CN108550762A - A kind of coating diaphragm of ternary lithium ion battery and preparation method thereof - Google Patents
A kind of coating diaphragm of ternary lithium ion battery and preparation method thereof Download PDFInfo
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- CN108550762A CN108550762A CN201810213936.0A CN201810213936A CN108550762A CN 108550762 A CN108550762 A CN 108550762A CN 201810213936 A CN201810213936 A CN 201810213936A CN 108550762 A CN108550762 A CN 108550762A
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- lithium ion
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- ion battery
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- 238000000576 coating method Methods 0.000 title claims abstract description 92
- 239000011248 coating agent Substances 0.000 title claims abstract description 60
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 52
- 239000000919 ceramic Substances 0.000 claims abstract description 47
- 239000002033 PVDF binder Substances 0.000 claims abstract description 41
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 41
- 239000002131 composite material Substances 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 37
- 230000004888 barrier function Effects 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 18
- 239000004698 Polyethylene Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000004575 stone Substances 0.000 claims description 5
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 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 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 238000010422 painting Methods 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229910052573 porcelain Inorganic materials 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 3
- 229920000858 Cyclodextrin Polymers 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910001593 boehmite 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
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 238000007306 functionalization reaction Methods 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- BFMKFCLXZSUVPI-UHFFFAOYSA-N ethyl but-3-enoate Chemical compound CCOC(=O)CC=C BFMKFCLXZSUVPI-UHFFFAOYSA-N 0.000 claims 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 238000004880 explosion Methods 0.000 abstract description 4
- 230000014759 maintenance of location Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011268 mixed slurry Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000011076 safety test Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of coating diaphragms of ternary lithium ion battery and preparation method thereof, including barrier film base material, ceramics/graphene composite coating, PVDF coatings, the ceramics/graphene composite coating, PVDF coatings are respectively coated in the both sides of barrier film base material, the ceramics/graphene composite coating corresponds to anode, and the PVDF coatings correspond to battery cathode.Anode side of the invention is ceramics/graphene composite coating, it is ensured that coating diaphragm is not susceptible to shrink at high temperature, avoids it that the security risks such as short circuit, explosion occur；Cathode side is PVDF coatings, the heat transfer of inside battery, the high-temperature storage performance of improvement battery can be enhanced to a certain extent, moreover it is possible to increase coating diaphragm to the wetability of electrolyte and guarantor's fluidity, bonding diaphragm and pole piece to inhibit cathode recurring structure in charge and discharge process to cave in；It is superimposed using two kinds of coatings, greatly improves the safety, cycle and high rate performance of ternary lithium ion battery material, promote large-scale application of the system on power battery.
Description
Technical field
The present invention is a kind of preparing technical field of lithium ion battery separator more particularly to a kind of ternary lithium ion battery
Coat diaphragm and preparation method thereof.
Background technology
With the continuous attention that China develops new-energy automobile, how the energy density of power battery has effectively been promoted
It is extremely urgent.The promotion of current driving force lithium ion battery energy density is mainly by using tertiary cathode (NCM/NCA) collocation silicon
The system of Carbon anode solves, and this system is although have higher energy density, since ternary material thermal stability is poor,
200 DEG C or so will occur thermal decomposition and generate oxygen, are acted on electrolyte or carbon material, generate burning and explosion, in addition, by
In ternary lithium ion battery, easily decomposed characteristic, high-temperature storage performance are also had a greatly reduced quality simultaneously at high temperature.So improving
The fuel factor of ternary lithium ion battery, it is that can it applied to most critical in terms of power battery to improve its thermostabilization and security performance
One of factor.
In order to solve this problem, the main work of people in recent years is divided into following two aspects：First, in the electrolytic solution
Various additives are added to improve the interface stability of material, inhibit its decomposition, but the inhibition of electrolyte is limited；Other one
It is a, it is that coating processing is carried out to diaphragm, ceramic coating membrane enhances the mechanical strength and heat resistance of diaphragm, prevents its contraction
Lead to short circuit, effectively promotes the thermally safe stability of battery, improve the fuel factor of ternary lithium ion battery to a certain extent, carry
Its high thermal stability, but since there is ceramic material lower thermal coefficient, the temperature in subrange to be not easy to spread, be easy
Hot stack is generated, causes the security performance of battery and cycle performance inadequate.
Invention content
The purpose of the present invention is to provide a kind of coating diaphragms of ternary lithium ion battery and preparation method thereof, to improve three
The fuel factor of first lithium-ion battery system promotes its safety and cycle performance, widens its application on power battery.
To achieve the above object, the present invention provides the following technical solutions：
A kind of coating diaphragm of ternary lithium ion battery, including barrier film base material, ceramics/graphene composite coating, PVDF are applied
Layer, the ceramics/graphene composite coating, PVDF coatings are respectively coated and in the both sides of barrier film base material, the ceramics/graphenes
Composite coating corresponds to anode, and the PVDF coatings correspond to battery cathode.
As the further scheme of the present invention, the ceramics/graphene composite coating is by ceramic powders, graphene, bonding
Agent and dispersant, the ceramic powders, graphene, binder, dispersant mass ratio be 1：0.01~0.5：0.01~0.5：
0.01~0.2.
As the present invention further scheme, the ceramic powders, graphene, binder, dispersant mass ratio be
1：0.1~0.5：0.1~0.2：0.1~0.2.
As the further scheme of the present invention, the barrier film base material is PP films, PE films or PP and PE multilayer complex films, diaphragm
Base material thickness is 4-30 μm.
As the further scheme of the present invention, the thickness of the ceramics/graphene composite coating and PVDF coatings is 0.5-
10μm。
The ceramic powders are one or more of nano-alpha aluminium oxide, silica, titanium oxide, calcium oxide, boehmite.
The binder is polyacrylic acid, polyethyl acrylate, polytetrafluoroethylene (PTFE), Kynoar, polyvinyl alcohol, hydroxyl first
One or more of base sodium cellulosate, butadiene-styrene rubber, ethylene vinyl acetate, sodium alginate, gelatin, LA133, cyclodextrin.
The graphene is one kind in graphene oxide, redox graphene, functionalization graphene.
The dispersant is polyvinylpyrrolidone, sodium carboxymethylcellulose, poly amic acid, triethyl phosphate, poly- second
One or more of glycol.
A kind of preparation method of the coating diaphragm of ternary lithium ion battery is：
Ceramic powders, graphene, binder, dispersant are added to according to quality proportioning in solvent and are stirred dispersion,
Obtain ceramics/graphene slurry that solid content is 50-80%；The ceramics/graphene slurry is coated on the one of barrier film base material
On face, 60-240min is stood after drying roller process；PVDF is added in solvent and is stirred dispersion, obtaining solid content is
The PVDF slurries of 5-50%；The PVDF slurries are coated on the another side of barrier film base material, are applied after drying roller process
Cover diaphragm.
Coating diaphragm provided by the invention, ceramics/graphene composite coating of positive side is since ceramics are as a kind of nothing
Machine oxide has higher mechanical strength and heat-resistant quality, diaphragm can be effectively ensured and be not susceptible to shrink at high temperature, avoid
The security risks such as short circuit, explosion occur in it, to promote the thermally safe stability of ternary lithium ion battery.And grapheme material by
It is up to 5300W/ (mK) in thermal coefficient and electronic conductivity can protrude, the heat transfer of inside battery can not only be substantially improved,
It avoids part from generating thermal response, ensures its thermally safe stabilization, moreover it is possible to which the electronics conduction for promoting inside battery to a certain extent changes
Kind cycle and high rate performance；The PVDF coatings of cathode side can not only enhance again to a certain extent inside battery heat transfer,
Improve the high-temperature storage performance of battery, moreover it is possible to increase diaphragm and come to the wetability of electrolyte and guarantor's fluidity, bonding diaphragm and pole piece
Inhibit cathode recurring structure in charge and discharge process to cave in, is effectively improved cycle performance of battery.Two kinds of coating effect superpositions, greatly
The safety, cycle and high rate performance that ternary lithium ion battery material must be improved promote big rule of the system on power battery
Mould application.
The solvent is deionized water, ethyl alcohol, normal propyl alcohol, isopropanol, dimethylformamide, dimethylacetylamide, diformazan
One or more of sulfoxide, tetramethylurea, N-Methyl pyrrolidone, trimethyl phosphate, triethyl phosphate.
The drying temperature is 35-70 DEG C.
The roll-in is carried out in the roll squeezer that and central axis parallel in idler wheel or so is located in same level.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) the positive side of the present invention is ceramics/graphene composite coating, it is ensured that coating diaphragm is not susceptible to receive at high temperature
Contracting avoids it that the security risks such as short circuit, explosion occur, to promote the thermally safe stability of ternary lithium ion battery.
(2) cathode side of the present invention is PVDF coatings, can enhance the heat transfer of inside battery to a certain extent, improve electricity
The high-temperature storage performance in pond, moreover it is possible to increase coating diaphragm to the wetability of electrolyte and guarantor's fluidity, bonding diaphragm and pole piece to press down
Cathode processed recurring structure in charge and discharge process caves in, and is effectively improved cycle performance of battery.
(3) present invention is superimposed using two kinds of coatings, greatly improves the safety of ternary lithium ion battery material, cycle and again
Rate performance promotes large-scale application of the system on power battery.
Description of the drawings
Fig. 1 is the structural schematic diagram that diaphragm is coated in the present invention, 1- cathode in figure, 2-PVDF coatings, 3- barrier film base materials, 4-
Ceramics/graphene composite coating, 5- anodes.
Specific implementation mode
Embodiment 1
A kind of coating diaphragm of ternary lithium ion battery, including PE barrier film base materials 3, ceramics/graphene composite coating 4,
PVDF coatings 2, ceramics/graphene composite coating 4, PVDF coatings 2 are respectively coated in the both sides of barrier film base material 3, the ceramics/stone
Black alkene composite coating 4 corresponds to anode 5, and the PVDF coatings 2 correspond to battery cathode 1, and the PE barrier film base materials 3 are 20 μm thick,
The thickness of the ceramics/graphene composite coating 4 and PVDF coatings 2 is 5 μm.
It is 70 by mass ratio：15：10：5 nano-alpha aluminium oxide powder, graphene oxide, gelatin, polyvinylpyrrolidone
It is added in a certain amount of deionized water and is stirred dispersion, obtain the mixed slurry that solid content is 67%, then apply the slurry
It is overlying in PE barrier film base material one sides, 120min is stood after drying, roll-in.A little oiliness PVDF powder is taken to be added to again a certain amount of
Stirring is sized mixing in N-Methyl pyrrolidone, obtains the slurry that solid content is 5%, and the slurry is anotherly coated in diaphragm uniform
On face, required coating diaphragm is obtained after 35 DEG C of drying, roll-ins.The composite diaphragm and NCM523 tertiary cathodes are assembled into Soft Roll electricity
Chi Hou can additionally pass through needle thorn, short circuit, the safety test for overcharging, heating；1C/1C charge and discharge cycles (2.8-4.2V) service life from
It increases within 2000 weeks 3000 weeks (capacity retention ratio 80%)；Multiplying power discharging 20C/1C capacity retention ratios increase to 90% from 83%, multiplying power
Charging 15C/1C capacity retention ratios increase to 81% from 76%.
Embodiment 2
A kind of coating diaphragm of ternary lithium ion battery, including PP barrier film base materials 3, ceramics/graphene composite coating 4,
PVDF coatings 2, ceramics/graphene composite coating 4, PVDF coatings 2 are respectively coated in the both sides of barrier film base material 3, the ceramics/stone
Black alkene composite coating 4 corresponds to anode 5, and the PVDF coatings 2 correspond to battery cathode 1, and the PP barrier film base materials 3 are 4 μm thick, institute
The thickness for stating ceramics/graphene composite coating 4 and PVDF coatings 2 is 0.5 μm.
It is 65 by mass ratio：20：8：7 silicon oxide powder, reduction-oxidation graphite, LA133, polyethylene glycol are added to centainly
It is stirred dispersion in amount deionized water and normal propyl alcohol, the mixed slurry that solid content is 59% is obtained, then coats the slurry
In in PP barrier film base material one sides, 240min is stood after drying, roll-in.A small amount of aqueous PVDF powder is taken to be added to a certain amount of go again
Stirring is sized mixing in ionized water, obtains the slurry that solid content is 15%, and the slurry is so uniform that be coated on the other side of diaphragm, and 50
DEG C drying, obtain after roll-in needed for coat diaphragm.After the composite diaphragm and NCM333 tertiary cathodes are assembled into soft-package battery, energy
Additionally pass through needle thorn, short circuit, the safety test for overcharging, heating；3C/3C charge and discharge cycles (2.8-4.1V) service life increased from 3000 weeks
To 5000 weeks (capacity retention ratio 80%)；Multiplying power discharging 30C/1C capacity retention ratios increase to 92% from 85%, multiplying power charging 20C/
1C capacity retention ratios increase to 83% from 78%.
Embodiment 3
A kind of coating diaphragm of ternary lithium ion battery, including PE/PP composite diaphragms base material 3, the compound painting of ceramics/graphene
Layer 4, PVDF coatings 2, ceramics/graphene composite coating 4, PVDF coatings 2 are respectively coated in the both sides of barrier film base material 3, the pottery
Porcelain/graphene composite coating 4 corresponds to anode 5, and the PVDF coatings 2 correspond to battery cathode 1, the PE/PP composite diaphragms
Base material 3 is 30 μm thick, and the thickness of the ceramics/graphene composite coating 4 and PVDF coatings 2 is 10 μm.
It is 72 by mass ratio：11：9：8 lime powder, functional graphene containing N doping, sodium alginate, polyethylene glycol
It is added in a certain amount of deionized water and is stirred dispersion, obtain the mixed slurry that solid content is 61%, then apply the slurry
It is overlying in PE/PP composite diaphragm base material one sides, 60min is stood after drying, roll-in.A small amount of oiliness PVDF is taken to be added to again a certain amount of
N-Methyl pyrrolidone in stir and size mixing, obtain the slurry that solid content is 10%, the slurry is uniform coated in diaphragm
On another side, required coating diaphragm is obtained after 50 DEG C of drying, roll-ins.The composite diaphragm is assembled into NCM622 tertiary cathodes soft
After packet battery, it can additionally pass through needle thorn, short circuit, the safety test for overcharging, heating；1C/1C charge and discharge cycles (2.8-4.2V) longevity
Life increased to 2000 weeks (capacity retention ratio 80%) from 1500 weeks；Multiplying power discharging 10C/1C capacity retention ratios increase to 79% from 72%,
Multiplying power charging 5C/1C capacity retention ratios increase to 71% from 66%.
Embodiment 4
A kind of coating diaphragm of ternary lithium ion battery, including PE/PP composite diaphragms base material 3, the compound painting of ceramics/graphene
Layer 4, PVDF coatings 2, ceramics/graphene composite coating 4, PVDF coatings 2 are respectively coated in the both sides of barrier film base material 3, the pottery
Porcelain/graphene composite coating 4 corresponds to anode 5, and the PVDF coatings 2 correspond to battery cathode 1, the PE/PP composite diaphragms
Base material 3 is 20 μm thick, and the thickness of the ceramics/graphene composite coating 4 and PVDF coatings 2 is 5 μm.
It is 66 by mass ratio：12：10：12 nano-alpha aluminium oxide powder, graphene oxide, butadiene-styrene rubber, polyacrylic acid
Amine, which is added in a certain amount of deionized water and isopropanol, is stirred dispersion, obtains the mixed slurry that solid content is 52%, then
By slurry coating in the one side of PP/PE composite diaphragm base materials, 120min is stood after drying, roll-in.It takes again a small amount of aqueous
PVDF is added to be stirred in a certain amount of deionized water and size mixing, and obtains the slurry that solid content is 13%, and the slurry is uniform
It obtains on the another side coated in diaphragm, required coating diaphragm is obtained after 70 DEG C of drying, roll-ins.By the composite diaphragm and NCM811 tri-
After first anode is assembled into soft-package battery, it can additionally pass through needle thorn, short circuit, the safety test for overcharging, heating；1C/1C charge and discharge follow
Ring (2.8-4.2V) service life increased to 1300 weeks (capacity retention ratio 80%) from 800 weeks；Multiplying power discharging 3C/1C capacity retention ratios from
76% increases to 82%, and multiplying power charging 2C/1C capacity retention ratios increase to 75% from 71%.
The better embodiment of this patent is explained in detail above, but this patent is not limited to above-mentioned embodiment party
Formula, one skilled in the relevant art within the scope of knowledge, can also be under the premise of not departing from this patent objective
It makes a variety of changes.
Claims (10)
1. a kind of coating diaphragm of ternary lithium ion battery, which is characterized in that including barrier film base material, the compound painting of ceramics/graphene
Layer, PVDF coatings, the ceramics/graphene composite coating, PVDF coatings are respectively coated in the both sides of barrier film base material, the pottery
Porcelain/graphene composite coating corresponds to anode, and the PVDF coatings correspond to battery cathode.
2. the coating diaphragm of ternary lithium ion battery according to claim 1, which is characterized in that the ceramics/graphene
Composite coating is made of ceramic powders, graphene, binder and dispersant, the ceramic powders, graphene, binder, dispersion
The mass ratio of agent is 1：0.01~0.5：0.01~0.5：0.01~0.2.
3. the coating diaphragm of ternary lithium ion battery according to claim 2, which is characterized in that the ceramic powders, stone
Black alkene, binder, dispersant mass ratio be 70：15：10：5.
4. the coating diaphragm of ternary lithium ion battery according to claim 2, which is characterized in that the ceramic powders, stone
Black alkene, binder, dispersant mass ratio be 65：20：8：7.
5. the coating diaphragm of ternary lithium ion battery according to claim 2, which is characterized in that the ceramic powders, stone
Black alkene, binder, dispersant mass ratio be 72：11：9：8.
6. the coating diaphragm of ternary lithium ion battery according to claim 1, which is characterized in that the barrier film base material is PP
Film, PE films or PP and PE multilayer complex films, the barrier film base material thickness are 4-30 μm.
7. the coating diaphragm of ternary lithium ion battery according to claim 1, which is characterized in that the ceramics/graphene
The thickness of composite coating and PVDF coatings is 0.5-10 μm.
8. the coating diaphragm of ternary lithium ion battery according to claim 2, which is characterized in that the ceramic powders are to receive
One or more of rice Alpha-alumina, silica, titanium oxide, calcium oxide, boehmite, the binder are polyacrylic acid, gather
Ethyl acrylate, polytetrafluoroethylene (PTFE), Kynoar, polyvinyl alcohol, sodium cellulose glycolate, butadiene-styrene rubber, ethyl vinyl acetate second
One or more of ester, sodium alginate, gelatin, LA133, cyclodextrin, the graphene are graphene oxide, oxygen reduction fossil
One kind in black alkene, functionalization graphene, the dispersant are polyvinylpyrrolidone, sodium carboxymethylcellulose, polyacrylic acid
One or more of amine, triethyl phosphate, polyethylene glycol.
9. a kind of preparation method of the coating diaphragm of ternary lithium ion battery as described in claim 1, which is characterized in that including
Following steps：Ceramic powders, graphene, binder, dispersant are added to according to quality proportioning in solvent and are stirred dispersion,
Obtain ceramics/graphene slurry that solid content is 50-80%；The ceramics/graphene slurry is coated on the one of barrier film base material
On face, 60-240min is stood after drying roller process；PVDF is added in solvent and is stirred dispersion, obtaining solid content is
The PVDF slurries of 5-50%；The PVDF slurries are coated on the another side of barrier film base material, are applied after drying roller process
Cover diaphragm.
10. the preparation method of the coating diaphragm of ternary lithium ion battery according to claim 10, which is characterized in that described
Roll-in be to be carried out in the roll squeezer that and central axis parallel in idler wheel or so is located in same level.
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