CN114243214A - Inorganic ceramic coating diaphragm and preparation method and application thereof - Google Patents
Inorganic ceramic coating diaphragm and preparation method and application thereof Download PDFInfo
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- CN114243214A CN114243214A CN202111649061.7A CN202111649061A CN114243214A CN 114243214 A CN114243214 A CN 114243214A CN 202111649061 A CN202111649061 A CN 202111649061A CN 114243214 A CN114243214 A CN 114243214A
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- 238000005524 ceramic coating Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 105
- 239000000919 ceramic Substances 0.000 claims abstract description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000000843 powder Substances 0.000 claims abstract description 54
- 239000011230 binding agent Substances 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 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
- 239000011247 coating layer Substances 0.000 claims abstract description 21
- 239000002562 thickening agent Substances 0.000 claims abstract description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 71
- 239000010408 film Substances 0.000 claims description 38
- 239000011787 zinc oxide Substances 0.000 claims description 35
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 26
- 229910052744 lithium Inorganic materials 0.000 claims description 26
- 239000003792 electrolyte Substances 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 25
- 238000000576 coating method Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000002844 melting Methods 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 239000006255 coating slurry Substances 0.000 claims description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 10
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 10
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 10
- 230000009477 glass transition Effects 0.000 claims description 10
- 230000035699 permeability Effects 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 238000007756 gravure coating Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 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 2
- 239000003570 air Substances 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 239000004760 aramid Substances 0.000 claims description 2
- 229920003235 aromatic polyamide Polymers 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 238000007765 extrusion coating Methods 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 2
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 239000011295 pitch Substances 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 abstract description 21
- 150000002500 ions Chemical class 0.000 abstract description 5
- 230000010287 polarization Effects 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 26
- 229920000058 polyacrylate Polymers 0.000 description 16
- 239000004698 Polyethylene Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 9
- DHGWZWRJBUSWOV-UHFFFAOYSA-L dichlorozinc dihydrate Chemical compound O.O.[Cl-].[Cl-].[Zn+2] DHGWZWRJBUSWOV-UHFFFAOYSA-L 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000008595 infiltration Effects 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
- H01M50/434—Ceramics
-
- 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses an inorganic ceramic coating diaphragm and a preparation method and application thereof, wherein the inorganic ceramic coating diaphragm comprises a base film and an inorganic ceramic layer, at least one surface of the base film is coated with an inorganic ceramic coating, the inorganic ceramic coating comprises inorganic ceramic powder, a binder and a thickening agent, the surface of the inorganic ceramic powder particle is coated with an activated carbon coating layer, and the inorganic ceramic powder comprises three types of particle size distribution and more than two different polyhedral morphologies. The diaphragm is low in porosity and high in density, heat resistance, liquid retention and safety are obviously improved, contact sites and conduction paths can be added for lithium ions, ion conductivity is obviously enhanced, conduction distance is shortened, concentration polarization caused by lithium ion concentration during high-rate charge and discharge of the battery is relieved, and quick charging performance of the battery is obviously improved.
Description
Technical Field
The invention belongs to the field of battery diaphragms, and particularly relates to an inorganic ceramic coating diaphragm and a preparation method and application thereof.
Background
Most of isolating membranes used by the lithium ion batteries and the lithium ion polymer batteries are polyolefin membranes, such as polyethylene membranes (PE), polypropylene membranes (PP) or polypropylene/polyethylene/polypropylene composite membranes (PP/PE/PP), and are widely used in the lithium ion batteries; however, when short circuit, overcharge, thermal shock or puncture occurs, the internal temperature of the lithium ion battery reaches above 100 ℃, and at the moment, the polyolefin film is greatly shrunk or melted, so that the volume of the diaphragm is changed, direct contact between the positive electrode and the negative electrode is further caused, the phenomena of internal short circuit and thermal runaway occur, and the lithium ion battery is easy to catch fire and even explode. In addition, because the surface tension of the polyolefin film is very low, the wetting capacity and the liquid absorption capacity of the carbonate electrolyte used by the lithium ion secondary battery are poor, and the requirement of the lithium ion secondary battery on long cycle life cannot be met. Therefore, in order to ensure the use safety and long cycle life of the battery, it is necessary to provide a functionally modified composite separator.
In order to solve the above problem, a conventional method is to coat a ceramic layer on one or both surfaces of a polyolefin barrier film to form an organic/inorganic composite separator, wherein the thickness of the coating on one surface is generally 3 to 5 μm. The method can improve the thermal stability and mechanical strength of the diaphragm; secondly, the liquid retention of the diaphragm is enhanced, so that the cycle life of the battery is prolonged; and thirdly, the wettability of the diaphragm is improved. In addition, the ceramic coating is rich in ceramic particles, so that the separator has excellent foreign particle resistance. However, the liquid retention and wettability of the separator are still insufficient, and the density of the separator is insufficient, so that the heat resistance of the coated separator still needs to be improved, and in addition, when the coated separator is used for a lithium ion battery, the quick charging performance is not good.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide an inorganic ceramic coating diaphragm which has excellent liquid retention property, wettability and heat resistance and can remarkably improve the quick charging performance of a lithium ion battery.
In order to achieve the purpose, the invention provides the following technical scheme:
the inorganic ceramic coating diaphragm for the lithium ion battery comprises a base film and an inorganic ceramic coating, wherein at least one surface of the base film is coated with the inorganic ceramic coating, the inorganic ceramic coating comprises inorganic ceramic powder, a binder and a thickening agent, the surface of inorganic ceramic powder particles is coated with an activated carbon coating layer, the inorganic ceramic powder comprises first-particle-size inorganic ceramic powder, second-particle-size inorganic ceramic powder and third-particle-size inorganic ceramic powder, and the inorganic ceramic powder comprises more than two different polyhedral morphologies.
Preferably, the inorganic ceramic powder accounts for 80-95% of the total mass of the raw materials forming the inorganic ceramic coating, the binder accounts for 0.2-10%, and the thickening agent accounts for 0.2-10%.
Preferably, the inorganic ceramic powder comprises one or more of aluminum oxide, silicon oxide, zirconium oxide, zinc oxide, calcium oxide, yttrium oxide, magnesium oxide, tin oxide, nickel oxide, silicon dioxide, titanium dioxide, hafnium oxide, aluminum hydroxide, calcium hydroxide, magnesium hydroxide and boehmite;
the binder is one or more of polyacrylic acids, polyacrylonitrile, polyvinyl alcohol, organic silicon, epoxy resin, polyurethane, PVDF and styrene butadiene rubber;
the thickener is at least one of sodium carboxymethyl cellulose, lithium carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polyacrylamide, sodium alginate and polyvinyl alcohol.
Preferably, the first particle size is 0.1-0.3 μm, the second particle size is 0.5-1 μm, and the third particle size is 2-3 μm; the proportion of the first particle size is 50-60%, the proportion of the second particle size is 30-40%, and the proportion of the third particle size is 0-10%;
the polyhedron morphology comprises more than two of a sphere, a tetrahedron, a hexahedron, a heptahedron, an octahedron, a decahedron, a dodecahedron and an icosahedron.
Preferably, the thickness of the activated carbon coating layer is 10-50 nm; the active carbon coating layer is realized by adopting an in-situ coating chemical method.
Preferably, the thickness of the inorganic ceramic coating is 1-5 μm.
Preferably, the contact angle between the binder particles and the electrolyte is 10-80 ℃, the melting temperature is 130-280 ℃, and the glass transition temperature is-10-80 ℃. The preferable contact angle of the binder particles with the electrolyte facilitates wetting of the electrolyte in the separator.
Preferably, the base film is PP, PE, a PP/PE/PP composite film, aramid or non-woven fabric; the melting point of the base film is 130-180 ℃, the thickness of the base film is 3-12 mu m, the porosity of the base film is 30-60%, and the air permeability of the base film is 30-400 sec/100 cc.
As a general inventive concept, the present invention also provides a method for preparing an inorganic ceramic-coated separator for a lithium ion battery, comprising the steps of:
s1, dissolving the binder in the solvent to form a binder solution;
s2, dispersing more than two inorganic ceramic powders with different polyhedral morphologies and three different particle size ranges in a solvent, and then mixing the inorganic ceramic powders with a pre-dissolved thickening agent to form uniform dispersion liquid; the inorganic ceramic powder is in-situ synthesized active carbon coated inorganic ceramic powder;
s3, adding the binder solution into the dispersion liquid, uniformly dispersing, and adjusting until the solid content accounts for 30-60% of the total amount of the slurry to obtain coating slurry;
and S4, coating the obtained coating slurry on at least one surface of a base material in a micro-gravure or extrusion coating mode, and drying to obtain the inorganic ceramic coating diaphragm.
Preferably, the method of coating with activated carbon comprises:
(1) dissolving PVP and a carbon source substance in water and/or ethanol, stirring and carrying out ultrasonic treatment until the PVP and the carbon source substance are uniformly dispersed;
(2) adding inorganic ceramic powder into the solution environment for uniform dispersion;
(3) filtering and drying in a vacuum environment;
(4) carbonizing the dried powder at a high temperature of 500-1000 ℃ to obtain black powder;
(5) and (3) placing the black powder in an environment of 500-800 ℃, and carrying out oxidation activation in the atmosphere of air, carbon dioxide, water vapor or mixed gas of the air, the carbon dioxide, the water vapor or the mixed gas of the air, the carbon dioxide and the water vapor to obtain the inorganic ceramic powder coated with the activated carbon.
Preferably, the carbon source substance is one or more of asphalt, glucose, urea, terephthalic acid, 1, 3, 5-benzenetricarboxylic acid and 2-methylimidazole, and the mass ratio of the carbon source substance is 1-10% of the ceramic powder.
The invention also provides a preparation method of the zinc oxide polyhedral ceramic powder, which comprises the following steps:
(1) uniformly dissolving zinc chloride dihydrate or zinc nitrate hexahydrate and hexadecyl trimethyl ammonium bromide in a solvent according to a molar ratio of 1-5 to obtain a solution A; dissolving 2-methylimidazole with zinc chloride dihydrate or zinc nitrate hexahydrate in a molar ratio of 1-10 in a solvent to obtain a solution B;
(2) rapidly adding the solution B into the solution A, stirring, and reacting at a water bath temperature of 60-80 ℃;
(3) after cooling, carrying out solid-liquid separation and cleaning to obtain powder, and then drying;
(4) and calcining the dried powder, and cooling to obtain the polyhedral zinc oxide ceramic powder.
The shape of the zinc oxide ceramic powder is controlled by regulating and controlling solvents such as deionized water, ethanol, glycol, methanol, dimethylformamide and the like, and the particle size of the zinc oxide ceramic powder is controlled by regulating and controlling the stoichiometric ratio of zinc chloride dihydrate or zinc nitrate hexahydrate and 2-methylimidazole.
In the step (1), the solvent is one or more of ionized water, glycol, methanol, ethanol and dimethylformamide.
Preferably, in the step (4), the calcination temperature is 400-800 ℃, the temperature rise speed is 0.2-1 ℃/min, and the calcination time is 1-3 h.
Preferably, in the step (2), the reaction time is 6-8 h.
Compared with the prior art, the invention has the following beneficial effects:
1. aiming at the technical problems of insufficient liquid retention, wettability and heat resistance and poor quick charge performance when being applied to a lithium ion battery and the like of the existing inorganic ceramic coating diaphragm, the invention develops an inorganic ceramic coating diaphragm, wherein an inorganic ceramic coating of the diaphragm comprises inorganic ceramic powder, a binder and a thickening agent, the diaphragm is prepared by coating an active carbon coating layer on the surface of inorganic ceramic powder particles and adopting more than two different polyhedral inorganic ceramic powder particles with different particle size ranges as raw materials, the obtained diaphragm not only has low porosity and high density, but also has obviously improved heat resistance, liquid retention and safety, can also increase contact sites and conduction paths for lithium ions, obviously enhances ion conduction performance and shortens conduction distance, relieves concentration polarization caused by lithium ion concentration when the battery is charged and discharged at large multiplying power, thereby obviously improving the quick charging performance of the battery.
Because the diaphragm of the invention can accelerate infiltration and absorb more electrolyte, the manufacturing time of the liquid injection step can be reduced in the manufacturing process; and after assembling into a cell, one of: the increase of the electrolyte amount is beneficial to fully utilizing the capacity of the active substance, because the electrolyte amount is insufficient, the anode plate is not fully soaked, and the diaphragm is not soaked, the internal resistance is larger, and the capacity exertion is lower; the second step is as follows: the electrolyte amount is small, the conductivity is reduced, the internal resistance is increased quickly after circulation, the decomposition or volatilization of the electrolyte at the local part of the battery is accelerated, the deterioration speed of the circulation performance of the battery is gradually accelerated, and the increase of the electrolyte is beneficial to improving the circulation performance of the battery; and thirdly: when the amount of the electrolyte is too small, the internal resistance of the battery is large and heat generation is large. The temperature rise causes the electrolyte to be rapidly decomposed to generate gas, the diaphragm is melted, and the battery is inflated, short-circuited and exploded, so that the safety characteristic of the battery is improved.
2. According to the invention, through the optimized particle size distribution, the proportion of each particle size distribution and the polygonal shape of the inorganic ceramic powder particles in three different particle size ranges, the heat resistance of the coated diaphragm can be maximally improved, and the liquid retention and wettability of the diaphragm can be remarkably enhanced.
3. According to the invention, by optimizing the thickness, raw materials, preparation method and the like of the active carbon coating layer, the binding force between the coating layer and the ceramic particles can be further improved, the structural stability is improved, and the specific surface area and microporosity can be further improved, so that the liquid absorption property, the liquid retention property and the wettability of the diaphragm can be further improved, the number of contact sites and a conduction path can be further improved, the ion conductivity is further enhanced, the conduction distance is shortened, the concentration polarization is reduced, and the quick charging performance of the battery is further improved.
4. The preparation method of the inorganic ceramic coating diaphragm is simple to operate and easy to realize, the inorganic ceramic coating diaphragm with low porosity, high density, high heat resistance, high liquid absorption, high safety and high ionic conductivity can be stably prepared, and the prepared inorganic ceramic diaphragm can obviously improve the quick charge performance when being used for a lithium ion battery.
5. The carbon-coated ceramic particles prepared by the preparation method of the activated carbon-coated ceramic particles have strong binding force between the coating layer and the ceramic particles, good structural stability and higher specific surface area and microporosity, so that the liquid absorption, liquid retention and wettability of the diaphragm can be effectively improved, the number of contact sites and a conduction path can be further improved, the ion conductivity can be further enhanced, the conduction distance can be shortened, the concentration polarization can be reduced, and the quick charging performance of the battery can be further improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic cross-sectional view of an inorganic ceramic-coated separator according to the present invention.
Reference numerals:
1. a first tetrahedron; 2. a second tetrahedron; 3. a first hexahedron; 4. a second hexahedron; 5. a first sphere; 6. a second sphere; 7. a binder; 8. a base film.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Example 1
The non-solvent raw materials of the coating slurry formula comprise three major parts, namely inorganic ceramic particles, a binder and a thickening agent, and the mixture ratio is measured according to the weight percentage, specifically, 94% of activated carbon-coated polyhedral zinc oxide particles, 3% of lithium polyacrylate and 3% of lithium carboxymethyl cellulose. Wherein the polyhedron comprises a hexahedron and a dodecahedron, and the mass ratio is 30%: 70 percent; wherein the hexahedral zinc oxide particles and the dodecahedral zinc oxide particles comprise three particle sizes, D50 is respectively 0.3 mu m, 0.8 mu m and 2.5 mu m, the mass percentages of the three particle sizes are respectively 60%, 30% and 10%, and the thickness of the activated carbon coating layer is 15 nm; the contact angle between the lithium polyacrylate solid particles and the electrolyte is 60 degrees, the melting temperature is 240 degrees centigrade, and the glass transition temperature is 5 degrees centigrade; the solid content of the finally obtained slurry is about 50 percent of the total weight of the slurry by using water as a solvent; the base film was a PE film having a melting point of 170 ℃, a thickness of 10 μm, a porosity of 45% and an air permeability of 200 sec/100 cc.
The obtained coating slurry was uniformly applied to the above-mentioned base film by gravure coating, and completely dried to obtain a coating layer having a thickness of 4 μm, the total thickness of the base film plus the coating layer being 14 μm.
The activated carbon coated ceramic particles are prepared by the following method: dissolving PVP and terephthalic acid uniformly in a molar ratio of 1: 1, performing ultrasonic treatment to uniformly disperse in the deionized water/ethanol mixed solution; uniformly dispersing zinc oxide powder in the solution; filtering and then drying for 12h at 80 ℃ in a vacuum environment; carbonizing the dried powder at 600 ℃ for 2h under argon atmosphere to obtain black powder; and (3) placing the obtained black powder in air with the humidity of 95% to carry out high-temperature activation at 800 ℃ to finally obtain the activated carbon coated zinc oxide particles.
Wherein the hexahedral zinc oxide ceramic particles having a particle size D50 of 2.5 μm are prepared by the following method: the molar ratio is 1: 0.3 of zinc chloride dihydrate and cetyltrimethylammonium bromide (CTAB) were uniformly dissolved in a molar ratio of 1: 1, in a mixed solution of ethylene glycol/dimethylformamide, marked as solution 1; the molar ratio of the zinc chloride to the zinc chloride dihydrate is 8: 2-methylimidazole of 1 is additionally dissolved in a molar ratio of 1: 1, labeled as solution 2; solution 2 was poured rapidly into solution 1 and stirred vigorously for 30min, and reacted for 6h at a water bath temperature of 80 ℃. After the reaction is finished, filtering, cleaning, drying for 18h at 80 ℃, and then calcining for 1h at 550 ℃ in air atmosphere to obtain hexahedral zinc oxide ceramic particles, wherein the heating rate is 0.5 ℃/min.
Particle sizes D50 were 0.3 μm and 0.8 μm, respectively, the molar ratio of zinc chloride dihydrate to 2-methylimidazole was adjusted to 4: 1 and 1.8: 1.
the preparation method of the dodecahedral zinc oxide particles with the particle size of 2.5 mu m changes the solvent into the zinc oxide particles with the mass ratio of 1: 1, and mixing the dimethyl formamide and the glycol.
The preparation method of dodecahedral zinc oxide particles having a particle diameter of 0.8 μm requires adjusting the molar ratio of zinc chloride dihydrate to 2-methylimidazole to 4: 1; the preparation method of dodecahedral zinc oxide particles with a particle size of 0.3 μm requires adjusting the molar ratio of zinc chloride dihydrate to 2-methylimidazole to 1.8: 1, the rest steps are consistent with the preparation method of the dodecahedral zinc oxide particles with the particle size of 2.5 mu m.
Comparative example 1
The non-solvent raw materials of the coating slurry formula comprise three major parts, namely inorganic ceramic particles, a binder and a thickening agent, and the mixture ratio is measured according to weight percentage and comprises 94 percent of common zinc oxide particles, 3 percent of lithium polyacrylate and 3 percent of lithium carboxymethyl cellulose. Wherein the zinc oxide particles D50 are 2.5 μm; the contact angle between the lithium polyacrylate solid particles and the electrolyte is 60 degrees, the melting temperature is 240 degrees centigrade, and the glass transition temperature is 5 degrees centigrade; the solid content of the finally obtained slurry is about 50 percent of the total weight of the slurry by using water as a solvent; the base film was a PE film having a melting point of 170 ℃, a thickness of 10 μm, a porosity of 45% and an air permeability of 200 sec/100 cc.
The coating method was the same as in example 1.
Comparative example 2
The non-solvent raw materials of the coating slurry formulation of this example include three major components, namely inorganic ceramic particles, a binder and a thickener, and the mixture ratio is measured by weight percentage and includes 94% of hexahedral zinc oxide particles, 3% of lithium polyacrylate and 3% of lithium carboxymethyl cellulose. Wherein the zinc oxide particles D50 are 2.5 μm; the contact angle between the lithium polyacrylate solid particles and the electrolyte is 60 degrees, the melting temperature is 240 degrees centigrade, and the glass transition temperature is 5 degrees centigrade; the solid content of the finally obtained slurry is about 50 percent of the total weight of the slurry by using water as a solvent; the base film was a PE film having a melting point of 170 ℃, a thickness of 10 μm, a porosity of 45% and an air permeability of 200 sec/100 cc.
The coating method was the same as in example 1.
The preparation method of the hexahedral zinc oxide particles was identical to that of example 1 in which hexahedral zinc oxide particles having a particle size of 2.5 μm were prepared.
Comparative example 3
The non-solvent raw materials of the coating slurry formula comprise three major parts, namely inorganic ceramic particles, a binder and a thickening agent, and the proportion is measured by weight percentage, specifically, 94% of common zinc oxide particles, 3% of lithium polyacrylate and 3% of lithium carboxymethyl cellulose. The zinc oxide particles comprise three particle sizes, D50 is respectively 0.3 μm, 0.8 μm and 2.5 μm, and the mass percentages of the three particle sizes are respectively 60%, 30% and 10%; the contact angle between the lithium polyacrylate solid particles and the electrolyte is 60 degrees, the melting temperature is 240 degrees centigrade, and the glass transition temperature is 5 degrees centigrade; the solid content of the finally obtained slurry is about 50 percent of the total weight of the slurry by using water as a solvent; the base film was a PE film having a melting point of 170 ℃, a thickness of 10 μm, a porosity of 45% and an air permeability of 200 sec/100 cc.
The coating method was the same as in example 1.
Comparative example 4
The non-solvent raw materials of the coating slurry formula comprise three major parts, namely inorganic ceramic particles, a binder and a thickening agent, and the mixture ratio is measured according to the weight percentage, specifically, 94% of activated carbon coated common zinc oxide particles, 3% of lithium polyacrylate and 3% of lithium carboxymethyl cellulose. Wherein the zinc oxide particle D50 is 2.5 μm, and the thickness of the activated carbon coating layer is 15 nm; the contact angle between the lithium polyacrylate solid particles and the electrolyte is 60 degrees, the melting temperature is 240 degrees centigrade, and the glass transition temperature is 5 degrees centigrade; the solid content of the finally obtained slurry is about 50 percent of the total weight of the slurry by using water as a solvent; the base film was a PE film having a melting point of 170 ℃, a thickness of 10 μm, a porosity of 45% and an air permeability of 200 sec/100 cc.
The coating method was the same as in example 1.
The activated carbon coating method was the same as in example 1.
Comparative example 5
The non-solvent raw materials of the coating slurry formula comprise three major parts, namely inorganic ceramic particles, a binder and a thickening agent, and the mixture ratio is measured according to weight percentage, specifically comprising 94% of hexahedral zinc oxide particles, 3% of lithium polyacrylate and 3% of lithium carboxymethyl cellulose. Wherein the hexahedral zinc oxide particles comprise three particle sizes, D50 is respectively 0.3 μm, 0.8 μm and 2.5 μm, and the mass percentages of the three particle sizes are respectively 60%, 30% and 10%; the contact angle between the lithium polyacrylate solid particles and the electrolyte is 60 degrees, the melting temperature is 240 degrees centigrade, and the glass transition temperature is 5 degrees centigrade; the solid content of the finally obtained slurry is about 50 percent of the total weight of the slurry by using water as a solvent; the base film was a PE film having a melting point of 170 ℃, a thickness of 10 μm, a porosity of 45% and an air permeability of 200 sec/100 cc.
The coating method was the same as in example 1.
The preparation of the hexahedral zinc oxide particles was in accordance with example 1.
Comparative example 6
The non-solvent raw materials of the coating slurry formula comprise three major parts, namely inorganic ceramic particles, a binder and a thickening agent, and the mixture ratio is measured according to the weight percentage, specifically, 94% of active carbon coated hexahedral zinc oxide particles, 3% of lithium polyacrylate and 3% of lithium carboxymethyl cellulose. Wherein the zinc oxide particle D50 is 2.5 μm, and the thickness of the activated carbon coating layer is 15 nm; the contact angle between the lithium polyacrylate solid particles and the electrolyte is 60 degrees, the melting temperature is 240 degrees centigrade, and the glass transition temperature is 5 degrees centigrade; the solid content of the finally obtained slurry is about 50 percent of the total weight of the slurry by using water as a solvent; the base film was a PE film having a melting point of 170 ℃, a thickness of 10 μm, a porosity of 45% and an air permeability of 200 sec/100 cc.
The coating method was the same as in example 1.
The preparation method of the hexahedral zinc oxide particles having a particle size of 2.5 μm was the same as in example 1, and the activated carbon coating method was the same as in example 1.
Comparative example 7
The non-solvent raw materials of the coating slurry formula comprise three major parts, namely inorganic ceramic particles, a binder and a thickening agent, and the mixture ratio is measured according to the weight percentage, specifically, 94% of activated carbon coated common zinc oxide particles, 3% of lithium polyacrylate and 3% of lithium carboxymethyl cellulose. Wherein the hexahedral zinc oxide particles comprise three particle sizes, D50 is respectively 0.3 μm, 0.8 μm and 2.5 μm, the mass percentages of the three particle sizes are respectively 60%, 30% and 10%, and the thickness of the activated carbon coating layer is 15 nm; the contact angle between the lithium polyacrylate solid particles and the electrolyte is 60 degrees, the melting temperature is 240 degrees centigrade, and the glass transition temperature is 5 degrees centigrade; the solid content of the finally obtained slurry is about 50 percent of the total weight of the slurry by using water as a solvent; the base film was a PE film having a melting point of 170 ℃, a thickness of 10 μm, a porosity of 45% and an air permeability of 200 sec/100 cc.
The coating method was the same as in example 1.
The activated carbon coating process was consistent with example 1.
Assembling the isolating membranes prepared in comparative examples 1-7 and example 1 with a positive pole piece (lithium manganate) and a negative pole piece (artificial graphite) into a lithium ion battery, testing the electrolyte infiltration time and the electrolyte retention amount in the liquid injection process, and performing a normal-temperature cycle test and a 5C rate test; in addition, the prepared separator was subjected to a test of thermal shrinkage at 160 ℃ for 0.5 hour.
The test results are shown in table 1:
table 1:
| group item | Shrinkage rate | Soaking time | Liquid retention amount g/m2 | Retention rate of 500 cycles at normal temperature | Capacity retention ratio of 5C | |
| Example 1 | 1.1％ | 30s | 10.6 | 95.4％ | 90.5％ | |
| Comparative example 1 | 3.6 | 100s | 7 | 86.0％ | 84.2％ | |
| Comparative example 2 | 3.7％ | 80s | 8.2 | 88.1％ | 84.4％ | |
| Comparative example 3 | 2.0％ | 75s | 8.5 | 89.5％ | 84.7％ | |
| Comparative example 4 | 3.4％ | 55s | 9.1 | 90.3％ | 87.2％ | |
| Comparative example 5 | 1.8％ | 50s | 9.5 | 91.2％ | 84.8％ | |
| Comparative example 6 | 3.3％ | 41s | 9.7 | 92.1％ | 87.6％ | |
| Comparative example 7 | 2.1％ | 39s | 9.8 | 93.6％ | 88.3％ |
As can be seen from the test results of table 1:
(1) in the aspect of thermal shrinkage rate of the isolating membrane, the comparison examples 3, 5 and 7 are obviously lower than the comparison example 1, which shows that the use of different particle sizes in combination can effectively reduce the porosity of the coating to a reasonable space, improve the compactness, improve the heat resistance of the coated isolating membrane and further improve the safety characteristic of the battery; on the other hand, the thermal shrinkage rate of example 1 is lower than that of comparative examples 3, 5 and 7, which shows that the use of a plurality of particle sizes with different morphologies in combination can further reduce the porosity of the coating, improve the compactness, and further improve the safety characteristics of the battery.
(2) In terms of infiltration time and liquid retention amount, comparative example 2 and comparative example 3 are not greatly different, comparative example 4 is obviously shorter than comparative examples 2 and 3, and comparative examples 6 and 7 are shorter than example 1 than comparative example 5, which shows that the hexahedron and different particle size collocation have little contribution difference on the specific surface area, and the improvement of the coating of the activated carbon on the specific surface area is higher than that of the hexahedron and different particle size collocation. In summary, the hexahedron and the different particle sizes are matched to reduce the infiltration time and improve the liquid retention amount, and the active carbon coating can further strengthen the two aspects.
(3) The trend of the capacity retention rate in 500 cycles at normal temperature is consistent with the trend of the soaking time and the liquid retention amount, more liquid retention amount can reserve more electrolyte allowance to offset the consumption of the electrolyte in the circulation process, and the capacity retention rate of the circulation is further facilitated.
(4) In the aspect of 5C capacity retention rate, the retention rate of the embodiment 1, the comparative examples 4, 6 and 7 is obviously higher than that of the comparative example 1, and the differences between the comparative examples 2, 3 and 5 and the comparative example 1 are small, which shows that the porous activated carbon can provide more contact sites and conduction paths for lithium ions, can remarkably enhance ion conductivity and shorten conduction distance, is beneficial to relieving concentration polarization caused by lithium ion concentration during high-rate charge and discharge of a battery, and further plays a role in improving the quick charge performance of the battery.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. An inorganic ceramic coated separator comprising a base film and an inorganic ceramic coating layer, wherein at least one surface of the base film is coated with the inorganic ceramic coating layer, wherein the inorganic ceramic coating layer comprises an inorganic ceramic powder, a binder and a thickener, the surface of the inorganic ceramic powder particle is coated with an activated carbon coating layer, and the inorganic ceramic powder comprises a first particle size inorganic ceramic powder, a second particle size inorganic ceramic powder and a third particle size inorganic ceramic powder, and the inorganic ceramic powder comprises two or more different polyhedral morphologies.
2. The inorganic ceramic coated separator according to claim 1, wherein the inorganic ceramic powder accounts for 80 to 95% by mass of the total mass of the raw materials forming the inorganic ceramic coating layer, the binder accounts for 0.2 to 10% by mass, and the thickener accounts for 0.2 to 10% by mass.
3. The inorganic ceramic coated separator according to claim 1, wherein the first particle size is 0.1 to 0.3 μm, the second particle size is 0.5 to 1 μm, and the third particle size is 2 to 3 μm; the proportion of the first particle size is 50-60%, the proportion of the second particle size is 30-40%, and the proportion of the third particle size is 0-10%;
the polyhedron morphology comprises more than two of a sphere, a tetrahedron, a hexahedron, a heptahedron, an octahedron, a decahedron, a dodecahedron and an icosahedron.
4. The inorganic ceramic coated separator according to claim 1, wherein the inorganic ceramic powder comprises one or more of alumina, silica, zirconia, zinc oxide, calcium oxide, yttrium oxide, magnesium oxide, tin oxide, nickel oxide, silica, titanium dioxide, hafnium dioxide, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, and boehmite;
the binder is one or more of polyacrylic acids, polyacrylonitrile, polyvinyl alcohol, organic silicon, epoxy resin, polyurethane, PVDF and styrene butadiene rubber;
the thickening agent is at least one of sodium carboxymethyl cellulose, lithium carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polyacrylamide, sodium alginate and polyvinyl alcohol;
the thickness of the inorganic ceramic coating is 1-5 mu m;
the thickness of the active carbon coating layer is 10-50 nm; the active carbon coating layer is realized by adopting an in-situ coating chemical method.
5. The inorganic ceramic coated separator according to any one of claims 1 to 4, wherein a contact angle between the binder particles and the electrolyte is 10 to 80 °, a melting temperature is 130 to 280 ℃, and a glass transition temperature is-10 to 80 ℃.
6. The inorganic ceramic-coated separator for a lithium ion battery according to any one of claims 1 to 4, wherein the base film is a PP, PE, PP/PE/PP composite film, aramid or non-woven fabric; the melting point of the base film is 130-180 ℃, the thickness of the base film is 3-12 mu m, the porosity of the base film is 30-60%, and the air permeability of the base film is 30-400 sec/100 cc.
7. A preparation method of an inorganic ceramic coating diaphragm is characterized by comprising the following steps:
s1, dissolving the binder in the solvent to form a binder solution;
s2, dispersing more than two inorganic ceramic powders with different polyhedral morphologies and three different particle size ranges in a solvent, and then mixing the inorganic ceramic powders with a pre-dissolved thickening agent to form uniform dispersion liquid; the inorganic ceramic powder is in-situ synthesized active carbon coated inorganic ceramic powder;
s3, adding the binder solution into the dispersion liquid, uniformly dispersing, and adjusting until the solid content accounts for 30-60% of the total amount of the slurry to obtain coating slurry;
and S4, coating the obtained coating slurry on at least one surface of a base material in a micro-gravure or extrusion coating mode, and drying to obtain the inorganic ceramic coating diaphragm.
8. The method of making an inorganic ceramic coated separator according to claim 7, wherein the activated carbon coating method comprises:
(1) adding PVP and a carbon source substance into water and/or ethanol to form a uniform dispersion liquid;
(2) adding inorganic ceramic powder into the solution environment for uniform dispersion;
(3) filtering and drying in a vacuum environment;
(4) carbonizing the dried powder at a high temperature of 500-1000 ℃ to obtain black powder;
(5) and (3) placing the black powder in an environment of 500-800 ℃, and carrying out oxidation activation in the atmosphere of air, carbon dioxide, water vapor or mixed gas of the air, the carbon dioxide, the water vapor or the mixed gas of the air, the carbon dioxide and the water vapor to obtain the inorganic ceramic powder coated with the activated carbon.
9. The method of manufacturing an inorganic ceramic-coated separator according to claim 8, wherein the carbon source substance is one or more of pitch, glucose, urea, terephthalic acid, 1, 3, 5-benzenetricarboxylic acid, and 2-methylimidazole; the mass of the carbon source substance is 1-10% of the inorganic ceramic powder.
10. Use of the inorganic ceramic coated separator according to any one of claims 1 to 6 or the inorganic ceramic coated separator prepared by the preparation method according to any one of claims 7 to 9 in a lithium ion battery.
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