CN105958075A - Multi-element functional modification polyvinyl alcohol-based lithium ion battery aqueous binder and application of the binder in electrochemical power storage device - Google Patents
Multi-element functional modification polyvinyl alcohol-based lithium ion battery aqueous binder and application of the binder in electrochemical power storage device Download PDFInfo
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- CN105958075A CN105958075A CN201610504108.3A CN201610504108A CN105958075A CN 105958075 A CN105958075 A CN 105958075A CN 201610504108 A CN201610504108 A CN 201610504108A CN 105958075 A CN105958075 A CN 105958075A
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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
- H01M4/623—Binders being polymers fluorinated 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
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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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- 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 a multi-element functional modification polyvinyl alcohol-based lithium ion battery aqueous binder and application of the binder in an electrochemical energy storage device. According to the binder, polyvinyl alcohol is taken as substrate, and hydrophilic monomers and oleophylic monomers are taken as functional modification monomers. Through adoption of Michael addition reaction modification preparation, the binder has good water solubility, elasticity and bonding performance. Through application of the binder in the preparation process of the lithium ion battery electrode plate, the homogeneity of electrode slurry can be improved. Therefore, the electrode slurry can form film on a current collector evenly and flatly, the material of the electrode plate will not fall off, the capacity will not be reduced, the high rate capability and circulation stability of the lithium ion battery cathode and anode materials can be greatly improved, and the service life of the battery can be effectively extended.
Description
Technical field:
The present invention relates to macromolecule lithium battery binding agent, be specifically related to a kind of pluralistic function modified polyvinylalcohol base lithium ion
Battery aqueous binders and the application in electrochemical energy storing device.
Background technology:
Binding agent is that electrode active material and conductive agent are adhered to the important non-active ingredient of lithium ion battery on a current collector, its property
The quality of energy directly affects the chemical property of battery.Except requiring that it has between electrode active material, conductive agent and collector
Outside good cementation, binding agent should have the best dispersibility, thus beneficially electronics, ion are at charge and discharge process
In conduction, reduce the impedance between collector and electrode material；It addition, binding agent should have enough elasticity, thus can keep away
Exempt from active material particle to come off because from the expansion during charging, discharging electric batteries and contraction, pine is swollen.
In the large-scale production of lithium ion battery industry, main employing is dissolved in the poly-inclined fluorine of N-Methyl pyrrolidone (NMP) at present
Ethylene (PVDF) is as binding agent.But it is owing to PVDF exists the shortcoming of self, as poor in electronics and ionic conductivity, in electrolysis
Liquid has certain swelling, and with lithium metal, LixC6, exothermic reaction occurs at relatively high temperatures, there is bigger potential safety hazard.
Additionally, the Young's modulus of PVDF is of a relatively high, the pliability of pole piece is the best, molecular weight and molecular weight after water suction, its tack,
Therefore, it is higher to the humidity requirement of environment, and energy consumption is big, and PVDF is expensive, production cost is high.Therefore, searching can
With the novel green binding agent of replacement PVDF, there is profound significance, be increasingly becoming the important development of lithium ion battery binding agent
Direction.
Exploitation aqueous binders is an important directions of lithium ion battery binding agent development.Butadiene-styrene rubber (SBR)/carboxymethyl is fine
Dimension element sodium (CMC), polyacrylate aqueous binders have had mass market to apply, but its cohesive force and suppression pole piece
The effect expanded is the most limited, therefore its range is subject to certain restrictions.Polyvinyl alcohol (PVA) is in synthesizing water-solubility resin
A kind of bulk product, with natural prodcuts starch, dextrin and protein-based compared with, the water-soluble polymer competitive advantage of synthesis is
Constant product quality is homogeneous, and combination property is preferable.Modified PVA is used as lithium ion battery binding agent and also studies have reported that, acetal changes
Property PVA resin (CN105518914A) and PVA graft copolymerized polymer (CN105637686A) can be used as oiliness bonding
Agent is applied to lithium ion battery；Cyanoethylation modified PVA composite polypropylene acid can be used as aqueous binders be applied to silicium cathode lithium from
Sub-battery (Journal of Power Sources 298 (2015) 8-13)；PVA is as emulsifying agent, styrene monomer and acrylic acid
Esters monomer copolymerization (CN105261759A) can be prepared aqueous binders and be applied to lithium ion battery, but the deficiency of polystyrene it
Being property of place is crisp, impact strength is low, stress cracking, poor heat resistance etc. easily occur.Research and develop novel PVA base lithium ion electricity
Pond aqueous binders improves its adhesive property, improves battery performance further, reduces production cost, opens in particular for positive pole
The focus that to send out aqueous binders corresponding the most current.
Summary of the invention:
It is an object of the invention to provide a kind of pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders, will have good
Get well water miscible acrylic acid and its esters, bonds well performance and the vinyl cyanide of chemical property or the propylene of good compliance
Amide monomer is bonded in PVA molecule by Michael addition reaction, and the aqueous binders of preparation has good water solublity, should
The homogeneity of electrode slurry can be improved, so that electrode slurry can be at collector in lithium ion cell electrode sheet preparation process
Upper uniformity and planarization ground film forming；The adhesion strength between electrode active material, conductive agent and collector can be strengthened, be conducive to
Electrons/ions conduction in charge and discharge process, reduces the electrochemical interface impedance of pole piece, bigger improves lithium battery positive and negative pole material
High rate capability and stable circulation performance, do not drop off, do not result in capacity and decline, use such that it is able to effectively extend battery
Life-span.Being compared to polymers function modified PVA binding agent, function monomer controllably can be introduced PVA by Michael addition reaction
In molecule, so that the binder product steady quality of preparation is homogeneous, combination property is preferable.
The present invention is achieved by the following technical programs:
A kind of pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders, this binding agent with polyvinyl alcohol as substrate,
Using hydrophilic monomer and oleophylic monomer as functional modification monomer, through water solublity glue prepared by Michael addition reaction modification, its
Solid content is 2-50%, and viscosity is 10～20000mPa s；Described hydrophilic monomer is to have at least one in following structures alone:
CH2=CR1R2；Wherein, R1Selected from-H ,-CH3、-CH2CH3；R2Selected from-COOH ,-COOLi ,-COONa ,-CONH2；
Described oleophylic monomer is to have at least one in the monomer of following structure: CH2=CR3R4；Wherein, R3Selected from-H ,-CH3、
-CH2CH3, R4Selected from-CN ,-OCOCH3、-CONHCH3、-CON(CH3)2, and-COOR5In at least one,
R5At least one in C1～C8 alkyl；The molecular weight of described polyvinyl alcohol is 10000-250000, polyvinyl alcohol containing hydroxyl
The mol ratio of the multiple polymerized unit of basic weight, hydrophilic monomer and oleophylic monomer is 1:0.01～1:0～0.99.
Described Michael addition reaction refers to that polyvinyl alcohol passes through base catalysis with one or more of hydrophilic monomer and lipophile monomer
Agent causes reacts under conditions of 0～90 DEG C.
Described base catalyst is preferably one or more in LiOH, NaOH, LiOH/ carbamide, NaOH/ carbamide；
The consumption of described catalyst is the 0.1～10wt% of monomer gross mass.
The present invention also provides for the preparation method of described pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders, including
Following steps:
1) first polyvinyl alcohol is dissolved in deionized water, and is sufficiently stirred for 0.5～2.5 hour driving away under protectiveness gas atmosphere
Oxygen obtains homogeneous, the solution of good dispersion；
2) base catalyst is added to step 1) in the solution that obtains, it is sufficiently stirred for obtaining mixed solution；Add hydrophilic monomer
Glue with the PVA-based lithium ion battery aqueous of oleophylic monomer 0～90 DEG C of stirring reactions prepared pluralistic functionization modification in 1～9 hour
Knot agent；The dissolubility of binding agent is regulated and controled by the mass ratio of regulation hydrophilic monomer and oleophylic monomer；The use of described base catalyst
Amount is the 0.1～10% of monomer gross mass；Described polyvinyl alcohol molecule amount is 10000-250000, and the hydroxyl of polyvinyl alcohol
The mol ratio of repeated polymerization unit, hydrophilic monomer and lipophile monomer is 1:0.01～1:0～0.99；Described base catalyst
Consumption is the 0.1～10wt% of monomer gross mass.
Preferably, step 1) described protectiveness gas is nitrogen and/or argon；
Preferably, step 2)；Described stirring reaction temperature is 80 DEG C.；
Preferably, step 2) described stirring the response time be 8h；Described base catalyst is selected from LiOH, NaOH, LiOH/
One or more in carbamide, NaOH/ carbamide.
The present invention also protect described pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders may be directly applied to lithium from
In sub-battery plus or minus pole piece, it is also possible to the binding agent LiOH, Li prepared2CO3, in the alkali such as NaOH and after reapply in
In lithium ion battery plus or minus pole piece.
The application in based lithium-ion battery positive plate of the described pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders,
Described anode electrode of lithium ion battery sheet includes collector and load lithium ion battery anode glue size on a current collector；Described lithium from
Sub-battery anode slurry includes that positive electrode active materials, conductive agent, described pluralistic function modified polyvinylalcohol base lithium ion battery are viscous
Knot agent and solvent；Described positive electrode active materials, conductive agent and described pluralistic function modified polyvinylalcohol base lithium ion battery bonding
The mass ratio of agent is=70～95:1～20:4～10；Described positive electrode active materials is selected from LiFePO4, cobalt acid lithium, LiMn2O4 or ternary
Material (LiNi1/3Mn1/3Co1/3O2, NMC) one or more；Described conductive agent is acetylene black；Described collector is aluminium foil；
The solids content of described lithium ion battery anode glue size is 30～75%, and the viscosity of lithium ion battery anode glue size is 3000～8000
mPa·s。
The application in anode plate for lithium ionic cell of the described pluralistic function modified polyvinylalcohol base lithium ion battery binding agent, described
Lithium ion battery negative electrode slice includes collector and load lithium ion battery cathode slurry on a current collector；Described lithium-ion electric
Pond cathode size includes negative active core-shell material, conductive agent, described pluralistic function modified polyvinylalcohol base lithium ion battery binding agent
And solvent；Described negative active core-shell material, conductive agent and described pluralistic function modified polyvinylalcohol base lithium ion battery binding agent
Mass ratio is 70～95:1～20:4～10；Described negative active core-shell material selected from silica-base material, lithium titanate or graphite one or both with
On；Described conductive agent is acetylene black；Described collector is Copper Foil.
Described binding agent is applied to other electrochemical energy storing device, such as other secondary cell, ultracapacitor or solaode.
Present invention also offers a kind of lithium ion battery, described lithium ion battery includes battery case, pole piece and electrolyte, described
Pole piece and electrolyte are sealed in battery case, and described pole piece includes containing described pluralistic function modified polyvinylalcohol base lithium ion electricity
The electrode of pond binding agent and the barrier film between electrode.
There is advantages that
1) the pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders that the present invention provides, is compared to glycerol polymerization
Thing function modified PVA binding agent (CN105637686A, CN105261759A), the present invention passes through Michael's addition
Function monomer can controllably be introduced in PVA molecule by reaction, so that the binder product steady quality of preparation is homogeneous,
Combination property is preferable.
2) the pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders that the present invention provides, has good water-soluble
Property, elasticity and adhesive property, be applied to improve in lithium ion cell electrode sheet preparation process the homogeneity of electrode slurry,
So that electrode slurry can on a current collector uniformity and planarization ground film forming；Therefore, pole piece does not drops off, Bu Huizao
Become capacity decline, the bigger high rate capability improving lithium ion battery plus-negative plate material and stable circulation performance thus
Effectively extend battery.
3) the pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders that the present invention provides is applied to lithium ion battery
Both positive and negative polarity, can strengthen the adhesion strength between electrode active material, conductive agent and collector, beneficially electrons/ions
Conduction in charge and discharge process, reduces the electrochemical interface impedance of pole piece, the bigger lithium battery positive and negative pole material of improving
High rate capability and stable circulation performance.
4) preparation method of the pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders that the present invention provides is easy, green
Colour circle is protected, and aboundresources can significantly reduce cost, have wide market prospect；Can apply lithium ion battery just,
Negative pole, can promote the technological progress of lithium ion battery industry, or even promote the development of the strategy new industries such as electric automobile
Significant.
5) described binding agent is applied to other electrochemical energy storing device, such as other secondary cell, ultracapacitor or solar-electricity
Pond.
Accompanying drawing illustrates:
Fig. 1 is the red of the pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders that obtains of embodiment of the present invention 1-3
Outer contrast spectrogram.
Fig. 2 is that the pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders that obtains of embodiment of the present invention 1-3 is to aluminum
The peel strength comparison diagram of paper tinsel.
Fig. 3 is that the pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders that obtains of the embodiment of the present invention 3 is to difference
The peel strength figure of electrode material.
Fig. 4 is the pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders that obtains of the embodiment of the present invention 3 and use
The LiFePO4 LiFePO of PVDF binding agent4The voltage discharged first of/Li battery-specific capacity correlation curve figure.
Fig. 5 is the pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders that obtains of the embodiment of the present invention 3 and use
The LiFePO4 LiFePO of PVDF binding agent4The cyclic voltammetric comparison diagram of/Li battery.
Fig. 6 is the phosphoric acid of the pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders that the embodiment of the present invention 3 obtains
Ferrum lithium LiFePO4The cycle performance of/Li battery.
Fig. 7 is the ternary of the pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders that the embodiment of the present invention 3 obtains
LiNi1/3Co1/3Mn1/3O2Impedance diagram before/Li circulating battery.
Fig. 8 is the ternary of the pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders that the embodiment of the present invention 3 obtains
LiNi1/3Co1/3Mn1/3O2The high rate performance figure of/Li battery.
Fig. 9 is the silica-based of the pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders that obtains of the embodiment of the present invention 3
The cycle performance figure of Si/Li battery.
Figure 10 embodiment of the present invention 1-3 is to Different electrodes material (positive pole: LFP, NMC；Negative pole: Si, Graphite)
Coat film flatness comparison diagram.
Detailed description of the invention:
The following is and the present invention is further illustrated rather than limitation of the present invention.
Embodiment 1:
(1) first 3 grams of polyvinyl alcohol are dissolved in 50ml deionized water (DI-Water) in advance, and the most abundant
Stir and within 0.5-2.5 hour, obtain homogeneous, the solution of good dispersion；
(2) weigh in 0.1g NaOH catalyst reaction system in (1), be sufficiently stirred for obtaining homogeneous system；Add 2.5g
Acrylic monomers, the hydroxyl repeated polymerization unit of polyvinyl alcohol and the mol ratio of acrylic monomers are 1:0.51, regulation reaction temperature
Degree, to 80 DEG C, is always maintained at stirring, isothermal reaction 8h, obtains transparent homogeneous glue, be then neutralized to pH with LiOH
For 6-7, for pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders；
Embodiment 2:
Binding agent preparation method reference example 1 in the present embodiment, except that: the monomer of addition is mixture: 2.5g third
Olefin(e) acid and 0.84g acrylonitrile, the hydroxyl repeated polymerization unit of polyvinyl alcohol, acrylic monomers, and acrylonitrile monemer mole
Ratio is 1:0.51:0.23, and the temperature of reaction is 80 DEG C, obtains white glue, and being then neutralized to pH with LiOH is 6-7,
For pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders；
Embodiment 3:
Binding agent preparation method reference example 1 in the present embodiment, except that: the monomer of addition is mixture: 2.5g third
Olefin(e) acid, 0.84g acrylonitrile and 1g acrylamide, the hydroxyl repeated polymerization unit of polyvinyl alcohol, acrylic monomers, acrylonitrile
Monomer, and the mol ratio of acrylamide monomer is 1:0.51:0.23:0.21, the temperature of reaction is 80 DEG C, obtains white glue,
Then being neutralized to pH with LiOH is 6-7, for pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders；
Fig. 1 is the infrared of the pluralistic function modified polyvinylalcohol lithium ion battery aqueous binders that obtains of embodiment of the present invention 1-3
Contrast spectrogram.From figure 1 it appears that embodiment 1 is at 1668cm-1The flexible of C=O in obvious carboxyl is had to shake at wave number
Dynamic signal, and embodiment 2 and embodiment 3 are except there being the stretching vibration signal of carbonyl, also 2250cm-1At wave number ,-CN's shakes
Dynamic signal.
Table 1
* acrylic acid is abbreviated as AA, and acrylonitrile is abbreviated as AN, and acrylamide is abbreviated as AM.
The viscosity, right of the pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders that table 1 prepares for embodiment 1-3
The peeling force of current collector aluminum foil and mean peel strength table.In table, mean peel strength is so to survey, and first makes pure binder electrode sheet:
Directly by 2wt% adhesive coated on Al paper tinsel, coating thickness is 200 μm, then tests its peel strength, method of testing: intercept one section wide
The electrode slice that degree is 15mm, then uses stripping test instrunment (Shenzhen, 180 ° of stripping testers of triumphant strength) to test it and (peels off speed
Degree is 20mm/min), finally it is aggregated into table.From pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders to collector
The mean peel strength value of aluminium foil is it can be seen that pass through pluralistic functionization modification, its peel strength number up to 60-70mN/mm
Magnitude.Its peel strength is as shown in Figure 2.
Embodiment 4:
With LiFePO4 as positive electrode, utilizing white glue synthesized in embodiment 3 is aqueous binders.
One, the preparation of test battery:
A kind of embodiment of anode electrode of lithium ion battery sheet of the present invention, described anode electrode of lithium ion battery sheet includes afflux
Body and load lithium ion battery anode glue size on a current collector；Described lithium ion battery anode glue size include positive electrode active materials,
Conductive agent, binding agent and solvent；Described binding agent is white glue synthesized in embodiment 3；And described positive electrode active materials,
The mass ratio of conductive agent and binding agent is positive electrode active materials: conductive agent: binding agent=90:5:5, and described solvent is water.Described just
Pole active material is LiFePO4 (LiFePO4, LFP)；Described conductive agent is acetylene black；Described collector is aluminum foil current collector；
The solids content of described lithium ion battery anode glue size is 45%, and the viscosity of lithium ion battery anode glue size is 3000mPa s.
LFP and conductive agent are mixed to dispersed；It is that aqueous binders adds by glue synthesized in embodiment 3 again
Above-mentioned system stirs, adds appropriate amount of deionized water regulation viscosity, obtain LFP electrode slurry；Prepared slurry is uniformly coated with
It is overlying on Al paper tinsel, 90 DEG C of vacuum drying, obtains LFP positive plate.After the pole piece cut-parts being vacuum dried are weighed, by it
Glove box is assembled in 2025 battery cases, with lithium sheet for electrode, with polyethylene film as barrier film, with 1M LiPF6
EC/DMC/DEC (v/v/v=1/1) is that electrolyte assembled battery is circulated volt-ampere test, constant current charge-discharge test.
Two, the preparation of control cell:
Use PVDF as binding agent, with NMP as solvent, prepare control cell in the same way.
Three, electro-chemical test:
Test battery, the charge-discharge performance of control cell are carried out electro-chemical test.
Four, interpretation of result:
Fig. 4, Fig. 5 are respectively the present embodiment test battery and control cell voltage-specific capacity under 0.2C charging and discharging currents density
Curve and the cyclic voltammetry curve under 0.2mV/s sweep speed.It can be seen that use the modified poly-second of pluralistic functionization
LFP battery prepared by enol base aqueous binders, it has bigger discharge capacity and higher discharge platform, and oxidoreduction
Voltage spaces between peak is relatively small, it means that it is the less polarization process of experience when electric discharge, it was demonstrated that pluralistic function
Modified poly ethylene alcohol radical aqueous binders is for the improvement of electrode system conductive performance.
Fig. 6 is that the present embodiment tests battery cycle performance curve under 0.2C charging and discharging currents density, and after 30 circulations, battery puts
Electricity specific capacity is up to 158mAh/g, and its capability retention is up to 99%.
Embodiment 5:
With ternary material as positive electrode, utilizing white glue synthesized in embodiment 3 is aqueous binders.
One, the preparation of test electrode:
A kind of embodiment of anode electrode of lithium ion battery sheet of the present invention, described anode electrode of lithium ion battery sheet includes afflux
Body and load lithium ion battery anode glue size on a current collector；Described lithium ion battery anode glue size include positive electrode active materials,
Conductive agent, binding agent and solvent；Described binding agent is white glue synthesized in embodiment 3；And described positive electrode active materials,
The mass ratio of conductive agent and binding agent is positive electrode active materials: conductive agent: binding agent=85:9:6, and described solvent is water.Described just
Pole active material is ternary material (LiNi1/3Mn1/3Co1/3O2, NMC)；Described conductive agent is acetylene black；Described collector is
Aluminum foil current collector；The solids content of described lithium ion battery anode glue size is 45wt%, and the viscosity of lithium ion battery anode glue size is
3000mPa·s。
NMC and conductive agent are mixed to dispersed；It is that aqueous binders adds by glue synthesized in embodiment 3 again
Enter in above-mentioned system and stir, add appropriate amount of deionized water regulation viscosity, obtain NMC electrode slurry；By equal for prepared slurry
Even it is coated on Al paper tinsel, 90 DEG C of vacuum drying, obtains NMC positive plate.After the pole piece cut-parts being vacuum dried are weighed, will
Be assembled in glove box in 2025 battery cases, with lithium sheet for electrode, with polyethylene film as barrier film, with 1M LiPF6
EC/DMC/DEC (v/v/v=1/1) is that electrolyte assembled battery carries out constant current charge-discharge test.
Two, electro-chemical test:
Test battery is carried out testing impedance, charge-discharge performance test.
Three, interpretation of result:
Fig. 7 is the impedance diagram before the present embodiment test circulating battery.Fig. 8 is the high rate performance figure of the present embodiment test battery.From
It can be seen that the present embodiment battery has less impedance operator in figure, pluralistic function modified poly ethylene alcohol radical aqueous is used to glue
NMC battery prepared by knot agent, has good high rate performance, and battery specific discharge capacity under the conditions of 2C multiplying power still can be high
Reach 112mAh/g.
Embodiment 6:
With Si base as negative material, utilizing white emulsion synthesized in embodiment 3 is aqueous binders.
One, the preparation of test electrode:
A kind of embodiment of lithium ion battery negative electrode slice of the present invention, described lithium ion battery negative electrode slice includes afflux
Body and load lithium ion battery cathode slurry on a current collector；Described lithium ion battery cathode slurry include negative active core-shell material,
White emulsion synthesized in conductive agent, embodiment 3 is as binding agent and solvent；And described negative active core-shell material, conductive agent and
The mass ratio 70:20:10 of binding agent, described solvent is water.Described negative active core-shell material is Si sill；Described conductive agent is second
Acetylene black；Described collector is copper foil current collector；The solids content of described lithium ion battery cathode slurry is 45wt%, lithium-ion electric
The viscosity of pond cathode size is 3000mPa s.
Si and conductive agent are mixed to dispersed；Again white emulsion synthesized in embodiment 3 is bondd as aqueous
The agent above-mentioned system of addition stirs, adds appropriate amount of deionized water regulation viscosity, obtain Si electrode slurry；By equal for prepared slurry
Even it is coated on Cu paper tinsel, 60 DEG C of vacuum drying, obtains Si base negative plate.After the pole piece cut-parts being vacuum dried are weighed, will
Be assembled in glove box in 2025 battery cases, with lithium sheet for electrode, with polyethylene film as barrier film, with 1M LiPF6
EC/DMC/DEC (v/v/v=1/1) is that electrolyte assembled battery carries out constant current charge-discharge test.
Two, electro-chemical test:
Test electrode, the charge and discharge cycles stability of comparison electrode are carried out electro-chemical test.
Three, interpretation of result:
Fig. 9 is that the present embodiment tests battery cycle performance test curve under 400mA/g charging and discharging currents density, can from figure
To find out, use the Si base battery that pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders is prepared as binding agent
First charge-discharge coulombic efficiency up to 82%, the most tentatively show good charge-discharge performance.
Embodiment 7:
With graphite as negative material, utilizing white emulsion synthesized in embodiment 3 is aqueous binders.
One, the preparation of test electrode:
Reference example 6, the preparation of graphite electrode is a difference in that, described negative active core-shell material (graphite), conductive agent and bonding
The mass ratio 90:5:5 of agent.
Table 2
| Electrode slice | Binding agent | Mean peel strength (mN/mm) | |
| Embodiment 4 | LiFePO4 | PVA-AA-AN-AM | 61 |
| Embodiment 5 | Ternary material | PVA-AA-AN-AM | 35 |
| Embodiment 6 | Nano silica fume | PVA-AA-AN-AM | 40 |
| Embodiment 7 | Graphite | PVA-AA-AN-AM | 60 |
Table 2 is the peel strength of wherein embodiment 4-7 electrode slice, thickness parameter during film: positive pole-LiFePO4It is 100 μm,
Ternary LiNi1/3Co1/3Mn1/3O2Being 100 μm, negative pole-Si is 80 μm, graphite-50 μm.From experimental result it can be seen that many
The PVA-based aqueous binders of meta functionization modification has higher peel strength, is compared to the binding agent containing polystyrene
System (CN 105261759A), its peel strength enhances an order of magnitude.
Embodiment 8:
With graphite, Si base as negative material, with LiFePO4, ternary material as positive electrode, it is utilized respectively embodiment 1,2
Or PVA-AA, PVA-AA-AN or PVA-AA-AN-AM macromolecule lithium battery binding agent synthesized by embodiment 3 is
Binding agent makes electrode slice, and is respectively compared the planarization of pole piece.
One, the preparation of test electrode:
The preparation reference example 7 of graphite electrode, different parts is, the binding agent used is PVA-AA；
The preparation reference example 6 of Si base electrode, different parts is, the binding agent used is PVA-AA-AN；
The preparation reference example 4 of LFP base electrode.
The preparation reference example 5 of NCM electrode.
Two, pole piece planarization test:
The planarization of test electrode slice is observed, contrasted.
Four, interpretation of result:
Figure 10 is the pole piece planarization comparison diagram of the present embodiment difference test electrode slice.It can be seen that employing pluralistic function
Change graphite, Si negative plate that modified PVA-AA, PVA-AA-AN macromolecule lithium battery binding agent are prepared respectively, and
Use pluralistic function modified PVA-AA-AN-AM macromolecule lithium battery binding agent prepare LiFePO4, ternary material
Positive plate, all has excellent uniformity and planarization, granular sensation or discontinuous point does not occur, is conducive to improving battery long circulating
During electrochemical stability, thus improve the service life of battery, gather around and have broad application prospects and development potentiality.
Claims (7)
1. a pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders, it is characterised in that it is with polyvinyl alcohol
For substrate, using hydrophilic monomer and oleophylic monomer as functional modification monomer, through water prepared by Michael addition reaction modification
Dissolubility glue, its solid content is 2-50%, and viscosity is 10～20000mPa s；Described hydrophilic monomer is for having following structure
At least one in monomer: CH2=CR1R2；Wherein, R1Selected from-H ,-CH3、-CH2CH3；R2Selected from-COOH,
-COOLi、-COONa、-CONH2；Described oleophylic monomer is to have at least one in the monomer of following structure:
CH2=CR3R4；Wherein, R3Selected from-H ,-CH3、-CH2CH3, R4Selected from-CN ,-OCOCH3、-CONHCH3、
-CON(CH3)2, and-COOR5In at least one, R5At least one in C1～C8 alkyl；Described polyethylene
The molecular weight of alcohol is 10000-250000, hydroxyl repeated polymerization unit, hydrophilic monomer and the oleophylic monomer of polyvinyl alcohol
Mol ratio is 1:0.01～1:0～0.99.
Pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders the most according to claim 1, it is characterised in that
Described Michael addition reaction refers to that polyvinyl alcohol passes through base catalysis with one or more of hydrophilic monomer and lipophile monomer
Agent causes reacts under conditions of 0～90 DEG C；The consumption of described base catalyst is the 0.1～10wt% of monomer gross mass.
Pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders the most according to claim 2, it is characterised in that
Described base catalyst is selected from one or more in LiOH, NaOH, LiOH/ carbamide, NaOH/ carbamide.
4. pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders described in claim 1 is at based lithium-ion battery positive plate
In application, it is characterised in that described anode electrode of lithium ion battery sheet includes collector and load lithium on a current collector
Ion battery anode sizing agent；Described lithium ion battery anode glue size includes positive electrode active materials, conductive agent, claim 1
Described pluralistic function modified polyvinylalcohol base lithium ion battery binding agent and solvent；Described positive electrode active materials, conductive agent
It is=70～95:1～20:4～10 with the mass ratio of described pluralistic function modified polyvinylalcohol base lithium ion battery binding agent；Described
Positive electrode active materials is selected from one or more of LiFePO4, cobalt acid lithium, LiMn2O4 or ternary material；Described conductive agent is
Acetylene black；Described collector is aluminium foil；The solids content of described lithium ion battery anode glue size is 30～75%, lithium ion
The viscosity of battery anode slurry is 3000～8000mPa s.
5. pluralistic function modified polyvinylalcohol base lithium ion battery binding agent described in claim 1 is in anode plate for lithium ionic cell
Application, it is characterised in that described lithium ion battery negative electrode slice includes collector and load lithium ion on a current collector
Battery cathode slurry；Described lithium ion battery cathode slurry includes described in negative active core-shell material, conductive agent, claim 1
Pluralistic function modified polyvinylalcohol base lithium ion battery binding agent and solvent；Described negative active core-shell material, conductive agent and institute
The mass ratio stating pluralistic function modified polyvinylalcohol base lithium ion battery binding agent is 70～95:1～20:4～10；Described negative pole
Active material is selected from one or more of silica-base material, lithium titanate or graphite；Described conductive agent is acetylene black；Described
Collector is Copper Foil.
6. described in claim 1, pluralistic function modified polyvinylalcohol base lithium ion battery binding agent is applied to electrochemical energy storing device,
It is characterized in that, described electrochemical energy storing device is ultracapacitor or solaode.
7. a lithium ion battery, described lithium ion battery includes that battery case, pole piece and electrolyte, described pole piece and electrolysis are liquid-tight
It is encapsulated in battery case, it is characterised in that described pole piece includes the modified poly-second of pluralistic functionization described in claim 1 or 2
The electrode of enol base lithium ion battery binding agent and the barrier film between electrode.
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| CN201610504108.3A CN105958075B (en) | 2016-06-28 | 2016-06-28 | Pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders and the application in electrochemical energy storing device |
| PCT/CN2016/098378 WO2018000578A1 (en) | 2016-06-28 | 2016-09-08 | Multi-functional modified polyvinyl alcohol-based water-borne adhesive for lithium ion battery and application thereof in electrochemical energy storage device |
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| CN201610504108.3A CN105958075B (en) | 2016-06-28 | 2016-06-28 | Pluralistic function modified polyvinylalcohol base lithium ion battery aqueous binders and the application in electrochemical energy storing device |
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| WO2018000578A1 (en) | 2018-01-04 |
| CN105958075B (en) | 2018-09-28 |
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