CN109148886A - Binder, preparation method thereof and lithium ion battery negative plate - Google Patents
Binder, preparation method thereof and lithium ion battery negative plate Download PDFInfo
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- CN109148886A CN109148886A CN201810990807.2A CN201810990807A CN109148886A CN 109148886 A CN109148886 A CN 109148886A CN 201810990807 A CN201810990807 A CN 201810990807A CN 109148886 A CN109148886 A CN 109148886A
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- pyrenyl
- polyacrylic acid
- binder
- preparation
- silicon
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- 239000011230 binding agent Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 10
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 100
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 65
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 125000001725 pyrenyl group Chemical group 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 27
- 229910052744 lithium Inorganic materials 0.000 claims description 26
- 239000010703 silicon Substances 0.000 claims description 26
- 229910052710 silicon Inorganic materials 0.000 claims description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 25
- 239000006258 conductive agent Substances 0.000 claims description 19
- 229910002804 graphite Inorganic materials 0.000 claims description 19
- 239000010439 graphite Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 10
- 239000007773 negative electrode material Substances 0.000 claims description 10
- 150000001721 carbon Chemical group 0.000 claims description 9
- 125000003700 epoxy group Chemical group 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003273 ketjen black Substances 0.000 claims description 4
- 229910000676 Si alloy Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910021384 soft carbon Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910003978 SiClx Inorganic materials 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000003993 interaction Effects 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 20
- -1 Polypropylene Polymers 0.000 description 17
- 239000008247 solid mixture Substances 0.000 description 17
- 239000011267 electrode slurry Substances 0.000 description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-Butanol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 239000011149 active material Substances 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 238000010792 warming Methods 0.000 description 7
- 239000006256 anode slurry Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of an adhesive, which comprises the steps of firstly adding polyacrylic acid into deionized water, stirring until the polyacrylic acid is completely dissolved, and preparing a polyacrylic acid aqueous solution; then adding pyrenyl substituent into the polyacrylic acid aqueous solution, keeping the system in an inert atmosphere, stirring, slowly heating to 120-180 ℃, and continuously reacting for 6-10 hours to obtain a product; and finally, centrifugally washing and drying the product to prepare the binder. The pyrenyl functional group is introduced into the PAA, so that the binding power between the PAA and the active substance is improved, the interaction force between the active substance and the conductive carbon is improved, and the cycle performance of the lithium ion battery is improved.
Description
Technical field
The present invention relates to lithium ion battery production fields, and in particular to a kind of binder and preparation method thereof further relates to one
Kind anode plate for lithium ionic cell.
Background technique
With the development of mancarried electronic aid and electric car, requirement of the people to the energy density of lithium ion battery also exists
Increasingly improve.The theoretical specific capacity of the most wide graphite negative electrodes material of commercial applications only has 372mAh/g at present, cannot expire
The growth requirement of sufficient lithium ion battery with high energy density, furthermore its intercalation potential gives battery very close to the deposition potential of lithium
Bring huge security risk.A large amount of work concentrated on silicon based anode material in recent years, the reason is that the theory of silicon superelevation
Capacity (4200mAh/g), but nano-silicon is battery adjoint very big body in charge and discharge process as the defect of negative electrode material
Product effect leads to the dusting of silicon particle, to lose electrical contact between conductive agent, destroys entire electrode structure, causes
The decaying of battery capacity and very poor cycle performance.In order to improve the performance of silicium cathode and its cycle life, a conjunction is selected
Suitable high-performance adhesive is a kind of very important method, and binder common at present has PAA (polyacrylic acid), CMC (carboxylic first
Base cellulose)/SBR (butadiene-styrene rubber), sodium alginate, chitosan, PI (polyimides), PAI etc., wherein PAA, PVA and seaweed
Contain a large amount of carboxyl on the binder strand of sour sodium form, very strong phase can be formed between active material and collector
Interaction, and stable SEI film is advantageously formed, to can be applicable in the silicon-based anode system of high capacity.But in order to mention
The electric conductivity of high electrode, is usually added into conductive carbon, the silion cell system obvious for bulk effect, in the removal lithium embedded mistake of silicon
Cheng Zhong, conductive carbon is easy to disengage between active material, so that conductive network avalanche, declines rapidly so as to cause capacity
Subtract.
Summary of the invention
In view of the above-mentioned problems, the present invention provides a kind of preparation method of binder, by introducing pyrenyl function in PAA
Group improves the cohesive force between PAA and active material, while improving the interaction force between active material and conductive carbon,
From the cycle performance for improving lithium ion battery.
The present invention to achieve the goals above, using following technical scheme:
A kind of preparation method of binder, comprising the following steps:
A, stirring in deionized water is added in polyacrylic acid and polyacrylic acid aqueous solution is made to dissolving completely；
B, pyrenyl substituent is added into polyacrylic acid aqueous solution, system is kept in an inert atmosphere, stirring and slow
120~180 DEG C are warming up to, product is made in the reaction was continued 6~10h；
C, by after product centrifugation washing, binder is made in drying.
Preferably, the molecular weight of the polyacrylic acid is 5000~100000, and the polyacrylic acid and the pyrenyl replace
The weight ratio of object is 3:1~5:1.
Further, the mass fraction of the polyacrylic acid aqueous solution is 5~20%.
Further, the pyrenyl substituent is the aliphatic hydrocarbon containing amino of the alkylol of pyrenyl substitution, pyrenyl substitution
Or the aliphatic hydrocarbon containing epoxy group that pyrenyl replaces.
Preferably, carbon atom number 4≤n≤10 in the alkylol that the pyrenyl replaces, number 1≤n≤3 of hydroxyl；It is described
Carbon atom number 4≤n≤10 in the aliphatic hydrocarbon containing amino that pyrenyl replaces, number 1≤n≤3 of amino；What the pyrenyl replaced
Carbon atom number 3≤n≤8 in aliphatic hydrocarbon containing epoxy group, the number of epoxy group are 1.
It is another object of the present invention to provide a kind of binders prepared with above-mentioned preparation method.
Third object of the present invention is to provide a kind of anode plate for lithium ionic cell containing binder.
Further, the anode plate for lithium ionic cell further includes negative electrode material, conductive agent, each component by weight,
Additive amount are as follows:
85~97 parts of negative electrode material；
1~10 part of conductive agent；
2~5 parts of binder.
Preferably, the negative electrode material is silicon/graphite composite material, in silicon alloy, graphite, hard carbon, soft carbon, lithium titanate
It is a kind of, wherein the silicon in the silicon/graphite composite material is silicon carbide or silica, and content is silicon/graphite composite material
3~35wt%；
The conductive agent is at least one of superconducting carbon black, carbon nanotube, graphene, Ketjen black, acetylene black.
Compared with prior art, the invention has the following advantages:
PAA introduces pyrenyl functional group by esterification modification, eliminates PAA molcohesion, improves itself and active matter
Cohesive force between matter, and the interaction force between active material and conductive carbon can be improved in the pyrenyl functional group introduced,
Bulk effect of silicon during removal lithium embedded can be buffered, ensure that the integrality of entire electrode structure, to improve cyclicity
Energy.This method simple process, cost are controllable, are suitble to large-scale production.
Detailed description of the invention
1 gained negative electrode tab of Fig. 1 embodiment of the present invention button electricity obtained exists with 1 gained negative electrode tab of comparative example button electricity obtained
The cycle performance comparison diagram of 0.1C.
Specific embodiment
Present invention firstly provides a kind of preparation methods of binder, and modified PAA cathode is made by esterification modification in PAA
Binder, specific preparation process are as follows: stirring in deionized water is added in polyacrylic acid, and, to dissolving completely, it is 5 that mass fraction, which is made,
~20% polyacrylic acid aqueous solution；Pyrenyl substituent is added into polyacrylic acid aqueous solution, pyrenyl substituent here is pyrenyl
Substituted alkylol, the aliphatic hydrocarbon containing amino that pyrenyl replaces or the aliphatic hydrocarbon containing epoxy group of pyrenyl substitution, and will
Reaction system is kept in an inert atmosphere, and inert atmosphere here is most preferably nitrogen, then proceedes to stir and be to slowly warm up to
120~180 DEG C, 6~10h is reacted, product is made；After product centrifugation washing, binder is made in drying, i.e. m-PAA is (modified
Polypropylene negative electrode binder).
Preferably, carbon atom number 4≤n≤10 in the alkylol that the pyrenyl replaces, number 1≤n≤3 of hydroxyl are optimal
It is selected as 4- (1- pyrenyl)-n-butyl alcohol；Carbon atom number 4≤n≤10 in the aliphatic hydrocarbon containing amino that the pyrenyl replaces, amino
Number 1≤n≤3；Carbon atom number 3≤n≤8 in the aliphatic hydrocarbon containing epoxy group that the pyrenyl replaces, epoxy group
Number is 1.By taking the modified PAA of 4- (1- pyrenyl)-n-butyl alcohol as an example, the reaction equation of the modifying process are as follows:
During the preparation process, the molecular weight of used PAA is preferably 5000~100000, this is because PAA molecular weight
If excessively high, slower, to obtain solution viscosity height is dissolved, the progress of modified-reaction is unfavorable for.In addition, each component in reaction process
The weight ratio of additive amount be preferably PAA: pyrenyl substituent=3:1~5:1, being defined to the ratio of the two is to control
The content of the upper COOH reacted away of PAA can have a great impact to its cohesive force if COOH consumption is excessive.
The present invention still further provides a kind of binder being prepared by above-mentioned preparation method, the binder due to
Pyrenyl is introduced in polyacrylic acid backbone, improves the interaction force between active material and conductive carbon, avoids silicon in deintercalation
It is detached between conductive agent and active material caused by bulk effect caused by during lithium, to substantially increase battery
Cycle performance.
The present invention further discloses a kind of anode plate for lithium ionic cell, and the anode plate for lithium ionic cell contains above-mentioned
M-PAA, the preparation process of the lithium-ion negative pole piece are one of this field conventional process, in the present invention its preparation process are as follows:
By weight, 85~97 parts of negative electrode materials and 1~10 part of conductive agent are weighed, grinding obtains finely dispersed solid mixing
Object；2~5 parts of m-PAA is add to deionized water and is stirred, obtaining concentration after mixing evenly is the viscous of 0.5~5wt%
Tie agent solution；Solid mixture and binder solution are mixed, 12~20min is stirred, uniformly mixed cathode is obtained after defoaming
Slurry；Negative electrode slurry is coated on copper foil, vacuum drying obtains anode plate for lithium ionic cell.Here the negative electrode material used
It can be silicon/graphite composite material, silicon alloy, graphite, hard carbon, soft carbon, any one in lithium titanate, when negative electrode material is
Silicon/graphite composite material, the silicon materials are SiC or SiO, and content is 3~35wt% of silicon/graphite composite material；Institute
The conductive agent used is at least one of superconducting carbon black, carbon nanotube, graphene, Ketjen black, acetylene black；It is obtained after defoaming
Uniformly mixed negative electrode slurry, here uniformly mixed, which refers to that negative electrode slurry appearance is normal and room temperature stands 12h, to sink
Drop.Anode plate for lithium ionic cell is prepared using binder of the invention, can be improved mutual between active material and conductive carbon
Active force can buffer bulk effect of silicon during removal lithium embedded, ensure that the integrality of entire electrode structure, to improve
Cycle performance.This method simple process, cost are controllable, are suitble to large-scale production.
With reference to the accompanying drawing and specific embodiment does further clear and complete explanation to technical solution of the present invention.
Embodiment 1
A, stirring in deionized water is added in polyacrylic acid and the polyacrylic acid that mass fraction is 5% is made to dissolving completely
Aqueous solution；
B, 4- (1- pyrenyl)-n-butyl alcohol is added into polyacrylic acid aqueous solution, keeping body ties up in nitrogen atmosphere, stirs and delay
Slowly 150 DEG C are warming up to, product is made in the reaction was continued 6h, wherein the weight ratio of polyacrylic acid and 4- (1- pyrenyl)-n-butyl alcohol is
3:1；
C, by after product centrifugation washing, m-PAA is made in drying.
85 parts of SiO/ graphite (wherein SiO accounts for whole 25wt%) and 10 parts of SP conductive agent are weighed according to parts by weight, are ground
Mill obtains finely dispersed solid mixture；5 parts of m-PAA is add to deionized water and is stirred, with turning for 2000rpm
Speed obtains the m-PAA solution that concentration is 5wt% after mixing evenly；Solid mixture and m-PAA solution are mixed, with 2000rpm
Revolving speed stir 20min, uniformly mixed silicon-based anode slurry is obtained after defoaming；With 80g/cm2Surface density by silicon-based anode
Slurry is coated on copper foil, and 85 DEG C of vacuum dryings obtain anode plate for lithium ionic cell.
Embodiment 2
A, stirring in deionized water is added in polyacrylic acid and the polyacrylic acid that mass fraction is 20% is made to dissolving completely
Aqueous solution；
B, 4- (1- pyrenyl)-n-butyl alcohol is added into polyacrylic acid aqueous solution, keeping body ties up in nitrogen atmosphere, stirs and delay
Slowly 120 DEG C are warming up to, product is made in the reaction was continued 10h, wherein the weight ratio of polyacrylic acid and 4- (1- pyrenyl)-n-butyl alcohol is
5:1；
C, by after product centrifugation washing, m-PAA is made in drying.
97 parts of SiO/ graphite (wherein SiO accounts for whole 25wt%) and 1 part of Ketjen black conductive agent are weighed according to parts by weight,
Grinding obtains finely dispersed solid mixture；2 parts of m-PAA is add to deionized water and is stirred, with 800rpm's
Revolving speed obtains the m-PAA solution that concentration is 0.5wt% after mixing evenly；Solid mixture and m-PAA solution are mixed, with
The revolving speed of 1000rpm stirs 12min, and uniformly mixed silicon-based anode slurry is obtained after defoaming；With 20g/cm2Surface density by silicon
Base negative electrode slurry is coated on copper foil, and 85 DEG C of vacuum dryings obtain anode plate for lithium ionic cell.
Embodiment 3
A, stirring in deionized water is added in polyacrylic acid and the polyacrylic acid that mass fraction is 15% is made to dissolving completely
Aqueous solution；
B, 4- (1- pyrenyl)-n-butyl alcohol is added into polyacrylic acid aqueous solution, keeping body ties up in nitrogen atmosphere, stirs and delay
Slowly 180 DEG C are warming up to, product is made in the reaction was continued 8h, wherein the weight ratio of polyacrylic acid and 4- (1- pyrenyl)-n-butyl alcohol is
4:1；
C, by after product centrifugation washing, m-PAA is made in drying.
91 parts of SiC/ graphite (wherein SiC accounts for whole 5wt%) and 5 parts of SP conductive agent are weighed according to parts by weight, are ground
Obtain finely dispersed solid mixture；4 parts of m-PAA is add to deionized water and is stirred, with the revolving speed of 1000rpm
The m-PAA solution that concentration is 3.5wt% is obtained after mixing evenly；Solid mixture and m-PAA solution are mixed, with 1500rpm
Revolving speed stir 15min, uniformly mixed silicon-based anode slurry is obtained after defoaming；With 60g/cm2Surface density by silicon-based anode
Slurry is coated on copper foil, and 85 DEG C of vacuum dryings obtain anode plate for lithium ionic cell.
Embodiment 4
A, stirring in deionized water is added in polyacrylic acid and the polyacrylic acid that mass fraction is 10% is made to dissolving completely
Aqueous solution；
B, 4- (1- pyrenyl)-n-butyl alcohol is added into polyacrylic acid aqueous solution, keeping body ties up in helium-atmosphere, stirs and delay
Slowly 160 DEG C are warming up to, product is made in the reaction was continued 9h, wherein the weight ratio of polyacrylic acid and 4- (1- pyrenyl)-n-butyl alcohol is
3:1；
C, by after product centrifugation washing, m-PAA is made in drying.
The SP conductive agent of 96 parts of graphite and 2 parts is weighed according to parts by weight, grinding obtains finely dispersed solid mixture；It will
4 parts of m-PAA, which is add to deionized water, to be stirred, and obtains concentration after mixing evenly with the revolving speed of 1200rpm as 3wt%'s
M-PAA solution；Solid mixture and m-PAA solution are mixed, 16min is stirred with the revolving speed of 1800rpm, is mixed after defoaming
Uniform negative electrode slurry；With 60g/cm2Surface density by negative electrode slurry be coated on copper foil on, 85 DEG C of vacuum dryings, obtain lithium from
Sub- battery cathode sheet.
Embodiment 5
A, stirring in deionized water is added in polyacrylic acid and the polyacrylic acid that mass fraction is 8% is made to dissolving completely
Aqueous solution；
B, 4- (1- pyrenyl)-n-butyl alcohol is added into polyacrylic acid aqueous solution, keeping body ties up in nitrogen atmosphere, stirs and delay
Slowly 140 DEG C are warming up to, product is made in the reaction was continued 7h, wherein the weight ratio of polyacrylic acid and 4- (1- pyrenyl)-n-butyl alcohol is
4:1；
C, by after product centrifugation washing, m-PAA is made in drying.
The SP conductive agent of 92 parts of hard carbons and 4 parts is weighed according to parts by weight, grinding obtains finely dispersed solid mixture；It will
4 parts of m-PAA, which is add to deionized water, to be stirred, and obtains concentration after mixing evenly with the revolving speed of 1000rpm as 1.5wt%
M-PAA solution；Solid mixture and m-PAA solution are mixed, 15min is stirred with the revolving speed of 2000rpm, is mixed after defoaming
Close uniform negative electrode slurry；With 60g/cm2Surface density by negative electrode slurry be coated on copper foil on, 85 DEG C of vacuum dryings obtain lithium
Ion battery negative electrode tab.
Embodiment 6
A, stirring in deionized water is added in polyacrylic acid and the polyacrylic acid that mass fraction is 5% is made to dissolving completely
Aqueous solution；
B, 4- (1- pyrenyl) -1- fourth ammonia is added into polyacrylic acid aqueous solution, keeping body ties up in nitrogen atmosphere, stirs and delay
Slowly 140 DEG C are warming up to, product is made in the reaction was continued 7h, wherein the weight ratio of polyacrylic acid and 4- (1- pyrenyl) -1- fourth ammonia is
4:1；
C, by after product centrifugation washing, m-PAA is made in drying.
The SP conductive agent of 92 parts of hard carbons and 4 parts is weighed according to parts by weight, grinding obtains finely dispersed solid mixture；It will
4 parts of m-PAA, which is add to deionized water, to be stirred, and obtains concentration after mixing evenly with the revolving speed of 1000rpm as 1.5wt%
M-PAA solution；Solid mixture and m-PAA solution are mixed, 15min is stirred with the revolving speed of 2000rpm, is mixed after defoaming
Close uniform negative electrode slurry；With 60g/cm2Surface density by negative electrode slurry be coated on copper foil on, 85 DEG C of vacuum dryings obtain lithium
Ion battery negative electrode tab.
Embodiment 7
A, stirring in deionized water is added in polyacrylic acid and the polyacrylic acid that mass fraction is 10% is made to dissolving completely
Aqueous solution；
B, 4- (1- pyrenyl) -1- epoxy butane is added into polyacrylic acid aqueous solution, keeping body ties up in argon atmospher, stirs
And 160 DEG C are to slowly warm up to, product is made in the reaction was continued 9h, wherein polyacrylic acid and 4- (1- pyrenyl) -1- epoxy butane
Weight ratio is 3:1；
C, by after product centrifugation washing, m-PAA is made in drying.
The SP conductive agent of 96 parts of graphite and 2 parts is weighed according to parts by weight, grinding obtains finely dispersed solid mixture；It will
4 parts of m-PAA, which is add to deionized water, to be stirred, and obtains concentration after mixing evenly with the revolving speed of 1200rpm as 3wt%'s
M-PAA solution；Solid mixture and m-PAA solution are mixed, 16min is stirred with the revolving speed of 1800rpm, is mixed after defoaming
Uniform negative electrode slurry；With 60g/cm2Surface density by negative electrode slurry be coated on copper foil on, 85 DEG C of vacuum dryings, obtain lithium from
Sub- battery cathode sheet.
Comparative example 1
85 parts of SiO/ graphite (wherein SiO accounts for whole 25wt%) and 10 parts of SP conductive agent are weighed according to parts by weight, are ground
Mill obtains finely dispersed solid mixture；5 parts of PAA powder is add to deionized water and is stirred, with 2000rpm's
Revolving speed obtains the PAA solution that concentration is 5wt% after mixing evenly；Solid mixture and PAA solution are mixed, with 2000rpm's
Revolving speed stirs 20min, and uniformly mixed silicon-based anode slurry is obtained after defoaming；With 80g/cm2Surface density silicon-based anode is starched
Material is coated on copper foil, and 85 DEG C of vacuum dryings obtain anode plate for lithium ionic cell.
It is to make it respectively with negative electrode tab obtained by Examples 1 to 2 and 1 gained negative electrode tab of comparative example to electrode with lithium metal
At button electricity, carry out cycle performance evaluation and test (temperature be 25 DEG C, voltage be 5mV~1.5V, electric current 0.1C, capacity retention ratio >=
80%).Test result see the table below and Fig. 1.
| Embodiment 1 | Embodiment 2 | Comparative example 1 | |
| Active material percentage | 85% | 97% | 85% |
| Cycle performance | 472 cycle | 338 cylce | 37 cycle |
By upper table and Fig. 1 result it is found that when adding proportion is identical, compared to pure PAA, the pole present invention gained m-PAA
The big cycle performance for improving lithium ion battery, cycle life was increased to 472 weeks from 37 weeks, this is because on m-PAA
The pyrenyl of introducing can improve the interaction force between conductive agent, maintain structural integrity of the battery in charge and discharge process
Property, so cycle performance is improved.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent alternative, be included within the scope of the present invention.
Claims (9)
1. a kind of preparation method of binder, it is characterised in that: the following steps are included:
A, stirring in deionized water is added in polyacrylic acid and polyacrylic acid aqueous solution is made to dissolving completely；
B, pyrenyl substituent is added into polyacrylic acid aqueous solution, system is kept in an inert atmosphere, stirring and slowly heating up
To 120 ~ 180 DEG C, product is made in the reaction was continued 6 ~ 10h；
C, by after product centrifugation washing, binder is made in drying.
2. preparation method as described in claim 1, it is characterised in that: the molecular weight of the polyacrylic acid is 5000 ~ 100000,
The weight ratio of the polyacrylic acid and the pyrenyl substituent is 3:1 ~ 5:1.
3. preparation method as described in claim 1, it is characterised in that: the mass fraction of the polyacrylic acid aqueous solution be 5 ~
20%。
4. preparation method as described in claim 1, it is characterised in that: the pyrenyl substituent be pyrenyl replace alkylol,
The aliphatic hydrocarbon containing epoxy group that the aliphatic hydrocarbon containing amino or pyrenyl that pyrenyl replaces replace.
5. preparation method as claimed in claim 4, it is characterised in that: 4≤n of carbon atom number in the alkylol that the pyrenyl replaces
≤ 10, number 1≤n≤3 of hydroxyl；Carbon atom number 4≤n≤10 in the aliphatic hydrocarbon containing amino that the pyrenyl replaces, amino
Number 1≤n≤3；Carbon atom number 3≤n≤8 in the aliphatic hydrocarbon containing epoxy group that the pyrenyl replaces, epoxy group
Number be 1.
6. a kind of binder with the described in any item preparation method preparations of claim 1 ~ 5.
7. a kind of anode plate for lithium ionic cell containing binder as claimed in claim 6.
8. anode plate for lithium ionic cell as claimed in claim 7, it is characterised in that: further include negative electrode material, conductive agent, each group
Divide by weight, additive amount are as follows:
85 ~ 97 parts of negative electrode material；
1 ~ 10 part of conductive agent；
2 ~ 5 parts of binder.
9. anode plate for lithium ionic cell as claimed in claim 7, it is characterised in that: the negative electrode material is that silicon/graphite is compound
One of material, silicon alloy, graphite, hard carbon, soft carbon, lithium titanate, wherein the silicon in the silicon/graphite composite material is carbon
SiClx or silica, content are 3 ~ 35wt% of silicon/graphite composite material；
The conductive agent is at least one of superconducting carbon black, carbon nanotube, graphene, Ketjen black, acetylene black.
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| CN111769285A (en) * | 2020-07-01 | 2020-10-13 | 苏州凌威新能源科技有限公司 | Lithium battery negative electrode adhesive and negative electrode plate |
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