CN116435507A - Method for preparing modified polyacrylic acid binder and application - Google Patents
Method for preparing modified polyacrylic acid binder and application Download PDFInfo
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- CN116435507A CN116435507A CN202211603876.6A CN202211603876A CN116435507A CN 116435507 A CN116435507 A CN 116435507A CN 202211603876 A CN202211603876 A CN 202211603876A CN 116435507 A CN116435507 A CN 116435507A
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- polyacrylic acid
- initiator
- mixed solution
- stirring
- acid binder
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- 229920002125 Sokalan® Polymers 0.000 title claims abstract description 69
- 239000011230 binding agent Substances 0.000 title claims abstract description 69
- 239000004584 polyacrylic acid Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000011259 mixed solution Substances 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 33
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 32
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 31
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 22
- -1 acrylonitrile monomer free radical Chemical class 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 238000010517 secondary reaction Methods 0.000 claims abstract description 9
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 14
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 150000003254 radicals Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 150000008360 acrylonitriles Chemical class 0.000 claims 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 claims 1
- 239000007774 positive electrode material Substances 0.000 abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 29
- 229910052799 carbon Inorganic materials 0.000 description 27
- 229910052782 aluminium Inorganic materials 0.000 description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 23
- 239000011888 foil Substances 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- 239000002002 slurry Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000006258 conductive agent Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 239000013543 active substance Substances 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 7
- 239000011149 active material Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000006255 coating slurry Substances 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- WOFDVDFSGLBFAC-UHFFFAOYSA-N lactonitrile Chemical compound CC(O)C#N WOFDVDFSGLBFAC-UHFFFAOYSA-N 0.000 description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 4
- 239000001095 magnesium carbonate Substances 0.000 description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000002560 nitrile group Chemical group 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 238000010280 constant potential charging Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229920003081 Povidone K 30 Polymers 0.000 description 1
- 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 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
-
- 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
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- 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)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a method for preparing a modified polyacrylic acid binder and application thereof. The method comprises the following steps: firstly, obtaining a substituted acrylonitrile monomer free radical; secondly, stirring the obtained substituted acrylonitrile monomer free radical, polyacrylic acid and a first initiator to obtain a first mixed solution, carrying out primary reaction, then adding acrylonitrile and 1, 3-butadiene to mix, adding a second initiator to obtain a second mixed solution, and carrying out secondary reaction to obtain a precursor material; and then mixing the precursor material with styrene, adding a third initiator to obtain a third mixed solution, and carrying out three reactions to obtain the modified polyacrylic acid binder. The modified polyacrylic acid binder provided by the invention has strong binding capacity with the positive electrode current collector and the positive electrode active material, and is suitable for various systems.
Description
Technical Field
The invention belongs to the technical field of binder materials, and particularly relates to a method for preparing a modified polyacrylic acid binder and application thereof.
Background
In recent years, lithium ion batteries have been used in the fields of energy storage and new energy automobiles because of their advantages of higher energy density, higher output power, smaller self-discharge, and the like. Wherein lithium iron phosphate (LiFeO) 4 ) The positive electrode material has the characteristics of large capacity, long cycle life, high safety, no memory effect and the like. Currently, liFeO 4 The positive electrode current collector in the power battery system mostly adopts carbon-coated aluminum foil, and the carbon-coated aluminum foil material is used as LiFeO 4 The positive current collector reduces the internal resistance and interface contact impedance of the battery, weakens the internal polarization phenomenon of the battery, and can improve the electrical performance (such as rate performance, HPPC test and the like) of the battery to a certain extent.
The carbon-coated aluminum foil mainly comprises an aluminum optical foil and a carbon-coated layer, wherein the carbon-coated layer mainly comprises a conductive agent, a binder and other additives, and the binder is one of important factors affecting the performance of the pole piece and the performance of the battery cell. It mainly plays the following roles: (1) adhering the components such as the conductive agent, the additive and the like in the coating slurry; (2) providing adhesion between the coating slurry and the aluminum optical foil to prevent the coating from falling off; (3) providing adhesion between the carbon-coated layer and the positive electrode active material.
In the prior art, the pole piece stripping force, the pole piece resistance, the charge-discharge direct current resistance, the multiplying power performance and the like are important parameters for evaluating the pole piece performance and the battery cell performance, and in order to improve the pole piece stripping force, reduce the pole piece resistance and the like, researchers mainly adopt the following methods:
firstly, the mass ratio of the binder in the coating slurry is improved, but on the one hand, the coating slurry is difficult to disperse due to the increase of the mass ratio of the binder, so that the processing difficulty is improved; on the other hand, the mass ratio of the binder is improved, which means that the content of the conductive agent is reduced, so that the interface impedance is improved, the polarization in the battery is increased, and the internal resistance of the battery is also increased.
Secondly, the binder matrix adopted in the prior art is mainly water-based polyacrylic acid, and the currently used modification method mainly comprises the following steps: (1) grafting modification: a reaction in which a suitable branched or functional side group is bonded by a chemical bond in the macromolecular chain; (2) block modification: inserting other chain segments into the macromolecular chain; (3) crosslinking modification: the macromolecular chains are connected into three-dimensional space net macromolecules through branched chains; (4) substitution modification: some atoms or groups of atoms in the organic molecular structure are replaced by other atoms or groups of atoms by chemical reactions.
However, the polyacrylic acid binder modified by the above method has the disadvantages of small adhesion, strong orientation, and the like, for example: the bonding force between the aluminum foil and the aluminum foil is strong, but the bonding force between the aluminum foil and an anode active material is weak, so that the stripping force of the pole piece is low, and the performance requirement of the pole piece is not met; the modified polyacrylic acid binder has strong orientation, but has poor suitability with various positive electrode active materials, and increases the production cost of the battery.
Therefore, in the art, there is a need to develop a polyacrylic acid-based binder that not only has good adhesion with the positive electrode current collector and the positive electrode active material, but also has a small addition amount.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing a modified polyacrylic acid binder and application thereof. The modified polyacrylic acid binder provided by the invention has strong binding capacity with the positive electrode current collector and the positive electrode active material, and is suitable for various systems.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method of preparing a modified polyacrylic acid binder, the method comprising the steps of:
(1) Mixing acrylonitrile, 3-hydroxy propionic acid, azodiisovaleronitrile, acrylamide, N-methylol acrylamide and a solvent, and reacting to obtain a substituted acrylonitrile monomer free radical;
(2) Stirring the substituted acrylonitrile monomer free radical obtained in the step (1), polyacrylic acid and a first initiator to obtain a first mixed solution, carrying out primary reaction, then adding acrylonitrile and 1, 3-butadiene to carry out mixing, adding a second initiator to obtain a second mixed solution, and carrying out secondary reaction to obtain a precursor material;
(3) And (3) mixing the precursor material obtained in the step (2) with styrene, adding a third initiator to obtain a third mixed solution, and carrying out three reactions to obtain the modified polyacrylic acid binder.
Firstly, the branched chain of the modified polyacrylic acid binder prepared by the method contains-C 2 O 2 NR、-CH 2 CN and-COOH functions, wherein-C 2 O 2 The nitrogen atoms contained in the NR functional groups have stronger polarity, have stronger adsorption force on metal aluminum, and can provide adsorption force between the active material layer and the aluminum foil; the nitrile group has stronger polarity, and can form stronger intermolecular force with the aluminum foil and the positive electrode active material; the hydroxyl structure contained in the carboxyl functional group can also form strong intermolecular forces of hydrogen bonds with the active material layer. The binding force among the conductive agent particles, between the carbon coating and the aluminum foil and between the carbon coating and the positive electrode active substance is improved by the three groups, and compared with the traditional polyacrylic acid binder, the binding force of the modified polyacrylic acid binder provided by the invention is improved by 2-3 times, so that the stripping force of the pole piece is improved and the binding performance of the pole piece is enhanced.
Secondly, the groups in the binder structure not only provide stronger intermolecular force, but also provide stronger physical binding force, such as winding or embedding, and the like, and the polyacrylic acid binder disclosed in the prior art can cause the risk of low stripping force (less than or equal to 0.1N) of the pole piece due to weaker binding force, but the modified polyacrylic acid binder provided by the invention has strong mechanical binding capacity, can provide binding force between the carbon coating and the positive electrode active substance, ensures higher stripping force of the pole piece, and further improves the suitability of the carbon coating and various positive electrode active substance systems, thereby reducing the production cost of the battery and improving the production efficiency of a production line.
Finally, the modified polyacrylic acid binder provided by the invention can reduce the content of the binder (the reduction range is up to 20% -30%) in the carbon-coated slurry formula, and has the following advantages: (1) the content of the binder is reduced, so that the carbon-coated slurry is easier to disperse, the processing difficulty is reduced, and the production cost is saved; (2) the reduction of the content of the binder means that the content of the conductive agent in the slurry can be increased, so that the interface impedance between the positive electrode active substance and the carbon coating layer and the resistance of the pole piece are reduced, the ohmic polarization degree, the internal resistance of the battery and the direct current resistance of the battery core are further reduced, and the rate performance and the low-temperature performance of the battery core can be improved.
In the present invention, acrylonitrile can be produced by the following method by way of example:
mixing ethylene oxide, hydrocyanic acid, deionized water and trimethylamine according to the mass ratio of 5:3:0.5:1.5, and generating cyanoethanol under the conditions that the reaction temperature is 80-100 ℃; after 1h of reaction, adding a catalyst magnesium carbonate, and then carrying out dehydration reaction for 0.5h at the temperature of 230-270 ℃ to obtain acrylonitrile.
Preferably, the mass ratio of 3-hydroxypropionic acid, azodiisovaleronitrile, acrylamide and N-methylolacrylamide in the step (1) is (3-5): (2-4): (0.5-2): (1-3), and for example, may be 3:2:0.5:1, 3.5:2.5:1:1.5, 4:3:1:2, 5:4:2:3, etc.
In the invention, the mass ratio of 3-hydroxy propionic acid, azodiisovaleronitrile, acrylamide and N-methylol acrylamide is adjusted to ensure that the reaction is complete, so that the required product is obtained, if the mass ratio is too low, the reaction is incomplete, the required product cannot be prepared, otherwise, other byproducts are generated, and the yield is affected.
3-hydroxy propionic acid, azo-bis-iso-valeronitrile, acrylamide and N-methylol acrylamide are all monomer initiator, which has the function of inducing the polymerization of acrylonitrile monomer and generates free radical copolymerization reaction with acrylonitrile to obtain acrylonitrile monomer free radical.
Preferably, the solvent in step (1) is deionized water.
Preferably, the temperature of the reaction in step (1) is from 100 ℃ to 150 ℃, for example, it may be 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃; the time is 1 to 2 hours, for example, 1 hour, 1.2 hours, 1.5 hours, 1.8 hours, 2 hours.
Preferably, the substituent of the substituted acrylonitrile monomer radical in step (1) comprises any one or a combination of at least two of carboxyl, hydroxyl, alkyl, alkenyl, alkynyl, haloalkyl or cycloalkenyl groups.
In the invention, the substituent groups can increase the length of the branched chains in the binder, thereby improving the mechanical bonding capability of the carbon coating layer and the positive electrode active material.
Preferably, the first initiator in step (2) comprises dilute sulfuric acid.
Preferably, in the step (2), the mass percentage of the first initiator in the first mixed solution is 3% -5%, for example, may be 3%, 3.2%, 3.5%, 3.8%, 4%, 4.2%, 4.5%, 4.8%, 5%.
Preferably, the temperature of the first reaction in step (2) is 90 ℃ and the time is 2.5 hours.
Preferably, the primary reaction in step (2) is carried out with stirring.
Preferably, the temperature of the mixing in step (2) is 50℃and the rate of mixing is 50rpm/min.
Preferably, the second initiator in step (2) comprises α, α -dimethoxy- α -phenylacetophenone;
preferably, the mass percentage of the second initiator in the second mixed solution in the step (2) is 1-2%, for example, may be 1%, 1.2%, 1.5%, 1.8%, 2%.
Preferably, the temperature of the secondary reaction in the step (2) is 120 ℃, and the time of the secondary reaction is 3 hours.
Preferably, the secondary reaction of step (2) is carried out with stirring.
Preferably, the stirring rate is 100rpm/min.
In the invention, in the step (2), the polyacrylic acid can undergo a substitution reaction after the double bond is opened, and the carboxyl group is replaced by a functional group with stronger polarity, so that the polyacrylic acid can undergo a substitution reaction with an acrylonitrile monomer free radical.
Preferably, the temperature of the mixing in step (3) is 60 ℃ for 0.5h.
Preferably, the mixing in step (3) is performed under stirring.
Preferably, the stirring rate is 20rpm/min.
Preferably, the third initiator in step (3) comprises sodium methacrylate sulfonate.
Preferably, the mass percentage of the third initiator in the third mixed solution in the step (3) is 2-3%, for example, may be 2%, 2.2%, 2.5%, 2.8%, 3%.
Preferably, the mass ratio of the free radicals of the polyacrylic acid, the acrylonitrile, the 1, 3-butadiene, the styrene and the substituted acrylonitrile monomer is (4-6): (0.5-2.5), and for example, can be 4:0.5:0.5:0.5:0.5, 5:1:1:1, 5:2:1.5:1.5:2, 5:1:1.5:1.5, 6:2:2.5:2.5, and the like.
In the invention, the mass ratio of polyacrylic acid, acrylonitrile, 1, 3-butadiene, styrene and substituted acrylonitrile monomer free radical is adjusted to ensure that the reaction is complete, so that the required product is obtained, if the mass ratio is too low, the reaction is incomplete, the required product cannot be prepared, and other byproducts are generated to influence the yield.
Preferably, the temperature of the three reactions in step (3) is 100 ℃, and the time of the three reactions is 1h.
Preferably, the three reactions in step (3) are followed by a post-treatment step.
Preferably, the post-treatment step comprises stirring for 2 hours at room temperature.
In the invention, in the step (3), the benzene ring of the styrene in the reaction process is subjected to ring opening reaction (in the presence of alpha, alpha-dimethoxy-alpha-phenylacetophenone as a catalyst, the benzene ring of the styrene and oxygen are subjected to ring opening reaction), and the ring-opened benzene ring generates a maleic anhydride compound which is substituted by a nitrogen atom in acrylonitrile to generate-C 2 O 2 An NR group.
In addition, the reaction product obtained after the substitution reaction is copolymerized with the 1, 4-addition product of 1, 3-butadiene to be linked.
In a second aspect, the present invention provides a modified polyacrylic acid binder prepared according to the method for preparing a modified polyacrylic acid binder of the first aspect.
In a third aspect, the present invention provides a lithium ion battery comprising a positive electrode sheet, a negative electrode sheet, an electrolyte and a separator, the positive electrode sheet comprising the modified polyacrylic acid binder according to the second aspect.
The modified polyacrylic acid binder provided by the invention improves the suitability of the carbon coating and the bonding performance of the pole piece, reduces the ohmic internal resistance of the battery cell, further improves the electrical performance of the battery cell and reduces the production cost of the battery cell.
Compared with the prior art, the invention has the following beneficial effects:
firstly, -C contained in the branched chain of the modified polyacrylic acid binder prepared by the method 2 O 2 NR、-CH 2 CN and-COOH functions, wherein-C 2 O 2 The nitrogen atoms contained in the NR functional groups have stronger polarity, have stronger adsorption force on metal aluminum, and can provide adsorption force between the active material layer and the aluminum foil; the nitrile group has stronger polarity, and can form stronger intermolecular force with the aluminum foil and the positive electrode active material; the hydroxyl structure contained in the carboxyl functional group can also form strong intermolecular forces of hydrogen bonds with the active material layer. The binding force among the conductive agent particles, between the carbon coating and the aluminum foil and between the carbon coating and the positive electrode active substance is improved by the three groups, and compared with the traditional polyacrylic acid binder, the binding force of the modified polyacrylic acid binder provided by the invention is improved by 2-3 times, so that the stripping force of the pole piece is improved and the binding performance of the pole piece is enhanced.
Secondly, the groups in the binder structure not only provide stronger intermolecular force, but also provide stronger physical binding force, such as winding or embedding, and the like, and the polyacrylic acid binder disclosed in the prior art can cause the risk of low stripping force (less than or equal to 0.1N) of the pole piece due to weaker binding force, but the modified polyacrylic acid binder provided by the invention has strong mechanical binding capacity, can provide binding force between the carbon coating and the positive electrode active substance, ensures higher stripping force of the pole piece, and further improves the suitability of the carbon coating and various positive electrode active substance systems, thereby reducing the production cost of the battery and improving the production efficiency of a production line.
Finally, the modified polyacrylic acid binder provided by the invention can reduce the content of the binder (the reduction range is up to 20% -30%) in the carbon-coated slurry formula, and has the following advantages: (1) the content of the binder is reduced, so that the carbon-coated slurry is easier to disperse, the processing difficulty is reduced, and the production cost is saved; (2) the reduction of the content of the binder means that the content of the conductive agent in the slurry can be increased, so that the interface impedance between the positive electrode active substance and the carbon coating layer and the resistance of the pole piece are reduced, the ohmic polarization degree, the internal resistance of the battery and the direct current resistance of the battery core are further reduced, and the rate performance and the low-temperature performance of the battery core can be improved.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a modified polyacrylic acid binder and a preparation method thereof, wherein the modified polyacrylic acid binder comprises the following steps:
(1) Mixing ethylene oxide, hydrocyanic acid, deionized water and trimethylamine according to the mass ratio of 5:3:0.5:1.5, wherein the reaction temperature is 90 ℃, and cyanoethanol is generated under the conditions; after reacting for 1h, adding a catalyst magnesium carbonate, and then dehydrating at the temperature of 250 ℃ for 0.5h to obtain acrylonitrile; mixing the obtained acrylonitrile, 3-hydroxy propionic acid, azodiisovaleronitrile, acrylamide, N-methylol acrylamide and deionized water, wherein the mass ratio of the 3-hydroxy propionic acid to the azodiisovaleronitrile to the acrylamide to the N-methylol acrylamide is 4:3:1:2, and reacting for 1.5 hours at 120 ℃ to obtain a carboxyl-substituted acrylonitrile monomer free radical;
(2) Stirring the carboxyl-substituted acrylonitrile monomer free radical, polyacrylic acid and dilute sulfuric acid obtained in the step (1) to obtain a first mixed solution, wherein the mass percent of the dilute sulfuric acid in the first mixed solution is 4%, stirring and reacting for 2.5 hours at 90 ℃, then adding acrylonitrile and 1, 3-butadiene, mixing at 50 ℃ at the speed of 50rpm/min, and adding alpha, alpha-dimethoxy-alpha-phenylacetophenone to obtain a second mixed solution, wherein the mass percent of the alpha, alpha-dimethoxy-alpha-phenylacetophenone in the second mixed solution is 1.5%, and stirring and reacting for 3 hours at 120 ℃ at the speed of 100rpm/min to obtain a precursor material;
(3) Stirring the precursor material obtained in the step (2) and styrene at the speed of 20rpm/min for 0.5h at the temperature of 60 ℃, then adding sodium methacrylate to obtain a third mixed solution, wherein the mass percent of sodium methacrylate in the third mixed solution is 2.5%, and reacting for 1h at the temperature of 100 ℃, wherein the mass ratio of polyacrylic acid, acrylonitrile, 1, 3-butadiene, styrene and substituted acrylonitrile monomer free radicals is 5:1:1.5:1:1.5, and stirring for 2h when the temperature is reduced to room temperature, thus obtaining the modified polyacrylic acid binder.
Example 2
The embodiment provides a modified polyacrylic acid binder and a preparation method thereof, wherein the modified polyacrylic acid binder comprises the following steps:
(1) Mixing ethylene oxide, hydrocyanic acid, deionized water and trimethylamine according to the mass ratio of 5:3:0.5:1.5, wherein the reaction temperature is 80 ℃, and cyanoethanol is generated under the conditions; after reacting for 1h, adding a catalyst magnesium carbonate, and then dehydrating at 230 ℃ for 0.5h to obtain acrylonitrile; mixing the obtained acrylonitrile, 3-hydroxy propionic acid, azodiisovaleronitrile, acrylamide, N-methylol acrylamide and deionized water, wherein the mass ratio of the 3-hydroxy propionic acid to the azodiisovaleronitrile to the acrylamide to the N-methylol acrylamide is 3:2:0.5:1, and reacting for 2 hours at 100 ℃ to obtain a carboxyl-substituted acrylonitrile monomer free radical;
(2) Stirring the carboxyl-substituted acrylonitrile monomer free radical, polyacrylic acid and dilute sulfuric acid obtained in the step (1) to obtain a first mixed solution, wherein the mass percent of the dilute sulfuric acid in the first mixed solution is 3%, stirring and reacting for 2.5 hours at 90 ℃, then adding acrylonitrile and 1, 3-butadiene, mixing at 50 ℃ at the speed of 50rpm/min, and adding alpha, alpha-dimethoxy-alpha-phenylacetophenone to obtain a second mixed solution, wherein the mass percent of the alpha, alpha-dimethoxy-alpha-phenylacetophenone in the second mixed solution is 1%, and stirring and reacting for 3 hours at the speed of 100rpm/min at 120 ℃ to obtain a precursor material;
(3) Stirring the precursor material obtained in the step (2) and styrene at the speed of 20rpm/min for 0.5h at 60 ℃, then adding sodium methacrylate to obtain a third mixed solution, wherein the mass percent of sodium methacrylate in the third mixed solution is 2%, and reacting for 1h at 100 ℃, wherein the mass ratio of polyacrylic acid, acrylonitrile, 1, 3-butadiene, styrene and substituted acrylonitrile monomer free radicals is 4:0.5:0.5:0.5:0.5, and stirring for 2h when the temperature is reduced to room temperature, thus obtaining the modified polyacrylic acid binder.
Example 3
The embodiment provides a modified polyacrylic acid binder and a preparation method thereof, wherein the modified polyacrylic acid binder comprises the following steps:
(1) Mixing ethylene oxide, hydrocyanic acid, deionized water and trimethylamine according to the mass ratio of 5:3:0.5:1.5, wherein the reaction temperature is 100 ℃, and cyanoethanol is generated under the conditions; after reacting for 1h, adding a catalyst magnesium carbonate, and then dehydrating at 270 ℃ for 0.5h to obtain acrylonitrile; mixing the obtained acrylonitrile, 3-hydroxy propionic acid, azodiisovaleronitrile, acrylamide, N-methylol acrylamide and deionized water, wherein the mass ratio of the 3-hydroxy propionic acid to the azodiisovaleronitrile to the acrylamide to the N-methylol acrylamide is 5:4:2:3, and reacting for 1h at 150 ℃ to obtain an acrylonitrile monomer free radical substituted by carboxyl;
(2) Stirring the carboxyl-substituted acrylonitrile monomer free radical, polyacrylic acid and dilute sulfuric acid obtained in the step (1) to obtain a first mixed solution, wherein the mass percent of the dilute sulfuric acid in the first mixed solution is 5%, stirring and reacting for 2.5 hours at 90 ℃, then adding acrylonitrile and 1, 3-butadiene, mixing at 50 ℃ at the speed of 50rpm/min, and adding alpha, alpha-dimethoxy-alpha-phenylacetophenone to obtain a second mixed solution, wherein the mass percent of the alpha, alpha-dimethoxy-alpha-phenylacetophenone in the second mixed solution is 2%, and stirring and reacting for 3 hours at the speed of 100rpm/min at 120 ℃ to obtain a precursor material;
(3) Stirring the precursor material obtained in the step (2) and styrene at the speed of 20rpm/min for 0.5h at the temperature of 60 ℃, then adding sodium methacrylate to obtain a third mixed solution, wherein the mass percent of sodium methacrylate in the third mixed solution is 3%, and reacting for 1h at the temperature of 100 ℃, wherein the mass ratio of polyacrylic acid, acrylonitrile, 1, 3-butadiene, styrene and substituted acrylonitrile monomer free radicals is 6:2:2.5:2:2.5, and stirring for 2h when the temperature is reduced to room temperature, thus obtaining the modified polyacrylic acid binder.
Example 4
This example differs from example 1 in that the mass ratio of 3-hydroxypropionic acid, azobisisovaleronitrile, acrylamide, and N-methylol acrylamide in step (1) is 1:1:0.1:0.5, and the other is the same as in example 1.
Example 5
This example differs from example 1 in that the mass ratio of 3-hydroxypropionic acid, azobisisovaleronitrile, acrylamide, and N-methylol acrylamide in step (1) is 7:8:4:5, and the other is the same as in example 1.
Example 6
This example differs from example 1 in that the mass ratio of polyacrylic acid, acrylonitrile, 1, 3-butadiene, styrene and substituted acrylonitrile monomer radicals is 2:0.1:0.1:0.1:0.1, all other things being equal to example 1.
Example 7
This example differs from example 1 in that the mass ratio of polyacrylic acid, acrylonitrile, 1, 3-butadiene, styrene and substituted acrylonitrile monomer radicals is 8:5:5:3:5, all other things being equal to example 1.
Comparative example 1
This comparative example provides an unmodified polyacrylic acid binder.
Comparative example 2
This comparative example provides a polyvinylidene fluoride binder.
Comparative example 3
The comparative example provides a modified polyacrylic acid binder purchased from Guangdong Hui Valley chemical company with the following structural formula:
application examples 1 to 7 and comparative application examples 1 to 3
The modified polyacrylic acid binders provided in examples 1 to 7 and comparative examples 1 to 3 were prepared to obtain lithium ion batteries, and the preparation methods were as follows:
preparing carbon-coated aluminum foil: fully and uniformly stirring the conductive agent carbon black, the modified polyacrylic acid binder and the additive PVP-K30 according to the mass ratio of 75 percent to 20 percent to 5 percent to obtain carbon-coated slurry, coating the prepared carbon-coated slurry on an aluminum optical foil, and drying to obtain the carbon-coated aluminum foil;
preparation of a positive plate: fully and uniformly stirring the main materials of the positive electrode, namely lithium iron phosphate, conductive carbon black, carbon nano tubes and an oil-based binder according to the mass ratio of 97.4 percent to 0.6 percent to 0.4 percent to 1.6 percent to obtain positive electrode slurry, coating the prepared slurry on the carbon-coated aluminum foil, and drying and rolling to obtain a positive electrode plate;
preparing a negative plate: fully and uniformly stirring negative electrode active material graphite, conductive agent/sodium carboxymethylcellulose and styrene-butadiene rubber according to the mass ratio of 96.5% to 0.8% to 1.0% to 1.7% to obtain negative electrode slurry, coating the prepared slurry on copper foil, drying and rolling to obtain a negative electrode plate;
preparation of electrolyte: lithium hexafluorophosphate with the concentration of 1mol/L is used, and the solvent is formed by mixing ethylene carbonate and diethyl carbonate in the volume ratio of 1:1.
Preparation of a lithium ion battery: the positive plate, the negative plate, the diaphragm and the electrolyte are matched to assemble the button cell with the model number of 2032.
Test conditions
The lithium ion batteries prepared in application examples 1 to 7 and comparative application examples 1 to 3 were respectively subjected to performance tests, and the test methods were as follows:
(1) Pole piece peel force: (1) preparing a tool: paper cutters, 30mm wide 3M gummed paper, 50mm wide green glue and 50mm wide steel plates; (2) selecting a smooth surface of the steel plate, and paving green gummed paper on the surface of the steel plate to be stuck; (3) sticking 3M gummed paper with the width of 30mm on the green glue; (4) cutting the prepared pole piece to be tested according to the coating direction to obtain a pole piece sample, wherein the width of each side of the pole piece sample exceeds the edge of the 3M adhesive by 1-2mm; (5) sticking the prepared pole piece on 3M gummed paper of tearing surface paper, and noticing that the surface of the pole piece cannot be wrinkled; (6) the compression roller is placed at one end of the steel plate, slowly presses along the steel plate towards the other end, and ends three times back and forth; (7) and opening the tension machine to set related parameters, and clicking to start testing after the sample is placed.
(2) Resistance of the pole piece: (1) punching a 45mm multiplied by 45mm pole piece sample; (2) opening the switches of all parts of the ACCFilm diaphragm tester, the resistor meter and the computer host; (3) rotating a right side pressure adjusting knob of the diaphragm testing machine to adjust the pressure to be between 0.3 and 0.4 MPa; (4) the dust-free paper is soaked in a small amount of absolute ethyl alcohol, and the upper probe and the lower probe are respectively wiped and tested, so that the test probe is ensured to be clean; (5) the pole piece resistance starts to be tested.
(3) 25 ℃ hybrid power pulse characterization test (HPPC): (1) standing for 10min at 25+ -2deg.C;
(2) standard cycle of the cell for 13 weeks; (3) when the battery is charged to 3.65V at the constant current of 0.5C (A) under the condition of 25+/-2 ℃, the constant voltage charging is switched to the constant voltage charging, the current is cut off by 0.05C, and the battery is left for 30min;
(4) adjusting the SOC and placing for 1h; (5) when testing the discharge direct current resistance, discharging for 10s at a constant current of 1.0C, and standing for 1min after discharging; (6) when the charging direct current resistance is tested, the constant current charging is carried out for 10s at 1.0C, and the charging is carried out for 1min; (7) and (3) calculating discharge direct current resistance: after SOC adjustment, the mixture was left for 1h, and the terminal voltage was recorded as VD 0 .1.0C constant current discharge for 10s, and (8) terminal voltage is recorded as VD 10 The method comprises the steps of carrying out a first treatment on the surface of the (9) Direct current resistances at 90%, 60% and 30% soc were tested, respectively.
Direct current resistance= (VD 0 -VD 10 )/I
The test results are shown in table 1:
TABLE 1
As can be seen from the data in Table 1, the modified polyacrylic acid binder prepared by the above method of the present invention contains-C in the branched chain 2 O 2 NR、-CH 2 CN and-COOH functions, wherein-C 2 O 2 The nitrogen atoms contained in the NR functional groups have stronger polarity, have stronger adsorption force on metal aluminum, and can provide adsorption force between the active material layer and the aluminum foil; the nitrile group has stronger polarity, and can form stronger intermolecular force with the aluminum foil and the positive electrode active material; the hydroxyl structure contained in the carboxyl functional group can also form strong intermolecular forces of hydrogen bonds with the active material layer.
Compared with the example 1, the unmodified polyacrylic acid binder, the oily polyvinylidene fluoride binder and the modified polyacrylic acid binder in the prior art have the combination property which is not as good as that of the modified polyacrylic acid binder prepared by the application and contains-C 2 O 2 NR、-CH 2 CN and-COOH functional groups.
The applicant states that the process of the invention is illustrated by the above examples, but the invention is not limited to, i.e. does not mean that the invention must be carried out in dependence on the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A method of preparing a modified polyacrylic acid binder, the method comprising the steps of:
(1) Mixing acrylonitrile, 3-hydroxy propionic acid, azodiisovaleronitrile, acrylamide, N-methylol acrylamide and a solvent, and reacting to obtain a substituted acrylonitrile monomer free radical;
(2) Stirring the substituted acrylonitrile monomer free radical obtained in the step (1), polyacrylic acid and a first initiator to obtain a first mixed solution, carrying out primary reaction, then adding acrylonitrile and 1, 3-butadiene to carry out mixing, adding a second initiator to obtain a second mixed solution, and carrying out secondary reaction to obtain a precursor material;
(3) And (3) mixing the precursor material obtained in the step (2) with styrene, adding a third initiator to obtain a third mixed solution, and carrying out three reactions to obtain the modified polyacrylic acid binder.
2. The method according to claim 1, wherein the mass ratio of 3-hydroxypropionic acid, azodiisovaleronitrile, acrylamide, and N-methylolacrylamide in step (1) is (3-5): 2-4): 0.5-2): 1-3;
preferably, the solvent in step (1) is deionized water;
preferably, the temperature of the reaction in the step (1) is 100-150 ℃ and the time is 1-2 h;
preferably, the substituent of the substituted acrylonitrile monomer radical in step (1) comprises any one or a combination of at least two of carboxyl, hydroxyl, alkyl, alkenyl, alkynyl, haloalkyl or cycloalkenyl groups.
3. The process of claim 1 or 2, wherein in step (2) the first initiator comprises dilute sulfuric acid;
preferably, in the step (2), the mass percentage of the first initiator in the first mixed solution is 3% -5%;
preferably, the temperature of the primary reaction in step (2) is 90 ℃ for 2.5 hours;
preferably, the primary reaction in step (2) is carried out with stirring.
4. A method according to any one of claims 1 to 3, wherein the temperature of mixing in step (2) is 50 ℃, and the rate of mixing is 50rpm/min;
preferably, the second initiator in step (2) comprises α, α -dimethoxy- α -phenylacetophenone;
preferably, in the step (2), the mass percentage of the second initiator in the second mixed solution is 1-2%.
5. The method according to any one of claims 1 to 4, wherein the temperature of the secondary reaction in step (2) is 120 ℃ and the time of the secondary reaction is 3 hours;
preferably, the secondary reaction of step (2) is carried out with stirring;
preferably, the stirring rate is 100rpm/min.
6. The method according to any one of claims 1 to 5, wherein the temperature of the mixing in step (3) is 60 ℃ for 0.5h;
preferably, the mixing in step (3) is performed with stirring;
preferably, the stirring rate is 20rpm/min.
7. The process of any one of claims 1-6, wherein the third initiator in step (3) comprises sodium methallyl sulfonate;
preferably, in the step (3), the mass percentage of the third initiator in the third mixed solution is 2-3%;
preferably, the mass ratio of the free radicals of the polyacrylic acid, the acrylonitrile, the 1, 3-butadiene, the styrene and the substituted acrylonitrile monomers is (4-6): (0.5-2.5): (0.5-2): (0.5-2.5).
8. The method according to any one of claims 1 to 7, wherein the temperature of the three reactions in step (3) is 100 ℃, and the time of the three reactions is 1h;
preferably, the three reactions in step (3) are followed by a post-treatment step;
preferably, the post-treatment step comprises stirring for 2 hours at room temperature.
9. A modified polyacrylic acid binder, characterized in that the modified polyacrylic acid binder is produced according to the method for producing a modified polyacrylic acid binder according to any one of claims 1 to 8.
10. A lithium ion battery comprising a positive electrode sheet, a negative electrode sheet, an electrolyte, and a separator, wherein the positive electrode sheet comprises the modified polyacrylic acid binder according to claim 9.
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| JP2014063676A (en) * | 2012-09-24 | 2014-04-10 | Unitika Ltd | Aqueous binder liquid for secondary battery positive electrode, aqueous paste for secondary battery positive electrode produced with aqueous binder liquid, secondary battery positive electrode, and secondary battery |
| CN108929401A (en) * | 2018-06-25 | 2018-12-04 | 重庆云天化瀚恩新材料开发有限公司 | A kind of lithium battery silicium cathode adhesive and preparation method thereof |
| CN109786749B (en) * | 2019-02-18 | 2021-03-30 | 珠海冠宇电池股份有限公司 | Cross-linked SBR (styrene butadiene rubber) microsphere binder, preparation method thereof and lithium ion battery containing binder |
| CN115093520A (en) * | 2022-08-04 | 2022-09-23 | 上海兰钧新能源科技有限公司 | Aqueous binder, manufacturing method of positive pole piece and lithium ion battery |
| CN116435507A (en) * | 2022-12-13 | 2023-07-14 | 湖北亿纬动力有限公司 | Method for preparing modified polyacrylic acid binder and application |
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