CN108281591A - A kind of preparation method of lithium ion battery ceramic coating composite diaphragm - Google Patents
A kind of preparation method of lithium ion battery ceramic coating composite diaphragm Download PDFInfo
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- CN108281591A CN108281591A CN201711480666.1A CN201711480666A CN108281591A CN 108281591 A CN108281591 A CN 108281591A CN 201711480666 A CN201711480666 A CN 201711480666A CN 108281591 A CN108281591 A CN 108281591A
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- ceramic coating
- composite diaphragm
- coating composite
- lithium ion
- ion battery
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- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000005524 ceramic coating Methods 0.000 title claims abstract description 33
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000004698 Polyethylene Substances 0.000 claims abstract description 33
- 239000002105 nanoparticle Substances 0.000 claims abstract description 26
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 10
- 239000002002 slurry Substances 0.000 claims abstract description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000004743 Polypropylene Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000000839 emulsion Substances 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 8
- -1 polyethylene Polymers 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical group [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 claims 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract description 2
- 229920001451 polypropylene glycol Polymers 0.000 abstract 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 235000013877 carbamide Nutrition 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 208000016261 weight loss Diseases 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000003643 water by type Substances 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of preparation method of lithium ion battery ceramic coating composite diaphragm, using cetyl trimethylammonium bromide, polyethylene oxide polypropylene oxide polyethylene oxide triblock copolymer as template, urea is as precipitating reagent, alumina precursor is prepared by hydro-thermal method, passes through N successively2Atmosphere roasts and air atmosphere roasting, obtains porous aluminum oxide nano particle, then prepare the finely dispersed slurry of porous aluminum oxide nano particle, is coated on PE diaphragms.Ceramic coating composite diaphragm prepared by the present invention is applied to lithium ion battery, and battery is made to have good charge/discharge capacity and cycle performance.
Description
【Technical field】
The invention belongs to battery diaphragm material technical field more particularly to a kind of lithium ion battery ceramic coating composite diaphragms
Preparation method.
【Background technology】
In recent years, there are many diaphragm be applied to battery, experienced by cellulose paper and glassine paper manufacture non-woven fabrics,
The a series of transformation such as perforated membrane made of foamed material, amberplex and polymer material.Select the main consideration of diaphragm
Factor has chemical stability, mechanical performance, thermal stability, transmitance, surface without electrostatic, electrolyte wellability, uniformity etc., every
The quality of film directly affects the security performance and capacity of battery.Currently, most of the diaphragm being used on battery is that micropore is poly-
Alkene film, such as PE, PP or PP/PE/PP composite membrane.Although these diaphragm mechanical strengths and chemical stability are excellent, in height
Apparent thermal pinch can occur under warm environment, to cause the short circuit of inside battery positive and negative anodes or thermal runaway.
For the high heat-resisting diaphragm of exploitation, a lot of research work has been carried out both at home and abroad.[the Journal of Power such as such as Kim
Sources, 2012,212,22-27] utilize chemical vapour deposition technique to generate SiO in membrane surface2Thin layer, Jeong etc.
[Journal of Membrane Science, 2012,415-415,513-519] is using evaporation revulsion in membrane surface system
Standby SiO2Coating, Yao's equal [University of Anhui's journal, 2014,38,73-79] will be mixed with of aluminium oxide using dimple version coating processes
Grain slurry is coated uniformly on conventional PE diaphragms unilateral side, obtains better effects.However, these methods preparation process is complicated, to applying
Layer thickness, inorganic particle type, size controlling condition are harsh；And inorganic particle surfaces gap and channel are inadequate, be easy block every
Film surface hole, causes battery internal resistance to become larger, and capacity reduces.In consideration of it, it is really necessary to provide a kind of lithium ion battery pottery
The preparation method of porcelain coating composite diaphragm is to overcome drawbacks described above.
【Invention content】
The object of the present invention is to provide a kind of preparation methods of lithium ion battery ceramic coating composite diaphragm, using double-template
Agent and hydro-thermal method are made alumina particle and are coated on lithium ion battery separator surface, and ceramic coating composite diaphragm is made to have high temperature resistance
While thermal stability, also there is good invertibity and cyclical stability.
The present invention provides a kind of preparation method of lithium ion battery ceramic coating composite diaphragm, includes the following steps：
1) by hexamethylene, n-amyl alcohol and silicon source according to 20:(0.75~1.25):5 mass ratio mixing, is placed in 30~35 DEG C
Stirred in water bath is uniform, forms mixed liquor A；Cetyl trimethylammonium bromide and urea are dissolved in deionized water be placed in 30~
35 DEG C of stirred in water bath are uniform, formed mixed liquid B, the cetyl trimethylammonium bromide, urea and deionized water mass ratio
For (0.0075~0.015):0.04:2.5；By polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and dense
Hydrochloric acid, which is dissolved in deionized water, to stir evenly, and forms mixed liquor C, the polyethylene oxide-polypropylene oxide-polyethylene oxide three
The mass ratio of block copolymer, concentrated hydrochloric acid and deionized water is (0.025~0.035):2:7.5；
2) mixed liquid B is slowly added into stirring in mixed liquor A and forms emulsion, then mixed liquor C is slowly added into emulsion
In continue 11~15h of stirring, obtain mixed liquor D；
3) mixed liquor D is placed in 6~10h of hydrothermal crystallizing at 100~120 DEG C, product is obtained after cooling, product is filtered,
Washing, after vacuum dried, the N at 500~600 DEG C26~8h is roasted in atmosphere, then is placed in air atmosphere at 500~600 DEG C
6~8h of middle roasting, obtains porous aluminum oxide nano particle；
4) by N-Methyl pyrrolidone and Kynoar according to 92:8 mass ratio prepares glue, then will be in step 3)
Porous aluminum oxide nano particle is added in glue, then dispersant is added in vacuum 18~36h of high-speed stirred, is uniformly mixed and is formed
Slurry；Slurry is spread evenly across to the side of PE diaphragms, 18~36h is dried in vacuo in 80~110 DEG C.
In a preferred embodiment, in step 1), source of aluminium is aluminium isopropoxide, aluminum nitrate or aluminium chloride；Institute
State a concentration of the 37~40% of concentrated hydrochloric acid.
In a preferred embodiment, in step 2), mixed liquor A, mixed liquid B and mixed liquor C according to (0.75~
1.25):0.5:2 mass ratio mixing.
In a preferred embodiment, in step 3), it is less than using the multiple washed product of acetone to concentration impurity ion
20ppm；Vacuum drying temperature is 80~110 DEG C and the time is 4~8h.
In a preferred embodiment, in step 4), the dispersant is polyvinylpyrrolidone；The PE diaphragms
Thickness is 16 μm.
In a preferred embodiment, the Kynoar, porous aluminum oxide nano particle and polyvinylpyrrolidine
The mass ratio of ketone is 2:47:(0.75~1).
In a preferred embodiment, in step 4), the speed of vacuum high-speed stirred is 1600r/min.
The present invention is using cetyl trimethylammonium bromide, polyethylene oxide-polypropylene oxide-polyethylene oxide three block
Copolymer prepares alumina precursor as template, urea as precipitating reagent, by hydro-thermal method, passes through N successively2Atmosphere roast and
Air atmosphere roasts, and obtains porous aluminum oxide nano particle, then prepare the finely dispersed slurry of porous aluminum oxide nano particle,
Coated on PE diaphragms.Compared with the existing technology, the porous aluminum oxide nano particle prepared using double template and hydro-thermal method is big
Small uniform and surface possesses a large amount of ducts, and the composite diaphragm for being coated with porous aluminum oxide nano particle has higher thermostabilization
Property, electrolyte wellability and lower diaphragm impedance, be conducive to the charge/discharge capacity and cycle performance that improve lithium ion battery.
【Description of the drawings】
Fig. 1 is the SEM figures of the porous aluminum oxide nano particle prepared by embodiment.
Fig. 2 is the SEM figures of the ceramic coating composite diaphragm cross section prepared by embodiment.
Fig. 3 is the ruler of the porous aluminum oxide nano particle and the coating layer thickness of ceramic coating composite diaphragm prepared by embodiment
Very little distribution map.
Fig. 4 is nitrogen adsorption desorption curve and the aperture size distribution of the porous aluminum oxide nano particle prepared by embodiment
Figure.
Fig. 5 is the TG-DSC analysis charts of common PE diaphragm.
Fig. 6 is the TG-DSC analysis charts of the ceramic coating composite diaphragm prepared by embodiment.
Fig. 7 is that ceramic coating composite diaphragm and common PE diaphragm prepared by embodiment assembles following after button cell respectively
Ring test curve graph.
【Specific implementation mode】
The present invention provides a kind of preparation method of lithium ion battery ceramic coating composite diaphragm, includes the following steps：
1) by hexamethylene, n-amyl alcohol and silicon source according to 20:(0.75~1.25):5 mass ratio mixing, is placed in 30~35 DEG C
Stirred in water bath is uniform, forms mixed liquor A；Cetyl trimethylammonium bromide and urea are dissolved in deionized water be placed in 30~
35 DEG C of stirred in water bath are uniform, formed mixed liquid B, the cetyl trimethylammonium bromide, urea and deionized water mass ratio
For (0.0075~0.015):0.04:2.5；By polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and dense
Hydrochloric acid, which is dissolved in deionized water, to stir evenly, and forms mixed liquor C, the polyethylene oxide-polypropylene oxide-polyethylene oxide three
The mass ratio of block copolymer, concentrated hydrochloric acid and deionized water is (0.025~0.035):2:7.5；
2) mixed liquid B is slowly added into stirring in mixed liquor A and forms emulsion, then mixed liquor C is slowly added into emulsion
In continue 11~15h of stirring, obtain mixed liquor D；
3) mixed liquor D is placed in 6~10h of hydrothermal crystallizing at 100~120 DEG C, product is obtained after cooling, product is filtered,
Washing, after vacuum dried, the N at 500~600 DEG C26~8h is roasted in atmosphere, then is placed in air atmosphere at 500~600 DEG C
6~8h of middle roasting, obtains porous aluminum oxide nano particle；
4) by N-Methyl pyrrolidone and Kynoar according to 92:8 mass ratio prepares glue, then will be in step 3)
Porous aluminum oxide nano particle is added in glue, then dispersant is added in vacuum 18~36h of high-speed stirred, is uniformly mixed and is formed
Slurry；Slurry is spread evenly across to the side of PE diaphragms, 18~36h is dried in vacuo in 80~110 DEG C.
Specifically, in step 1), source of aluminium is aluminium isopropoxide, aluminum nitrate or aluminium chloride；The concentration of the concentrated hydrochloric acid
It is 37~40%.In step 2), mixed liquor A, mixed liquid B and mixed liquor C are according to (0.75~1.25):0.5:2 mass ratio is mixed
It closes.In step 3), 20ppm is less than using the multiple washed product of acetone to concentration impurity ion；Vacuum drying temperature be 80~
110 DEG C and time are 4~8h.In step 4), the dispersant is polyvinylpyrrolidone；The Kynoar, porous oxygen
The mass ratio for changing aluminum nanoparticles and polyvinylpyrrolidone is 2:47:(0.75~1)；The thickness of the PE diaphragms is 16 μm；
The speed of vacuum high-speed stirred is 1600r/min.
Embodiment
1) 320g hexamethylenes, 16g n-amyl alcohols and 80g aluminium isopropoxides are placed in 30~35 DEG C of water-baths and are mixed and stirred for
0.5~1h is uniformly mixed to solution, forms mixed liquor A；0.8g cetyl trimethylammonium bromides and 3.2g ureas are dissolved in 200g
In deionized water, it is placed in 0.5~1h of stirring in 30~35 DEG C of water-baths and is uniformly mixed to solution, form mixed liquid B；By 2.4g
Polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and 160g concentrated hydrochloric acids are dissolved in 600g deionized waters,
0.5~1h of stirring is uniformly mixed to solution at room temperature, forms mixed liquor C；
2) 160g mixed liquid Bs are slowly added into the emulsion that stirring in 400g mixed liquor As forms white, then 640g is mixed
Liquid C, which is slowly added into emulsion, to be continued to stir 12h at 35 DEG C, obtains mixed liquor D；
3) mixed liquor D is packed into reaction kettle hydrothermal crystallizing 6h at 100 DEG C, product is obtained after cooling, by product filtering, simultaneously
It is repeatedly washed with acetone to concentration impurity ion and is less than 20ppm, obtained alumina precursor after being dried in vacuo 4h in 110 DEG C, set
The N at 550 DEG C26h is roasted in atmosphere, then is placed at 550 DEG C and roasts 6h in air atmosphere, obtains porous aluminum oxide nano particle；
4) 4g Kynoar is slowly added into 46gN- methyl pyrrolidones and stirs 4h preparation glues in 40 DEG C, then
The 18.8g porous aluminum oxide nano particles in step 3) are taken to be added in 10g glues, for 24 hours, 0.4g is then added in vacuum high-speed stirred
Polyvinylpyrrolidone is uniformly mixed and forms slurry；Slurry is spread evenly across the common PE diaphragm one that thickness is 16 μm
Side, for 24 hours in 80 DEG C of vacuum drying.
Fig. 1 is scanning electron microscope (SEM) figure of the porous aluminum oxide nano particle prepared by the present embodiment, and Fig. 2 is this implementation
The SEM figures of ceramic coating composite diaphragm cross section prepared by example, Fig. 3 are the porous aluminum oxide nano prepared by the present embodiment
The size distribution plot of grain and the coating layer thickness of ceramic coating composite diaphragm.As seen from the figure, porous aluminum oxide nano particle is in spherical
And uniform in size, Average Particle Diameters 400nm, there are a large amount of channels between particle；The painting thickness of ceramic coating composite diaphragm
About 2.25 μm of degree.
Fig. 4 is nitrogen adsorption desorption curve and the aperture size distribution of the porous aluminum oxide nano particle prepared by the present embodiment
Figure.As seen from the figure, the relative adsorption pressure P/Po of adsorbance is to illustrate porous prepared by the present embodiment in 0.4~0.9 range
There are abundant duct, pore size is 3.5nm or so on aluminum oxide nanoparticle surface.
Fig. 5 and Fig. 6 is respectively the TG- of the common PE diaphragm and prepared ceramic coating composite diaphragm used in the present embodiment
Dsc analysis figure.As seen from the figure, the melting temperature of common PE diaphragm is 145.2 DEG C；The melting temperature of ceramic coating composite diaphragm is
150.9 DEG C, illustrate that porous aluminum oxide nano particle has protective effect to PE diaphragms；The weight-loss ratio of PE diaphragms is 99.61%, ceramics
The weight-loss ratio of coating composite diaphragm is 50.65%, and porous aluminum oxide nano particle accounts for ceramic coating composite diaphragm after illustrating coating
The 49.35% of gross weight.
Further, it is assembled into and is buckled respectively with common PE diaphragm using the ceramic coating composite diaphragm prepared by the present embodiment
Formula battery, and the new prestige test systems of Neware BTS is selected to carry out the first charge-discharge capacity of button cell and recycle electric discharge survey
Examination, charge-discharge magnification 0.2C, charge and discharge blanking voltage 2.0~3.8V of range, test temperature are 25 DEG C, result such as Fig. 7 institutes
Show.Button cell is assembled with the ceramic coating composite diaphragm prepared by the present embodiment, the specific steps are：Anode is selected a diameter of
The metal lithium sheet of 16mm, electrolyte select the LiPF6 (V (EC of 1mol/L:DMC)=1:1), successively according to negative electrode casing-shrapnel-pad
The sequence of piece-electrolyte-lithium piece-electrolyte-ceramic coating composite diaphragm-electrolyte-positive plate-gasket-anode cover filled with
The glove box of argon gas carries out cell package.Button cell is assembled with common PE diaphragm, the specific steps are：Anode is selected a diameter of
The metal lithium sheet of 16mm, electrolyte select the LiPF6 (V (EC of 1mol/L:DMC)=1:1), successively according to negative electrode casing-shrapnel-pad
The sequence of piece-electrolyte-lithium piece-electrolyte-common PE diaphragm-electrolyte-positive plate-gasket-anode cover is filled with argon gas
Glove box carries out cell package.
As shown in Figure 7：It is almost the same with the battery initial discharge amount of common PE diaphragm using ceramic coating composite diaphragm, it adopts
It is 158mAh/g with the electricity of buckleing of common PE diaphragm, uses the button electricity of ceramic coating composite diaphragm for 157mAh/g；In cyclic process
In, it is slower than common PE membrane degradation using the battery discharge capacity of ceramic coating composite diaphragm；After cycle 300 times, using ceramics
The discharge capacity of the cell conservation rate of coating composite diaphragm is 94.63%, and the discharge capacity of the cell of common PE diaphragm is used to keep
Rate is 91.01%.Therefore, illustrate that there is good charge/discharge capacity and cyclicity using the battery of ceramic coating composite diaphragm
Energy.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is to combine specific preferred embodiment to institute of the present invention
The further description of work is, and it cannot be said that the specific implementation of the present invention is confined to these explanations.It is all the present invention spirit and
All any modification, equivalent and improvement made by within principle etc., should be included within the scope of the present invention.
Claims (7)
1. a kind of preparation method of lithium ion battery ceramic coating composite diaphragm, which is characterized in that include the following steps：
1) by hexamethylene, n-amyl alcohol and silicon source according to 20:(0.75~1.25):5 mass ratio mixing, is placed in 30~35 DEG C of water-baths
In stir evenly, formed mixed liquor A；Cetyl trimethylammonium bromide and urea are dissolved in deionized water and are placed in 30~35 DEG C
Stirred in water bath is uniform, forms mixed liquid B, and the mass ratio of the cetyl trimethylammonium bromide, urea and deionized water is
(0.0075~0.015):0.04:2.5；By polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and dense salt
Acid, which is dissolved in deionized water, to stir evenly, and forms mixed liquor C, and the polyethylene oxide-polypropylene oxide-polyethylene oxide three is embedding
The mass ratio of section copolymer, concentrated hydrochloric acid and deionized water is (0.025~0.035):2:7.5；
2) mixed liquid B is slowly added into stirring in mixed liquor A and forms emulsion, then mixed liquor C is slowly added into emulsion relaying
11~15h of continuous stirring, obtains mixed liquor D；
3) mixed liquor D is placed in 6~10h of hydrothermal crystallizing at 100~120 DEG C, obtains product after cooling, product is filtered, washed,
After vacuum dried, the N at 500~600 DEG C26~8h is roasted in atmosphere, then is placed at 500~600 DEG C and is roasted in air atmosphere
6~8h obtains porous aluminum oxide nano particle；
4) by N-Methyl pyrrolidone and Kynoar according to 92:8 mass ratio prepares glue, then will be porous in step 3)
Aluminum oxide nanoparticle is added in glue, then dispersant is added in vacuum 18~36h of high-speed stirred, is uniformly mixed and forms pulpous state
Object；Slurry is spread evenly across to the side of PE diaphragms, 18~36h is dried in vacuo in 80~110 DEG C.
2. the preparation method of lithium ion battery ceramic coating composite diaphragm as described in claim 1, it is characterised in that：Step 1)
In, source of aluminium is aluminium isopropoxide, aluminum nitrate or aluminium chloride；A concentration of the 37~40% of the concentrated hydrochloric acid.
3. the preparation method of lithium ion battery ceramic coating composite diaphragm as described in claim 1, it is characterised in that：Step 2)
In, mixed liquor A, mixed liquid B and mixed liquor C are according to (0.75~1.25):0.5:2 mass ratio mixing.
4. the preparation method of lithium ion battery ceramic coating composite diaphragm as described in claim 1, it is characterised in that：Step 3)
In, 20ppm is less than using the multiple washed product of acetone to concentration impurity ion；Vacuum drying temperature be 80~110 DEG C and when
Between be 4~8h.
5. the preparation method of lithium ion battery ceramic coating composite diaphragm as described in claim 1, it is characterised in that：Step 4)
In, the dispersant is polyvinylpyrrolidone；The thickness of the PE diaphragms is 16 μm.
6. the preparation method of lithium ion battery ceramic coating composite diaphragm as claimed in claim 5, it is characterised in that：It is described poly-
The mass ratio of vinylidene, porous aluminum oxide nano particle and polyvinylpyrrolidone is 2:47:(0.75~1).
7. the preparation method of lithium ion battery ceramic coating composite diaphragm as described in claim 1, it is characterised in that：Step 4)
In, the speed of vacuum high-speed stirred is 1600r/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114597595A (en) * | 2022-03-15 | 2022-06-07 | 河南惠强新能源材料科技股份有限公司 | Lithium ion battery composite diaphragm with uniform pore structure and preparation method thereof |
| CN114759312A (en) * | 2022-06-15 | 2022-07-15 | 宁德卓高新材料科技有限公司 | Ceramic diaphragm and preparation method and application thereof |
-
2017
- 2017-12-29 CN CN201711480666.1A patent/CN108281591A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114597595A (en) * | 2022-03-15 | 2022-06-07 | 河南惠强新能源材料科技股份有限公司 | Lithium ion battery composite diaphragm with uniform pore structure and preparation method thereof |
| CN114759312A (en) * | 2022-06-15 | 2022-07-15 | 宁德卓高新材料科技有限公司 | Ceramic diaphragm and preparation method and application thereof |
| CN114759312B (en) * | 2022-06-15 | 2022-10-18 | 宁德卓高新材料科技有限公司 | Ceramic diaphragm and preparation method and application thereof |
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