CN103985910A - Method for preparing all-solid-state electrolyte of lithium sulfur battery - Google Patents
Method for preparing all-solid-state electrolyte of lithium sulfur battery Download PDFInfo
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- CN103985910A CN103985910A CN201410208769.2A CN201410208769A CN103985910A CN 103985910 A CN103985910 A CN 103985910A CN 201410208769 A CN201410208769 A CN 201410208769A CN 103985910 A CN103985910 A CN 103985910A
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- butyric acid
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- diatomite
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 62
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 34
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims abstract description 131
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims abstract description 131
- 229910001386 lithium phosphate Inorganic materials 0.000 claims abstract description 131
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims abstract description 130
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000002904 solvent Substances 0.000 claims abstract description 56
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000007598 dipping method Methods 0.000 claims abstract description 40
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 238000001704 evaporation Methods 0.000 claims abstract description 16
- 230000008020 evaporation Effects 0.000 claims abstract description 15
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical class [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims description 144
- 238000006243 chemical reaction Methods 0.000 claims description 134
- GFLFKGYNEFFWTR-UHFFFAOYSA-N lithium;2-(methylamino)butanoic acid Chemical compound [Li].CCC(NC)C(O)=O GFLFKGYNEFFWTR-UHFFFAOYSA-N 0.000 claims description 130
- 239000007787 solid Substances 0.000 claims description 57
- -1 polypropylene Polymers 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000012545 processing Methods 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 33
- 229920005989 resin Polymers 0.000 claims description 33
- 239000004743 Polypropylene Substances 0.000 claims description 32
- 229920001155 polypropylene Polymers 0.000 claims description 32
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 25
- 239000013078 crystal Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000009413 insulation Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 229920000297 Rayon Polymers 0.000 claims description 20
- 239000003292 glue Substances 0.000 claims description 20
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 15
- 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 claims description 14
- 238000010992 reflux Methods 0.000 claims description 12
- 238000002242 deionisation method Methods 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 11
- 230000000630 rising effect Effects 0.000 claims description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 239000013590 bulk material Substances 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 20
- 229920001021 polysulfide Polymers 0.000 abstract description 6
- 239000005077 polysulfide Substances 0.000 abstract description 6
- 150000008117 polysulfides Polymers 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006073 displacement reaction Methods 0.000 abstract 1
- 230000037427 ion transport Effects 0.000 abstract 1
- YGLBXEHGQGOHPL-UHFFFAOYSA-M lithium;2-(methylamino)butanoate Chemical compound [Li+].CCC(NC)C([O-])=O YGLBXEHGQGOHPL-UHFFFAOYSA-M 0.000 abstract 1
- 229920006350 polyacrylonitrile resin Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 46
- 229920000642 polymer Polymers 0.000 description 27
- 239000007784 solid electrolyte Substances 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 10
- 238000010494 dissociation reaction Methods 0.000 description 10
- 230000005593 dissociations Effects 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 9
- 239000005864 Sulphur Substances 0.000 description 8
- 229910003002 lithium salt Inorganic materials 0.000 description 8
- 159000000002 lithium salts Chemical class 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000033001 locomotion Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 3
- 230000003252 repetitive effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229920001427 mPEG Polymers 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical compound OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 230000007646 directional migration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 230000019086 sulfide ion homeostasis Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- 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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a method for preparing all-solid-state electrolyte of a lithium sulfur battery. The method comprises the following steps: adding polyacrylonitrile resin micro powder and diatomite into a high-speed mixing stirrer according to a mass ratio of (46-56) to (54-66), adding an NMP solvent which accounts for 18-24 weight percent of diatomite, uniformly mixing to obtain viscous paste, and preparing a block material in a corresponding shape according to needs; allowing the block viscous paste to form block diatomite which only contains carbon in a high-temperature furnace subjected to nitrogen displacement; and dipping the block diatomite in a 18-33 weight percent of NMP solution containing lithium polysulfide, lithium methylaminobutyrate, lithium perchlorate and lithium phosphate for 13-18 minutes, and performing repeated dipping and high-temperature evaporation in the high-temperature furnace to obtain the all-solid-state electrolyte of the lithium sulfur battery. The preparation method is simple and is low in cost, the prepared all-solid-state electrolyte of the lithium sulfur battery has high sulfur containing capacity, high ion transport capacity and high conductive performance, and the high rate performance and high cycle performance of the lithium sulfur battery can be improved.
Description
Affiliated field
The present invention relates to a kind of lithium-sulfur cell all solid state electrolyte and preparation method thereof, belong to new energy materials field.
Background technology
Along with the development of human society, the becoming increasingly conspicuous of the problems such as energy shortage, environmental pollution, people are to the understanding of chemical power source and require also more and more highlyer, and impelling people constantly to explore new chemical power source is main energy storage system.In recent decades, take lithium metal has led the developing direction of high-performance chemical power supply as basic battery.Along with the successful commercialization of lithium ion battery, countries in the world are all in the research that steps up to carry out vehicle lithium-ion power battery.But due to factors such as energy density, fail safe, prices, conventional lithium ion battery lithium as sour in cobalt, LiMn2O4 and ferric phosphate lithium cell cannot meet the requirement of electric automobile as power source.
Lithium-sulfur cell is the high-energy density secondary battery that has development potentiality and application prospect.It has height
Beyond specific capacity and high-energy-density, sulphur is showing incomparable advantage as positive active material aspect source, cost and environmental friendliness, and at present, lithium-sulfur cell exists the problems such as cycle performance is poor, the further raising of high rate performance needs.And two main problems that lithium-sulfur cell exists are active material sulfur materials itself and final discharging product Li on the one hand
2s is the insulator of industrial one-level and ion; On the other hand, the intermediate product polysulfide in discharge process is soluble in electrolyte, and these can cause irreversible loss and the capacity attenuation of active material.For this reason, how to suppress the diffusion of polysulfide, the conductivity improving in the anodal cyclic process of sulphur is the research emphasis of sulfenyl all solid state electrolyte.
Academia mainly spread and improved two aspects of all solid state electrolyte conductivity around inhibition polysulfide and conducted a research in recent years.On material structure, first consider it is that elemental sulfur is adsorbed on porous material skeleton, such as by porous charcoal as the material with carbon elements such as active carbon, carbon nano-tube, Graphene and sulphur compound, prevent that the polysulfide that course of reaction is produced is dissolved in electrolyte, by electrolyte, spread, contribute to like this to reduce shuttle back and forth effect and self-discharge phenomenon.These new material structures have more or less improved the cyclical stability of electrode.But the general specific area of traditional porous carbon material is less, aperture size is single, structural integrity is poor, aperture is difficult to regulation and control, the adsorption activity material sulphur of material is limited in one's ability, causes that sulfur content in the compound all solid state electrolyte of preparation is lower, skewness, poor electric conductivity, be assembled into circulating battery after a few, still have a large amount of active materials from carbon structure duct, to dissolve, cause the loss of active material, lithium-sulfur cell energy density is difficult to further improve.
This area is in the urgent need to developing a kind of lithium-sulfur cell all solid state electrolyte that has good conductivity and hierarchical pore structure concurrently, suppress the diffusion of polysulfide, the conductivity in the anodal cyclic process of raising sulphur, and then ion transfer ability and the conductivity of raising all solid state electrolyte, can effectively reduce and discharge and recharge polarization, reduce the internal resistance of cell, improve the greatly doubly forthright of lithium-sulfur cell.
Most macromolecular compound is electrical insulator in addition, but certainly report certain macromolecular material, for example poly(ethylene oxide) (PEO) with such as the such electrolytic salt of lithium salts, formed crystalline complex compound and since showing high ionic conductivity, using PEO or other polyalkylene oxide, also have and in molecule, there are equally the polymine of ionic dissociation base or polyphosphazene etc. and just attract much attention as the research of the polymer solid electrolyte of matrix.Particularly reported and manyly usingd polyalkylene oxide as the research of the polymer solid electrolyte of the composition of matrix, recently, the ionic conduction degree of near room temperature is modified to 10
-4～10
-6s/cm.But, in order to obtain high ion-conductivity, just need to improve the content of the polyalkylene oxide in matrix, this reduces electrolyte thin film strength or thermal endurance on the contrary significantly, thereby the solid electrolyte that obtains practicality is difficult, if had again at low temperature, for example, below 0 ℃, it is also that problem is as polymer solid electrolyte that ionic conductivity reduces terrifically, proposed to using to make the ABA type triblock copolymer of methoxy poly (ethylene glycol) monomethacrylates (A) and styrene (B) copolymerization as the polymer solid electrolyte of matrix base material by active anionic polymerization, but, homopolymers as the methoxy poly (ethylene glycol) monomethacrylates of composition six, although be high molecular weight material, but be aqueous in room temperature, in order to using the matrix base material of A-B-A type copolymer as solid electrolyte, so the content of composition A is restricted, this means as the shape and size of the PEO regional structure in the diffusion transport space of lithium ion restricted, ionic conductivity in the time of actual 40 ℃ is many does not meet 10
-6s/cm.
From the conductive mechanism of polymer solid electrolyte, forming phase, and lithium in polymer melting point 60 ℃ below the SPE is usually composed of polymer crystal amorphous compound and a solvent salt polymer amorphous phase electric conduction mechanism research shows that under the action of the electric field of ion mobility mainly occurs in the amorphous region and the polymer short-range chain segment movement helps promote between polymer and Li+ coordination bond destruction and formation provides free volume for the migration of Li+ thus reducing crystallinity and glass transition temperature of polymer (Tg) increase the polymer chain flexibility and increase the free volume density are helpful to get high conductivity SPE without and the polymer complex anion is generally considered the vacancy migration and conducting on the other hand, the low dielectric constant of the polymer to make ion and ion exists between the strong interaction results in SPE in addition to the free anion and solvent cation is solvated ions on the tight ion pair three ion aggregates and other ionic aggregates which determines the carrier concentration and mobility is also conducting ability is an important factor affecting SPE.But, among the solid electrolyte film being formed by polymer and lithium salts, according to the electrical conduction mechanism of lithium salts, under certain voltage, make lithium salts be dissociated into zwitterion, these zwitterions are under the effect of voltage, there is directional migration, but, because polymer plays supporting role in solid electrolyte, simultaneously, be subject to the restriction of the structure of polymer, if this polymer is crystal structure, the zwitterion that can make lithium salts dissociation form hinders the motion of these zwitterions under the effect of voltage, therefore, capacity for the battery that improves the electric conduction quantity of solid electrolyte and manufactured by this electrolyte, on the one hand, needing polymer is unbodied form, on the other hand, need lithium salts to there is good dissociating power, for this reason, study the target that a kind of high-effect electrolysis matter is each researcher.
In Chinese patent application: introduced a kind of so that the polymer solid electrolyte that thermal characteristics, physical characteristic and ionic conduction degree are good, approach realistic scale to be provided in 03817326.3, total solids electrolyte particularly, and the copolymer compositions becoming for the manufacture of this electrolytical matrix is object.This polymer solid electrolyte contains copolymer and electrolytic salt, has the block chain A of the repetitive representing with formula (I) in this copolymer, have with formula (II) (in formula, R
9represent aryl) the block chain B of the repetitive that represents and have with formula (III) (in formula, R
13representing aryl or heteroaryl) the block chain C of the repetitive that represents arranges with the order of B, A, C.This polymer solid electrolyte is also the synthetic needed amorphous polymer of a kind of solid electrolyte of method that adopts block polymerization, compare with other polymer, this solid electrolyte fully utilizes the cyberspace structure of polymer, thereby obtain conducting electrolyte and the battery capacity of corresponding effect, but the side chain of polymer too much can hinder the motion after electrolyte dissociation again.
At Chinese Patent Application No. code 96197348.X, a kind of NEW TYPE OF COMPOSITE polyelectrolyte of being made by the closed pore porous polymer foaming body that has flooded nonaqueous electrolytic solution is disclosed, it comprises a plurality of closed pores that limited by hole wall, hole wall has formed the continuous solid phase parent with nonaqueous electrolytic solution dipping, form continuous solid phase microcell, wherein a plurality of closed pores have been filled nonaqueous electrolytic solution substantially to form a plurality of liquid phase micro-areas, and they are dispersed in above-mentioned continuous solid phase microcell.This invention composite polymer electrolyte not only has very high ionic conductance string and very high mechanical strength, and can prevent that nonaqueous electrolytic solution from leaking, so the electrolyte of this invention can be advantageously used in various non-aqueous electrochemical devices.That is to say, the non-aqueous electrochemical device that comprises composite polymer electrolyte of the present invention not only has good electrochemistry, and can maintain electrolyte wherein, and for this reason, this invention exists significantly not enough in manufacturing process.
In Chinese patent number No:02125137.1, introduced a kind of employing at the surface-coated layer of surface passivating material of sulfur-containing compound lithium-sulfur cell all solid state electrolyte, its objective is the loss that reduces sulfur-containing compound sulphur in charge and discharge process, but because coated surface passivation layer is carbonate or the hydroxyl carbonate of the chemical elements such as some Mg, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, can cause the conductivity of this electrode material to reduce.
In Chinese patent number No:1143369.8, introduce a kind of all solid state electrolyte that adopts several raw material such as sulfur-containing compound and conductive agent and adhesive to prepare lithium-sulfur cell, because conductive agent is the moulding material of metal material, the impact of adhesive, makes the conductivity of its lithium-sulfur cell all solid state electrolyte can be subject to corresponding impact simultaneously.
In Chinese Patent Application No. code No:201310418375.5, introduced a kind of manufacturing process of inorganic electrolyte, wherein apply diatomite and be used as a kind of electrolytical backing material, wherein adopt polysiloxanes organic siliconresin, with the diatomite material that preparation can adsorbing electrolyte material of coming together, but, owing to can be subject to the impact of polyorganosiloxane resin strand in preparing the process of carborundum, can cause its voidage to decline.
Above shortcoming in view of prior art, the object of the invention is to overcome the deficiency of current solid electrolyte, adopt many lithium sulfides of charge-discharge performance excellence, in order to improve the dispersiveness of lithium salts in diatomite, and then capacitance and the charge-discharge velocity of raising solid electrolyte, adopt this polymer of the fine resin of polypropylene to prepare conductive carrier simultaneously, reduce the mobile obstruction under the effect of voltage of lithium ion and anion after lithium salts dissociation, thereby improve the conductance of this solid electrolyte and by this electrolyte, made the capacity of battery.
Summary of the invention
The present invention is directed to the compound all solid state electrolyte obtaining of porous charcoal of the prior art and sulphur because existing adsorption activity material sulphur problem limited in one's ability, poor electric conductivity that its application in battery is limited to, object is to be to provide a kind of high rate capability of lithium-sulfur cell and the lithium-sulfur cell all solid state electrolyte of high cycle performance.
The object of the invention is to realize by following means.
A kind of manufacture method of lithium-sulfur cell all solid state electrolyte, it is characterized in that, by the fine resin micropowder of polypropylene and diatomite with mass ratio 46～56:54～44, add in mixed at high speed blender, add again the diatomaceous nmp solvent of 18～24%wt/, under well-beaten condition, be uniformly mixed into viscosity viscose glue mud, then by viscose glue mud according to the bulk material that need to be made into respective shapes of lithium-sulfur cell all solid state electrolyte, bulk material is placed in to the high temperature furnace through nitrogen replacement, under the condition of suitable extracting vacuum, make block viscose glue mud become the block diatomite that only contains carbon composition, then by many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate is dissolved in nmp solvent with the mass ratio of 58～66:33～18:6～8:3～8, form containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, the nmp solution of 18～33%wt of lithium phosphate, then the block diatomite after high-temperature process is immersed and contains many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, in the nmp solution of lithium phosphate, dipping 13～18min, after taking-up, to contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, the block diatomite of lithium phosphate and nmp solvent is placed in another high temperature furnace through nitrogen replacement, under the condition of suitable extracting vacuum, nmp solvent in block diatomite is fully evaporated, the dipping of 6～8 times and high temperature evaporation go out NMP so repeatedly, make to contain in block diatomite many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, the lithium-sulfur cell all solid state electrolyte of lithium phosphate 18～21%wt.
Its concrete manufacturing process is as follows:
1) in the 316L of 1L stainless steel cauldron, constantly passing under the protection of 360～390ml/min nitrogen, add 3.3～4.8mol industry one-level NMP, 1.0mol industry one-level vulcanized sodium and 0.003mol industry one sodium hydroxide, under 360～390rpm stirring condition, slowly the temperature of reaction system is elevated to 108～118 ℃, then add 1.003mol industry top grade lithium chloride, continue temperature to 160～190 ℃ of rising reaction system, and under this temperature conditions, make reaction system insulation 18～33min, until while having tiny white crystal to separate out in reaction system, water evaporates in reaction system is removed simultaneously, and stop heating,
2) by 1) the anhydrous response system that obtains is under the protection of nitrogen, filter while hot, white crystal in reaction system is filtered out, filtrate rejoins reaction system, the stirring intensity of reactor is 360～390rpm, add sublimed sulfur and deionization anaerobic water in formula, treat that temperature rises to 108～118 ℃, and the insulation 4～6h that refluxes under this temperature conditions, until in reaction system during without sublimed sulfur powder, stop reaction system heating, the temperature of reaction system is dropped to room temperature slowly simultaneously, now, in reaction system, separate out a small amount of light yellow or white pressed powder,
3) by 2) the light yellow or white solid powder of separating out filters out from reaction system, measure the mass concentration of many lithium sulfides, then according to recipe ratio, add methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, and temperature is heated to 108～118 ℃, under this temperature conditions, be incubated 33～66min, then, be cooled to room temperature stand-by; Thereby obtain the nmp solution containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate;
4), by the fine resin micropowder powder of polypropylene and diatomite in formula, add again the diatomaceous nmp solvent of 18～24%wt/, under well-beaten condition, be uniformly mixed into viscose glue mud, after homogenizer fully mixes, be pressed into the thick thin slice of 180～660 μ m;
5), by 4) to insert temperature be in the high temperature furnace of 240～260 ℃ for the thin slice of gained, suitably extracting under the condition of the vacuum that negative pressure is 0.078～0.084Mpa, after processing time is 48～68min, again thin slice is inserted in the high temperature furnace of 1280～1390 ℃, under the condition that is 0.098～0.0999Mpa in negative pressure, process 166～188min, in the normal temperature air chamber of anhydrous steam, be cooled to normal temperature; To deviate from hydrogen, the oxygen atom on the fine molecular resin chain of polypropylene; Making porosity is 66～88%, and aperture is the diatomite thin slice that 3～5um structure contains carbon;
6), by 5) thin slice that obtains inserts 3) containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, in the nmp solution of lithium phosphate 28～33%wt, through flooding after 33～38min taking-up, to contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, being placed in temperature with the block diatomite of nmp solvent is the high temperature furnace of 220～240 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.068～0.088Mpa, after processing time is 36～48min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtain flooding for the first time many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, the diatomite thin slice of lithium phosphate,
7) by 6) thin slice that obtains insert again contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, nmp solution in, dipping 18～33min, insert again temperature and be in the high temperature furnace of 260～266 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.088～0.091Mpa, after processing time is 33～36min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the second time the diatomite thin slice of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate;
8) by 7) thin slice that obtains adopts 7) process conditions in step, through dipping and the high temperature evaporation of 6～8 times repeatedly, go out NMP, make the lithium-sulfur cell all solid state electrolyte that contains many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 18～21%wt in block diatomite; Wherein the thickness of all solid state electrolyte thin slice is 0.1～1.0mm
Technical characterstic of the present invention:
1, first the present invention utilizes the industrial top grade lithium chloride that can be dissolved in nmp solvent, its normal-temperature dissolution degree in nmp solvent can be up to 26g/100mlNMP, in order to improve the solubility of industrial top grade lithium chloride, need to carry out heat temperature raising to a certain degree to solution system, in addition, because NMP is under heating condition, can be because contacting and make it to occur oxidation reaction yellowing with air, and then the purity of reduction NMP, therefore, need to synthetic dicyandiamide solution, protect with inert gas (as: nitrogen), in order to avoid cause the generation of other side reactions, thereby reduce the purity of lithium sulfide and/or many lithium sulfides.
2, secondly the present invention utilizes very common industrial one-level vulcanized sodium industrial raw materials, although these raw material are also insoluble to nmp solvent under the condition of normal temperature and heat temperature raising, but, under the condition that has anaerobic water to exist, by adding an industrial sodium hydroxide to react with it, generation contains impurity level industrial one-level vulcanized sodium seldom, and then after heating by intensification, by industrial one-level vulcanized sodium and industrial top grade lithium chloride, there is therein ionic reaction, simultaneously, evaporating under the condition of anaerobic water wherein, synthetic lithium sulfide, because the solubility of sodium chloride in the nmp solvent of 150～360 ℃ only has 5mg/100mlNMP, solubility at normal temperature is also low-down, and lithium sulfide is dissolved in nmp solvent, for this reason, the present invention makes full use of this specific character of the easy NMP of lithium sulfide, comparatively be easy to obtain lithium sulfide, its objective is because lithium sulfide is easy to oxidized decomposition in air, discharge hydrogen sulfide poison gas, the object that adopts technological process of the present invention is that the lithium sulfide that can avoid on the one hand synthetic is not oxidized, in order to obtain highly purified anhydrous lithium sulfide on the one hand in addition.
3, the present invention is oxidized in the deionized water of aerobic for fear of lithium sulfide, therefore, make full use of utilizable condition, be exactly deionized water can be passed through to physics or/and the mode of chemistry, dissolved oxygen in deionized water is dropped to very low degree, remove even completely, not oxidized to guarantee lithium sulfide, and then improve many lithium sulfides and methylamino butyric acid lithium and lithium perchlorate and lithium phosphate with a certain proportion of purity.
4, the present invention is in order to synthesize the required many lithium sulfides of lithium-sulfur cell and methylamino butyric acid lithium and lithium perchlorate and lithium phosphate with a certain proportion of raw material.Because elemental sulfur is soluble among ethanol, according to the principles of chemistry of similar compatibility, elemental sulfur and lithium sulfide all can be soluble among nmp solvent, still, due to the difference of solubility, can make aggregate velocity be affected, in order to improve aggregate velocity, the present invention makes full use of the light water solvent that can make lithium sulfide generation electrolysis, and will make like this aggregate velocity is that solvent has improved nearly 2 times with ethanol or ammoniacal liquor, simultaneously, nearly reduce costs 40%, be more conducive to realize suitability for industrialized production.
5, the present invention is in order to make full use of reflux solvent and aqueous systems, is in order to guarantee temperature stable of synthetic system, to improve raw-material utilance, and then provides many lithium sulfides and methylamino butyric acid lithium and lithium perchlorate and lithium phosphate with a certain proportion of productive rate.
6, to adopt diatomaceous object be to make full use of diatomaceous open structure in the present invention, also utilizes the diatomite can sinter molding simultaneously, can make diatomite sinter the material of various shapes into, is conducive to be made into the required electrode material of lithium-sulfur cell.
7, the present invention is in order to increase electrolytical conductivity, make full use of the characteristic that the fine resin micropowder of polypropylene is dissolved in organic solvent, dissolving by organic solvent makes the fine resin micropowder of polypropylene fully mix with diatomite, being conducive to make the fine resin micropowder of polypropylene to be transformed into carbonaceous conductive material after forming processes subsequently merges with the diatom soil phase better, and carbon be uniformly distributed better with diatomite among, be conducive to lithium-sulfur cell all solid state electrolyte conductivity more stable, in strand due to the fine resin of polypropylene, contain phenyl simultaneously, this phenyl is after carbonization treatment, in the structure of its strand, can form the carbocyclic ring of a fixed ring assembling structure, be conducive to many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, the absorption of lithium phosphate molecule, thereby obtain good capacitance and charge-discharge performance.
8, the present invention adopts many lithium sulfides that can be dissolved in nmp solvent, methylamino butyric acid lithium, lithium perchlorate, the object of lithium phosphate compound, to make to have the many lithium sulfides of the better adsorption and permeation of very microporous carbon containing diatomite material, methylamino butyric acid lithium, lithium perchlorate, the nmp solution of lithium phosphate, thereby make carbonaceous conductive material and many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate organically combines better, this is conducive to many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, the dissociation of lithium phosphate in charge and discharge process and dissociating, simultaneously, because diatomaceous micropore is when improving lithium-sulfur cell all solid state electrolyte conductivity, also prevent many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, the excessive dissociation of lithium phosphate, be conducive to lithium-sulfur cell charge and discharge cycles, with prevent lithium-sulfur cell that discharge and recharge with decay number of times, to extend the useful life of lithium-sulfur cell, the present invention adopts the polypropylene of complete straight chain fine in addition, its objective is and utilizes this resin to hold very much with carbonization, because the fine resin of polypropylene is the original material of carbon fiber, thereby is not subject to the impact of molecular chain structure and causes its porosity to decline.
9, the raw material that the present invention adopts are its object of technical grade and utilize its raw-material impurity level, are conducive to improve electrolytical electric conductivity.Its reason be due to the raw material at these technical grades more or less contain some metals or nonmetallic compound, some compounds are under uniform temperature condition, stable, when but these compounds are subject to exciting of electron stream, can make it dissociation occurs and conduct electricity, because ion can further excite the electrolyte dissociation that dissociation does not occur of the present invention under the effect of electric field, and then improve the electrolytical degree of dissociation and electrolytical capacitance.
Technological process brief introduction of the present invention
A kind of manufacture method of lithium-sulfur cell all solid state electrolyte, it is characterized in that, the fine resin micropowder of polypropylene and diatomite are added in mixed at high speed blender with certain mass ratio, add again a certain proportion of nmp solvent, under well-beaten condition, be uniformly mixed into the viscose glue mud of certain viscosity, then by viscose glue mud according to the bulk material that need to be made into respective shapes of lithium-sulfur cell all solid state electrolyte, bulk material is placed in to the high temperature furnace through nitrogen replacement, under the condition of suitable extracting vacuum, make block viscose glue mud become the block diatomite that only contains carbon composition, then by many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate is dissolved in nmp solvent with certain proportion, forms containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, the certain density industrial one-level nmp solution of lithium phosphate, then immerses the block diatomite after high-temperature process to contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, in the nmp solution of lithium phosphate, dipping certain hour, after taking-up, will contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, the block diatomite of lithium phosphate and nmp solvent is placed in another high temperature furnace through nitrogen replacement, under the condition of suitable extracting vacuum, nmp solvent in block diatomite is fully evaporated, and dipping and high temperature evaporation several times goes out NMP so repeatedly, makes to contain in block diatomite many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, a certain amount of lithium-sulfur cell all solid state electrolyte of lithium phosphate.
Accompanying drawing explanation:
Fig. 1 is the electric property table of the obtained battery of the embodiment of the present invention.
Embodiment
Embodiment 1
1) in the 316L of 1L stainless steel cauldron, constantly passing under the protection of 360ml/min nitrogen, add 3.3mol industry one-level NMP, 1.0mol industry one-level vulcanized sodium and 0.003mol industry one sodium hydroxide, under 360rpm stirring condition, slowly the temperature of reaction system is elevated to 108 ℃, then add 1.003mol industry top grade lithium chloride, continue the temperature to 160 ℃ of rising reaction system, and under this temperature conditions, make reaction system insulation 33min, until while having tiny white crystal to separate out in reaction system, water evaporates in reaction system is removed simultaneously, and stop heating, and filter while hot, white crystal in reaction system is filtered out, and filtrate rejoins reaction system, and the stirring intensity of reactor is 360rpm, add sublimed sulfur and deionization anaerobic water in formula, treat that temperature rises to 108 ℃, and the insulation 6h that refluxes under this temperature conditions, until in reaction system during without sublimed sulfur powder, stop reaction system heating, the temperature of reaction system is dropped to room temperature slowly simultaneously, now, in reaction system, separate out a small amount of light yellow or white pressed powder, from reaction system, filter out the light yellow or white solid powder of separating out, measure the mass concentration of many lithium sulfides, then according to recipe ratio, add methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, and temperature is heated to 108 ℃, under this temperature conditions, be incubated 66min, then, be cooled to room temperature stand-by, thereby obtain the nmp solution containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, wherein many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate are dissolved in nmp solvent with the mass ratio of 58:33:6:3, form the nmp solution containing the 18%wt of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate.
The fine resin micropowder of polypropylene and diatomite is with mass ratio 46:54, then adds the diatomaceous nmp solvent of 18%wt/, under well-beaten condition, is uniformly mixed into viscose glue mud, after homogenizer fully mixes, is pressed into the thick thin slice of 180 μ m, it is in the high temperature furnace of 240 ℃ that thin slice is inserted to temperature, suitably extracting under the condition of the vacuum that negative pressure is 0.084Mpa, after processing time is 68min, again thin slice is inserted in the high temperature furnace of 1280 ℃, under the condition that is 0.0999Mpa in negative pressure, process 188min, in the normal temperature air chamber of anhydrous steam, be cooled to normal temperature, to deviate from hydrogen, the oxygen atom on the fine molecular resin chain of polypropylene, making porosity is 66%, and aperture is the diatomite thin slice that 3um structure contains carbon, thin slice is inserted containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, in the nmp solution of lithium phosphate 28%wt, after dipping 38min takes out, to contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, being placed in temperature with the block diatomite of nmp solvent is the high temperature furnace of 220 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.088Mpa, after processing time is 48min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtain flooding for the first time many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, the diatomite thin slice of lithium phosphate, and then insert contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, nmp solution in, dipping 33min, insert again temperature and be in the high temperature furnace of 260 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.091Mpa, after processing time is 36min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the second time the diatomite thin slice of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, through dipping and the high temperature evaporation of 6 times so repeatedly, go out NMP, the lithium-sulfur cell all solid state electrolyte that to make to contain in block diatomite many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 18%wt thickness be 0.1mm.
Embodiment 2
1) in the 316L of 1L stainless steel cauldron, constantly passing under the protection of 390ml/min nitrogen, add 4.8mol industry one-level NMP, 1.0mol industry one-level vulcanized sodium and 0.003mol industry one sodium hydroxide, under 390rpm stirring condition, slowly the temperature of reaction system is elevated to 118 ℃, then add 1.003mol industry top grade lithium chloride, continue the temperature to 190 ℃ of rising reaction system, and under this temperature conditions, make reaction system insulation 18min, until while having tiny white crystal to separate out in reaction system, water evaporates in reaction system is removed simultaneously, and stop heating, and filter while hot, white crystal in reaction system is filtered out, and filtrate rejoins reaction system, and the stirring intensity of reactor is 390rpm, add sublimed sulfur and deionization anaerobic water in formula, treat that temperature rises to 118 ℃, and the insulation 4h that refluxes under this temperature conditions, until in reaction system during without sublimed sulfur powder, stop reaction system heating, the temperature of reaction system is dropped to room temperature slowly simultaneously, now, in reaction system, separate out a small amount of light yellow or white pressed powder, from reaction system, filter out the light yellow or white solid powder of separating out, measure the mass concentration of many lithium sulfides, then according to recipe ratio, add methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, and temperature is heated to 118 ℃, under this temperature conditions, be incubated 33min, then, be cooled to room temperature stand-by, thereby obtain containing the nmp solution of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate wherein many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate with the mass ratio of 66:18:8:8, be dissolved in nmp solvent, form the nmp solution containing the 33%wt of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate.
The fine resin micropowder of polypropylene and diatomite is with mass ratio 56:44, then adds the diatomaceous nmp solvent of 24%wt/, under well-beaten condition, is uniformly mixed into viscose glue mud, after homogenizer fully mixes, is pressed into the thick thin slice of 660 μ m, it is in the high temperature furnace of 260 ℃ that thin slice is inserted to temperature, suitably extracting under the condition of the vacuum that negative pressure is 0.078Mpa, after processing time is 48min, again thin slice is inserted in the high temperature furnace of 1390 ℃, under the condition that is 0.098Mpa in negative pressure, process 166min, in the normal temperature air chamber of anhydrous steam, be cooled to normal temperature, to deviate from hydrogen, the oxygen atom on the fine molecular resin chain of polypropylene, making porosity is 88%, and aperture is the diatomite thin slice that 5um structure contains carbon, thin slice is inserted containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, in the nmp solution of lithium phosphate 33%wt, after dipping 33min takes out, to contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, being placed in temperature with the block diatomite of nmp solvent is the high temperature furnace of 240 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.068Mpa, after processing time is 36min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtain flooding for the first time many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, the diatomite thin slice of lithium phosphate, and then insert contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, nmp solution in, dipping 18min, insert again temperature and be in the high temperature furnace of 266 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.088Mpa, after processing time is 33min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the second time the diatomite thin slice of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, through such dipping and the high temperature evaporation of 8 times repeatedly, go out NMP, make the lithium-sulfur cell all solid state electrolyte that contains many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 21%wt in block diatomite, wherein the thickness of lithium-sulfur cell all solid state electrolyte thin slice is 0.664mm
Embodiment 3
1) in the 316L of 1L stainless steel cauldron, constantly passing under the protection of 370ml/min nitrogen, add 3.6mol industry one-level NMP, 1.0mol industry one-level vulcanized sodium and 0.003mol industry one sodium hydroxide, under 370rpm stirring condition, slowly the temperature of reaction system is elevated to 110 ℃, then add 1.003mol industry top grade lithium chloride, continue the temperature to 188 ℃ of rising reaction system, and under this temperature conditions, make reaction system insulation 21min, until while having tiny white crystal to separate out in reaction system, water evaporates in reaction system is removed simultaneously, and stop heating, and filter while hot, white crystal in reaction system is filtered out, and filtrate rejoins reaction system, and the stirring intensity of reactor is 370rpm, add sublimed sulfur and deionization anaerobic water in formula, treat that temperature rises to 112 ℃, and the insulation 5h that refluxes under this temperature conditions, until in reaction system during without sublimed sulfur powder, stop reaction system heating, the temperature of reaction system is dropped to room temperature slowly simultaneously, now, in reaction system, separate out a small amount of light yellow or white pressed powder, from reaction system, filter out the light yellow or white solid powder of separating out, measure the mass concentration of many lithium sulfides, then according to recipe ratio, add methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, and temperature is heated to 113 ℃, under this temperature conditions, be incubated 44min, then, be cooled to room temperature stand-by, thereby obtain containing the nmp solution of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate wherein many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate with the mass ratio of 60:30:7:3, be dissolved in nmp solvent, form the nmp solution containing 18～33%wt of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate.
The fine resin micropowder of polypropylene and diatomite is with mass ratio 48:52, then adds the diatomaceous nmp solvent of 19%wt/, under well-beaten condition, is uniformly mixed into viscose glue mud, after homogenizer fully mixes, is pressed into the thick thin slice of 210 μ m, it is in the high temperature furnace of 243 ℃ that thin slice is inserted to temperature, suitably extracting under the condition of the vacuum that negative pressure is 0.081Mpa, after processing time is 51min, again thin slice is inserted in the high temperature furnace of 1310 ℃, under the condition that is 0.0991Mpa in negative pressure, process 168min, in the normal temperature air chamber of anhydrous steam, be cooled to normal temperature, to deviate from hydrogen, the oxygen atom on the fine molecular resin chain of polypropylene, making porosity is 68%, and aperture is the diatomite thin slice that 4um structure contains carbon, thin slice is inserted containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, in the nmp solution of lithium phosphate 31%wt, after dipping 34min takes out, to contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, being placed in temperature with the block diatomite of nmp solvent is the high temperature furnace of 223 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.071Mpa, after processing time is 38min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtain flooding for the first time many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, the diatomite thin slice of lithium phosphate, and then insert contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, nmp solution in, dipping 21min, insert again temperature and be in the high temperature furnace of 261 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.089Mpa, after processing time is 34min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the second time the diatomite thin slice of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, through such dipping and the high temperature evaporation of 7 times repeatedly, go out NMP, make the lithium-sulfur cell all solid state electrolyte that contains many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 19%wt in block diatomite, wherein the thickness of lithium-sulfur cell all solid state electrolyte thin slice is 0.21mm
Embodiment 4
1) in the 316L of 1L stainless steel cauldron, constantly passing under the protection of 380ml/min nitrogen, add 3.9mol industry one-level NMP, 1.0mol industry one-level vulcanized sodium and 0.003mol industry one sodium hydroxide, under 380rpm stirring condition, slowly the temperature of reaction system is elevated to 114 ℃, then add 1.003mol industry top grade lithium chloride, continue the temperature to 178 ℃ of rising reaction system, and under this temperature conditions, make reaction system insulation 24min, until while having tiny white crystal to separate out in reaction system, water evaporates in reaction system is removed simultaneously, and stop heating, and filter while hot, white crystal in reaction system is filtered out, and filtrate rejoins reaction system, and the stirring intensity of reactor is 380rpm, add sublimed sulfur and deionization anaerobic water in formula, treat that temperature rises to 114 ℃, and the insulation 4.8h that refluxes under this temperature conditions, until in reaction system during without sublimed sulfur powder, stop reaction system heating, the temperature of reaction system is dropped to room temperature slowly simultaneously, now, in reaction system, separate out a small amount of light yellow or white pressed powder, from reaction system, filter out the light yellow or white solid powder of separating out, measure the mass concentration of many lithium sulfides, then according to recipe ratio, add methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, and temperature is heated to 113 ℃, under this temperature conditions, be incubated 49min, then, be cooled to room temperature stand-by, thereby obtain the nmp solution containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, wherein many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate are dissolved in nmp solvent with the mass ratio of 62:22:8:8, form the nmp solution containing the 21%wt of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate.
The fine resin micropowder of polypropylene and diatomite is with mass ratio 50:50, then adds the diatomaceous nmp solvent of 21%wt/, under well-beaten condition, is uniformly mixed into viscose glue mud, after homogenizer fully mixes, is pressed into the thick thin slice of 430 μ m, it is in the high temperature furnace of 253 ℃ that thin slice is inserted to temperature, suitably extracting under the condition of the vacuum that negative pressure is 0.082Mpa, after processing time is 59min, again thin slice is inserted in the high temperature furnace of 1364 ℃, under the condition that is 0.0994Mpa in negative pressure, process 171min, in the normal temperature air chamber of anhydrous steam, be cooled to normal temperature, to deviate from hydrogen, the oxygen atom on the fine molecular resin chain of polypropylene, making porosity is 74%, and aperture is the diatomite thin slice that 4.3um structure contains carbon, thin slice is inserted containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, in the nmp solution of lithium phosphate 30%wt, after dipping 36min takes out, to contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, being placed in temperature with the block diatomite of nmp solvent is the high temperature furnace of 234 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.075Mpa, after processing time is 41min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtain flooding for the first time many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, the diatomite thin slice of lithium phosphate, and then insert contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, nmp solution in, dipping 29min, insert again temperature and be in the high temperature furnace of 262 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.090Mpa, after processing time is 35min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the second time the diatomite thin slice of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, through such dipping and the high temperature evaporation of 6 times repeatedly, go out NMP, make the lithium-sulfur cell all solid state electrolyte that contains many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 20%wt in block diatomite, wherein the thickness of lithium-sulfur cell all solid state electrolyte thin slice is 0.430mm
Embodiment 5
1) in the 316L of 1L stainless steel cauldron, constantly passing under the protection of 381ml/min nitrogen, add 4.4mol industry one-level NMP, 1.0mol industry one-level vulcanized sodium and 0.003mol industry one sodium hydroxide, under 384rpm stirring condition, slowly the temperature of reaction system is elevated to 108～118 ℃, then add 1.003mol industry top grade lithium chloride, continue the temperature to 174 ℃ of rising reaction system, and under this temperature conditions, make reaction system insulation 26min, until while having tiny white crystal to separate out in reaction system, water evaporates in reaction system is removed simultaneously, and stop heating, and filter while hot, white crystal in reaction system is filtered out, and filtrate rejoins reaction system, and the stirring intensity of reactor is 384rpm, add sublimed sulfur and deionization anaerobic water in formula, treat that temperature rises to 116 ℃, and the insulation 5.1h that refluxes under this temperature conditions, until in reaction system during without sublimed sulfur powder, stop reaction system heating, the temperature of reaction system is dropped to room temperature slowly simultaneously, now, in reaction system, separate out a small amount of light yellow or white pressed powder, from reaction system, filter out the light yellow or white solid powder of separating out, measure the mass concentration of many lithium sulfides, then according to recipe ratio, add methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, and temperature is heated to 117 ℃, under this temperature conditions, be incubated 51min, then, be cooled to room temperature stand-by, thereby obtain the nmp solution containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, wherein many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate are dissolved in nmp solvent with the mass ratio of 64:24:6:6, form the nmp solution containing the 26%wt of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate.
The fine resin micropowder of polypropylene and diatomite is with mass ratio 52:48, then adds the diatomaceous nmp solvent of 23%wt/, under well-beaten condition, is uniformly mixed into viscose glue mud, after homogenizer fully mixes, is pressed into the thick thin slice of 540 μ m, it is in the high temperature furnace of 254 ℃ that thin slice is inserted to temperature, suitably extracting under the condition of the vacuum that negative pressure is 0.083Mpa, after processing time is 61min, again thin slice is inserted in the high temperature furnace of 1384 ℃, under the condition that is 0.0996Mpa in negative pressure, process 184min, in the normal temperature air chamber of anhydrous steam, be cooled to normal temperature, to deviate from hydrogen, the oxygen atom on the fine molecular resin chain of polypropylene, making porosity is 81%, and aperture is the diatomite thin slice that 4.3um structure contains carbon, thin slice is inserted containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, in the nmp solution of lithium phosphate 32%wt, after dipping 34min takes out, to contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, being placed in temperature with the block diatomite of nmp solvent is the high temperature furnace of 237 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.086Mpa, after processing time is 44min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtain flooding for the first time many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, the diatomite thin slice of lithium phosphate, and then insert contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, nmp solution in, dipping 29min, insert again temperature and be in the high temperature furnace of 264 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.089Mpa, after processing time is 34min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the second time the diatomite thin slice of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, through such dipping and the high temperature evaporation of 8 times repeatedly, go out NMP, make the lithium-sulfur cell all solid state electrolyte that contains many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 19.0%wt in block diatomite, wherein the thickness of lithium-sulfur cell all solid state electrolyte thin slice is 0.54mm
Embodiment 6
1) in the 316L of 1L stainless steel cauldron, constantly passing under the protection of 386ml/min nitrogen, add 4.6mol industry one-level NMP, 1.0mol industry one-level vulcanized sodium and 0.003mol industry one sodium hydroxide, under 374rpm stirring condition, slowly the temperature of reaction system is elevated to 117 ℃, then add 1.003mol industry top grade lithium chloride, continue the temperature to 183 ℃ of rising reaction system, and under this temperature conditions, make reaction system insulation 32min, until while having tiny white crystal to separate out in reaction system, water evaporates in reaction system is removed simultaneously, and stop heating, and filter while hot, white crystal in reaction system is filtered out, and filtrate rejoins reaction system, and the stirring intensity of reactor is 374rpm, add sublimed sulfur and deionization anaerobic water in formula, treat that temperature rises to 115 ℃, and the insulation 5.8h that refluxes under this temperature conditions, until in reaction system during without sublimed sulfur powder, stop reaction system heating, the temperature of reaction system is dropped to room temperature slowly simultaneously, now, in reaction system, separate out a small amount of light yellow or white pressed powder, from reaction system, filter out the light yellow or white solid powder of separating out, measure the mass concentration of many lithium sulfides, then according to recipe ratio, add methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, and temperature is heated to 115 ℃, under this temperature conditions, be incubated 63min, then, be cooled to room temperature stand-by, thereby obtain the nmp solution containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, wherein many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate are dissolved in nmp solvent with the mass ratio of 66:18:8:8, form the nmp solution containing the 28%wt of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate.
The fine resin micropowder of polypropylene and diatomite is with mass ratio 54:46, then adds the diatomaceous nmp solvent of 22%wt/, under well-beaten condition, is uniformly mixed into viscose glue mud, after homogenizer fully mixes, is pressed into the thick thin slice of 380 μ m, it is in the high temperature furnace of 246 ℃ that thin slice is inserted to temperature, suitably extracting under the condition of the vacuum that negative pressure is 0.083Mpa, after processing time is 66min, again thin slice is inserted in the high temperature furnace of 1386 ℃, under the condition that is 0.0994Mpa in negative pressure, process 188min, in the normal temperature air chamber of anhydrous steam, be cooled to normal temperature, to deviate from hydrogen, the oxygen atom on the fine molecular resin chain of polypropylene, making porosity is 86%, and aperture is the diatomite thin slice that 4.8um structure contains carbon, thin slice is inserted containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, in the nmp solution of lithium phosphate 32%wt, after dipping 37min takes out, to contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, being placed in temperature with the block diatomite of nmp solvent is the high temperature furnace of 238 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.086Mpa, after processing time is 46min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtain flooding for the first time many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, the diatomite thin slice of lithium phosphate, and then insert contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, nmp solution in, dipping 29min, insert again temperature and be in the high temperature furnace of 265 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.091Mpa, after processing time is 35min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the second time the diatomite thin slice of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, through such dipping and the high temperature evaporation of 6 times repeatedly, go out NMP, make the lithium-sulfur cell all solid state electrolyte that contains many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 20.4%wt in block diatomite, wherein the thickness of lithium-sulfur cell all solid state electrolyte thin slice is 0.380mm
Embodiment 7
1) in the 316L of 1L stainless steel cauldron, constantly passing under the protection of 367ml/min nitrogen, add 3.94mol industry one-level NMP, 1.0mol industry one-level vulcanized sodium and 0.003mol industry one sodium hydroxide, under 379rpm stirring condition, slowly the temperature of reaction system is elevated to 111 ℃, then add 1.003mol industry top grade lithium chloride, continue the temperature to 181 ℃ of rising reaction system, and under this temperature conditions, make reaction system insulation 27min, until while having tiny white crystal to separate out in reaction system, water evaporates in reaction system is removed simultaneously, and stop heating, and filter while hot, white crystal in reaction system is filtered out, and filtrate rejoins reaction system, and the stirring intensity of reactor is 379rpm, add sublimed sulfur and deionization anaerobic water in formula, treat that temperature rises to 113 ℃, and the insulation 5.6h that refluxes under this temperature conditions, until in reaction system during without sublimed sulfur powder, stop reaction system heating, the temperature of reaction system is dropped to room temperature slowly simultaneously, now, in reaction system, separate out a small amount of light yellow or white pressed powder, from reaction system, filter out the light yellow or white solid powder of separating out, measure the mass concentration of many lithium sulfides, then according to recipe ratio, add methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, and temperature is heated to 115 ℃, under this temperature conditions, be incubated 63min, then, be cooled to room temperature stand-by, thereby obtain the nmp solution containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, wherein many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate are dissolved in nmp solvent with the mass ratio of 62:26:6:6, form the nmp solution containing the 30%wt of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate.
The fine resin micropowder of polypropylene and diatomite is with mass ratio 49:51, then adds the diatomaceous nmp solvent of 20%wt/, under well-beaten condition, is uniformly mixed into viscose glue mud, after homogenizer fully mixes, is pressed into the thick thin slice of 260 μ m, it is in the high temperature furnace of 244 ℃ that thin slice is inserted to temperature, suitably extracting under the condition of the vacuum that negative pressure is 0.081Mpa, after processing time is 67min, again thin slice is inserted in the high temperature furnace of 1344 ℃, under the condition that is 0.0997Mpa in negative pressure, process 179min, in the normal temperature air chamber of anhydrous steam, be cooled to normal temperature, to deviate from hydrogen, the oxygen atom on the fine molecular resin chain of polypropylene, making porosity is 86.3%, and aperture is the diatomite thin slice that 4.8um structure contains carbon, thin slice is inserted containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, in the nmp solution of lithium phosphate 29%wt, after dipping 36min takes out, to contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, being placed in temperature with the block diatomite of nmp solvent is the high temperature furnace of 235 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.079Mpa, after processing time is 43min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtain flooding for the first time many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, the diatomite thin slice of lithium phosphate, and then insert contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, nmp solution in, dipping 21min, insert again temperature and be in the high temperature furnace of 261 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.088Mpa, after processing time is 35min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the second time the diatomite thin slice of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, through such dipping and the high temperature evaporation of 7 times repeatedly, go out NMP, make the lithium-sulfur cell all solid state electrolyte that contains many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 19.8%wt in block diatomite, wherein the thickness of lithium-sulfur cell all solid state electrolyte thin slice is 0.260mm
Embodiment 8
1) in the 316L of 1L stainless steel cauldron, constantly passing under the protection of 386ml/min nitrogen, add 4.5mol industry one-level NMP, 1.0mol industry one-level vulcanized sodium and 0.003mol industry one sodium hydroxide, under 381rpm stirring condition, slowly the temperature of reaction system is elevated to 114 ℃, then add 1.003mol industry top grade lithium chloride, continue the temperature to 188 ℃ of rising reaction system, and under this temperature conditions, make reaction system insulation 32min, until while having tiny white crystal to separate out in reaction system, water evaporates in reaction system is removed simultaneously, and stop heating, and filter while hot, white crystal in reaction system is filtered out, and filtrate rejoins reaction system, and the stirring intensity of reactor is 381rpm, add sublimed sulfur and deionization anaerobic water in formula, treat that temperature rises to 116 ℃, and the insulation 5.5h that refluxes under this temperature conditions, until in reaction system during without sublimed sulfur powder, stop reaction system heating, the temperature of reaction system is dropped to room temperature slowly simultaneously, now, in reaction system, separate out a small amount of light yellow or white pressed powder, from reaction system, filter out the light yellow or white solid powder of separating out, measure the mass concentration of many lithium sulfides, then according to recipe ratio, add methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, and temperature is heated to 117 ℃, under this temperature conditions, be incubated 64min, then, be cooled to room temperature stand-by, thereby obtain the nmp solution containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, wherein many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate are dissolved in nmp solvent with the mass ratio of 63:21:8:8, form the nmp solution containing the 31%wt of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate.
The fine resin micropowder of polypropylene and diatomite is with mass ratio 51:49, then adds the diatomaceous nmp solvent of 21%wt/, under well-beaten condition, is uniformly mixed into viscose glue mud, after homogenizer fully mixes, is pressed into the thick thin slice of 630 μ m, it is in the high temperature furnace of 256 ℃ that thin slice is inserted to temperature, suitably extracting under the condition of the vacuum that negative pressure is 0.083Mpa, after processing time is 64min, again thin slice is inserted in the high temperature furnace of 1388 ℃, under the condition that is 0.0998Mpa in negative pressure, process 184min, in the normal temperature air chamber of anhydrous steam, be cooled to normal temperature, to deviate from hydrogen, the oxygen atom on the fine molecular resin chain of polypropylene, making porosity is 84.1%, and aperture is the diatomite thin slice that 4.67um structure contains carbon, thin slice is inserted containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, in the nmp solution of lithium phosphate 30.8%wt, after dipping 36min takes out, to contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, being placed in temperature with the block diatomite of nmp solvent is the high temperature furnace of 229 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.085Mpa, after processing time is 45min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtain flooding for the first time many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, the diatomite thin slice of lithium phosphate, and then insert contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, nmp solution in, dipping 18～33min, insert again temperature and be in the high temperature furnace of 263 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.089Mpa, after processing time is 35min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the second time the diatomite thin slice of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, through dipping and the high temperature evaporation of 7 times go out NMP repeatedly like this
, make the lithium-sulfur cell all solid state electrolyte that contains many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 20.69%wt in block diatomite; Wherein the thickness of lithium-sulfur cell all solid state electrolyte thin slice is 0.630mm
Embodiment 9
1) in the 316L of 1L stainless steel cauldron, constantly passing under the protection of 387ml/min nitrogen, add 4.7mol industry one-level NMP, 1.0mol industry one-level vulcanized sodium and 0.003mol industry one sodium hydroxide, under 389rpm stirring condition, slowly the temperature of reaction system is elevated to 117 ℃, then add 1.003mol industry top grade lithium chloride, continue the temperature to 187 ℃ of rising reaction system, and under this temperature conditions, make reaction system insulation 19min, until while having tiny white crystal to separate out in reaction system, water evaporates in reaction system is removed simultaneously, and stop heating, and filter while hot, white crystal in reaction system is filtered out, and filtrate rejoins reaction system, and the stirring intensity of reactor is 389rpm, add sublimed sulfur and deionization anaerobic water in formula, treat that temperature rises to 116 ℃, and the insulation 4.3h that refluxes under this temperature conditions, until in reaction system during without sublimed sulfur powder, stop reaction system heating, the temperature of reaction system is dropped to room temperature slowly simultaneously, now, in reaction system, separate out a small amount of light yellow or white pressed powder, from reaction system, filter out the light yellow or white solid powder of separating out, measure the mass concentration of many lithium sulfides, then according to recipe ratio, add methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, and temperature is heated to 116 ℃, under this temperature conditions, be incubated 41min, then, be cooled to room temperature stand-by, thereby obtain the nmp solution containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, wherein many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate are dissolved in nmp solvent with the mass ratio of 65:19:8:8, form the nmp solution containing the 29%wt of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate.
The fine resin micropowder of polypropylene and diatomite is with mass ratio 53:47, then adds the diatomaceous nmp solvent of 20%wt/, under well-beaten condition, is uniformly mixed into viscose glue mud, after homogenizer fully mixes, is pressed into the thick thin slice of 590 μ m, it is in the high temperature furnace of 247 ℃ that thin slice is inserted to temperature, suitably extracting under the condition of the vacuum that negative pressure is 0.078～0.084Mpa, after processing time is 64min, again thin slice is inserted in the high temperature furnace of 1387 ℃, under the condition that is 0.0998Mpa in negative pressure, process 186min, in the normal temperature air chamber of anhydrous steam, be cooled to normal temperature, to deviate from hydrogen, the oxygen atom on the fine molecular resin chain of polypropylene, making porosity is 87.3%, and aperture is the diatomite thin slice that 3～5um structure contains carbon, thin slice is inserted containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, in the nmp solution of lithium phosphate 29%wt, after dipping 37min takes out, to contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, being placed in temperature with the block diatomite of nmp solvent is the high temperature furnace of 238 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.083Mpa, after processing time is 47min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtain flooding for the first time many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, the diatomite thin slice of lithium phosphate, and then insert contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, nmp solution in, dipping 24min, insert again temperature and be in the high temperature furnace of 261 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.091Mpa, after processing time is 36min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the second time the diatomite thin slice of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, through such dipping and the high temperature evaporation of 8 times repeatedly, go out NMP, make the lithium-sulfur cell all solid state electrolyte that contains many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 20.4%wt in block diatomite, wherein the thickness of lithium-sulfur cell all solid state electrolyte thin slice is 0.590mm.
Claims (2)
1. the manufacture method of a lithium-sulfur cell all solid state electrolyte, it is characterized in that, by the fine resin micropowder of polypropylene and diatomite with mass ratio 46～56:54～44, add in mixed at high speed blender, add again the diatomaceous nmp solvent of 18～24%wt/, under well-beaten condition, be uniformly mixed into viscosity viscose glue mud, then by viscose glue mud according to the bulk material that need to be made into respective shapes of lithium-sulfur cell all solid state electrolyte, bulk material is placed in to the high temperature furnace through nitrogen replacement, under the condition of suitable extracting vacuum, make block viscose glue mud become the block diatomite that only contains carbon composition, then by many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate is dissolved in nmp solvent with the mass ratio of 58～66:33～18:6～8:3～8, form containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, the nmp solution of 18～33%wt of lithium phosphate, then the block diatomite after high-temperature process is immersed and contains many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, in the nmp solution of lithium phosphate, dipping 13～18min, after taking-up, to contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, the block diatomite of lithium phosphate and nmp solvent is placed in another high temperature furnace through nitrogen replacement, under the condition of suitable extracting vacuum, nmp solvent in block diatomite is fully evaporated, the dipping of 6～8 times and high temperature evaporation go out NMP so repeatedly, make to contain in block diatomite many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, the lithium-sulfur cell all solid state electrolyte of lithium phosphate 18～21%wt.
2. the manufacture method of lithium-sulfur cell all solid state electrolyte according to claim 1, is characterized in that, comprises following concrete steps:
1) in the 316L of 1L stainless steel cauldron, constantly passing under the protection of 360～390ml/min nitrogen, add 3.3～4.8mol industry one-level NMP, 1.0mol industry one-level vulcanized sodium and 0.003mol industry one sodium hydroxide, under 360～390rpm stirring condition, slowly the temperature of reaction system is elevated to 108～118 ℃, then add 1.003mol industry top grade lithium chloride, continue temperature to 160～190 ℃ of rising reaction system, and under this temperature conditions, make reaction system insulation 18～33min, until while having tiny white crystal to separate out in reaction system, water evaporates in reaction system is removed simultaneously, and stop heating,
2) by 1) the anhydrous response system that obtains is under the protection of nitrogen, filter while hot, white crystal in reaction system is filtered out, filtrate rejoins reaction system, the stirring intensity of reactor is 360～390rpm, add sublimed sulfur and deionization anaerobic water in formula, treat that temperature rises to 108～118 ℃, and the insulation 4～6h that refluxes under this temperature conditions, until in reaction system during without sublimed sulfur powder, stop reaction system heating, the temperature of reaction system is dropped to room temperature slowly simultaneously, now, in reaction system, separate out a small amount of light yellow or white pressed powder,
3) by 2) the light yellow or white solid powder of separating out filters out from reaction system, measure the mass concentration of many lithium sulfides, then according to recipe ratio, add methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, and temperature is heated to 108～118 ℃, under this temperature conditions, be incubated 33～66min, then, be cooled to room temperature stand-by; Thereby obtain the nmp solution containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate;
4) by the fine resin micropowder powder of polypropylene and diatomite in formula, add again the diatomaceous nmp solvent of 18～24%wt/, under well-beaten condition, be uniformly mixed into viscose glue mud, after homogenizer fully mixes, be pressed into the thick thin slice of 180～660 μ m;
5) by 4) to insert temperature be in the high temperature furnace of 240～260 ℃ for the thin slice of gained, suitably extracting under the condition of the vacuum that negative pressure is 0.078～0.084Mpa, after processing time is 48～68min, again thin slice is inserted in the high temperature furnace of 1280～1390 ℃, under the condition that is 0.098～0.0999Mpa in negative pressure, process 166～188min, in the normal temperature air chamber of anhydrous steam, be cooled to normal temperature; To deviate from hydrogen, the oxygen atom on the fine molecular resin chain of polypropylene; Making porosity is 66～88%, and aperture is the diatomite thin slice that 3～5um structure contains carbon;
6) by 5) thin slice that obtains inserts 3) containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, in the nmp solution of lithium phosphate 28～33%wt, through flooding after 33～38min taking-up, to contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, being placed in temperature with the block diatomite of nmp solvent is the high temperature furnace of 220～240 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.068～0.088Mpa, after processing time is 36～48min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtain flooding for the first time many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, the diatomite thin slice of lithium phosphate,
7) by 6) thin slice that obtains insert again contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, nmp solution in, dipping 18～33min, insert again temperature and be in the high temperature furnace of 260～266 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.088～0.091Mpa, after processing time is 33～36min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the second time the diatomite thin slice of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate;
8) by 7) thin slice that obtains adopts 7) process conditions in step, through dipping and the high temperature evaporation of 6～8 times repeatedly, go out NMP, make the lithium-sulfur cell all solid state electrolyte that contains many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 18～21%wt in block diatomite; Wherein the thickness of lithium-sulfur cell all solid state electrolyte thin slice is 0.1～0.664mm.
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| CN109449494A (en) * | 2018-11-06 | 2019-03-08 | 成都市银隆新能源产业技术研究有限公司 | The preparation method and lithium ion battery of lithium ion battery solid electrolyte interface layer |
| CN115135617A (en) * | 2020-02-17 | 2022-09-30 | 坚固力量公司 | Method for producing water-reactive sulfide materials |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104681853A (en) * | 2015-02-26 | 2015-06-03 | 广东烛光新能源科技有限公司 | Preparation method of lithium sulfur battery and lithium sulfur battery prepared by employing preparation method |
| CN104681853B (en) * | 2015-02-26 | 2017-03-01 | 广东烛光新能源科技有限公司 | A kind of lithium-sulfur cell preparation method and the lithium-sulfur cell using the method preparation |
| CN109449494A (en) * | 2018-11-06 | 2019-03-08 | 成都市银隆新能源产业技术研究有限公司 | The preparation method and lithium ion battery of lithium ion battery solid electrolyte interface layer |
| CN109449494B (en) * | 2018-11-06 | 2022-12-20 | 成都市银隆新能源产业技术研究有限公司 | Preparation method of solid electrolyte interface layer of lithium ion battery and lithium ion battery |
| CN115135617A (en) * | 2020-02-17 | 2022-09-30 | 坚固力量公司 | Method for producing water-reactive sulfide materials |
| US11958742B2 (en) | 2020-02-17 | 2024-04-16 | Solid Power Operating, Inc. | Method of preparing a water-reactive sulfide material |
| CN115135617B (en) * | 2020-02-17 | 2024-04-23 | 坚固力量营运公司 | Method for producing water-reactive sulfide materials |
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