CN115093834B - Phase change material and preparation method and application thereof - Google Patents
Phase change material and preparation method and application thereof Download PDFInfo
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- CN115093834B CN115093834B CN202210813285.5A CN202210813285A CN115093834B CN 115093834 B CN115093834 B CN 115093834B CN 202210813285 A CN202210813285 A CN 202210813285A CN 115093834 B CN115093834 B CN 115093834B
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- 239000012782 phase change material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000004005 microsphere Substances 0.000 claims abstract description 37
- 150000003839 salts Chemical class 0.000 claims abstract description 36
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 22
- 230000008859 change Effects 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 9
- 230000007704 transition Effects 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims description 41
- 238000000576 coating method Methods 0.000 claims description 41
- 239000002994 raw material Substances 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000006258 conductive agent Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- IAQLJCYTGRMXMA-UHFFFAOYSA-M lithium;acetate;dihydrate Chemical compound [Li+].O.O.CC([O-])=O IAQLJCYTGRMXMA-UHFFFAOYSA-M 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 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 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- GNDOSKKVQUGWFB-UHFFFAOYSA-L dilithium;2,3-dihydroxybutanedioate;hydrate Chemical compound [Li+].[Li+].O.[O-]C(=O)C(O)C(O)C([O-])=O GNDOSKKVQUGWFB-UHFFFAOYSA-L 0.000 claims description 5
- WNCZOFYWLAPNSS-UHFFFAOYSA-M lithium;3-carboxy-3,5-dihydroxy-5-oxopentanoate Chemical compound [Li+].OC(=O)CC(O)(C(O)=O)CC([O-])=O WNCZOFYWLAPNSS-UHFFFAOYSA-M 0.000 claims description 5
- 229920000141 poly(maleic anhydride) Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 229920000289 Polyquaternium Polymers 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 241000220479 Acacia Species 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 235000010643 Leucaena leucocephala Nutrition 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- FHYAZOCAASAEQM-UHFFFAOYSA-L dilithium 2-hydroxy-2-oxoacetate hydroxide hydrate Chemical compound C(C(=O)O)(=O)[O-].[Li+].O.[OH-].[Li+] FHYAZOCAASAEQM-UHFFFAOYSA-L 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- SKQWWJVTSPXPSF-UHFFFAOYSA-M lithium 2-hydroxybenzoate hydrate Chemical compound [Li+].O.Oc1ccccc1C([O-])=O SKQWWJVTSPXPSF-UHFFFAOYSA-M 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 239000011888 foil Substances 0.000 description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 24
- 229910052782 aluminium Inorganic materials 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- 239000010410 layer Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 239000011889 copper foil Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 239000011267 electrode slurry Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000004880 explosion Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000007756 gravure coating Methods 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
- C09D101/08—Cellulose derivatives
- C09D101/26—Cellulose ethers
- C09D101/28—Alkyl ethers
- C09D101/286—Alkyl ethers substituted with acid radicals
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/16—Homopolymers or copolymers of vinylidene fluoride
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
- H01M10/61—Types of temperature control
- H01M10/613—Cooling or keeping cold
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
- H01M10/65—Means for temperature control structurally associated with the cells
- H01M10/659—Means for temperature control structurally associated with the cells by heat storage or buffering, e.g. heat capacity or liquid-solid phase changes or transition
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention belongs to the technical field of lithium ion battery preparation, and particularly relates to a phase change material, a preparation method and application thereof. The phase change material comprises phase change microspheres, wherein the phase change microspheres comprise hydrated organic salts and water-soluble polymers; the water-soluble polymer has a melting temperature not higher than the phase transition temperature of the hydrated organic salt; the phase transition temperature of the hydrated organic salt is 80-200 ℃. The phase-change material provided by the invention has the advantages of high heat conductivity, strong phase-change heat absorption capacity, stable and reliable structural system and the like, and can quickly respond when being used for a lithium ion battery, and can absorb heat generated in the battery through a phase-change process when overheat or thermal runaway occurs in the battery, so that the safety of the lithium ion battery is ensured.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery preparation, and particularly relates to a phase change material, a preparation method and application thereof.
Background
Currently, lithium ion batteries are increasingly pursued to have high energy density and long-term cycling stability, and lithium ion batteries assembled by utilizing liquid electrolyte are easy to generate thermal runaway so as to cause fire and even explosion and other safety problems, so that the safety becomes a key obstacle for restricting the development of the lithium ion batteries. Under the conditions of overcharge, overheat, extrusion, impact or short circuit, and the like, the solid electrolyte passivation film on one side of the negative electrode is unstable and is extremely easy to thermally decompose, so that the liquid electrolyte contacts with the negative electrode active substance to generate chemical exothermic reaction, the continuously increased temperature promotes the decomposition and the heat release of the positive electrode material, combustion-supporting gases such as oxygen are released, and the heat release reaction can further occur between the combustion-supporting gases such as oxygen and the electrolyte; the rapid generation of heat causes the lithium ion battery to be higher in heat generation speed than heat dissipation speed, so that the lithium ion battery evolves into thermal runaway, and finally fires and explosions are caused.
In order to improve the safety of the lithium ion battery in the prior art, a layer of safety coating is generally added on the surface of the positive electrode plate or the negative electrode plate to absorb the redundant heat in the lithium ion battery. The main components of the safety coating are nano inorganic particles and organic binders, the interface contact resistance between the safety coating and the positive electrode plate or the negative electrode plate is generally larger, and the cycle life loss of the lithium ion battery is more. Meanwhile, the lithium ion battery has the advantages that the internal temperature is increased sharply, the side reaction of the organic binder is increased, and the safe coating structure is easy to collapse and lose the protection effect.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the problems of thermal runaway of the battery, limitation of protection due to the arrangement of a safety coating and the like caused by high heat generated in the lithium ion battery in the prior art, thereby providing a phase change material, a preparation method and application thereof.
For this purpose, the invention provides the following technical scheme.
The invention provides a phase-change material, which comprises phase-change microspheres,
the phase-change microspheres comprise hydrated organic salt and water-soluble polymer as raw materials;
the phase transition temperature of the hydrated organic salt is 80-200 ℃;
the water-soluble polymer has a melting temperature not higher than the phase transition temperature of the hydrated organic salt.
The hydrated organic salt is at least one of lithium acetate dihydrate, lithium oxalate dihydrate, lithium citrate tetrahydrate, lithium salicylate monohydrate and lithium tartrate monohydrate;
preferably, the water-soluble polymer is at least one of polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polymaleic anhydride, polyacrylamide and polyquaternium.
The mass ratio of the water-soluble polymer to the hydrated organic salt is (1-20): (80-99).
The phase change material satisfying at least one of (1) to (2),
(1) The raw materials of the phase change material also comprise a conductive agent;
preferably, the conductive agent is at least one of carbon black, carbon nanotubes, graphene, carbon fibers and graphite;
(2) The raw materials of the phase change material further comprise a binder;
preferably, the binder is at least one of polyvinylidene fluoride, polyacrylate, polyacrylonitrile, styrene-butadiene rubber, polyamide, polyimide, polyvinyl alcohol, acacia, chitosan, gelatin, sodium carboxymethyl cellulose and starch.
The mass ratio of the phase-change microspheres to the conductive agent to the binder is (10-60)/(20-80)/(0.5-10).
The invention also provides a preparation method of the phase-change material, which comprises the steps of,
preparing a water-soluble polymer solution, and then mixing the hydrated organic salt with the water-soluble polymer solution to form a supersaturated solution of the hydrated organic salt;
and decompressing and grinding to obtain the phase-change microsphere.
The temperature is 20-80 ℃ and the pressure is 0.2-0.5MPa when the hydrated organic salt and the water-soluble polymer solution are mixed;
preferably, the depressurization is carried out at 50-100 KPa.
The preparation method of the phase change material comprises the specific steps of,
preparing a water-soluble polymer solution, and then mixing the hydrated organic salt with the water-soluble polymer solution to form a supersaturated solution of the hydrated organic salt;
decompressing until no condensed water is separated out, naturally cooling to room temperature, and grinding to obtain phase-change microspheres;
and mixing the phase-change microspheres, the conductive agent and the binder to obtain the phase-change material.
Further, the phase-change microspheres, the conductive agent and the binder are mixed and then stirred under the vacuum condition of-80 KPa to-95 Kpa, so as to obtain slurry with the solid content of 10-30%, namely the phase-change material.
The substrate may be, but is not limited to, copper foil, aluminum foil, and the like.
The invention also provides a current collector, which comprises a base material and a phase-change coating attached to the base material;
the phase-change coating comprises the phase-change material or the phase-change material prepared by the preparation method;
preferably, the phase-change coating has a thickness of 1-10 μm.
Further, the invention provides a pole piece, which comprises the current collector;
preferably, the pole piece further comprises an active layer;
preferably, the active layer is disposed on at least one side of the current collector.
The active layer refers to a coating layer formed by a positive electrode slurry or a negative electrode slurry coated on a current collector when preparing a pole piece.
The pole piece can be a positive pole piece or a negative pole piece.
The invention further provides a lithium ion battery, which comprises the phase change material, the phase change material prepared by the preparation method, the current collector or the pole piece.
The technical scheme of the invention has the following advantages:
1. the phase change material provided by the invention comprises phase change microspheres, wherein the phase change microspheres comprise hydrated organic salt and water-soluble polymer; the water-soluble polymer has a melting temperature not higher than the phase transition temperature of the hydrated organic salt; the phase transition temperature of the hydrated organic salt is 80-200 ℃. The phase-change material provided by the invention has the advantages of high heat conductivity, strong phase-change heat absorption capacity, stable and reliable structural system and the like, and can quickly respond when being used for a lithium ion battery, and can absorb heat generated in the battery through a phase-change process when overheat or thermal runaway occurs in the battery, so that the safety of the lithium ion battery is ensured.
The phase change material of the invention adopts the hydrated organic salt with specific phase change temperature, and limits the melting temperature of the water-soluble polymer not higher than the phase change temperature of the hydrated organic salt, thus ensuring that the hydrated organic salt can more effectively perform phase change, having high response speed, absorbing heat generated in the battery in time, simultaneously enabling the phase change material to have high heat conductivity and strong heat absorption capacity, and improving the safety of the battery. The water-soluble polymer can form a compact film layer on the surface of the phase-change microsphere, so that the influence of the hydrated organic salt on the battery performance is avoided, meanwhile, the melting temperature of the water-soluble polymer is not higher than the phase-change temperature of the hydrated organic salt, so that when heat is generated in the battery, the water-soluble polymer can quickly respond, the phase-change process of the hydrated organic salt is not prevented, the phase-change hydrated organic salt is released, the heat in the battery can be absorbed more quickly and effectively through the phase-change process of the hydrated organic salt, and the safety of the battery is enhanced. In addition, the water-soluble polymer can also effectively improve the compatibility between the hydrated organic salt and the conductive agent, and ensure the process processability and the structural stability.
Furthermore, when the phase change material provided by the invention is used for a lithium ion battery, the defect that the safety coating coated on the battery collapses and cannot protect the battery due to heat release in the battery in the prior art can be overcome.
2. The phase change material provided by the invention uses at least one of polyethylene glycol, polyvinyl alcohol, polymethyl pyrrolidone, polymaleic anhydride, polyacrylamide and polyquaternium as a water-soluble polymer, the polymers have good film forming property, a compact film layer can be formed on the phase change microsphere, and the problem that the performance of the battery is affected due to the contact of hydrated organic salt with a positive electrode plate or a negative electrode plate when the problem of high heat quantity or thermal runaway does not occur in the battery is avoided.
3. According to the preparation method of the phase change material, provided by the invention, the phase change microspheres can be formed by the hydrated organic salt and the water-soluble polymer, the evaporation of the hydrated organic salt crystal water in the preparation process of the phase change material can be reduced by dissolving the water-soluble polymer in certain deionized water in advance and combining the limitation of parameters such as pressure, temperature and the like, and meanwhile, the polymer can be uniformly adsorbed and wrapped on the surface of the phase change material, so that the reliability and consistency of the performance of the phase change material are ensured.
4. According to the pole piece provided by the invention, the phase-change coating taking the phase-change material as the raw material is arranged between the active layer and the base material, so that the internal resistance of the battery can be reduced, the problem of increased internal resistance of the battery caused by coating the surface of the positive pole piece or the negative pole piece in the prior art is solved, meanwhile, the problem of thermal runaway of the battery can be reduced, and the exertion of the electrochemical performance of the lithium ion battery is facilitated.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of a current collector prepared in example 1 of the present invention;
FIG. 2 is a SEM image of a cross-section of a positive electrode sheet of example 1 of the present invention;
FIG. 3 is a graph showing the test of cells made from the phase change materials of example 1 and comparative example 2 at different heating temperatures at different times;
fig. 4 shows the discharge capacity retention rates of the phase change materials of example 1, example 3, and comparative examples 1-3 at different cycle numbers.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a phase change material, which comprises, by weight, 30 parts of phase change microspheres, 60 parts of conductive carbon black and 10 parts of polyvinylidene fluoride, wherein the raw materials of the phase change microspheres comprise lithium acetate dihydrate and polyethylene glycol 10000 in a mass ratio of 85:15.
The preparation method of the phase change material comprises the following steps,
(1) In a high-pressure reaction kettle with the pressure of 0.2MPa and the temperature of 65 ℃, 30g of polyethylene glycol 10000 is dissolved in 3g of deionized water to form a solution, then 170g of lithium acetate dihydrate is mixed with the solution, stirred and continuously heated for 1h to form a supersaturated solution of the lithium acetate dihydrate; and (3) decompressing to 90KPa, naturally cooling to room temperature after no condensed water is separated out, and grinding to obtain the phase-change microspheres.
(2) Adding the phase-change microspheres, the conductive carbon black and the vinylidene fluoride into deionized water according to the parts by weight, and uniformly stirring under the condition of-95 Kpa to obtain the phase-change material with the solid content of 15%.
The embodiment also provides a current collector, which comprises an aluminum foil and a phase-change coating attached to the aluminum foil, wherein the preparation method of the current collector comprises the steps of coating the phase-change material on the surfaces of two sides of the aluminum foil by adopting a micro-gravure coating method, and drying at 45 ℃ to form the phase-change coating to obtain the current collector; wherein the thickness of the phase-change coating is 3 μm, and the thickness of the aluminum foil is 12 μm.
The embodiment also provides a positive electrode plate, which comprises the current collector.
The embodiment also provides a negative electrode plate, which comprises a copper foil current collector with the thickness of 6 mu m.
Fig. 1 is an SEM image of the current collector prepared in this example, from which it can be seen that the phase-change microspheres and conductive carbon black are uniformly distributed in the phase-change coating.
Fig. 2 is a sectional SEM image of the positive electrode sheet of this example, from which it can be seen that the foil, the phase-change coating layer, and the active layer are uniformly laminated in this order, wherein the average thickness of the phase-change coating layer is 3 μm.
Example 2
The embodiment provides a phase-change material, which comprises, by weight, 25 parts of phase-change microspheres, 65 parts of conductive graphite and 10 parts of polyacrylate, wherein the raw materials of the phase-change microspheres comprise lithium tartrate monohydrate and polyvinylpyrrolidone in a mass ratio of 85:15.
The preparation method of the phase change material comprises the following steps,
(1) In a high-pressure reaction kettle with the pressure of 0.2MPa and the temperature of 70 ℃, 30g of polyvinylpyrrolidone is dissolved in 3g of deionized water to form a solution, then 170g of lithium tartrate monohydrate is mixed with the solution, and stirring and continuous heating are carried out for 1h to form a supersaturated solution of lithium tartrate monohydrate; and (3) decompressing to 90KPa, naturally cooling to room temperature after no condensed water is separated out, and grinding to obtain the phase-change microspheres.
(2) Adding the phase-change microspheres, the conductive graphite and the polyacrylate into deionized water according to the parts by weight, and uniformly stirring under the condition of-95 Kpa to obtain the phase-change material with the solid content of 15%.
The embodiment also provides a current collector, which comprises an aluminum foil and a phase-change coating attached to the aluminum foil, wherein the preparation method of the current collector comprises the steps of coating the phase-change material on the surfaces of two sides of the aluminum foil by adopting a micro-gravure coating method, and drying at 50 ℃ to form the phase-change coating to obtain the current collector; wherein the thickness of the phase-change coating is 3 μm, and the thickness of the aluminum foil is 12 μm.
The embodiment also provides a positive electrode plate, which comprises the current collector.
The embodiment also provides a negative electrode plate, which comprises a copper foil current collector with the thickness of 6 mu m.
Example 3
The embodiment provides a phase change material, which comprises, by weight, 35 parts of phase change microspheres, 55 parts of conductive carbon black and 10 parts of sodium carboxymethyl cellulose, wherein the raw materials of the phase change microspheres comprise lithium citrate tetrahydrate and polymaleic anhydride in a mass ratio of 90:10.
The preparation method of the phase change material comprises the following steps,
(1) In a high-pressure reaction kettle with the pressure of 0.2MPa and the temperature of 60 ℃, dissolving 20g of polymaleic anhydride in 2g of deionized water to form a solution, then mixing 180g of lithium citrate tetrahydrate with the solution, stirring and continuously heating for 1h to form a supersaturated solution of the lithium citrate tetrahydrate; and (3) decompressing to 90KPa, naturally cooling to room temperature after no condensed water is separated out, and grinding to obtain the phase-change microspheres.
(2) Adding the phase-change microspheres, the conductive carbon black and the sodium carboxymethylcellulose into deionized water according to the parts by weight, and uniformly stirring under the condition of-95 Kpa to obtain the phase-change material with the solid content of 15%.
The embodiment also provides a current collector, which comprises a copper foil and a phase-change coating attached to the copper foil, wherein the preparation method of the current collector comprises the steps of coating the phase-change material on the surfaces of two sides of the copper foil by adopting a micro-gravure coating method, and drying at 45 ℃ to form the phase-change coating to obtain the current collector; wherein the thickness of the phase-change coating is 3 μm, and the thickness of the copper foil is 6 μm.
The embodiment also provides a positive electrode plate, which comprises an aluminum foil current collector with the thickness of 12 mu m.
The embodiment also provides a negative electrode plate, which comprises the current collector.
Example 4
The embodiment also provides a positive electrode plate, and a current collector in the positive electrode plate is the same as the current collector in the positive electrode plate of embodiment 1.
The embodiment also provides a negative electrode plate, and the current collector in the negative electrode plate is the same as the current collector in the negative electrode plate in embodiment 3.
Example 5
The embodiment provides a phase change material, which comprises, by weight, 55 parts of phase change microspheres, 40 parts of conductive carbon black and 5 parts of polyvinylidene fluoride, wherein the raw materials of the phase change microspheres comprise lithium acetate dihydrate and polyethylene glycol 10000 in a mass ratio of 97:3.
The preparation method of the phase change material comprises the following steps,
(1) In a high-pressure reaction kettle with the pressure of 0.2MPa and the temperature of 65 ℃, 6g of polyethylene glycol 10000 are dissolved in 0.6g of deionized water to form a solution, then 194g of lithium acetate dihydrate is mixed with the solution, stirred and continuously heated for 1h to form a supersaturated solution of the lithium acetate dihydrate; and (3) decompressing to 90KPa, naturally cooling to room temperature after no condensed water is separated out, and grinding to obtain the phase-change microspheres.
(2) Adding the phase-change microspheres, the conductive carbon black and the vinylidene fluoride into deionized water according to the parts by weight, uniformly stirring under a vacuum condition, and uniformly stirring under a-95 Kpa condition to obtain the phase-change material with the solid content of 15%.
The embodiment also provides a current collector, which comprises an aluminum foil and a phase-change coating attached to the aluminum foil, wherein the preparation method of the current collector comprises the steps of coating the phase-change material on the surfaces of two sides of the aluminum foil by adopting a micro-gravure coating method, and drying at 45 ℃ to form the phase-change coating to obtain the current collector; wherein the thickness of the phase-change coating is 3 μm, and the thickness of the aluminum foil is 12 μm.
The embodiment also provides a positive electrode plate, which comprises the current collector.
The embodiment also provides a negative electrode plate, which comprises a copper foil current collector with the thickness of 6 mu m.
Comparative example 1
The comparative example provides a positive electrode sheet comprising an aluminum foil current collector having a thickness of 12 μm;
the comparative example also provides a negative electrode tab comprising a copper foil current collector having a thickness of 6 μm.
Comparative example 2
The comparative example provides a positive electrode sheet comprising aluminum foil and a conductive layer attached to a substrate, the preparation method comprising the following steps,
adding conductive carbon black and polyacrylic acid into deionized water according to the weight ratio of 90:10, stirring uniformly under the vacuum condition of-95 Kpa to obtain slurry with the solid content of 15%, coating the slurry on the surfaces of two sides of an aluminum foil by adopting a micro-gravure coating method, and drying at 45 ℃ to form a conductive layer to obtain a current collector; wherein the thickness of the conductive layer is 3 μm, and the thickness of the aluminum foil is 12 μm.
The comparative example also provides a negative electrode tab comprising a copper foil current collector having a thickness of 6 μm.
Comparative example 3
The comparative example also provides a positive electrode sheet comprising an aluminum foil, an active layer coated on the aluminum foil and a safety coating coated on the active layer and far away from one side of the aluminum foil; wherein, the raw material of the active layer is positive electrode slurry, and the positive electrode slurry in the test example is referred to; the raw materials of the safety coating comprise boehmite and polyacrylic acid; the thickness of the safety coating is 5 mu m, and the thickness of the aluminum foil is 12 mu m;
the preparation method of the positive electrode plate comprises the following steps,
coating positive electrode slurry on an aluminum foil to form an active layer;
adding boehmite and polyacrylic acid into N-methyl pyrrolidone (NMP) according to the weight ratio of 85:15, stirring uniformly under the vacuum condition of-95 Kpa to obtain slurry with the solid content of 15%, coating the slurry on one side of an active layer far away from an aluminum foil by adopting a micro-gravure coating method, and drying at 75 ℃ to form a safe coating to obtain the positive electrode plate.
The comparative example also provides a negative electrode tab comprising a copper foil current collector having a thickness of 6 μm.
Test examples
The performance of the positive electrode sheet and the negative electrode sheet in each of the examples and comparative examples was tested in this test example, specifically as follows,
preparation of the battery:
positive pole piece: mixing nickel cobalt lithium manganate (NCM 811), conductive carbon black, carbon nano tubes and polyvinylidene fluoride according to the mass ratio of 97:1:0.5:1.5, adding the mixture into N-methyl pyrrolidone (NMP) to obtain positive electrode slurry, coating the positive electrode slurry on a current collector, and baking to obtain the positive electrode plate.
Negative pole piece: mixing artificial graphite, conductive carbon black, sodium carboxymethylcellulose and styrene-butadiene rubber according to the mass ratio of 96:1.5:1.0:1.5, adding the mixture into deionized water to obtain negative electrode slurry, coating the negative electrode slurry on a current collector, and baking to obtain a negative electrode plate.
A diaphragm: the commercial diaphragm is selected, and specifically comprises: PE with the thickness of 9 μm is taken as a base film, and ceramic layers with the thickness of 2 μm are coated on two sides of the base film.
Electrolyte solution: the volume ratio of 2:4:4 ethylene carbonate, ethylmethyl carbonate and diethyl carbonate as solvent, liPF 6 Configured as lithium salt, liPF 6 The concentration was 1.05mol/L.
And assembling the positive pole piece, the negative pole piece and the diaphragm, and obtaining the lithium ion battery through liquid injection, encapsulation and formation.
The test method of the 50% SOC discharge DCR of the battery comprises the following steps: charging the battery to 4.2V at 25deg.C constant current, charging to 0.05C constant voltage at 4.2V, standing for 10min, discharging at 1C constant current for 30min, standing for 10min, and taking the voltage value V at the end of standing 1 The voltage value V at the end of pulse discharge is taken by 1C pulse discharge for 10s 2 ，V 1 And V is equal to 2 The ratio of the voltage difference value to the 1C current value is the 50% SOC discharge DCR of the battery.
The test method of the 500-week cycle discharge capacity retention rate of the battery comprises the following steps: at 25 ℃, (1) charging the battery to 4.2V at a constant current of 1C, charging the battery to 0.05C at a constant voltage of 4.2V, and standing for 10min; (2) then discharging to 2.8V at a constant current of 1C, and standing for 10min; (3) And (3) testing the steps (1) - (2) for 500 times, and taking the percentage of the ratio of the discharge capacity of the nth time to the discharge capacity of the 1 st time as the discharge capacity retention rate of the nth time.
The test method for the overcharge of the battery comprises the following steps: charging the battery to 4.2V at a constant current of 1C, charging to 0.05C at a constant voltage of 4.2V, stopping the charging, standing for 30min, then charging to 6.3V at a constant current of 1C or ending the charging for more than 1h, standing and observing for 1h, and observing whether phenomena such as fire and explosion occur.
The battery needling test method comprises the following steps: charging the battery to 4.2V at a constant current of 1C, charging to 0.05C at a constant voltage of 4.2V, stopping, standing for 30min, selecting a 5mm steel needle and penetrating from a direction perpendicular to the battery at a speed of 25mm/s, wherein the penetrating position is close to the geometric center of the needling surface, the steel needle stays in the battery, standing for observing for 1h, and observing whether phenomena such as fire and explosion occur or not.
The heating test method at 150 ℃ comprises the following steps: charging the battery to 4.2V at constant current of 1C, charging to 0.05C at constant voltage of 4.2V, stopping, standing for 30min, heating the battery to 150 ℃ at a heating rate of 5 ℃/min, maintaining and observing for 1h, and observing whether phenomena such as fire and explosion occur.
Table 1 results of performance tests of lithium ion batteries prepared in examples 1 to 4 and comparative examples 1 to 2
As can be seen from the experimental results described in table 1, compared with comparative example 1, the 50% soc cells prepared using the phase change material of the present invention have lower DCR, and the average drop is about 13%, and the current collector coated with the phase change material can exert excellent conductivity between the active layer and the foil; further, when the battery is subjected to tests such as needling, overcharging and heating, the problems of ignition, explosion and the like do not occur, which means that when the battery is overheated or in thermal runaway, the phase-change material absorbs heat in the battery through a phase-change process, and the safety of the battery is ensured.
Compared with comparative example 2, the phase-change microspheres are added into the phase-change material, so that the battery can pass the tests of overcharge, needling, heating and the like, the problems of ignition, explosion and the like can not occur, and the safety performance of the battery is improved.
The 50% soc discharge DCR of the battery prepared by changing the raw material of the safety coating layer and coating the safety coating layer on the active layer was larger than that of comparative example 3, increased by about 27% compared with the present invention, and the 500-week discharge capacity retention rate was low, reduced by about 8% compared with the present invention, indicating that the internal resistance of the battery prepared by this comparative example was large and the cycle stability was poor.
Fig. 3 is a graph showing the heating temperature curves of fig. 3 for the battery prepared from the phase change materials of example 1 and comparative example 2 at different heating temperatures at different times, wherein the temperature of the first plateau of the heating curve is 130 c and the temperature of the second plateau is 150 c, and the results of example 1 and comparative example 2 are shown in fig. 3. As can be seen from fig. 3, the battery made of the phase change material of example 1 is heated at 130 ℃ for about 1.5 hours and 150 ℃ for about 1 hour, and the voltage of the battery can still be maintained at about 4.2V, which indicates that the battery has a stable structural system, good reliability and safety, and no problem of failure caused by overhigh temperature in the battery. The battery prepared from the phase change material of comparative example 2 has the advantages that after the battery is heated at 130 ℃ and 150 ℃, the voltage of the battery is instantaneously reduced and is ignited to explode, so that the battery has the problems of thermal runaway and the like when the internal temperature of the battery is too high.
Fig. 4 shows the discharge capacity retention rates of the phase change materials of example 1, example 3 and comparative examples 1-3 at different cycle times, and it can be seen from the graph that the phase change materials of the present invention provide batteries with good cycle stability at different cycle times.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (12)
1. A phase-change material is characterized in that the raw materials comprise phase-change microspheres, a conductive agent and a binder,
the phase-change microspheres comprise hydrated organic salt and water-soluble polymer as raw materials;
the phase transition temperature of the hydrated organic salt is 80-200 ℃;
the water-soluble polymer has a melting temperature not higher than the phase transition temperature of the hydrated organic salt;
the hydrated organic salt is at least one of lithium acetate dihydrate, lithium oxalate dihydrate, lithium citrate tetrahydrate, lithium salicylate monohydrate and lithium tartrate monohydrate;
the water-soluble polymer is at least one of polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polymaleic anhydride, polyacrylamide and polyquaternium;
the mass ratio of the water-soluble polymer to the hydrated organic salt is (1-20): (80-99);
the mass ratio of the phase-change microspheres to the conductive agent to the binder is (10-60)/(20-80)/(0.5-10).
2. The phase change material of claim 1, wherein the conductive agent is at least one of carbon black, carbon nanotubes, graphene, carbon fibers, and graphite.
3. The phase change material according to claim 1 or 2, wherein the binder is at least one of polyvinylidene fluoride, polyacrylate, polyacrylonitrile, styrene butadiene rubber, polyamide, polyimide, polyvinyl alcohol, acacia, chitosan, gelatin, sodium carboxymethyl cellulose, and starch.
4. A process for preparing a phase change material according to any one of claims 1 to 3, comprising,
preparing a water-soluble polymer solution, and then mixing the hydrated organic salt with the water-soluble polymer solution to form a supersaturated solution of the hydrated organic salt;
decompressing and grinding to obtain the phase-change microspheres;
and uniformly mixing the phase-change microspheres with a conductive agent and a binder to obtain the phase-change material.
5. The method according to claim 4, wherein the hydrated organic salt is mixed with the water-soluble polymer solution at a temperature of 20 to 80℃and a pressure of 0.2 to 0.5MPa.
6. The process according to claim 5, wherein the depressurization is carried out under 50 to 100 KPa.
7. A current collector comprising a substrate and a phase change coating attached to the substrate;
the raw materials of the phase-change coating comprise the phase-change material according to any one of claims 1 to 3 or the phase-change material prepared by the preparation method according to any one of claims 4 to 6.
8. The current collector of claim 7, wherein the phase-change coating has a thickness of 1-10 μm.
9. A pole piece comprising the current collector of claim 7.
10. The pole piece of claim 9, further comprising an active layer.
11. The pole piece of claim 10, wherein the active layer is disposed on at least one side of the current collector.
12. A lithium ion battery comprising a phase change material according to any one of claims 1-3, a phase change material produced by a method according to any one of claims 4-6, a current collector according to any one of claims 7-8 or a pole piece according to any one of claims 9-11.
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