CN115141598A - Lithium ion battery electrode adhesive and preparation method and application thereof - Google Patents
Lithium ion battery electrode adhesive and preparation method and application thereof Download PDFInfo
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- CN115141598A CN115141598A CN202110335522.7A CN202110335522A CN115141598A CN 115141598 A CN115141598 A CN 115141598A CN 202110335522 A CN202110335522 A CN 202110335522A CN 115141598 A CN115141598 A CN 115141598A
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- 239000000853 adhesive Substances 0.000 title claims abstract description 44
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 44
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 33
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 24
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 15
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 9
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 7
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 25
- 239000011883 electrode binding agent Substances 0.000 claims description 24
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 22
- 238000006138 lithiation reaction Methods 0.000 claims description 18
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 16
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 13
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000012493 hydrazine sulfate Substances 0.000 claims description 11
- 229910000377 hydrazine sulfate Inorganic materials 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims description 7
- 159000000002 lithium salts Chemical class 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000015271 coagulation Effects 0.000 claims description 4
- 238000005345 coagulation Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims 1
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 16
- 239000011230 binding agent Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000013543 active substance Substances 0.000 description 8
- 239000001768 carboxy methyl cellulose Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229920002125 Sokalan® Polymers 0.000 description 7
- 239000006258 conductive agent Substances 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- 230000009191 jumping Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910008626 Li1.2Ni0.13Co0.13Mn0.54O2 Inorganic materials 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical group C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/08—Polyhydrazides; Polytriazoles; Polyaminotriazoles; Polyoxadiazoles
-
- 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
-
- 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
Abstract
The invention relates to a lithium ion battery electrode adhesive and a preparation method and application thereof. The lithium ion battery electrode adhesive is a polyoxadiazole lithium sulfonate polymer, has carboxylic acid groups, oxadiazole groups and lithium sulfonate groups, and has a phenylate structure on a main chain; the chemical structural formula of the polyoxadiazole lithium sulfonate polymer is as follows:
X:Y＝1：9‑9：1。
Description
Technical Field
The invention relates to the technical field of materials, in particular to a lithium ion battery electrode adhesive and a preparation method and application thereof.
Background
The high-speed development of new energy automobiles greatly improves the comprehensive performance requirements on lithium ion batteries. The development of high-performance power batteries is fundamentally supported by various advanced materials in power battery systems. Particularly, the high-capacity anode and cathode materials directly determine the energy density of the power battery. Most of high-capacity positive and negative electrode materials are accompanied by repeated expansion/contraction processes caused by the insertion and extraction of a large amount of lithium ions, so that the volume of the electrode plate is changed dramatically.
The contact integrity among the active substance, the conductive additive and the current collector is maintained through the binder, and the cracking and crushing caused by volume change of the main material in the charge-discharge cycle process are reduced, so that the method is one of the simplest methods for dealing with the violent volume change accompanied by high-capacity positive and negative electrode materials at present.
The most commonly used binder polyvinylidene fluoride (PVDF) for lithium ion batteries has good elasticity and electrochemical stability, but PVDF and active material particles can only be connected by simple van der waals force, and cannot maintain large volume change of a pole piece in the lithiation/delithiation process under multiple cycles. While the pole pieces made of binders such as sodium carboxymethylcellulose (CMC) and polyacrylic acid (PAA) are generally harder, it is necessary to add softer materials such as Styrene Butadiene Rubber (SBR) or to improve the performance of the pole pieces by introducing flexible groups. Otherwise, the pole piece can obviously fall off and crack, and finally the conductivity, the capacity and the cycle performance of the battery are reduced sharply. This process therefore requires an adhesive which not only has strong adhesion but also withstands drastic changes in expansion and contraction. Moreover, cracking and powdering of the main material are inevitably caused by the expansion process, and thus the electrical contact is deteriorated. This requires that the binder also have ionic and electronic conductivity.
Therefore, new application scenarios impose higher requirements on the battery, reflected in the binder material, and a "multifunctional" binder having multiple properties is required.
Disclosure of Invention
The embodiment of the invention provides a lithium ion battery electrode adhesive and a preparation method and application thereof. The carboxylic acid group provides adhesiveness and hardness, the flexibility of the polymer is increased through the phenyl ether structure of the main chain, and the electronic conductivity of the oxadiazole structure and the lithium sulfonate group provide lithium ion jumping points for the active substance, so that the active substance becomes a potential all-purpose binder, and has good hardness, flexibility and electronic and ionic double conductivity.
In a first aspect, an embodiment of the present invention provides a lithium ion battery electrode binder, which is a polyoxadiazole sulfonic acid lithium polymer having a carboxylic acid group, an oxadiazole group, and a lithium sulfonate group, and having a phenylene ether structure in a main chain;
the chemical structural formula of the polyoxadiazole lithium sulfonate polymer is as follows:
X:Y＝1：9-9：1。
preferably, the polyoxadiazole lithium sulfonate polymer has a chemical structural formula in which X: Y = 5.
In a second aspect, an embodiment of the present invention provides a preparation method of the lithium ion battery electrode binder in the first aspect, where the preparation method includes:
prepolymerizing hydrazine sulfate and carboxylic acid monomers at 60-100 ℃ for 2-4 hours; wherein the molar ratio of hydrazine sulfate to carboxylic acid monomer is 1: 1-1.5;
polymerizing for 5-8 hours at 80-130 ℃, and adding an end capping agent after the polymerization is finished;
cyclizing for 3-5 hours at the temperature of 120-170 ℃ to obtain a polymer;
solidifying and forming the obtained polymer in a water coagulation bath, washing the polymer to be neutral, and soaking the polymer in a lithium salt aqueous solution for 1 to 5 days to carry out lithiation on the polymer to obtain a lithiation product;
and drying the lithiation product, and dissolving the lithiation product in a solvent to form a uniform solution, namely the lithium ion battery electrode adhesive.
Preferably, the carboxylic acid monomers include terephthalic acid and diphenyl ether dicarboxylic acid; the molar ratio of terephthalic acid to diphenyl ether dicarboxylic acid is 1.
Preferably, the molar ratio of terephthalic acid to diphenyl ether dicarboxylic acid is 5.
Preferably, the molar ratio of terephthalic acid to biphenyl ether dicarboxylic acid is 1; the molar ratio of the hydrazine sulfate to the carboxylic acid monomer is 1.05.
Preferably, the end-capping agent is benzoic acid;
the lithium salt aqueous solution is lithium hydroxide or lithium carbonate aqueous solution.
Preferably, the solvent comprises: any one of N-methylpyrrolidone NMP, N-dimethylformamide DMF, N-dimethylacetamide DMAC or dimethylsulfoxide DMSO.
In a third aspect, an embodiment of the present invention provides a lithium battery electrode, including the lithium ion battery electrode binder described in the first aspect.
In a fourth aspect, an embodiment of the present invention provides a lithium battery, including the lithium ion battery electrode binder described in the first aspect, or including the lithium ion battery electrode described in the second aspect.
The lithium ion battery electrode adhesive provided by the invention provides adhesiveness and hardness through carboxylic acid groups, increases the flexibility of a polymer through a phenyl ether structure of a main chain, and provides lithium ion jumping points for active substances by combining the electronic conductivity of an oxadiazole structure and a lithium sulfonate group, so that the lithium ion battery electrode adhesive becomes a potential all-round adhesive, and has better hardness, flexibility and electron-ion double conductivity.
Based on the advantages, the lithium ion battery electrode adhesive provided by the invention is adopted in the battery pole piece, so that the using amount of a conductive agent in the battery pole piece can be properly reduced, and the using amount of a main material is increased, thereby improving the capacity of the battery electrode; due to the electron-ion double conduction characteristic, the impedance can be effectively reduced; meanwhile, the existence of carboxylic acid groups enhances the adhesiveness, and the flexibility of the main chain of the phenylate structure is improved, so that the cycle characteristic of the battery cell can be further improved.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail with reference to the accompanying drawings and embodiments.
FIG. 1 is a flow chart of a method for preparing a lithium battery electrode binder according to an embodiment of the present invention;
FIG. 2 is a graph showing the cycle profiles of the batteries of example 1 of the present invention and comparative example 1;
FIG. 3 is a graph comparing the effect on resistivity of examples of the invention and comparative binders;
fig. 4 is a comparative graph of adhesion test between the lithium battery electrode binder according to the embodiment of the present invention and a binder of sodium carboxymethyl cellulose (CMC) + styrene-butadiene rubber (SBR).
Detailed Description
The invention is further illustrated by the following figures and specific examples, but it should be understood that these examples are for the purpose of illustration only and are not to be construed as in any way limiting the present invention, i.e., as in no way limiting its scope.
The invention provides a lithium ion battery electrode adhesive, which is a polyoxadiazole lithium sulfonate polymer, which has carboxylic acid groups, oxadiazole groups and lithium sulfonate groups, and a main chain of which has a phenylate structure;
the chemical structural formula of the polyoxadiazole lithium sulfonate polymer is as follows:
y =1:9-9:1. preferably, the polyoxadiazole lithium sulfonate polymer has a chemical structural formula in which X: Y = 5.
The carboxylic acid group in the structure of the adhesive provided by the invention provides adhesion and is a relatively hard chain segment, so that the adhesion can be increased and the expansion of a pole piece can be inhibited; the oxadiazole structure has the characteristic of electron absorption, and can provide a channel for electron transportation for an active substance when the oxadiazole structure is used for an adhesive, so that the electronic conductivity is enhanced; the lithium sulfonate group can be used as a single ion conductor to provide a lithium ion jumping point for an active substance and enhance the ionic conductivity; the flexibility of the polymer is increased by the phenylate structure, and the main material and the current collector are not broken when the pole piece is over-expanded.
Therefore, the adhesive provided by the invention provides adhesiveness and hardness through carboxylic acid groups, the flexibility of the polymer is increased through the phenyl ether structure of the main chain, and the electronic conductivity of the oxadiazole structure and the lithium sulfonate group are combined to provide lithium ion jumping points for active substances, so that the adhesive becomes a potential all-purpose adhesive and has better hardness, flexibility and electronic-ion double conductivity.
The adhesive can be prepared by the method steps shown in figure 1, and the main steps of the adhesive comprise the following steps in combination with figure 1:
wherein the molar ratio of hydrazine sulfate to carboxylic acid monomer is 1: 1-1.5; most preferably 1.05.
Carboxylic acid monomers include terephthalic acid and diphenyl ether dicarboxylic acid; the terephthalic acid is 1,3, 5-benzene tricarboxylic acid. The molar ratio of terephthalic acid to biphenyl ether dicarboxylic acid is 1. More preferably 5.
specifically, the end-capping reagent is benzoic acid.
130, cyclizing for 3-5 hours at the temperature of 120-170 ℃ to obtain a polymer;
wherein the lithium salt aqueous solution is lithium hydroxide or lithium carbonate aqueous solution.
And 150, drying the lithiation product, and dissolving the lithiation product in a solvent to form a uniform solution, namely the lithium ion battery electrode adhesive.
Specifically, the solvent includes: any one of N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC), or Dimethylsulfoxide (DMSO).
According to the preparation method provided by the application, polyoxadiazole can be obtained, a molecular chain of polyoxadiazole carries a sulfonic acid group, and lithium polyoxadiazole sulfonate, namely a lithiation product, is obtained through a lithiation process. In the preparation process, the number of the sulfonic acid lithium groups in the polymer can be accurately regulated and controlled by adjusting the proportion of two carboxylic acid monomers, namely 1,3, 5-benzene tricarboxylic acid and diphenyl ether dicarboxylic acid, and the sulfonic acid groups can be delocalized by electron-withdrawing group nitrogen atoms in molecules, and the two groups have synergistic effect to promote the dissociation of lithium ions, so that the ionic conductivity of the polyoxadiazole lithium sulfonate is improved. The electric conductivity of the lithium polyoxadiazole sulfonate can be improved by adjusting the molar ratio of hydrazine sulfate to carboxylic acid monomers and further adjusting the molar ratio of 1,3, 5-benzenetricarboxylic acid to diphenyl ether dicarboxylic acid, and increasing the using amount of the 1,3, 5-benzenetricarboxylic acid, so that the lithium polyoxadiazole sulfonate has better electron-ion double-conductivity characteristics.
The binder can be applied to electrodes of lithium ion batteries together with electrode active materials and conductive agents. Because the electrode adhesive provided by the application has a good electron-ion double-conduction characteristic, the using amount of the conductive agent can be properly reduced in the lithium ion battery electrode, so that the using amount of other components, particularly the electrode active material can be increased, and the electrical property of the electrode can be improved. Preferably, in the scheme of the binder of the invention, the mass ratio of the electrode active material, the conductive agent and the electrode binder is (5-9): (0.1-3): 0.1-4), and the specific steps can include: 0.1, 8. In the present application, the sum of the proportions of the electrode active material, the conductive agent and the electrode binder is 10, wherein the proportion of the active material is greater than or equal to 50%, the electrode active material may be one of a positive electrode active material or a negative electrode active material, and the conductive agent may be at least one of conductive carbon black, conductive graphite, carbon fibers, carbon nanotubes, graphene or mixed conductive paste.
The preparation method for preparing the lithium ion battery electrode by adopting the binder provided by the invention comprises the following steps: mixing the electrode active material, the conductive agent and the electrode adhesive according to a proportion, adding a solvent N-methylpyrrolidone (NMP) and grinding into uniform slurry. Coated on a flat current collector and dried. The dried electrode was cut into a circular piece having a diameter of 13mm, and the battery was assembled. The drying method may be drying methods commonly used in the art, for example, drying in a forced air oven and a vacuum oven in sequence.
The lithium ion battery electrode provided by the application has good cohesive force, close connection can be kept between active substances, and the shape can be kept stable before and after circulation.
The lithium ion battery electrode is applied to the lithium ion battery, and the cycle characteristic of the battery can be effectively improved.
In order to better understand the technical scheme provided by the invention, the following describes a specific process for preparing the lithium battery electrode binder by applying the method provided by the above embodiment of the invention, and a method and characteristics for applying the lithium battery electrode binder to a lithium battery by using a plurality of specific examples.
Example 1
The embodiment provides an electrode adhesive, which is mainly prepared by the following steps:
in a three-necked flask equipped with a mechanical stirring bar, 5.96g of hydrazine sulfate, 3.44g of 1,3, 5-benzenetricarboxylic acid and 7.25g of diphenyl ether dicarboxylic acid were dissolved in 45ml of fuming sulfuric acid, and the temperature was raised to 80 ℃ for reaction for 3 hours. Then the temperature is raised to the polycondensation temperature of 100 ℃ for reaction for 6 hours. Adding an end-capping reagent, namely benzoic acid, continuing to heat to 150 ℃, and cyclizing for 4 hours to obtain the polymer. The molar ratio of the hydrazine sulfate to the carboxylic acid monomer is 1.05.
The obtained polymer is coagulated and formed in a water coagulation bath, washed to be neutral, and then soaked in a lithium salt aqueous solution for 3 days to complete the lithiation process and form a lithiation product.
And drying the lithiation product, and dissolving the lithiation product in N-methyl pyrrolidone to form a uniform solution to obtain the electrode adhesive.
Mixing Li rich in lithium manganese 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 Positive electrode active material: conductive carbon black: the electrode binder is mixed with conductive carbon black by a planetary mixer according to the proportion of 8Adding a proper amount of N-methyl pyrrolidone (NMP) as a solvent, grinding into uniform slurry, coating the uniform slurry on a flat aluminum foil, drying for 4 hours at 60 ℃ in a blast oven, transferring to a vacuum oven, drying for 18 hours at 110 ℃, cutting electrodes into circular sheets with the diameter of 13mm, and assembling the battery.
To facilitate evaluation of the performance of the binders prepared according to the present invention, a commercially available polyacrylic acid (PAA) binder was used as comparative example 1 for comparison. The preparation of the pole pieces and the assembly of the cell were the same as in the above example.
The positive pole piece prepared by the polyoxadiazole-containing binder provided by the invention and the positive pole piece prepared by the polyacrylic binder in the comparative example 1 are respectively used for manufacturing button cells for performance comparison. Adopting a Celgard2300 model diaphragm, metal lithium as a negative electrode and 1MLiPF 6 @1:1, ethylene Carbonate (EC) + dimethyl carbonate (DMC) are taken as electrolyte. The test results shown in fig. 1 were obtained by the test. As can be seen from fig. 1, the cycle stability and capacity retention rate of the positive electrode plate prepared by using the polyoxadiazole adhesive of the present invention at 0.1C for 100 weeks are significantly better than those of the positive electrode plate prepared by using the commercially available polyacrylic acid adhesive.
Further, the polyacrylic acid (PAA) adhesive of comparative example 1, the commercially available polyimide adhesive of comparative example 2, the sodium carboxymethylcellulose (CMC) + styrene-butadiene rubber (SBR) of comparative example 3 were used
(V: V = 1) electrode pastes (Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 Positive electrode active material: conductive carbon black: adhesive used =8:1: 1) After the electrode slurry 1 and the electrode slurry 2 prepared by the electrode binder are coated to prepare electrodes, resistivity comparison tests are carried out. Wherein the electrode paste 1 is Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 Positive electrode active material: conductive carbon black: electrode binder =8 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 Positive electrode active material: conductive carbon black: electrode binder =9:0.4:0.6.
from the test results shown in fig. 3, it can be seen that the resistance of the sample using the adhesive of the present invention, especially example 1, is significantly less than the current commercial adhesive.
In addition, the invention also compares the bond strength test of the adhesive obtained in example 1 with the CMC + SBR adhesive of comparative example 3, and the result is shown in FIG. 3, which clearly shows that the bond strength of the adhesive of the invention is obviously higher than that of the CMC + SBR combined adhesive.
Example 2
This example provides an electrode binder prepared by the same method as in example 1 except that the molar ratio of 1,3, 5-benzenetricarboxylic acid to diphenyl ether dicarboxylic acid was 4.
The preparation method of the positive pole piece and the battery assembly process are the same as those of the embodiment 1.
The positive pole piece prepared by the polyoxadiazole adhesive is cycled for 100 weeks at 0.1 ℃, the first-cycle specific discharge capacity and the cycle capacity retention rate are obviously superior to those of the positive pole piece prepared by the polyacrylic acid adhesive purchased on the market, and the measured data are compared in a table 1.
TABLE 1
Example 3
This example provides an electrode binder prepared by the same method as in example 1 except that the molar ratio of 1,3, 5-benzenetricarboxylic acid to diphenyl ether dicarboxylic acid was 5.
The preparation method of the positive pole piece and the battery assembly flow are the same as those of the embodiment 1.
The positive pole piece prepared by the polyoxadiazole adhesive is circulated for 100 weeks at 0.1 ℃, the specific discharge capacity and the retention rate of the circulation capacity of the first cycle are obviously superior to those of the positive pole piece prepared by the polyacrylic acid adhesive purchased from the market, and the measured data are compared and shown in table 2.
TABLE 2
Example 4
This example provides an electrode binder prepared by the same method as in example 1 except that the molar ratio of 1,3, 5-benzenetricarboxylic acid to diphenyl ether dicarboxylic acid was 9.
The preparation method of the positive pole piece and the battery assembly process are the same as those of the embodiment 1.
The positive pole piece prepared by the polyoxadiazole adhesive is circulated for 100 weeks at 0.1 ℃, the specific discharge capacity and the retention rate of the circulation capacity of the first cycle are obviously superior to those of the positive pole piece prepared by the polyacrylic acid adhesive purchased from the market, and the measured data are compared and shown in table 3.
TABLE 3
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The lithium ion battery electrode adhesive is characterized by being a polyoxadiazole lithium sulfonate polymer, having carboxylic acid groups, oxadiazole groups and lithium sulfonate groups, and having a phenylate structure on a main chain;
the chemical structural formula of the polyoxadiazole lithium sulfonate polymer is as follows:
X:Y＝1：9-9：1。
2. the lithium ion battery electrode binder of claim 1, wherein in the chemical structural formula of the lithium polyoxadiazole sulfonate polymer, X: Y = 5-9.
3. A method for preparing the lithium ion battery electrode binder of claim 1, wherein the method comprises:
prepolymerizing hydrazine sulfate and carboxylic acid monomers at 60-100 ℃ for 2-4 hours; wherein the molar ratio of hydrazine sulfate to carboxylic acid monomer is 1: 1-1.5;
polymerizing for 5-8 hours at 80-130 ℃, and adding an end capping agent after the polymerization is finished;
cyclizing for 3-5 hours at the temperature of 120-170 ℃ to obtain a polymer;
solidifying and forming the obtained polymer in a water coagulation bath, washing the polymer to be neutral, and soaking the polymer in a lithium salt aqueous solution for 1 to 5 days to carry out lithiation on the polymer to obtain a lithiation product;
and drying the lithiation product, and dissolving the lithiation product in a solvent to form a uniform solution, namely the lithium ion battery electrode adhesive.
4. The method of claim 3, wherein the carboxylic acid monomers comprise terephthalic acid and diphenyl ether dicarboxylic acid; the molar ratio of terephthalic acid to diphenyl ether dicarboxylic acid is 1.
5. The method for preparing the electrode binder for the lithium ion battery according to claim 4, wherein the molar ratio of terephthalic acid to diphenyl ether dicarboxylic acid is 5.
6. The method for preparing an electrode binder for a lithium ion battery according to claim 4, wherein the molar ratio of terephthalic acid to biphenyl ether dicarboxylic acid is 1; the molar ratio of the hydrazine sulfate to the carboxylic acid monomer is 1.05.
7. The method for preparing the lithium ion battery electrode binder according to claim 3, wherein the end-capping reagent is benzoic acid;
the lithium salt aqueous solution is lithium hydroxide or lithium carbonate aqueous solution.
8. The method of claim 3, wherein the solvent comprises: n-methylpyrrolidone NMP, N-dimethylformamide DMF, N-dimethylacetamide DMAC or dimethyl sulfoxide DMSO.
9. A lithium ion battery electrode comprising the lithium ion battery electrode binder of any one of claims 1 to 8.
10. A lithium ion battery comprising the lithium ion battery electrode binder of any one of claims 1 to 8 or the lithium ion battery electrode of claim 9.
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