the cycle performance of live electrode.
Embodiment 4
The preparation of anode plate for lithium ionic cell
The butadiene-styrene rubber that the epoxy resin and number-average molecular weight that step 1), number-average molecular weight are 11000 are 15000, with matter
For amount than being that 1:1 is matched, dispersing and dissolving adds the potassium peroxydisulfate of 20wt.% mass fraction in acetone, stirs 60 minutes, is formed
Uniform colloidal solution.
Step 2), in above-mentioned uniform colloidal solution, be added silicon based composite material and carbon black, binder and carbon black it is total
Dosage is the 20% of electrode pastes gross mass, the additional amount of carbon black is 20%, is stirred by high-speed homogenization machine at 2000 revs/min
It mixes and is mixed 10 minutes under speed, obtain uniform electrode pastes.
The electrode obtained lotion is applied on electrode current collecting body by step 3), promotes potassium peroxydisulfate to play by heating process
The function of its catalytic polymerization, heating temperature are 140 DEG C, and heating time is 60 minutes.
Wherein silicon based composite material is Si-C composite material, and the mass content of silicon in the composite is 60wt.%.
Embodiment 5
The preparation of anode plate for lithium ionic cell
The isoprene rubber that the acrylic resin and number-average molecular weight that step 1), number-average molecular weight are 7000 are 8000, with
Mass ratio is 1:1 proportion, and dispersing and dissolving adds the acetic acid of 10wt.% mass fraction in hexamethylene, stirs 300 minutes, formed
Uniform colloidal solution.
Step 2), in above-mentioned uniform colloidal solution, silicon based composite material, pure silicon material and Ketjen black, binder is added
Total dosage with Ketjen black is the 5% of electrode pastes gross mass, and the additional amount of Ketjen black is 10%, is existed by high-speed homogenization machine
It is mixed 10 minutes under 6000 revs/min of mixing speed, obtains uniform electrode pastes.
Step 3) sprays to the electrode obtained lotion on electrode current collecting body, promotes acetic acid to play it by heating process and urges
Change the function of polymerization, heating temperature is 130 DEG C, and heating time is 70 minutes.
Wherein silicon based composite material is silicon metal oxide composite material, and the mass content of silicon in the composite is
1wt.%.
Embodiment 6
The preparation of anode plate for lithium ionic cell
The EP rubbers that the phenolic resin and number-average molecular weight that step 1), number-average molecular weight are 8000 are 4000, with quality
Than matching for 1:1, dispersing and dissolving adds the azodiisobutyronitrile of 30wt.% mass fraction in tetrahydrofuran, stirs 10 points
Clock forms uniform colloidal solution.
Step 2), in above-mentioned uniform colloidal solution, be added Tin Composite Material and acetylene black, binder and acetylene black
Total dosage is the 30% of electrode pastes gross mass, and the additional amount of acetylene black is 10%, by high-speed homogenization machine at 700 revs/min
It is mixed 60 minutes under the mixing speed of clock, obtains uniform electrode pastes.
The electrode obtained lotion is applied on electrode current collecting body by step 3), promotes azodiisobutyronitrile by heating process
The function of its catalytic polymerization is played, heating temperature is 60 DEG C, and heating time is 120 minutes.
Embodiment 7
The preparation of anode plate for lithium ionic cell
The nitrile rubber that the amino resins and number-average molecular weight that step 1), number-average molecular weight are 1000 are 15000, with quality
Than matching for 1:1, dispersing and dissolving adds the sulfuric acid of 15wt.% mass fraction in N-Methyl pyrrolidone, and the concentration of sulfuric acid is
5%, it stirs 20 minutes, forms uniform colloidal solution.
Step 2), in above-mentioned uniform colloidal solution, iron oxide and gas-phase growth of carbon fibre is added, binder and gas phase are raw
Total dosage of long carbon fiber is the 20% of electrode pastes gross mass, and the additional amount of gas-phase growth of carbon fibre is 5%, by high speed
Refiner is mixed 45 minutes under 1000 revs/min of mixing speed, obtains uniform electrode pastes.
Step 3) sprays to the electrode obtained lotion on electrode current collecting body, promotes sulfuric acid to play it by heating process and urges
Change the function of polymerization, heating temperature is 90 DEG C, and heating time is 100 minutes.
Embodiment 8
The preparation of anode plate for lithium ionic cell
The butadiene rubber that the acrylic resin and number-average molecular weight that step 1), number-average molecular weight are 9000 are 17000, with matter
For amount than being that 1:1 is matched, dispersing and dissolving adds the oxalic acid and 5wt.% mass point of 10wt.% mass fraction in dimethyl sulfoxide
Several hydrochloric acid stirs 200 minutes, forms uniform colloidal solution.
Step 2), in above-mentioned uniform colloidal solution, be added graphite active material and carbon black, binder and carbon black it is total
Dosage is the 30% of electrode pastes gross mass, the additional amount of carbon black is 10%, is stirred by high-speed homogenization machine at 3000 revs/min
It mixes and is mixed 3 minutes under speed, obtain uniform electrode pastes.
The electrode obtained lotion is applied on electrode current collecting body by step 3), promotes oxalic acid and hydrochloric acid to send out by heating process
The function of its catalytic polymerization is waved, heating temperature is 120 DEG C, and heating time is 70 minutes.
Embodiment 9
The preparation of based lithium-ion battery positive plate
The butadiene rubber that the amino resins and number-average molecular weight that step 1), number-average molecular weight are 100 are 7000, with mass ratio
For the proportion of 1:1, dispersing and dissolving adds the ammonium persulfate of 25wt.% mass fraction in ethyl alcohol, stirs 30 minutes, is formed equal
One colloidal solution.
Step 2), in above-mentioned uniform colloidal solution, LiFePO4 and poly- sub- benzene derivative, binder and poly- sub- benzene is added
Total dosage of derivative is the 15% of electrode pastes gross mass, and the additional amount for gathering Asia benzene derivative is 5%, by high-speed homogenization
Machine is mixed 10 minutes under 3500 revs/min of mixing speed, obtains uniform electrode pastes.
The electrode obtained lotion is applied on electrode current collecting body by step 3), promotes ammonium persulfate to play by heating process
The function of its catalytic polymerization, heating temperature are 110 DEG C, and heating time is 50 minutes.
Embodiment 10
The preparation of based lithium-ion battery positive plate
The isoprene rubber that the phenolic resin and number-average molecular weight that step 1), number-average molecular weight are 2000 are 6000, with quality
Than matching for 1:1, dispersing and dissolving adds the peroxidating two of 10~30wt.% mass fraction in the mixed liquor of ethyl alcohol and acetone
Benzoyl stirs 150 minutes, forms uniform colloidal solution.Wherein the mass ratio of ethyl alcohol and acetone is 1:1.
Step 2), in above-mentioned mixed solution, be added sulfenyl composite material and Ketjen black, binder and Ketjen black it is total
Dosage is the 30% of electrode pastes gross mass, and the additional amount of Ketjen black is 10%, by high-speed homogenization machine at 2000 revs/min
It is mixed 45 minutes under mixing speed, obtains uniform electrode pastes.
Step 3) sprays to the electrode obtained lotion on electrode current collecting body, promotes diphenyl peroxide first by heating process
Acyl plays the function of its catalytic polymerization, and heating temperature is 100 DEG C, and heating time is 60 minutes.
Embodiment 11
The preparation of based lithium-ion battery positive plate
The polyacrylate material that the polyaniline and number-average molecular weight that step 1), number-average molecular weight are 7000 are 12000, with
Mass ratio is 1:1 proportion, and dispersing and dissolving adds the azodiisobutyronitrile of 25wt.% mass fraction, stirring 180 in isopropanol
Minute, form uniform colloidal solution.
Step 2), in above-mentioned uniform colloidal solution, LiMn2O4 and acetylene black, total use of binder and acetylene black is added
Amount is the 35% of electrode pastes gross mass, the additional amount of acetylene black is 5%, is stirred by high-speed homogenization machine at 1000 revs/min
It mixes and is mixed 55 minutes under speed, obtain uniform electrode pastes.
The electrode obtained lotion is applied on electrode current collecting body by step 3), promotes azodiisobutyronitrile by heating process
The function of its catalytic polymerization is played, heating temperature is 120 DEG C, and heating time is 70 minutes.
Embodiment 12
The assessment of battery performance
One, cycle performance test is carried out to lithium ion battery prepared by embodiment 1-11 and comparative example 1-3 respectively.
Normal-temperature circulating performance test: in 0.01-1V voltage range, charge and discharge under 0.5C multiplying power is carried out to working electrode and are grasped
Make, is spaced 300 seconds between charge and discharge, test result is shown in Table 1.
1 cycle performance of lithium ion battery test result of table
Two, to the face specific capacity of pole piece, and after being mixed into lithium battery, the energy density of full battery is tested,
Test process are as follows: anode matches rich lithium material, and electrolyte is dissolved in EC/DEC/FEC solvent (1:1:0.25 volume using 1M LiPF6
Than), test result is shown in Table 2.
The face specific capacity of 2 pole piece of table and the energy density of full battery
Embodiment 13
Mechanical property assessment
One, the silicon pole piece prepared respectively to embodiment 3 and comparative example 4 carries out electrolyte immersion test.
Fig. 4 is with the silicon pole piece microscopic appearance photo of embodiment 3.There it can be seen that PFA/PVA compound binding agent system
It can be good at bonding silicon electrode, be bonding to silicon materials.
Two, the silicon pole piece prepared respectively to embodiment 3 and comparative example 2-3 carries out the nano-indenter test of 2000 μ N.
Fig. 5-6 is the knot for the nano-indenter test that the silicon pole piece prepared with embodiment 3 and comparative example 2-3 carries out 2000 μ N
Fruit.Therefrom as can be seen that PFA/PVA compound binding agent system shows lower hardness and moderate reduction mould in data drawing list
Magnitude can be good at the volume expansion for constraining silicon materials, keep the stable structure of silicon electrode, be bonding to silicon materials.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (23)
1. battery electrode binder, it is characterised in that: the battery electrode binder includes rigid polymer and monomer, soft
Polymer and monomer, additive, the additive can excite rigid polymer and monomer, soft polymer and monomer mutual
Wear polymerization.
2. battery electrode binder according to claim 1, it is characterised in that: the rigid polymer and monomer, soft
Matter polymer and monomer and additive may be dissolved in water or organic solvent.
3. battery electrode binder according to claim 1 or 2, it is characterised in that: the rigid polymer, which is selected from, to be had
The polymeric material of hardening characteristics, including epoxy resin, acrylic resin, poly furfuryl alcohol, polyester resin, phenolic resin, ammonia
Base resin and polyaniline.
4. battery electrode binder according to claim 1-3, it is characterised in that: the soft polymer is selected from
Elastomer with deformation recovery capability, including polyacrylate material, polyamines material, butadiene-styrene rubber, polyvinyl alcohol,
Butadiene rubber, isoprene rubber, EP rubbers, butyl rubber, neoprene and nitrile rubber.
5. battery electrode binder according to claim 1-4, it is characterised in that: the additive is selected from catalysis
Agent or initiator, wherein the catalyst can provide Bronsted acid to be catalyzed.
6. battery electrode binder according to claim 5, it is characterised in that: the catalyst is selected from formic acid, acetic acid, grass
One of acid, hydrochloric acid, sulfuric acid or nitric acid are a variety of.
7. battery electrode binder according to claim 5 or 6, it is characterised in that: the initiator is to provide freely
Base, causing free radical polymerization perhaps the compound of copolyreaction and can promote the addition of rigid polymer or soft polymer
Reaction, reach be cross-linked with each other and interpenetrating polymerization purpose.
8. battery electrode binder according to claim 7, it is characterised in that: the initiator is selected from organic peroxide
Initiator, inorganic peroxide initiator, azo-initiator, redox initiator.
9. battery electrode binder according to claim 8, it is characterised in that: the initiator is selected from diphenyl peroxide first
Acyl, potassium peroxydisulfate, ammonium persulfate, azodiisobutyronitrile, one of hydrogen peroxide/sulfuric acid ferrous iron.
10. -9 described in any item battery electrode binders according to claim 1, it is characterised in that: the rigid polymer or
Weight ratio between monomer, soft polymer or monomer and additive is 3:1-3:0.3.
11. a kind of electrode liquid phase slurry, including electrode active material and suitable solvent, it is characterised in that: further include that right is wanted
Seek the described in any item battery electrode binders of 1-10.
12. electrode liquid phase slurry according to claim 11, it is characterised in that: it is living that the electrode active material is selected from anode
Property material or negative electrode active material.
13. electrode liquid phase slurry according to claim 11 or 12, it is characterised in that: the solvent is selected from aqueous solvent or has
Solvent；Wherein, the organic solvent is selected from N-Methyl pyrrolidone, tetrahydrofuran, n,N-Dimethylformamide, dimethyl Asia
Sulfone, one of hexamethylene, acetone, isopropanol, ethyl alcohol, furfural or its several mixture.
14. the described in any item electrode liquid phase slurries of 1-13 according to claim 1, it is characterised in that: the electrode liquid phase slurry
It further include conductive agent.
15. a kind of electrode, including electrode current collecting body, it is characterised in that: further include by the described in any item electricity of claim 11-14
The electrode pastes that pole liquid phase slurry is formed.
16. a kind of preparation method of electrode as claimed in claim 15, it is characterised in that: including following preparation step:
Step 1), by rigid polymer or monomer, soft polymer or monomer, with suitable proportion dispersing and dissolving in solvent
In, and additive is added, it stirs 10-300 minutes, forms uniform colloidal solution, obtain binder；
Step 2), in above-mentioned uniform colloidal solution, electrode active material and conductive agent is added, is mixed 1-60 minutes, obtains
To uniform electrode pastes；
Wherein, the additional amount of the electrode active material is the 60%-90% of electrode pastes gross mass, the addition of the conductive agent
Amount is the 5%-20% of electrode pastes gross mass, and the additional amount of the binder is the 5%-20% of electrode pastes gross mass；
The electrode obtained lotion is coated with or sprays on electrode current collecting body by step 3), and heating temperature is 60-150 DEG C, when heating
Between be 30-120 minutes, promote additive to play the function of its catalytic polymerization by heating process.
17. the preparation method of electrode according to claim 16, it is characterised in that: in step 1), the solution temperature choosing
From 30-60 DEG C.
18. the preparation method of electrode according to claim 16 or 17, it is characterised in that: in step 1), the binder
Glass transition temperature be 100-140 DEG C.
19. the preparation method of the described in any item electrodes of 6-18 according to claim 1, it is characterised in that: described to stir in step 2)
Speed when mixing is selected from 100-6000 revs/min, and mixing time is selected from 1-30 minutes.
20. the preparation method of the described in any item electrodes of 6-19 according to claim 1, it is characterised in that: described to add in step 3)
Hot temperature is selected from 100-140 DEG C.
21. the preparation method of the described in any item electrodes of 6-20 according to claim 1, it is characterised in that: in step 3), catalysis is poly-
The molecular weight ranges of the resinous polymer obtained after conjunction are 1000-20000, and thermal stable temperature is 0-400 DEG C.
22. the preparation method of electrode according to claim 16, it is characterised in that: in step 3), the spraying is will be electric
Pole lotion be sprayed on electrode current collecting body it is two-sided on, injection rate be 2-1000mg/ (minm2)。
23. a kind of lithium ion battery, it is characterised in that: include the electrode described in claim 15.
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