CN110600660A - Preparation method of surface modified alumina ceramic coating diaphragm - Google Patents
Preparation method of surface modified alumina ceramic coating diaphragm Download PDFInfo
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- CN110600660A CN110600660A CN201910756443.6A CN201910756443A CN110600660A CN 110600660 A CN110600660 A CN 110600660A CN 201910756443 A CN201910756443 A CN 201910756443A CN 110600660 A CN110600660 A CN 110600660A
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- modified alumina
- alumina ceramic
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- dispersing
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 238000005524 ceramic coating Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 54
- 238000001035 drying Methods 0.000 claims abstract description 50
- 238000003756 stirring Methods 0.000 claims abstract description 46
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 42
- 239000000843 powder Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000000576 coating method Methods 0.000 claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 27
- 239000002002 slurry Substances 0.000 claims abstract description 26
- 239000006185 dispersion Substances 0.000 claims abstract description 24
- 238000000227 grinding Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 12
- 229930195729 fatty acid Natural products 0.000 claims abstract description 12
- 239000000194 fatty acid Substances 0.000 claims abstract description 12
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 239000007822 coupling agent Substances 0.000 claims abstract description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 4
- 238000000197 pyrolysis Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 38
- 229910001868 water Inorganic materials 0.000 claims description 25
- 239000000919 ceramic Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 20
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000005642 Oleic acid Substances 0.000 claims description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000003828 vacuum filtration Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 3
- 239000004970 Chain extender Substances 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052744 lithium Inorganic materials 0.000 abstract description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 48
- 230000000052 comparative effect Effects 0.000 description 16
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 8
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 8
- 239000005048 methyldichlorosilane Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 5
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229960004488 linolenic acid Drugs 0.000 description 5
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 4
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 4
- 238000011031 large-scale manufacturing process Methods 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 4
- -1 Polyethylene Polymers 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- BITHHVVYSMSWAG-KTKRTIGZSA-N (11Z)-icos-11-enoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCC(O)=O BITHHVVYSMSWAG-KTKRTIGZSA-N 0.000 description 2
- GWHCXVQVJPWHRF-KTKRTIGZSA-N (15Z)-tetracosenoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCCCC(O)=O GWHCXVQVJPWHRF-KTKRTIGZSA-N 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 2
- 235000021357 Behenic acid Nutrition 0.000 description 2
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 2
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 2
- XJXROGWVRIJYMO-SJDLZYGOSA-N Nervonic acid Natural products O=C(O)[C@@H](/C=C/CCCCCCCC)CCCCCCCCCCCC XJXROGWVRIJYMO-SJDLZYGOSA-N 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- 235000021319 Palmitoleic acid Nutrition 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 229940116226 behenic acid Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 2
- GWHCXVQVJPWHRF-UHFFFAOYSA-N cis-tetracosenoic acid Natural products CCCCCCCCC=CCCCCCCCCCCCCCC(O)=O GWHCXVQVJPWHRF-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- BITHHVVYSMSWAG-UHFFFAOYSA-N eicosenoic acid Natural products CCCCCCCCC=CCCCCCCCCCC(O)=O BITHHVVYSMSWAG-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 2
- 235000021299 gondoic acid Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 235000021313 oleic acid Nutrition 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 238000003109 Karl Fischer titration Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000006467 substitution reaction Methods 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
- 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
-
- 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
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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)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Cell Separators (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of lithium battery diaphragms, and discloses a preparation method of a surface modified alumina ceramic coating diaphragm, which comprises the following steps: (1) dispersing to obtain a uniform alumina solution; (2) adding fatty acid with more than 6 carbon atoms to prepare lipophilic alumina; (3) adding siloxane coupling agent and organic solvent, mixing, stirring and hydrolyzing until the organic solvent is completely volatilized; (4) performing pyrolysis treatment in an ammonia atmosphere to obtain modified alumina ceramic powder with a hydrophobic effect; (5) dispersing the modified alumina ceramic powder into deionized water to obtain hydrophobically modified alumina; dispersing by using a dispersion machine, grinding by using a nano grinder, adding a binder, and then dispersing again to obtain modified alumina ceramic slurry; (6) and coating the modified alumina ceramic slurry on the surface of a base film which is prepared from the PE of the lithium ion battery, and drying. The diaphragm prepared by the method has good hydrophobic property.
Description
Technical Field
The invention belongs to the technical field of lithium battery diaphragms, and particularly relates to a preparation method of a diaphragm with a surface modified aluminum oxide ceramic coating.
Background
The lithium ion battery has the advantages of high specific energy density, light weight, long cycle life, low self-discharge rate, no memory effect, environmental friendliness and the like, and is widely applied to the large-scale application fields of 3C digital, new energy power automobiles, national defense industry and the like. The lithium ion battery diaphragm has the following main functions: the anode and the cathode are separated, so that the contact short circuit of the anode and the cathode is prevented, and lithium ions are transferred between the anode and the cathode to finish the charging and discharging process. The commercial lithium ion battery diaphragm is mainly a Polyethylene (PE), polypropylene (PP) microporous membrane and a polypropylene/polyethylene/polypropylene (PP/PE/PP) three-layer diaphragm, but the safety of a base membrane is not high, the performances such as heat resistance, puncture strength, liquid retention and the like are not good, the mechanical operation performance is not good, and the physical index and the electrochemical performance of the lithium ion battery cannot be obviously improved.
The alumina ceramic coating diaphragm appearing in recent years can obviously improve the thermal shrinkage performance of the diaphragm, and further improve the safety performance of the diaphragm, and mainly comprises a single-sided coating and a double-sided ceramic coating. The single-layer and double-layer ceramic composite diaphragms are composite lithium ion battery diaphragms prepared by mainly taking polyolefin microporous membranes, non-woven fabrics and the like as base membranes and coating ceramic layers by a certain process on the basis of the traditional lithium ion battery diaphragms. The main film forming processes of the ceramic composite diaphragm include coating, electrostatic spinning, wet method, mould pressing and high-temperature sintering. The coating film-forming process has the defects that the bonding force between the ceramic layer and the base film is weak, the surface water absorption problem of the alumina ceramic causes the stability problem caused by the long-time standing water absorption of the ceramic coating diaphragm, and the ceramic coating can be partially agglomerated and is not uniformly distributed.
Disclosure of Invention
The invention provides a preparation method of a surface modified alumina ceramic coating diaphragm, which solves the problems that the coating film forming process in the background technology has the defects that the bonding force between a ceramic layer and a base film is weak, and the surface water absorption problem of alumina ceramic causes the stability problem caused by long-time standing water absorption of the ceramic coating diaphragm.
The invention aims to realize the purpose through the following technical scheme, and the preparation method of the surface modified alumina ceramic coating diaphragm comprises the following steps:
(1) firstly dispersing alumina powder in water to obtain a uniformly dispersed alumina solution;
(2) adding fatty acid with more than 6 carbon atoms into the alumina solution prepared in the step (1), wherein the weight ratio of the added fatty acid to the alumina powder is 2-5%, stirring in a water bath at constant temperature of 50-80 ℃, and drying in a drying oven at constant temperature to prepare lipophilic alumina;
(3) adding lipophilic alumina into a siloxane coupling agent and an organic solvent, mixing, stirring and hydrolyzing until the organic solvent is completely volatilized to obtain a mixture;
(4) the mixture is put in ammonia atmosphere for pyrolysis treatment to obtain modified alumina ceramic powder with hydrophobic effect;
(5) dispersing the modified alumina ceramic powder into deionized water, and stirring to obtain hydrophobically modified alumina; pre-dispersing by using a dispersion machine, grinding by using a nano grinding machine to form a hydrophobic modified alumina solution, adding a binder LBG, wherein the weight ratio of the added binder LBG to the hydrophobic modified alumina solution is 1-5%, the LBG is a PVDF-HFP (polyvinylidene fluoride-hexafluoropropylene) copolymer, and dispersing by using a large dispersion machine at the rotation speed of 200-10000r/min to obtain modified alumina ceramic slurry;
(6) and coating the modified alumina ceramic slurry on the surface of a base membrane which takes the lithium ion battery PE as a raw material, and drying to obtain the lithium ion battery diaphragm coated with the hydrophobic modified ceramic.
According to the preparation method of the surface modified alumina ceramic coating diaphragm, the fatty acid is added to form surface active ingredients on the surface of the alumina, so that the lipophilic alumina is obtained, and the subsequent further modification is facilitated. The modified nano-alumina has small particle size and large specific surface area, and after a solvent in slurry is volatilized in the coating process, an effective three-dimensional network structure is formed between nano-scale particles of the alumina on the surface of the lithium ion battery diaphragm, so that the wettability and the liquid retention of the lithium ion battery diaphragm on electrolyte are improved, the quick migration of lithium ions is facilitated in the charging and discharging processes, the rate capability of the lithium ion battery is improved, and the cycle life of the lithium ion battery is prolonged; the compact but not compact three-dimensional network structure improves the heat resistance and puncture strength of the lithium ion battery diaphragm, can effectively prevent the problem of short circuit inside the lithium ion battery caused by dust, lithium crystal branches and the like, and improves the safety of the lithium ion battery. The modified nano alumina ceramic surface has a good hydrophobic structure, has the advantages of an alumina coated diaphragm, and can prevent the water absorption problem of the alumina diaphragm, thereby greatly improving the stability of the alumina ceramic coated diaphragm and leading the cyclicity of the lithium battery to be better.
Further, the stirring in the step (2) is mechanical stirring, and the stirring speed is 200-.
Further, the stirring speed in the step (2) is preferably 500-.
Further, in the step (2), the temperature range is preferably 70 to 90 ℃.
Further, the temperature in the step (2) is 80 ℃.
Further, the fatty acid added in the step (2) can be selected from one or more of the following organic acids: palmitoleic acid, palmitic acid, linolenic acid, linoleic acid, oleic acid, stearic acid, 11-eicosenoic acid, arachidic acid, erucic acid, behenic acid, nervonic acid and wood pyronic acid, when the organic acid is oleic acid, a surface active component is formed on the surface of the alumina to obtain lipophilic alumina, which is beneficial to subsequent further modification, and the principle reaction is as follows:
Al2O3-OH+HOOC-(CH2)7-C＝C-(CH2)7-CH3→ Al2O3-OOC-(CH2)7-C＝C-(CH2)7-CH3+H2O 。
further, in the step (2), the stirring time is 20-24h, and the drying at constant temperature in a drying oven specifically comprises the steps of cooling the mixed solution, performing vacuum filtration, and drying in an oven.
Further, in the step (6), the coating speed is 10 to 50m/min, and most preferably 20 m/min.
Further, after the step (6), drying in a long oven at the baking temperature of 80-100 ℃.
Further, after the step (6), the baking temperature in the oven is 75 ℃, and the drying time is 30 min.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a surface modified alumina ceramic coating diaphragm comprises the following steps:
(1) firstly dispersing alumina powder in water to obtain a uniformly dispersed alumina solution;
(2) adding fatty acid with more than 6 carbon atoms into the alumina solution prepared in the step (1), wherein the weight ratio of the added fatty acid to the alumina powder is 2-5%, stirring in a water bath at constant temperature of 50-80 ℃, and drying in a drying oven at constant temperature to prepare lipophilic alumina;
(3) adding lipophilic alumina into a siloxane coupling agent and an organic solvent, mixing, stirring and hydrolyzing until the organic solvent is completely volatilized to obtain a mixture;
(4) the mixture is put in ammonia atmosphere for pyrolysis treatment to obtain modified alumina ceramic powder with hydrophobic effect;
(5) dispersing the modified alumina ceramic powder into deionized water, and stirring to obtain hydrophobically modified alumina; pre-dispersing by using a dispersion machine, grinding by using a nano grinding machine to form a hydrophobic modified alumina solution, adding a binder LBG (long-chain extender) at a weight ratio of 1-5%, and dispersing by using a large dispersion machine at a rotation speed of 200-10000r/min to obtain modified alumina ceramic slurry;
(6) and coating the modified alumina ceramic slurry on the surface of a base membrane which takes the lithium ion battery PE as a raw material, and drying to obtain the lithium ion battery diaphragm coated with the hydrophobic modified ceramic.
The fatty acid added in step (2) in the present application may be selected from one or more of the following organic acids: palmitoleic acid, palmitic acid, linolenic acid, linoleic acid, oleic acid, stearic acid, 11-eicosenoic acid, arachidic acid, erucic acid, behenic acid, nervonic acid and wood pyronic acid, when the organic acid is oleic acid, a surface active component is formed on the surface of the alumina to obtain lipophilic alumina, which is beneficial to subsequent further modification, and the principle reaction is as follows:
Al2O3-OH+HOOC-(CH2)7-C＝C-(CH2)7-CH3→ Al2O3-OOC-(CH2)7-C＝C-(CH2)7-CH3+H2O 。
according to the preparation method of the surface modified alumina ceramic coating diaphragm, the fatty acid is added to form surface active ingredients on the surface of the alumina, so that the lipophilic alumina is obtained, and the subsequent further modification is facilitated. The modified nano-alumina has small particle size and large specific surface area, and after a solvent in slurry is volatilized in the coating process, an effective three-dimensional network structure is formed between nano-scale particles of the alumina on the surface of the lithium ion battery diaphragm, so that the wettability and the liquid retention of the lithium ion battery diaphragm on electrolyte are improved, the quick migration of lithium ions is facilitated in the charging and discharging processes, the rate capability of the lithium ion battery is improved, and the cycle life of the lithium ion battery is prolonged; the compact but not compact three-dimensional network structure improves the heat resistance and puncture strength of the lithium ion battery diaphragm, can effectively prevent the problem of short circuit inside the lithium ion battery caused by dust, lithium crystal branches and the like, and improves the safety of the lithium ion battery. The modified nano alumina ceramic surface has a good hydrophobic structure, has the advantages of an alumina coated diaphragm, and can prevent the water absorption problem of the alumina diaphragm, thereby greatly improving the stability of the alumina ceramic coated diaphragm and leading the cyclicity of the lithium battery to be better.
Example 2
(1) Adding 1kg of alumina powder and 100kg of water into a large-scale production reaction kettle to obtain a uniformly dispersed alumina solution;
(2) adding 0.2kg of oleic acid into an alumina solution, mechanically stirring at the stirring speed of 200r/min, heating to 70 ℃, stirring at a constant speed for 24 hours, cooling the mixed solution, performing vacuum filtration, drying in an oven, and drying at constant temperature in the oven to prepare lipophilic alumina;
(3) adding lipophilic alumina into 5L of n-heptane, mixing, adding 1L of methyldichlorosilane and 1L of dimethyldichlorosilane, stirring at room temperature for 30min, and completely volatilizing n-heptane to obtain a mixture;
(4) putting the mixture into a horizontal pipeline furnace, introducing ammonia gas for 5min, pyrolyzing the mixture for 2h at the temperature of 500 ℃, and drying the mixture to obtain modified alumina ceramic powder with a hydrophobic effect;
(5) dispersing the modified alumina ceramic powder into deionized water, and stirring for 1 h; obtaining hydrophobically modified alumina; pre-dispersing by using a dispersion machine at the rotating speed of 200 r/min; then, grinding by using a nano grinder at the grinding speed of 800 r/min; adding 1% of binder LBG, and dispersing by using a large-scale dispersion machine at the rotating speed of 200r/min to obtain modified alumina ceramic slurry;
(6) and coating the modified alumina ceramic slurry on the surface of the prepared lithium ion battery diaphragm at the coating speed of 10m/min, and then drying in a long drying oven at the operation speed of 10m/min and the baking temperature of 80 ℃ to obtain the hydrophobic modified ceramic coated lithium ion battery diaphragm.
The water content of the hydrophobic modified ceramic-coated lithium ion battery separator obtained in example 2 was tested by karl fischer titration, with a water content of 200ppm, which is the method used in the present application.
Comparative example 2:
(1) adding alumina powder into 5L of n-heptane, mixing uniformly, adding 1L of methyldichlorosilane and 1L of dimethyldichlorosilane, stirring at room temperature for 30min, and completely volatilizing n-heptane to obtain a mixture;
(2) putting the mixture into a horizontal pipeline furnace, introducing ammonia gas for 5min, pyrolyzing the mixture for 2h at the temperature of 500 ℃, and drying the mixture to obtain modified alumina ceramic powder with a hydrophobic effect;
(3) dispersing the modified alumina ceramic powder into deionized water, and stirring for 1 h; obtaining hydrophobically modified alumina; pre-dispersing by using a dispersion machine at the rotating speed of 200 r/min; then, grinding by using a nano grinder at the grinding speed of 800 r/min; adding 1% of binder LBG, and dispersing by using a large-scale dispersion machine at the rotating speed of 200r/min to obtain modified alumina ceramic slurry;
(4) and coating the modified alumina ceramic slurry on the surface of the prepared lithium ion battery diaphragm at the coating speed of 10m/min, and then drying in a long drying oven at the operation speed of 10m/min and the baking temperature of 80 ℃ to obtain the hydrophobic modified ceramic coated lithium ion battery diaphragm.
The water content of the separator was tested to 2200ppm for the hydrophobic modified ceramic coated lithium ion battery separator obtained in comparative example 2.
Comparative example 2 differs from example 2 in that: step (1) and step (2) of comparative example 1 were omitted, while the hydrophobic property decreased from 200ppm to 2200 ppm.
Example 3
(1) Adding 1kg of alumina powder and 100kg of water into a large-scale production reaction kettle to obtain a uniformly dispersed alumina solution;
(2) adding 0.5kg of linolenic acid into the alumina solution, mechanically stirring at the stirring speed of 2000r/min, heating to 90 ℃, stirring at a constant speed for 24 hours, cooling the mixed solution, performing vacuum filtration, drying in an oven, and drying at constant temperature in the oven to prepare lipophilic alumina;
(3) adding lipophilic alumina into 5L of n-heptane, mixing, adding 1L of methyldichlorosilane and 1L of dimethyldichlorosilane, stirring at room temperature for 30min, and completely volatilizing n-heptane to obtain a mixture;
(4) putting the mixture into a horizontal pipeline furnace, introducing ammonia gas for 5min, pyrolyzing the mixture for 2h at the temperature of 500 ℃, and drying the mixture to obtain modified alumina ceramic powder with a hydrophobic effect;
(5) dispersing the modified alumina ceramic powder into deionized water, and stirring for 1 h; obtaining hydrophobically modified alumina; pre-dispersing by using a dispersion machine at the rotating speed of 200 r/min; then, grinding by using a nano grinder at the grinding speed of 800 r/min; adding 5% of binder LBG, and dispersing by using a large-scale dispersion machine at the rotating speed of 1000r/min to obtain modified alumina ceramic slurry;
(6) and coating the modified alumina ceramic slurry on the surface of the prepared lithium ion battery diaphragm at the coating speed of 50m/min, and then drying in a long drying oven at the operation speed of 10m/min and the baking temperature of 100 ℃ to obtain the hydrophobic modified ceramic coated lithium ion battery diaphragm.
The water content of the separator was tested to be 100ppm for the hydrophobic modified ceramic coated lithium ion battery separator obtained in example 3.
Comparative example 3
(1) Adding alumina powder into 5L of n-heptane, mixing uniformly, adding 1L of methyldichlorosilane and 1L of dimethyldichlorosilane, stirring at room temperature for 30min, and completely volatilizing n-heptane to obtain a mixture;
(2) putting the mixture into a horizontal pipeline furnace, introducing ammonia gas for 5min, pyrolyzing the mixture for 2h at the temperature of 500 ℃, and drying the mixture to obtain modified alumina ceramic powder with a hydrophobic effect;
(3) dispersing the modified alumina ceramic powder into deionized water, and stirring for 1 h; obtaining hydrophobically modified alumina; pre-dispersing by using a dispersion machine at the rotating speed of 200 r/min; then, grinding by using a nano grinder at the grinding speed of 800 r/min; adding 5% of binder LBG, and dispersing by using a large-scale dispersion machine at the rotating speed of 1000r/min to obtain modified alumina ceramic slurry;
(4) and coating the modified alumina ceramic slurry on the surface of the prepared lithium ion battery diaphragm at the coating speed of 50m/min, and then drying in a long drying oven at the operation speed of 10m/min and the baking temperature of 100 ℃ to obtain the hydrophobic modified ceramic coated lithium ion battery diaphragm.
The water content of the separator was tested to 2000ppm for the hydrophobic modified ceramic coated lithium ion battery separator obtained in comparative example 3.
Comparative example 3 differs from example 3 in that: step (1) and step (2) in comparative example 1 were omitted, and the hydrophobic property was decreased from 100ppm to 2000 ppm.
Example 4
(1) Adding 1kg of alumina powder and 100kg of water into a large-scale production reaction kettle to obtain a uniformly dispersed alumina solution;
(2) adding 0.3kg of oleic acid and linolenic acid (weight ratio is 1:1) into an alumina solution, mechanically stirring at a stirring speed of 500r/min, heating to 80 ℃, stirring at a constant speed for 24 hours, cooling the mixed solution, performing vacuum filtration, drying in an oven, and drying at constant temperature in the oven to prepare lipophilic alumina;
(3) adding lipophilic alumina into 5L of n-heptane, mixing, adding 1L of methyldichlorosilane and 1L of dimethyldichlorosilane, stirring at room temperature for 30min, and completely volatilizing n-heptane to obtain a mixture;
(4) putting the mixture into a horizontal pipeline furnace, introducing ammonia gas for 5min, pyrolyzing the mixture for 2h at the temperature of 500 ℃, and drying the mixture to obtain modified alumina ceramic powder with a hydrophobic effect;
(5) dispersing the modified alumina ceramic powder into deionized water, and stirring for 1 h; obtaining hydrophobically modified alumina; pre-dispersing by using a dispersion machine at the rotating speed of 500 r/min; then grinding by using a nano grinder at the grinding speed of 1000 r/min; adding 3% of binder LBG, and dispersing by using a large-scale dispersion machine at the rotating speed of 500r/min to obtain modified alumina ceramic slurry;
(6) and coating the modified alumina ceramic slurry on the surface of the prepared lithium ion battery diaphragm at the coating speed of 30m/min, and then drying in a long drying oven at the operation speed of 10m/min and the baking temperature of 90 ℃ to obtain the hydrophobic modified ceramic coated lithium ion battery diaphragm.
The water content of the separator was tested to be 80ppm for the hydrophobic modified ceramic coated lithium ion battery separator obtained in example 4.
Comparative example 4
(1) Adding alumina powder into 5L of n-heptane, mixing uniformly, adding 1L of methyldichlorosilane and 1L of dimethyldichlorosilane, stirring at room temperature for 30min, and completely volatilizing n-heptane to obtain a mixture;
(2) putting the mixture into a horizontal pipeline furnace, introducing ammonia gas for 5min, pyrolyzing the mixture for 2h at the temperature of 500 ℃, and drying the mixture to obtain modified alumina ceramic powder with a hydrophobic effect;
(3) dispersing the modified alumina ceramic powder into deionized water, and stirring for 1 h; obtaining hydrophobically modified alumina; pre-dispersing by using a dispersion machine at the rotating speed of 500 r/min; then grinding by using a nano grinder at the grinding speed of 1000 r/min; adding 3% of binder LBG, and dispersing by using a large-scale dispersion machine at the rotating speed of 500r/min to obtain modified alumina ceramic slurry;
(4) and coating the modified alumina ceramic slurry on the surface of the prepared lithium ion battery diaphragm at the coating speed of 30m/min, and then drying in a long drying oven at the operation speed of 10m/min and the baking temperature of 90 ℃ to obtain the hydrophobic modified ceramic coated lithium ion battery diaphragm.
The water content of the separator was tested to be 1800ppm for the hydrophobic modified ceramic coated lithium ion battery separator obtained in comparative example 4.
Comparative example 4 is different from example 4 in that: step (1) and step (2) in comparative example 1 were omitted, and the hydrophobic property was decreased from 80ppm to 1800 ppm.
Example 5
(1) Adding 1kg of alumina powder and 100kg of water into a large-scale production reaction kettle to obtain a uniformly dispersed alumina solution;
(2) adding 0.4kg of oleic acid and linolenic acid (weight ratio is 2:1) into an alumina solution, mechanically stirring at the stirring speed of 800r/min, heating to 80 ℃, stirring at a constant speed for 24 hours, cooling the mixed solution, performing vacuum filtration, drying in an oven, and drying at constant temperature in the oven to prepare lipophilic alumina;
(3) adding lipophilic alumina into 5L of n-heptane, mixing, adding 1L of methyldichlorosilane and 1L of dimethyldichlorosilane, stirring at room temperature for 30min, and completely volatilizing n-heptane to obtain a mixture;
(4) putting the mixture into a horizontal pipeline furnace, introducing ammonia gas for 6min, pyrolyzing the mixture for 2h at the temperature of 500 ℃, and drying the mixture to obtain modified alumina ceramic powder with a hydrophobic effect;
(5) dispersing the modified alumina ceramic powder into deionized water, and stirring for 1 h; obtaining hydrophobically modified alumina; pre-dispersing by using a dispersion machine at the rotating speed of 800 r/min; then, grinding by using a nano grinder at the grinding speed of 2000 r/min; adding 4% of binder LBG, and dispersing by using a large-scale dispersion machine at the rotating speed of 800r/min to obtain modified alumina ceramic slurry;
(6) and coating the modified alumina ceramic slurry on the surface of the prepared lithium ion battery diaphragm at the coating speed of 30m/min, and then drying in a long drying oven at the operation speed of 30m/min and the baking temperature of 90 ℃ to obtain the hydrophobic modified ceramic coated lithium ion battery diaphragm.
The water content of the separator was tested to be 90ppm for the hydrophobic modified ceramic coated lithium ion battery separator obtained in example 5.
Comparative example 5
(1) Adding alumina powder into 5L of n-heptane, mixing uniformly, adding 1L of methyldichlorosilane and 1L of dimethyldichlorosilane, stirring at room temperature for 30min, and completely volatilizing n-heptane to obtain a mixture;
(2) putting the mixture into a horizontal pipeline furnace, introducing ammonia gas for 6min, pyrolyzing the mixture for 2h at the temperature of 500 ℃, and drying the mixture to obtain modified alumina ceramic powder with a hydrophobic effect;
(3) dispersing the modified alumina ceramic powder into deionized water, and stirring for 1 h; obtaining hydrophobically modified alumina; pre-dispersing by using a dispersion machine at the rotating speed of 800 r/min; then, grinding by using a nano grinder at the grinding speed of 2000 r/min; adding 4% of binder LBG, and dispersing by using a large-scale dispersion machine at the rotating speed of 800r/min to obtain modified alumina ceramic slurry;
(4) and coating the modified alumina ceramic slurry on the surface of the prepared lithium ion battery diaphragm at the coating speed of 30m/min, and then drying in a long drying oven at the operation speed of 30m/min and the baking temperature of 90 ℃ to obtain the hydrophobic modified ceramic coated lithium ion battery diaphragm.
The water content of the separator was tested to be 1900ppm for the hydrophobic modified ceramic coated lithium ion battery separator obtained in comparative example 5.
Comparative example 5 differs from example 5 in that: step (1) and step (2) in comparative example 1 were omitted, and the hydrophobic property was decreased from 90ppm to 1900 ppm.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (10)
1. A preparation method of a surface modified alumina ceramic coating diaphragm is characterized by comprising the following steps: the method comprises the following steps:
(1) firstly, dispersing alumina powder in water to obtain an alumina solution with uniform dispersion;
(2) adding fatty acid with more than 6 carbon atoms into the alumina solution prepared in the step (1), wherein the weight ratio of the added fatty acid to the alumina powder is 2-5%, stirring in a water bath at constant temperature of 50-80 ℃, and drying in a drying oven at constant temperature to prepare lipophilic alumina;
(3) adding lipophilic alumina into a siloxane coupling agent and an organic solvent, mixing, stirring and hydrolyzing until the organic solvent is completely volatilized to obtain a mixture;
(4) the mixture is put in ammonia atmosphere for pyrolysis treatment to obtain modified alumina ceramic powder with hydrophobic effect;
(5) dispersing the modified alumina ceramic powder into deionized water, and stirring to obtain hydrophobically modified alumina; pre-dispersing by using a dispersion machine, grinding by using a nano grinding machine to form a hydrophobic modified alumina solution, adding a binder LBG (long-chain extender) at a weight ratio of 1-5%, and dispersing by using a large dispersion machine at a rotation speed of 200-10000r/min to obtain modified alumina ceramic slurry;
(6) and coating the modified alumina ceramic slurry on the surface of a base membrane which takes the lithium ion battery PE as a raw material, and drying to obtain the lithium ion battery diaphragm coated with the hydrophobic modified ceramic.
2. The method for preparing the surface modified alumina ceramic coating diaphragm according to claim 1, wherein: the stirring in the step (2) is mechanical stirring, and the stirring speed is 200-.
3. The method for preparing the surface modified alumina ceramic coating diaphragm according to claim 2, wherein: the stirring speed in the step (2) is 500-600 r/min.
4. The method for preparing the surface modified alumina ceramic coating diaphragm according to claim 1, wherein: in the step (2), the temperature range is 70-90 ℃.
5. The method for preparing the surface modified alumina ceramic coating diaphragm according to claim 1, wherein: the temperature in the step (2) is 80 ℃.
6. The method for preparing the surface modified alumina ceramic coating diaphragm according to claim 1, wherein: the fatty acid added in the step (2) is oleic acid.
7. The method for preparing the surface modified alumina ceramic coating diaphragm according to claim 6, wherein: and (2) stirring for 20-24h, and drying at constant temperature in a drying oven, specifically, cooling the mixed solution, performing vacuum filtration, and drying in an oven.
8. The method for preparing the surface modified alumina ceramic coating diaphragm according to claim 1, wherein: in the step (6), the coating speed is 10-50 m/min.
9. The method for preparing the surface modified alumina ceramic coating diaphragm according to claim 8, wherein: and (4) after the step (6), drying in a long oven at the baking temperature of 80-100 ℃.
10. The method for preparing the surface modified alumina ceramic coating diaphragm according to claim 9, wherein: and (5) after the step (6), the baking temperature is 75 ℃, and the drying time is 30 min.
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Application publication date: 20191220 |