CN109786627A - A kind of preparation method of super-electrophilic lithium battery separator - Google Patents
A kind of preparation method of super-electrophilic lithium battery separator Download PDFInfo
- Publication number
- CN109786627A CN109786627A CN201910081392.1A CN201910081392A CN109786627A CN 109786627 A CN109786627 A CN 109786627A CN 201910081392 A CN201910081392 A CN 201910081392A CN 109786627 A CN109786627 A CN 109786627A
- Authority
- CN
- China
- Prior art keywords
- diaphragm
- lithium battery
- preparation
- super close
- electrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 85
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims abstract description 100
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- 239000002105 nanoparticle Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003618 dip coating Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000000725 suspension Substances 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 238000004513 sizing Methods 0.000 claims description 9
- 238000005192 partition Methods 0.000 claims description 8
- -1 Kynoar Polymers 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004113 Sepiolite Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 229910052624 sepiolite Inorganic materials 0.000 claims description 4
- 235000019355 sepiolite Nutrition 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 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
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 claims description 3
- 229960000892 attapulgite Drugs 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000013007 heat curing Methods 0.000 claims description 3
- 229910000271 hectorite Inorganic materials 0.000 claims description 3
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 3
- 229910052625 palygorskite Inorganic materials 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 229920000557 Nafion® Polymers 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
- 239000011152 fibreglass Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910052900 illite Inorganic materials 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052622 kaolinite Inorganic materials 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 229910052902 vermiculite Inorganic materials 0.000 claims description 2
- 239000010455 vermiculite Substances 0.000 claims description 2
- 235000019354 vermiculite Nutrition 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 241000209094 Oryza Species 0.000 claims 2
- 235000007164 Oryza sativa Nutrition 0.000 claims 2
- 235000009566 rice Nutrition 0.000 claims 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 1
- 239000002041 carbon nanotube Substances 0.000 claims 1
- 229910021393 carbon nanotube Inorganic materials 0.000 claims 1
- 229920000139 polyethylene terephthalate Polymers 0.000 claims 1
- 239000005020 polyethylene terephthalate Substances 0.000 claims 1
- 239000006228 supernatant Substances 0.000 claims 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 abstract description 24
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000001029 thermal curing Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- 239000012528 membrane Substances 0.000 description 10
- 239000005955 Ferric phosphate Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 229940032958 ferric phosphate Drugs 0.000 description 8
- 238000005213 imbibition Methods 0.000 description 8
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 8
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 230000003204 osmotic effect Effects 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000002525 ultrasonication Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 230000005611 electricity Effects 0.000 description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 4
- 229940068984 polyvinyl alcohol Drugs 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- VJGCZWVJDRIHNC-UHFFFAOYSA-N 1-fluoroprop-1-ene Chemical compound CC=CF VJGCZWVJDRIHNC-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 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
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- CHBCHAGCVIMDKI-UHFFFAOYSA-N [F].C=C Chemical group [F].C=C CHBCHAGCVIMDKI-UHFFFAOYSA-N 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- ZSDJVGXBJDDOCD-UHFFFAOYSA-N benzene dioctyl benzene-1,2-dicarboxylate Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1=CC=CC=C1 ZSDJVGXBJDDOCD-UHFFFAOYSA-N 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- 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
- Secondary Cells (AREA)
Abstract
本发明公开了一种超亲电解液锂电池隔膜的制备方法，是将无机纳米粒子超声分散在去离子水中得悬浮液；将粘结剂分散于有机溶剂中得粘结剂溶液；将粘结剂溶液添加到无机纳米粒子悬浮液中，搅拌、超声形成均匀浆料；然后采用浸涂法将浆料均匀涂覆于锂电池基底隔膜的两面，垂直悬挂干燥后经热固化得到。本发明制备的超亲电解液锂电池隔膜具有优异的电解液润湿性、电解液吸液率和保留率。由该隔膜组装的锂电池具有良好的倍率性能、循环稳定性和安全性。此外，由于无机纳米粒子的包覆机制，该隔膜同时具有良好的热稳定性。同时，该发明的工艺过程绿色环保、成本低廉，且易于规模化生产。The invention discloses a preparation method of a super-electrolyte lithium battery separator. The method comprises the following steps: ultrasonically dispersing inorganic nanoparticles in deionized water to obtain a suspension; dispersing a binder in an organic solvent to obtain a binder solution; The agent solution is added to the inorganic nanoparticle suspension, stirred and sonicated to form a uniform slurry; then the slurry is uniformly coated on both sides of the lithium battery base separator by the dip coating method, and it is obtained by vertical hanging and drying and then thermal curing. The super-electrophilic lithium battery separator prepared by the invention has excellent electrolyte wettability, electrolyte absorption rate and retention rate. The lithium battery assembled by this separator has good rate performance, cycle stability and safety. In addition, due to the coating mechanism of inorganic nanoparticles, the separator also has good thermal stability. At the same time, the technological process of the invention is environmentally friendly, has low cost, and is easy to produce on a large scale.
Description
Technical field
The present invention relates to a kind of preparation methods of super close electrolyte lithium battery diaphragm more particularly to one kind can be used for the next generation
The preparation method of the super close electrolyte diaphragm of high-energy density lithium battery.
Background technique
With flourishing for the markets such as electric car, consumption electronic product, traditional energy storage device (intercal type lithium
Ion battery, lead-acid battery etc.) be no longer satisfied demand of the people to energy storage equipment.Therefore, the lithium of high-energy density
Metal battery and new type power lithium ion battery become the next-generation energy storage device that people concentrate research and development.Whether scientific base
Plinth research or commodity production research focus primarily on the exploitation and research of high performance electrode material and electrolyte, and achieve
Significant progress, while having pushed the fast development of next-generation high energy density cells system.However, lithium battery diaphragm is as lithium
One of main composition component of battery, it is not only most important to the safety of lithium battery, but also to its capacity and energy density etc.
Performance is of great significance.Studies have shown that chemical property of the lithium battery under high magnification is mainly determined by the impedance of electrolyte.
Therefore, lithium battery diaphragm is to the wetability, imbibition rate and retention rate of electrolyte to following under lithium battery high rate performance and high magnification
Most important (the Energy Environ Sci 2016,9,3252 of ring stability; Adv Energy Mater 2018, 8,
1801778.).
Currently, the lithium battery diaphragm commercially produced and applied is mainly with polyalkene diaphragm (including PP, PE and PP/PE/PP
Sandwich diaphragm etc.) based on.Compared to other diaphragm types, polyolefins diaphragm is because having intensity high, good acid and alkali-resistance and molten
It the advantages that agent performance, electrochemically stable and closed pore, occupies an leading position in lithium battery market.But there is also poor electrolysis for it
The disadvantages of liquid wetting and thermal stability and lower electrolyte retention rate, therefore limit next-generation high-energy density lithium battery
Application.In recent years, it has been used based on the plurality of advantages of polyalkene diaphragm, scientific research and industry to polyalkene diaphragm table
Face carries out chemically or physically coating the methods of modified heat resistance and wetability for improving diaphragm.CN 104282869A discloses one
The preparation method of the close electrolyte lithium battery diaphragm of kind, using biogum as binder, by simple coating method, in polyolefin
The one or both sides on micro-pore septum surface coat close electrolyte polymer powder and close electrolyte lithium battery diaphragm have been prepared.It should
Although the diaphragm of method preparation has close electrolyte property, far it is not enough to reach super electrophilic solution fluidity.Further, since electrophilic solution
The limited thermostability of matter polymer powder, therefore next-generation high-energy density lithium is not still able to satisfy to the thermal stability of diaphragm
The growth requirement of battery.CN 104269509A discloses a kind of lithium battery ceramic coating membrane and preparation method thereof, is by water
Property the diaphragm that is prepared in membrane surface of ceramic slurry even application there is excellent thermal stability.However, using above-mentioned
The modified diaphragm of patented method preparation is still limited to the raising of electrolyte wetability, improves to lithium battery performance unobvious.
Summary of the invention
The purpose of the present invention is be existing lithium battery diaphragm there are aiming at the problem that, a kind of super close electrolyte lithium battery is provided
The preparation method of diaphragm, to push the development of next-generation high-energy density lithium battery.
One, the preparation of super close electrolyte lithium battery diaphragm
The preparation method of the super close electrolyte lithium battery diaphragm of the present invention, in deionized water by inorganic nano-particle ultrasonic disperse
Suspension；It disperses binder in organic solvent and obtains binder solution；By binder solution addition, (adding rate is 1 mL/s
~ 10 mL/s) into inorganic nano-particle suspension, it stirs, be ultrasonically formed uniform sizing material；Then using dip coating that slurry is equal
The even two sides coated on lithium battery basilar partition, vertical hanging and dry 10 ~ 60 min under 20 ~ 80 °C；Most afterwards through heat cure
(2 ~ 24 h are vacuum-treated under 30 ~ 80 °C), obtaining super close electrolyte lithium battery diaphragm, (super close electrolyte refers to diaphragm to each
The contact angle of the common organic electrolyte of kind is close to 0 °, such as carbonic acyl radical and ether electrolyte).
The binder is polyvinyl alcohol, polyethylene glycol oxide, sodium carboxymethylcellulose, Nafion, butadiene-styrene rubber, gathers inclined fluorine
At least one of ethylene, polytetrafluoroethylene (PTFE), polyvinyl alcohol, polymethyl methacrylate, polyurethane.
The inorganic nano-particle be attapulgite, sepiolite, galapectite, montmorillonite, serpentine, hectorite, hydrotalcite,
Illite, vermiculite, mica, kaolinite, diatomite, titanium dioxide, zinc oxide, nano silver, aluminium oxide, silica, carbon nanometer
At least one of pipe, graphene oxide or nano-cellulose.
The organic solvent be ethyl alcohol, ethylene glycol, isopropanol, acetonitrile, acetone,NN-methyl-2-2-pyrrolidone N,N,NMethyl
At least one of pyrrolidones.
The lithium battery basilar partition is PE diaphragm, PP diaphragm, PP/PE composite diaphragm, Kynoar diaphragm, gathers to benzene
Dioctyl phthalate second diester, polybutylene terephthalate, poly- (vinylidene-coHexafluoropropene) diaphragm, poly- (vinylidene-co-
Trifluoro-ethylene) diaphragm, polyester diaphragm, polyimide diaphragm, polyamide diaphragm, fibreglass diaphragm, cellulose composite diaphragm.
In the slurry, the concentration of nanoparticle is 0.01wt% ~ 9.99wt%, the concentration of binder be 0.01wt% ~
5.0wt%；The mass ratio of water and organic solvent is 1:0.1 ~ 1:20.
The dip coating coating is lithium battery diaphragm to be immersed in 5 ~ 120 s in uniform sizing material at room temperature, then use and mention
It draws film applicator at the uniform velocity to pull out diaphragm, slurry is made to be uniformly coated on lithium battery diaphragm surface.Dip coating process repeats 1 according to demand
~ 10 times；Diaphragm is at the uniform velocity pulled out using 7 pulling coating machines again after diaphragm is rotated 180 ° when repeating.Load capacity control is coated to exist
0.001~1.0 mg cm−2。
Two, the performance of super close electrolyte lithium battery diaphragm
The super close electrolyte battery diaphragm and ratio prepared below by embodiment 1, to the items of super close electrolyte battery diaphragm
Performance compares investigation.
1, the wetability of electrolyte
Fig. 1 is Celgard2400 diaphragm in the super close electrolyte lithium battery diaphragm and comparative example 1 of the preparation of embodiment 1 to ether (1
Mol LiTFSI is dissolved in isometric DOL and DEM in the mixed solvent) and carbonic acyl radical (1 mol LiPF6It is dissolved in equal bodies
Long-pending EC and DMC in the mixed solvent) electrolyte wetability.Contact of the carbonic acyl radical electrolyte in Gelgard2400 membrane surface
Angle is 43 ° ± 1.3 °；The contact angle of carbonic acyl radical and ether electrolyte on super close electrolyte lithium battery diaphragm surface is respectively 0 °.Table
Bright super close electrolyte lithium battery diaphragm has excellent wetability to electrolyte, to be obviously improved lithium ion conductivity.This
Outside studies have shown that the super electrophilic solution fluidity of diaphragm can help to improve performance of the battery under high magnification.
2, the imbibition rate and retention rate of electrolyte
Fig. 2 is the electrolyte of Celgard2400 diaphragm in super close electrolyte lithium battery diaphragm prepared by embodiment 1 and comparative example 1
Retention rate.Specific test method is to be placed in diaphragm in electrolyte after 1 h, and the electrolyte of membrane surface is sopped up with filter paper, is placed in
At room temperature after different time, the electrolyte retention rate of diaphragm is calculated.After 30 min, the electrolysis of the diaphragm prepared in embodiment 1
Liquid retention rate is still up to 86%, and the electrolyte retention rate of Celgard2400 diaphragm is only 43% in comparative example 1.In addition, 10
The carbonic acyl radical and ether electrolyte of μ L can be about 0 ° in super close electrolyte membrane surface rapid osmotic, contact angle.
3, ferric phosphate lithium cell performance
Fig. 3 is Celgard2400 diaphragm group in the super close electrolyte lithium battery diaphragm prepared respectively with embodiment 1 and comparative example 1
(a) cyclical stability and (b) high rate performance of the ferric phosphate lithium cell of dress.From Fig. 3 a it can be found that in 1.0 C discharge-rates
Under, the battery of the diaphragm assembling prepared in embodiment 1 has relatively stable discharge capacity in prolonged charge and discharge process.
However, apparent capacity attenuation has occurred in the battery of Celgard2400 assembling.After 350 circulations, 1 interval of embodiment
The battery capacity retention rate of film assembling is up to 92%.From Fig. 3 b it is found that prepared in embodiment 1 diaphragm assembling battery have compared with
Good high rate performance, this is mainly due to the super close electrolyte properties of diaphragm.
4, thermal stability
Fig. 4 is the phosphorus of Celgard2400 diaphragm assembling in the super close electrolyte battery diaphragm for preparing embodiment 1 and comparative example 1
Sour lithium iron battery is placed in the open-circuit voltage versus time curve under 160 °C.Obviously, the battery that Celgard2400 is assembled
There is apparent decline in voltage, causes battery that short circuit occurs this is because diaphragm occurs to be heat-shrinked at high temperature.However, with reality
Apply prepared in example 1 diaphragm assembling battery within the entire working time there is no voltage drop, show the diaphragm at high temperature
With good thermal stability.The result shows that: relative to Celgrad2400 diaphragm, the super close electrolyte that is prepared in embodiment 1 every
The obvious thermal stability with higher of film.
By above-mentioned the performance test results are analyzed: the design concept on bionical super infiltration surface is introduced into newly by the present invention
The preparation of type lithium battery diaphragm, obtained super close electrolyte lithium battery diaphragm all have excellent surpass to common organic electrolyte
The electrolyte imbibition rate and retention rate of wetting property and superelevation, to significantly improve under the high rate performance of battery, high magnification
Cyclical stability and coulombic efficiency；Further, since the cladding mechanism of inorganic nano-particle, which has good heat steady simultaneously
It is qualitative.There is good comprehensive performance and safety by the lithium battery that the diaphragm assembles.In addition, the present invention also has technical process
Simply, environmentally protective, low in cost and the advantages that be easy to large-scale production, it is provided to develop next-generation high-energy density lithium battery
New types of diaphragm material and its technology of preparing.
Detailed description of the invention
Fig. 1 is the electrolyte wetability comparison of super close electrolyte lithium battery diaphragm and Celgard2400 diaphragm.
Fig. 2 is the super close electrolyte lithium battery diaphragm soaked by electrolyte and Celgard2400 diaphragm in 30 min
Electrolyte retention rate situation of change.
Fig. 3 is the performance that super close electrolyte lithium battery diaphragm and Celgard2400 diaphragm assemble ferric phosphate lithium cell respectively
Comparison.
Fig. 4 is that super close electrolyte lithium battery diaphragm and Celgard2400 diaphragm assemble ferric phosphate lithium cell in high temperature respectively
Under open circuit voltage curve.
Specific embodiment
The preparation of the super close electrolyte lithium battery diaphragm of the present invention and performance are made furtherly below by specific embodiment
It is bright.
Embodiment 1
(1) it weighs 2.0 g attapulgites to be scattered in 100 mL deionized waters, 1 h of water bath sonicator；Weigh 1.0 g polyvinyl alcohol
It is dissolved in and is gone in acetonitrile in 50 mL in a heated condition；Then by poly-vinyl alcohol solution under stirring (800 r/min) effect
Slowly (2.5 mL/s) is added in attapulgite dispersion liquid；Then, 12 h of magnetic agitation under the conditions of 800 r/min, ultrasound
Wave handles 10 min, obtains uniform sizing material.Solid content is 2.0% in slurry.
(2) use pulling coating machine by slurry uniform load obtained by step (1) to Celgard2400 diaphragm two at room temperature
Face is subsequently placed at 30 min under 30 °C；It repeats the above process later 6 times；Coating average load amount is 0.1 mg cm−2。
24 h in 60 °C of vacuum environment are subsequently placed at, super close electrolyte lithium battery diaphragm is obtained.
The carbonic acyl radical and ether electrolyte of 10 μ L can be about in super close electrolyte membrane surface rapid osmotic, contact angle
0°；Carbonic acyl radical electrolyte imbibition rate has reached 283%, and after being placed in 30 min under room temperature, electrolyte retention rate still reaches
86.3%.There is not shrinkage phenomenon in 1 h under 160 °C, super close electrolyte lithium battery diaphragm.
Comparative example 1
Commercialized single layer PP diaphragm (Celgard2400): with a thickness of 25 μm, porosity 41%, MD shrinkage is 5%
(1 h under 90 °C), TD shrinkage are 1 h under 0%(90 °C).
Embodiment 2
(1) it weighs 1.0 g silica to be scattered in 200 mL deionized waters, 1 h of water bath sonicator；Weigh 0.5 g butadiene-styrene rubber
It is scattered in and is gone in ethyl alcohol in 10 mL in a heated condition；Then by butadiene-styrene rubber dispersion liquid in stirring (400 r/min) condition
Under at the uniform velocity (7 mL/s) be added in silica dispersions；Then, 6 h of magnetic agitation, ultrasonic wave under the conditions of 400 r/min
30 min are handled, uniform sizing material is obtained.Solid content is 0.7wt% in slurry.
(2) slurry obtained by step (1) is uniformly coated to by poly terephthalic acid fourth two using pulling coating machine at room temperature
Ester diaphragm two sides is hung on 60 min in 20 °C；It repeats the above process 3 times, coating average load amount is 0.16 mg cm−2.12 h in 80 °C of vacuum environment are subsequently placed at, stable super close electrolyte lithium battery diaphragm is obtained.
The carbonic acyl radical and ether electrolyte of 10 μ L can be about in super close electrolyte membrane surface rapid osmotic, contact angle
0°；The imbibition rate of carbonic acyl radical electrolyte reaches 270%, and after being placed in 30 min under room temperature, electrolyte retention rate still reaches 80%.
There is not shrinkage phenomenon in 1 h under 160 °C, super close electrolyte lithium battery diaphragm.
With the ferric phosphate lithium cell of super close electrolyte lithium battery diaphragm assembling: (1) at 2.0 C, recycling it by 300 times
Afterwards, battery capacity retention rate is up to 93.5%.(2) when discharge-rate increases to 2.0 C from 0.1 C, battery capacity retention rate is
72.86%, much higher than the 65.90% of basilar partition.(3) battery is placed under 160 °C, there is no electricity within the entire working time
Pressure drop, showing the diaphragm at high temperature has good thermal stability.
Embodiment 3
(1) it weighs 60 g hectorites to be scattered in 800 mL deionized waters, 30 min of ultrasonication；It weighs 0.2 g and gathers inclined fluorine
Ethylene is scattered in a heated condition in 10 mLN,NIn being gone in methylformamide solution；Then by Kynoar dispersion liquid
Slow (1 mL/s) is added in hectorite dispersion liquid under the conditions of stirring (700 r/min)；Then, in 700 r/min conditions
Lower 2 h of magnetic agitation, 2 h of ultrasonication obtain uniform sizing material.Solid content is 7.4wt% in slurry.
(2) use pulling coating machine by slurry uniform load obtained by step (1) to cellulose composite diaphragm two at room temperature
Side.Place it in 2 h in 25 °C.It repeats the above process 5 times, coating average load amount is 0.6 mg cm−2.It is subsequently placed at 40 °
24 h in C vacuum environment obtain stable super close electrolyte lithium battery diaphragm.
The carbonic acyl radical and ether electrolyte of 5 μ L can promote in super close electrolyte membrane surface rapid osmotic, and contact angle is about
It is 0 °；The imbibition rate of ether electrolyte reaches 252%, and after being placed in 30 min under room temperature, electrolyte retention rate still reaches 85%.
There is not receipts phenomenon in 1 h under 160 °C, super close electrolyte lithium battery diaphragm.
With the ferric phosphate lithium cell of super close electrolyte lithium battery diaphragm assembling: (1) at 2.0 C, recycling it by 500 times
Afterwards, battery capacity retention rate is up to 91.8%.(2) when discharge-rate increases to 2.0 C from 0.1 C, battery capacity retention rate is
68.63%, much higher than the 35.90% of basilar partition.(3) battery is placed under 160 °C, there is no electricity within the entire working time
Pressure drop, showing the diaphragm at high temperature has good thermal stability.
Embodiment 4
(1) it weighs 5 g serpentines to be scattered in 500 mL deionized waters, 20 min of ultrasonication；Weigh 10g polytetrafluoroethyl-ne
Alkene is scattered in a heated condition in 500 mLNIn being gone in N-methyl-2-2-pyrrolidone N solution；Then polytetrafluoroethylene (PTFE) is dispersed
Liquid slow (5 mL/s) under the conditions of stirring (600 r/min) is added in serpentine dispersion liquid；Then, in 600 r/min items
2 h of magnetic agitation under part, 3 h of ultrasonication, obtains uniform sizing material.Solid content is 1.5wt% in slurry.
(2) use pulling coating machine by slurry uniform load obtained by step (1) to poly- (vinylidene-at room temperatureco- three
Vinyl fluoride) diaphragm two sides.Place it in 2 h in 35 °C.It repeats the above process 7 times, coating average load amount is 0.25 mg cm−2.24 h in 80 °C of vacuum environment are subsequently placed at, stable super close electrolyte lithium battery diaphragm is obtained.
The carbonic acyl radical and ether electrolyte of 10 μ L can be about in super close electrolyte membrane surface rapid osmotic, contact angle
0°；The imbibition rate of ether electrolyte reaches 265%, and after being placed in 30 min under room temperature, electrolyte retention rate still reaches 78.6%.
There is not shrinkage phenomenon in 1 h under 160 °C, super close electrolyte lithium battery diaphragm.
With the ferric phosphate lithium cell of super close electrolyte lithium battery diaphragm assembling: (1) at 2.0 C, recycling it by 100 times
Afterwards, battery capacity retention rate is up to 93.2%.(2) when discharge-rate increases to 3.0 C from 0.1 C, battery capacity retention rate is
75.38%, much higher than the 55.90% of basilar partition.(3) battery is placed under 160 °C, there is no electricity within the entire working time
Pressure drop, showing the diaphragm at high temperature has good thermal stability.
Embodiment 5
(1) it weighs 0.18 g sepiolite to be scattered in 80 mL deionized waters, 1 h of water bath sonicator；Weigh 0.2g carboxymethyl cellulose
Plain sodium is scattered in be gone in 20 mL aqueous isopropanols；Then by sodium carboxymethylcellulose dispersion liquid in stirring (1000 r/
Min slow (10 mL/s) is added in sepiolite dispersion liquid under the conditions of)；Then, the magnetic agitation 24 under the conditions of 1000 r/min
H, 30 min of ultrasonication, obtains uniform sizing material.Solid content is 0.2wt% in slurry.
(2) use pulling coating machine by slurry uniform load obtained by step (1) to poly- (vinylidene-at room temperatureco- six
Fluoropropene) diaphragm two sides.Place it in 30 min in 30 °C.It repeats the above process 1 time, coating average load amount is 0.06 mg
cm−2.12 h in 80 °C of vacuum environment are subsequently placed at, stable super close electrolyte lithium battery diaphragm is obtained.
The carbonic acyl radical and ether electrolyte of 10 μ L can be about in super close electrolyte membrane surface rapid osmotic, contact angle
0°；The imbibition rate of carbonic acyl radical electrolyte reaches 170%, and after being placed in 30 min under room temperature, electrolyte retention rate still reaches 80%.
There is not shrinkage phenomenon in 1 h under 160 °C, super close electrolyte lithium battery diaphragm.
With the ferric phosphate lithium cell of super close electrolyte lithium battery diaphragm assembling: (1) at 1.0 C, recycling it by 500 times
Afterwards, battery capacity retention rate is up to 93.5%.(2) when discharge-rate increases to 5.0 C from 0.1 C, battery capacity retention rate is
67.86%, much higher than the 45.90% of basilar partition.(3) battery is placed under 160 °C, there is no electricity within the entire working time
Pressure drop, showing the diaphragm at high temperature has good thermal stability.
Claims (10)
1. a kind of preparation method of super close electrolyte lithium battery diaphragm, in deionized water by inorganic nano-particle ultrasonic disperse
Suspension；It disperses binder in organic solvent and obtains binder solution；Binder solution is added to inorganic nano-particle to hang
It in supernatant liquid, stirs, be ultrasonically formed uniform sizing material；Then slurry is evenly applied to the two of lithium battery basilar partition using dip coating
Face, vertical hanging and dry 10 ~ 60 min under 20 ~ 80 °C；Most super close electrolyte lithium battery diaphragm is obtained through heat cure afterwards.
2. a kind of preparation method of super close electrolyte lithium battery diaphragm as described in claim 1, it is characterised in that: the binder
For polyvinyl alcohol, polyethylene glycol oxide, sodium carboxymethylcellulose, Nafion, butadiene-styrene rubber, Kynoar, polytetrafluoroethylene (PTFE), gather
At least one of vinyl alcohol, polymethyl methacrylate, polyurethane.
3. a kind of preparation method of super close electrolyte lithium battery diaphragm as described in claim 1, it is characterised in that: described inorganic to receive
Rice corpuscles be attapulgite, sepiolite, galapectite, montmorillonite, serpentine, hectorite, hydrotalcite, illite, vermiculite, mica,
Kaolinite, diatomite, titanium dioxide, zinc oxide, nano silver, aluminium oxide, silica, carbon nanotube, graphene oxide are received
At least one of rice cellulose.
4. a kind of preparation method of super close electrolyte lithium battery diaphragm as described in claim 1, it is characterised in that: described organic molten
Agent be ethyl alcohol, ethylene glycol, isopropanol, acetonitrile, acetone,NN-methyl-2-2-pyrrolidone N,N,NAt least one in methyl pyrrolidone
Kind.
5. a kind of preparation method of super close electrolyte lithium battery diaphragm as described in claim 1, it is characterised in that: the lithium battery
Basilar partition is PE diaphragm, PP diaphragm, PP/PE composite diaphragm, Kynoar diaphragm, polyethylene terephthalate, poly- pair
Terephtha-late, poly- (vinylidene-coHexafluoropropene) diaphragm, poly- (vinylidene-coTrifluoro-ethylene) diaphragm, polyester
Diaphragm, polyimide diaphragm, polyamide diaphragm, fibreglass diaphragm, cellulose composite diaphragm.
6. a kind of preparation method of super close electrolyte lithium battery diaphragm as described in claim 1, it is characterised in that: the slurry
In, the concentration of nanoparticle is 0.01wt% ~ 9.99wt%, and the concentration of binder is 0.01wt% ~ 5.0wt%；Water with it is organic molten
The mass ratio of agent is 1:0.1 ~ 1:20.
7. a kind of preparation method of super close electrolyte lithium battery diaphragm as described in claim 1, it is characterised in that: the dip coating
Coating be lithium battery diaphragm is immersed in 5 ~ 120 s in uniform sizing material at room temperature, then using pulling coating machine by diaphragm at the uniform velocity
It pulls out, slurry is made to be uniformly coated on lithium battery diaphragm surface.
8. a kind of preparation method of super close electrolyte lithium battery diaphragm as described in claim 1, it is characterised in that: dip coating process root
It is repeated 1 ~ 10 time according to demand；Diaphragm is at the uniform velocity pulled out using pulling coating machine again after diaphragm is rotated 180 ° when repeating.
9. a kind of preparation method of super close electrolyte lithium battery diaphragm as described in claim 1, it is characterised in that: coating load capacity
For 0.001 ~ 1.0 mg cm−2。
10. a kind of preparation method of super close electrolyte lithium battery diaphragm as described in claim 1, it is characterised in that: at heat cure
Reason be be under 30 ~ 80 °C be vacuum-treated 2 ~ 24 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910081392.1A CN109786627A (en) | 2019-01-28 | 2019-01-28 | A kind of preparation method of super-electrophilic lithium battery separator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910081392.1A CN109786627A (en) | 2019-01-28 | 2019-01-28 | A kind of preparation method of super-electrophilic lithium battery separator |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109786627A true CN109786627A (en) | 2019-05-21 |
Family
ID=66502800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910081392.1A Pending CN109786627A (en) | 2019-01-28 | 2019-01-28 | A kind of preparation method of super-electrophilic lithium battery separator |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109786627A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110247010A (en) * | 2019-07-11 | 2019-09-17 | 河南师范大学 | A kind of preparation method of Novel lithium ion battery composite diaphragm |
| CN110783516A (en) * | 2019-11-15 | 2020-02-11 | 吉林大学 | Lithium ion battery diaphragm, lithium ion battery and preparation method thereof |
| CN111129397A (en) * | 2019-12-18 | 2020-05-08 | 中国科学院广州能源研究所 | Lithium ion battery diaphragm water-based coating and preparation method thereof |
| CN111224049A (en) * | 2020-01-14 | 2020-06-02 | 江苏厚生新能源科技有限公司 | Flame-retardant lithium battery coating diaphragm and preparation method thereof |
| CN111584805A (en) * | 2020-05-09 | 2020-08-25 | 中国科学院兰州化学物理研究所 | Preparation method of water-based clay mineral/polyvinyl alcohol crosslinked nano coating composite diaphragm |
| CN111725466A (en) * | 2020-06-12 | 2020-09-29 | 东北师范大学 | A kind of functionalized polyolefin composite membrane and its preparation method and application |
| CN112739971A (en) * | 2020-06-05 | 2021-04-30 | 广州理文科技有限公司 | Device and method for drying lithium battery electrolyte assisted by ultrasonic waves |
| CN113013547A (en) * | 2021-02-26 | 2021-06-22 | 武汉理工大学 | Lithium battery composite diaphragm and preparation method thereof |
| CN113013548A (en) * | 2021-02-26 | 2021-06-22 | 武汉理工大学 | Montmorillonite modified lithium battery diaphragm and preparation method thereof |
| CN113013551A (en) * | 2021-01-28 | 2021-06-22 | 清华大学 | Water-based nano composite modified material for lithium battery diaphragm, preparation method of water-based nano composite modified material and light-weight lithium battery diaphragm |
| CN113161683A (en) * | 2021-02-23 | 2021-07-23 | 中国地质大学（武汉） | Lithium ion battery diaphragm based on mineral modification and preparation method and application thereof |
| CN113328207A (en) * | 2021-06-02 | 2021-08-31 | 电子科技大学 | Lithium ion battery composite diaphragm and preparation method thereof |
| CN113346095A (en) * | 2021-05-17 | 2021-09-03 | 上海超碳石墨烯产业技术有限公司 | Button cell with high temperature resistant system |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107799699A (en) * | 2017-09-21 | 2018-03-13 | 中国科学院兰州化学物理研究所 | A kind of clay mineral composite lithium battery membrane and preparation method thereof |
| CN108269958A (en) * | 2018-01-24 | 2018-07-10 | 广州鹏辉能源科技股份有限公司 | Diaphragm and its preparation method and application |
-
2019
- 2019-01-28 CN CN201910081392.1A patent/CN109786627A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107799699A (en) * | 2017-09-21 | 2018-03-13 | 中国科学院兰州化学物理研究所 | A kind of clay mineral composite lithium battery membrane and preparation method thereof |
| CN108269958A (en) * | 2018-01-24 | 2018-07-10 | 广州鹏辉能源科技股份有限公司 | Diaphragm and its preparation method and application |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110247010A (en) * | 2019-07-11 | 2019-09-17 | 河南师范大学 | A kind of preparation method of Novel lithium ion battery composite diaphragm |
| CN110783516A (en) * | 2019-11-15 | 2020-02-11 | 吉林大学 | Lithium ion battery diaphragm, lithium ion battery and preparation method thereof |
| CN111129397A (en) * | 2019-12-18 | 2020-05-08 | 中国科学院广州能源研究所 | Lithium ion battery diaphragm water-based coating and preparation method thereof |
| CN111224049A (en) * | 2020-01-14 | 2020-06-02 | 江苏厚生新能源科技有限公司 | Flame-retardant lithium battery coating diaphragm and preparation method thereof |
| CN111584805A (en) * | 2020-05-09 | 2020-08-25 | 中国科学院兰州化学物理研究所 | Preparation method of water-based clay mineral/polyvinyl alcohol crosslinked nano coating composite diaphragm |
| CN112739971A (en) * | 2020-06-05 | 2021-04-30 | 广州理文科技有限公司 | Device and method for drying lithium battery electrolyte assisted by ultrasonic waves |
| CN111725466A (en) * | 2020-06-12 | 2020-09-29 | 东北师范大学 | A kind of functionalized polyolefin composite membrane and its preparation method and application |
| CN111725466B (en) * | 2020-06-12 | 2022-02-01 | 东北师范大学 | Functionalized polyolefin composite diaphragm and preparation method and application thereof |
| CN113013551A (en) * | 2021-01-28 | 2021-06-22 | 清华大学 | Water-based nano composite modified material for lithium battery diaphragm, preparation method of water-based nano composite modified material and light-weight lithium battery diaphragm |
| CN113013551B (en) * | 2021-01-28 | 2021-11-23 | 清华大学 | Water-based nano composite modified material for lithium battery diaphragm, preparation method of water-based nano composite modified material and light-weight lithium battery diaphragm |
| CN113161683A (en) * | 2021-02-23 | 2021-07-23 | 中国地质大学（武汉） | Lithium ion battery diaphragm based on mineral modification and preparation method and application thereof |
| CN113013547A (en) * | 2021-02-26 | 2021-06-22 | 武汉理工大学 | Lithium battery composite diaphragm and preparation method thereof |
| CN113013548A (en) * | 2021-02-26 | 2021-06-22 | 武汉理工大学 | Montmorillonite modified lithium battery diaphragm and preparation method thereof |
| CN113346095A (en) * | 2021-05-17 | 2021-09-03 | 上海超碳石墨烯产业技术有限公司 | Button cell with high temperature resistant system |
| CN113328207A (en) * | 2021-06-02 | 2021-08-31 | 电子科技大学 | Lithium ion battery composite diaphragm and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109786627A (en) | A kind of preparation method of super-electrophilic lithium battery separator | |
| CN107799699B (en) | A kind of clay mineral composite lithium battery separator and preparation method thereof | |
| Cao et al. | Integrated fast assembly of free-standing lithium titanate/carbon nanotube/cellulose nanofiber hybrid network film as flexible paper-electrode for lithium-ion batteries | |
| Zhang et al. | A high-performance supercapacitor based on a polythiophene/multiwalled carbon nanotube composite by electropolymerization in an ionic liquid microemulsion | |
| CN101781459B (en) | Graphene/polyaniline conductive composite material and preparation method thereof | |
| Chen et al. | Facilitated charge transport in ternary interconnected electrodes for flexible supercapacitors with excellent power characteristics | |
| CN105226254B (en) | A kind of silicon nanoparticle graphite nano plate carbon fibre composite and preparation method and application | |
| CN109309203A (en) | Nano carbon particle-stephanoporate framework composite material, its lithium metal compound, their preparation method and application | |
| Chen et al. | Preparation of polyaniline onto dl-tartaric acid assembled MXene surface as an electrode material for supercapacitors | |
| CN105895193A (en) | Silver conductive coating material of lithium ion battery, preparation method of silver conductive coating material and lithium ion battery | |
| CN104409709B (en) | A kind of lithium ion battery negative material, preparation method and lithium ion battery | |
| CN105489898A (en) | Conductive waterborne binder and preparation method therefor, and lithium ion battery | |
| CN106784714A (en) | A kind of silicon-based composite anode material for Li-ion battery and preparation method thereof | |
| CN108565406A (en) | A kind of preparation method of lithium ion battery composite material and its combination electrode | |
| CN106169379B (en) | A method of preparing graphite paper/carbon nanotube-graphene/polyaniline flexible compound electrode | |
| CN109768205A (en) | A kind of preparation method of super-hydrophobic/super-electrophilic lithium battery separator | |
| CN103840164A (en) | Method for using carbon nano conductive agent in lithium ion battery aqueous slurry | |
| CN106571454A (en) | Reticular silicon/graphite composite material of lithium battery and preparation method thereof | |
| Yao et al. | Supramolecular‐mediated ball‐in‐ball porous carbon nanospheres for ultrafast energy storage | |
| CN104617280A (en) | Adhesive-free graphene/silicon electrode for lithium ion battery and preparation method thereof | |
| Zhao et al. | Zn@ cellulose nanofibrils composite three-dimensional carbon framework for long-life Zn anode | |
| CN101935452A (en) | Preparation method of sulfonated carbon nanotube-loaded polyaniline nanorod supercapacitor electrode material | |
| Zeng et al. | Hierarchical 3D micro‐nanostructures based on in situ deposited bimetallic metal‐organic structures on carbon fabric for supercapacitor applications | |
| CN108047806A (en) | A kind of graphene/Ag- carbon microspheres aeroge coating and its preparation method and application | |
| CN109428062A (en) | A kind of graphene-silicon composite cathode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190521 |
|
| RJ01 | Rejection of invention patent application after publication |