CN103985910B - A kind of manufacture method of lithium-sulfur cell all solid state electrolyte - Google Patents
A kind of manufacture method of lithium-sulfur cell all solid state electrolyte Download PDFInfo
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- CN103985910B CN103985910B CN201410208769.2A CN201410208769A CN103985910B CN 103985910 B CN103985910 B CN 103985910B CN 201410208769 A CN201410208769 A CN 201410208769A CN 103985910 B CN103985910 B CN 103985910B
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- lithium
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- butyric acid
- diatomite
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- 239000007787 solid Substances 0.000 title claims abstract description 60
- 239000003792 electrolyte Substances 0.000 title claims abstract description 54
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims abstract description 120
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims abstract description 120
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical class [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims abstract description 120
- 229910001386 lithium phosphate Inorganic materials 0.000 claims abstract description 118
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims abstract description 118
- GFLFKGYNEFFWTR-UHFFFAOYSA-N lithium;2-(methylamino)butanoic acid Chemical compound [Li].CCC(NC)C(O)=O GFLFKGYNEFFWTR-UHFFFAOYSA-N 0.000 claims abstract description 105
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000002904 solvent Substances 0.000 claims abstract description 51
- -1 polypropylene Polymers 0.000 claims abstract description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 42
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 238000007598 dipping method Methods 0.000 claims abstract description 32
- 239000004743 Polypropylene Substances 0.000 claims abstract description 23
- 229920001155 polypropylene Polymers 0.000 claims abstract description 23
- 229920000297 Rayon Polymers 0.000 claims abstract description 22
- 239000003292 glue Substances 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 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 14
- 230000008569 process Effects 0.000 claims abstract description 14
- 230000008020 evaporation Effects 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000005864 Sulphur Substances 0.000 claims abstract description 9
- 239000013590 bulk material Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 117
- 229910052744 lithium Inorganic materials 0.000 claims description 53
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 35
- 239000000843 powder Substances 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 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
- 238000012545 processing Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000013078 crystal Substances 0.000 claims description 22
- 238000009413 insulation Methods 0.000 claims description 22
- 238000003756 stirring Methods 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
- 239000000706 filtrate Substances 0.000 claims description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 11
- 238000002242 deionisation method Methods 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000002689 soil Substances 0.000 claims description 8
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 44
- 229920000642 polymer Polymers 0.000 description 23
- 239000000463 material Substances 0.000 description 19
- 239000007784 solid electrolyte Substances 0.000 description 16
- 229910052717 sulfur Inorganic materials 0.000 description 16
- 239000011593 sulfur Substances 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 159000000002 lithium salts Chemical class 0.000 description 9
- RISRGKINPSVAJP-UHFFFAOYSA-N [Li].C(CCC)(=O)O Chemical compound [Li].C(CCC)(=O)O RISRGKINPSVAJP-UHFFFAOYSA-N 0.000 description 8
- 238000010494 dissociation reaction Methods 0.000 description 8
- 230000005593 dissociations Effects 0.000 description 8
- 229910003002 lithium salt Inorganic materials 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 230000005611 electricity Effects 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229920001021 polysulfide Polymers 0.000 description 5
- 239000005077 polysulfide Substances 0.000 description 5
- 150000008117 polysulfides Polymers 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- CQJAWZCYNRBZDL-UHFFFAOYSA-N 2-(methylazaniumyl)butanoate Chemical compound CCC(NC)C(O)=O CQJAWZCYNRBZDL-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- OFDCTUIOIVVFNE-UHFFFAOYSA-N [Li].NC(C(=O)O)CC Chemical compound [Li].NC(C(=O)O)CC OFDCTUIOIVVFNE-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000007614 solvation Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 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
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000003763 carbonization Methods 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
- 230000006378 damage Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007646 directional migration Effects 0.000 description 2
- 238000007599 discharging Methods 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000003252 repetitive effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 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
- 230000033228 biological regulation 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
- 239000003575 carbonaceous material Substances 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
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 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
- 230000005684 electric field 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
- 150000002148 esters Chemical class 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 239000010408 film Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005764 inhibitory process Effects 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
- 239000007788 liquid Substances 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
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 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
- 239000011780 sodium chloride Substances 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 230000019086 sulfide ion homeostasis Effects 0.000 description 1
- 230000002194 synthesizing effect 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
- 229910052720 vanadium 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 kind of manufacture method of lithium-sulfur cell all solid state electrolyte, by fine polypropylene resin micropowder and diatomite with mass ratio 46～56:54～66, add in high-speed mixing agitator, adding nmp solvent to make diatomaceous quality is 18～24%wt, be uniformly mixed into the bulk material that viscosity viscose glue mud is also made into respective shapes on demand, in the process high temperature furnace of nitrogen replacement, make block viscose glue mud become the block diatomite that only contains carbon composition, then be placed on containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, nmp solution dipping 13～18min of 18～33%wt of lithium phosphate, after taking-up, in high temperature furnace, after dipping repeatedly and high temperature evaporation, obtain lithium-sulfur cell all solid state electrolyte. preparation method of the present invention is simple, cost is low, the lithium-sulfur cell all solid state electrolyte of preparation have height hold the ability of sulphur, compared with macroion transmittability and electric conductivity, can improve high rate capability and the high cycle performance of lithium-sulfur cell.
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 electrochmical power sourceUnderstanding and requirement are also more and more higher, and impelling people constantly to explore new electrochmical power source is main energy storage system. Nearly decadesCome, led the developing direction of high-performance chemical power supply taking lithium metal as basic battery. Along with the successful business of lithium ion batteryIndustry, countries in the world are all in the research that steps up to carry out vehicle lithium-ion power battery. But due to energy density, security, priceEtc. factor, conventional lithium ion battery lithium as sour in cobalt, LiMn2O4 and ferric phosphate lithium cell cannot meet electric automobile as power sourceRequirement.
Lithium-sulfur cell is the high-energy density secondary battery that has development potentiality and application prospect. It has height ratio capacity andBeyond high-energy-density, sulphur as positive active material aspect source, cost and environmental friendliness, show incomparable excellentGesture, at present, there is the problems such as cycle performance is poor, the further raising of high rate performance needs in lithium-sulfur cell. And lithium-sulfur cell existsTwo main problems are active material sulfur materials itself and final discharging product Li on the one hand2S is industrial one-level and ionInsulator; On the other hand, the intermediate product polysulfide in discharge process is soluble in electrolyte, and these can cause activityThe irreversible loss of material and capacity attenuation. For this reason, how to suppress polysulfide diffusion, improve in the anodal cyclic process of sulphurElectric conductivity is the research emphasis of sulfenyl all solid state electrolyte.
Academia was mainly around suppressing polysulfide diffusion and improving two aspects of all solid state electrolyte electric conductivity in recent yearsConduct a research. On material structure, first consider be that elemental sulfur is adsorbed on porous material skeleton, for example by porous charcoal as workProperty the material with carbon element such as charcoal, CNT, Graphene and sulphur compound, prevent that the polysulfide that course of reaction is produced is dissolved into electrolyteIn, spread by electrolyte, contribute to like this to reduce shuttle back and forth effect and self-discharge phenomenon. These new material structures more or lessImprove the cyclical stability of electrode. But the general specific area of traditional porous carbon material is less, and aperture size is single, structure oneCausing property is poor, aperture is difficult to regulation and control, and the adsorption activity material sulphur of material is limited in one's ability, causes in the compound all solid state electrolyte of preparationLower, the skewness of sulfur content, poor electric conductivity, is assembled into circulating battery after a few, still has a large amount of active material meetingsFrom carbon structure duct, 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 that has good electric conductivity and hierarchical pore structure concurrently with all solid stateElectrolyte, the electric conductivity in diffusion, the anodal cyclic process of raising sulphur of inhibition polysulfide, and then raising all solid state electrolyteIon transfer ability and electric conductivity, can effectively reduce and discharge and recharge polarization, reduces the internal resistance of cell, improves the large multiplying power of lithium-sulfur cellProperty.
Most macromolecular compound is electrical insulator in addition, but certainly reports certain macromolecular material, for example poly-epoxyEthane (PEO) with formed crystalline complex compound and since showing high ionic conductivity such as the such electrolytic salt of lithium salts,With PEO or other polyalkylene oxide, also have the work such as polymine or polyphosphazene in molecule equally with ionic dissociation baseFor the research of the polymer solid electrolyte of matrix just attracts much attention. Particularly reported many using polyalkylene oxide asThe 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 is on the contrary significantlyReduce electrolyte thin film strength or heat resistance, thereby the solid electrolyte that obtains practicality is difficult, if then hadLow temperature, for example, below 0 DEG C, ionic conductivity reduce be terrifically also problem as polymer solid electrolyte, proposed to lead toCross ABA type three blocks that active anionic polymerization makes methoxy poly (ethylene glycol) monomethacrylates (A) and styrene (B) copolymerizationCopolymer is as the polymer solid electrolyte of matrix base material, still, and as the methoxy poly (ethylene glycol) monomethyl third of composition sixThe homopolymers of olefin(e) acid ester, although be high molecular weight material, is aqueous in room temperature, for using A-B-A type copolymer as solidElectrolytical matrix base material, so the content of composition A is restricted, this means the PEO as the diffusion transport space of lithium ionThe shape and size of regional structure are restricted, and ionic conductivity actual 40 DEG C time is many does not meet 10-6S/cm。
From the electrical conduction mechanism of solid electrolyte, melting point polymer its SPE below 60 DEG C conventionally by polymer crystalline phase,The crystalline compound that polymer and lithium salts form and form electrical conduction mechanism research containing the polymer amorphous phase of solvation salt and showUnder electric field action, ion migration mainly occurs in amorphous phase region again because the motion of polymer short range segment helps lend some impetus toPolymer and Li+Between coordinate bond destruction and be formed as Li+Migration provide free volume therefore to reduce the degree of crystallinity of polymerAnd the compliance of glass transition temperature (Tg) raising polymer chain all contributes to obtain high leading with its free volume density of increaseThe SPE of electrical property and be not commonly considered as leading by the directional migration to room with the anion of polymer generation associationThe polymer of the low-k on the other hand of electricity makes to exist strong interaction between ion and ion have been caused in SPEExcept the cation of anion and solvation freely, also exist the tight ion pair three ion aggregations of solvation ion pair andThey have determined that the concentration of carrier and transfer ability are also the key factors that affects SPE conductive capability other ion aggregation.But, among the solid electrolyte film being formed by polymer and lithium salts, according to the electrical conduction mechanism of lithium salts, in certain voltageUnder, make lithium salts be dissociated into zwitterion, under the effect of voltage, there is directional migration in these zwitterions, still, due to polymerizationThing plays supporting role in solid electrolyte, meanwhile, is subject to the restriction of the structure of polymer, if this polymer is crystal knotStructure, the zwitterion that can make lithium salts dissociation form hinders the motion of these zwitterions under the effect of voltage, therefore, forThe capacity of the battery that improves the electric conduction quantity of solid electrolyte and manufactured by this electrolyte, on the one hand, it is amorphous needing polymerForm, on the other hand, need lithium salts to there is good dissociating power, for this reason, studying a kind of high-effect electrolysis matter is eachResearcher's target.
In Chinese patent application: introduced a kind of so that thermal characteristics, physical characteristic and ionic conduction to be provided in 03817326.3Spend good, to approach realistic scale polymer solid electrolyte, particularly total solids electrolyte, and become for the manufacture of this electricityThe copolymer compositions of separating the matrix of matter is object. This polymer solid electrolyte contains copolymer and electrolytic salt, this copolymerizationIn thing, there is the block chain A of the repetitive representing with formula (I), have with formula (II) (in formula, R9Represent aryl) represent weightThe block chain B of multiple unit and have with formula (III) (in formula, R13Represent aryl or heteroaryl) embedding of the repetitive that representsSection chain C arranges with the order of B, A, C. This polymer solid electrolyte is also the synthetic a kind of solid electricity of method that adopts block polymerizationSeparate the needed amorphous polymer of matter, compare with other polymer, this solid electrolyte fully utilizes the net of polymerNetwork space structure, thus conducting electrolyte and the battery capacity of corresponding effect obtained, and still, the side chain of polymer too much can hinder againHinder the motion after electrolyte dissociation.
At Chinese Patent Application No. code 96197348.X, a kind of closed pore cellular by having flooded nonaqueous electrolytic solution is disclosedThe NEW TYPE OF COMPOSITE polyelectrolyte that micro-pore of polymer is made, it comprises multiple closed pores that limited by hole wall, hole wall has formedWith the continuous solid phase parent of nonaqueous electrolytic solution dipping, form continuous solid phase microcell, wherein multiple closed pores have been filled non-water substantiallyElectrolyte is to form multiple liquid phase micro-areas, and they are dispersed in above-mentioned continuous solid phase microcell. This invention composite polymer electrolyteNot only there is very high ionic conductance string and very high mechanical strength, and can prevent that nonaqueous electrolytic solution from leaking, therefore this inventionElectrolyte can be advantageously used in various non-aqueous electrochemical devices. That is to say, comprise composite polymer electrolyte of the present inventionNon-aqueous electrochemical device not only has good electrochemistry, and can maintain electrolyte wherein, and for this reason, this invention is being manufacturedIn technique, exist significantly not enough.
In Chinese patent number No:02125137.1, introduce a kind of employing all solid state at sulfur-containing compound lithium-sulfur cellElectrolytical surface applies layer of surface passivating material, its objective is the damage that reduces sulfur-containing compound sulphur in charge and discharge processLose, but because coated surface passivation layer is the chemistry units such as some Mg, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, ZrCarbonate or the hydroxyl carbonate of element, can cause the electric conductivity of this electrode material to reduce.
In Chinese patent number No:1143369.8, introduce a kind of sulfur-containing compound and conductive agent and adhesive of adoptingPrepare all solid state electrolyte of lithium-sulfur cell etc. several raw material, because conductive agent is the moulding material of metal material, simultaneouslyThe impact of adhesive, makes the electric conductivity of its lithium-sulfur cell all solid state electrolyte can be subject to corresponding impact.
In Chinese Patent Application No. code No:201310418375.5, introduce a kind of manufacturing process of inorganic electrolyte,Wherein apply diatomite and be used as a kind of electrolytical backing material, wherein adopted polysiloxanes organic siliconresin, and diatomThe soil material that preparation can adsorbing electrolyte material of coming together, still, owing to can be subject to poly-silicon in the process of preparing carborundumThe impact of oxygen alkane molecular resin chain, can cause its voidage to decline.
In view of the above shortcoming of prior art, the object of the invention is to overcome the deficiency of current solid electrolyte, employing is filledMany lithium sulfides of discharge performance excellence, in order to improve the dispersiveness of lithium salts in diatomite, and then the electricity of raising solid electrolyteCapacity and charge-discharge velocity adopt this polymer of the fine resin of polypropylene to prepare conductive carrier simultaneously, reduce after lithium salts dissociationLithium ion and anion mobile obstruction under the effect of voltage, thus the conductance of this solid electrolyte improved and by this electrolysisMatter is 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 there is adsorption activityMaterial sulphur is limited in one's ability, the problem of poor electric conductivity and its application in battery is limited to, and object is to be to provide onePlant the 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 manufacture method for lithium-sulfur cell all solid state electrolyte, is characterized in that, by fine polypropylene resin micropowder and siliconAlgae soil, with mass ratio 46～56:54～44, adds in high-speed mixing agitator, adds nmp solvent to make diatomaceous quality be18～24%wt, under well-beaten condition, is uniformly mixed into viscosity viscose glue mud, then by complete according to lithium-sulfur cell viscose glue mudThe bulk material that need to be made into respective shapes of solid electrolyte, is placed in the high temperature furnace through nitrogen replacement by bulk materialIn, under the condition of extracting vacuum, make block viscose glue mud become the block diatomite that only contains carbon composition, then will vulcanize moreLithium, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate are dissolved in nmp solvent with the mass ratio of 58～66:33～18:6～8:3～8In, form the nmp solution containing 18～33%wt of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, then will be throughCrossing high temperature block diatomite after treatment, to immerse the NMP that contains many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate moltenIn liquid, dipping 13～18min, after taking-up, will contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate and NMP moltenThe block diatomite of agent is placed in another high temperature furnace through nitrogen replacement, under the condition of extracting vacuum, makes block diatomiteIn nmp solvent fully evaporate, the dipping of 6～8 times and high temperature evaporation go out NMP so repeatedly, make to contain in block diatomiteThere is the lithium-sulfur cell all solid state electrolyte of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, 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, add3.3～4.8mol industry one-level NMP, 1.0mol industry one-level vulcanized sodium and 0.003mol industry one sodium hydroxide, 360～Under 390rpm stirring condition, slowly the temperature of reaction system is elevated to 108～118 DEG C, then adds 1.003mol industry excellentLevel lithium chloride, temperature to 160～190 DEG C of continuing 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, the water evaporates in reaction system is removed, simultaneouslyAnd stop heating;
2) by 1) the anhydrous response system that obtains under the protection of nitrogen, filter while hot, by the white crystalline substance in reaction systemBody filters out, and filtrate is under 360～390rpm condition in the mixing speed of reactor, add sublimed sulfur in formula and go fromSub-anaerobic water, treats temperature rise to 108～118 DEG C, and the insulation 4～6h that refluxes under this temperature conditions, until in reaction systemDuring without sublimed sulfur powder, stop, to reaction system heating, the temperature of reaction system being dropped to room temperature slowly simultaneously, now, anti-Answer and in 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, measures the matter of many lithium sulfidesAmount concentration, then adds methylamino butyric acid lithium, lithium perchlorate, lithium phosphate according to recipe ratio, and temperature is heated to 108～118DEG C, under this temperature conditions, be incubated 33～66min, then, be cooled to room temperature stand-by; Thereby obtain containing many lithium sulfides, methylaminoThe nmp solution of butyric acid lithium, lithium perchlorate, lithium phosphate;
4), by formula in the fine resin micropowder powder of polypropylene and diatomite, add nmp solvent to make diatomaceous qualityBe 18～24%wt, under well-beaten condition, be uniformly mixed into viscose glue mud, fully mix through homogenizerAfter, 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 DEG C, to be 0.078 suitably extracting negative pressure for the thin slice of gainedUnder the condition of the vacuum of～0.084Mpa, after the processing time is 48～68min, then thin slice is inserted to the high temperature of 1280～1390 DEG CIn stove, under the condition that is 0.098～0.0999Mpa in negative pressure, process 166～188min, in the normal temperature air chamber of anhydrous steamBe 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 3The diatomite thin slice that～5um structure contains carbon;
6), by 5) thin slice that obtains inserts 3) containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 28～In the nmp solution of 33%wt, through flooding after 33～38min taking-up, will contain many lithium sulfides, methylamino butyric acid lithium, perchloric acidIt is the high temperature furnace of 220～240 DEG C that the block diatomite of lithium, lithium phosphate and nmp solvent is placed in temperature, is suitably extracting negative pressureBe under the condition of vacuum of 0.068～0.088Mpa, after the processing time is 36～48min, through the normal temperature air chamber of anhydrous steamBe cooled to normal temperature, the diatomite that so just obtains flooding for the first time many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate is thinSheet;
7) by 6) thin slice that obtains insert again contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, NMPIn solution, dipping 18～33min, then to insert temperature be in the high temperature furnace of 260～266 DEG C, suitably extracting negative pressure and be 0.088～Under the condition of the vacuum of 0.091Mpa, the processing time is cooled to often through the normal temperature air chamber of anhydrous steam after being 33～36minTemperature, is so flooded the diatomite thin slice of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate for the second time;
8) by 7) thin slice that obtains adopts 7) process conditions in step, through dipping and the high temperature evaporation of 6～8 times repeatedlyGo out NMP, make the lithium sulphur that contains many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 18～21%wt in block diatomiteBattery all solid state electrolyte; 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, and its normal temperature in nmp solvent is moltenSolution degree can, up to 26g/100mlNMP, in order to improve the solubility of industrial top grade lithium chloride, need to carry out one to solution systemDetermine the heat temperature raising of degree, in addition, because NMP is under heating condition, can makes it to occur oxidation reaction and become because contacting with airYellowly, and then the purity of reduction NMP, therefore, need to protect synthetic dicyandiamide solution 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 at normal temperatureWith under the condition of heat temperature raising, be also insoluble to nmp solvent, still, under the condition that is having anaerobic water to exist, by adding industry oneSodium hydroxide reacts with it, and generate and contain the little industrial one-level vulcanized sodium of impurity level, and then after heating by intensification,There is therein ionic reaction by industrial one-level vulcanized sodium and industrial top grade lithium chloride, meanwhile, in the anaerobic evaporating whereinUnder the condition of water, synthetic lithium sulfide, because the solubility of sodium chloride in the nmp solvent of 150～360 DEG C only has 5mg/100mlNMP, be also low-down, and lithium sulfide is dissolved in nmp solvent in the solubility of normal temperature, and for this reason, the present invention is profit fullyBy this specific character of the easy NMP of lithium sulfide, be comparatively easy to obtain lithium sulfide, its objective is because lithium sulfide is easy in airOxidized decomposition, discharges hydrogen sulfide poison gas, and the object that adopts technological process of the present invention is can avoid synthesizing on the one handLithium sulfide is not oxidized, is 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, makes full use of and can utilizeCondition, be exactly can by deionized water by physics or/and chemistry mode, the dissolved oxygen in deionized water is dropped to very lowDegree, remove even completely, not oxidized to guarantee lithium sulfide, and then improve many lithium sulfides and methylamino butyric acid lithium and heightLithium chlorate and lithium phosphate are with a certain proportion of purity.
4, the present invention is for synthetic required many lithium sulfides and methylamino butyric acid lithium and lithium perchlorate and the phosphorus of lithium-sulfur cellAcid lithium is with a certain proportion of raw material. Because elemental sulfur is soluble among ethanol, according to the principles of chemistry of similar compatibility, elemental sulfurAll can be soluble among nmp solvent with lithium sulfide, still, due to the difference of solubility, can make aggregate velocity be affected, forImprove aggregate velocity, the present invention makes full use of the light water solvent that can make lithium sulfide generation electrolysis, will make so synthetic speedDegree is that solvent has improved nearly 2 times with ethanol or ammoniacal liquor, meanwhile, nearly reduces costs 40%, is more conducive to realize industrialization rawProduce.
5, the present invention is in order to make full use of reflux solvent and aqueous systems, is the stable of temperature in order to ensure synthetic system,Improve raw-material utilization rate, so provide many lithium sulfides and methylamino butyric acid lithium and lithium perchlorate and lithium phosphate with necessarily thanThe productive rate of example.
6, to adopt diatomaceous object be to make full use of diatomaceous open structure in the present invention, also utilizes the diatomite can simultaneouslyWith sinter molding, can make diatomite sinter the material of various shapes into, be conducive to be made into the required electrode material of lithium-sulfur cellMaterial.
7, the present invention is in order to increase electrolytical electric conductivity, makes full use of the fine resin micropowder of polypropylene and is dissolved in organic solventCharacteristic, make the fine resin micropowder of polypropylene fully mix with diatomite by the dissolving of organic solvent, is conducive to subsequentlyAfter forming processes, make the fine resin micropowder of polypropylene be transformed into carbonaceous conductive material and merge with the diatom soil phase better, and carbon is betterBe uniformly distributed with diatomite among, be conducive to lithium-sulfur cell all solid state electrolyte electric conductivity more stable, simultaneously due to poly-thirdIn the strand of the fine resin of alkene, contain phenyl, this phenyl, after carbonization treatment, can form certain in the structure of its strandThe carbocyclic ring of ring assembling structure, is conducive to the absorption of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate molecule, thereby obtainsWell capacitance and charge-discharge performance.
8, the present invention adopts many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, the phosphoric acid lithiumation that can be dissolved in nmp solventThe object of compound is to make to have the many lithium sulfides of the better adsorption and permeation of very microporous carbon containing diatomite material, methylamino butyric acidThe nmp solution of lithium, lithium perchlorate, lithium phosphate, thus make carbonaceous conductive material and many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate,Lithium phosphate organically combines better, and this is conducive to many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate and was discharging and rechargingDissociation in journey and dissociating, meanwhile, because diatomaceous micropore is in improving lithium-sulfur cell all solid state electrolyte electric conductivity,Also prevent the excessive dissociation of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, be conducive to lithium-sulfur cell and discharge and recharge and followRing, with prevent lithium-sulfur cell that discharge and recharge with decay number of times, to extend the service life of lithium-sulfur cell; The present invention adopts in additionThe polypropylene of straight chain is fine completely, its objective is and utilizes this resin to hold very much with carbonization, because the fine resin of polypropylene is the former of carbon fiberBeginning material, thus be not subject to the impact of molecular chain structure and cause 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 electricitySeparate the electric conductivity of matter. Its reason be due to the raw material at these technical grades more or less contain some metals or nonmetalCompound, some compounds, under uniform temperature condition, are stable, but when these compounds are subject to exciting of electron stream,Can make it dissociation occurs and conduct electricity, because ion can further excite the electricity that dissociation does not occur of the present invention under the effect of electric fieldSeparate matter dissociation, and then improve the electrolytical degree of dissociation and electrolytical capacitance.
Technological process brief introduction of the present invention
A manufacture method for lithium-sulfur cell all solid state electrolyte, is characterized in that, by fine polypropylene resin micropowder and siliconAlgae soil adds in high-speed mixing agitator with certain mass ratio, then adds a certain proportion of nmp solvent, at well-beatenUnder part, be uniformly mixed into the viscose glue mud of certain viscosity, then by viscose glue mud according to lithium-sulfur cell all solid state electrolyte need systemMake the bulk material of respective shapes, bulk material is placed in to the high temperature furnace through nitrogen replacement, in the condition of extracting vacuumUnder, make block viscose glue mud become the block diatomite that only contains carbon composition, then by many lithium sulfides, methylamino butyric acid lithium, high chlorineAcid lithium, lithium phosphate are dissolved in nmp solvent with certain proportion, form containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, phosphoric acidThe certain density industrial one-level nmp solution of lithium, then the block diatomite after high-temperature process is immersed contain many lithium sulfides,In the nmp solution of methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, dipping certain hour, after taking-up, will contain many lithium sulfides, firstThe block diatomite of aminobutyric acid lithium, lithium perchlorate, lithium phosphate and nmp solvent is placed in another high temperature furnace through nitrogen replacementIn, under the condition of extracting vacuum, the nmp solvent in block diatomite is fully evaporated, so repeatedly dipping several timesGo out NMP with high temperature evaporation, make to contain in block diatomite many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate a certain amount ofLithium-sulfur cell all solid state electrolyte.
Brief description of the drawings
Fig. 1 is the performance indications of the lithium-sulfur cell all solid state electrolyte of embodiment of the present invention 1-9.
Detailed description of the invention
Embodiment 1
1) in the 316L of 1L stainless steel cauldron, constantly passing under the protection of 360ml/min nitrogen, add 3.3molIndustry one-level NMP, 1.0mol industry one-level vulcanized sodium and 0.003mol industry one sodium hydroxide, at 360rpm stirring conditionUnder, slowly the temperature of reaction system is elevated to 108 DEG C, then add 1.003mol industry top grade lithium chloride, continue to raise anti-Answer the temperature to 160 DEG C of system, and under this temperature conditions, make reaction system insulation 33min, until have tiny in reaction systemWhite crystal while separating out, the water evaporates in reaction system is removed simultaneously, and stops heating; And filter while hot, will reactWhite crystal in system filters out, and filtrate rejoins reaction system, and the stirring intensity of reactor is 360rpm, adds and joinsSublimed sulfur in side and deionization anaerobic water, treat temperature rise to 108 DEG C, and the insulation 6h that refluxes under this temperature conditions, untilIn reaction system, during without sublimed sulfur powder, stop, to reaction system heating, the temperature of reaction system being dropped to chamber slowly simultaneouslyTemperature, now, separates out a small amount of light yellow or white pressed powder in reaction system; From reaction system, filter out separate out pale yellowLook or white solid powder, measure the mass concentration of many lithium sulfides, then adds methylamino butyric acid lithium, perchloric acid according to recipe ratioLithium, lithium phosphate, and temperature is heated to 108 DEG C, under this temperature conditions, be incubated 66min, then, be cooled to room temperature stand-by; FromAnd obtain the nmp solution containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, wherein many lithium sulfides, methylamino fourthAcid lithium, lithium perchlorate, lithium phosphate are dissolved in nmp solvent with the mass ratio of 58:33:6:3, form containing many lithium sulfides, methylamino fourthThe nmp solution of the 18%wt of 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, be uniformly mixed into viscose glue mud, after homogenizer fully mixes, be pressed into 180 μ m thickThin slice; It is in the high temperature furnace of 240 DEG C 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, then thin slice is inserted in the high temperature furnace of 1280 DEG C, under the condition that is 0.0999Mpa in negative pressure, process188min, is cooled to normal temperature in the normal temperature air chamber of anhydrous steam; Former to deviate from hydrogen, oxygen on the fine molecular resin chain of polypropyleneSon; Making porosity is 66%, and aperture is the diatomite thin slice that 3um structure contains carbon; Thin slice is inserted containing many lithium sulfides, first ammoniaIn the nmp solution of base butyric acid lithium, lithium perchlorate, lithium phosphate 28%wt, through dipping 38min take out after, will contain many lithium sulfides,It is the high temperature furnace of 220 DEG C that the block diatomite of methylamino butyric acid lithium, lithium perchlorate, lithium phosphate and nmp solvent is placed in temperature,Suitably extracting under the condition of the vacuum that negative pressure is 0.088Mpa, after the processing time is 48min, through the normal temperature air of anhydrous steamChamber is cooled to normal temperature, so just obtains flooding for the first time the diatomite of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphateThin slice; And then insert contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, nmp solution in, dipping33min, then to insert temperature be in the high temperature furnace of 260 DEG C, suitably extracting under the condition of the vacuum that negative pressure is 0.091Mpa, processesTime is cooled to normal temperature through the normal temperature air chamber of anhydrous steam after being 36min, so flooded for the second time many lithium sulfides,The diatomite thin slice of methylamino butyric acid lithium, lithium perchlorate, lithium phosphate; Through dipping and the high temperature evaporation of 6 times go out repeatedly like thisNMP, making to contain in block diatomite many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 18%wt thickness is 0.1mmLithium-sulfur cell all solid state electrolyte.
Embodiment 2
1) in the 316L of 1L stainless steel cauldron, constantly passing under the protection of 390ml/min nitrogen, add 4.8molIndustry one-level NMP, 1.0mol industry one-level vulcanized sodium and 0.003mol industry one sodium hydroxide, at 390rpm stirring conditionUnder, slowly the temperature of reaction system is elevated to 118 DEG C, then add 1.003mol industry top grade lithium chloride, continue to raise anti-Answer the temperature to 190 DEG C of system, and under this temperature conditions, make reaction system insulation 18min, until have tiny in reaction systemWhite crystal while separating out, the water evaporates in reaction system is removed simultaneously, and stops heating; And filter while hot, will reactWhite crystal in system filters out, and filtrate rejoins reaction system, and the stirring intensity of reactor is 390rpm, adds and joinsSublimed sulfur in side and deionization anaerobic water, treat temperature rise to 118 DEG C, and the insulation 4h that refluxes under this temperature conditions, untilIn reaction system, during without sublimed sulfur powder, stop, to reaction system heating, the temperature of reaction system being dropped to chamber slowly simultaneouslyTemperature, now, separates out a small amount of light yellow or white pressed powder in reaction system; From reaction system, filter out separate out pale yellowLook or white solid powder, measure the mass concentration of many lithium sulfides, then adds methylamino butyric acid lithium, perchloric acid according to recipe ratioLithium, lithium phosphate, and temperature is heated to 118 DEG C, under this temperature conditions, be incubated 33min, then, be cooled to room temperature stand-by; FromAnd obtain wherein many lithium sulfides, the methylamino butyric acid of nmp solution containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphateLithium, lithium perchlorate, lithium phosphate are dissolved in nmp solvent with the mass ratio of 66:18:8:8, form containing many lithium sulfides, methylamino butyric acidThe nmp solution of the 33%wt of 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, be uniformly mixed into viscose glue mud, after homogenizer fully mixes, be pressed into 660 μ m thickThin slice; It is in the high temperature furnace of 260 DEG C 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, then thin slice is inserted in the high temperature furnace of 1390 DEG C, under the condition that is 0.098Mpa in negative pressure, process166min, is cooled to normal temperature in the normal temperature air chamber of anhydrous steam; Former to deviate from hydrogen, oxygen on the fine molecular resin chain of polypropyleneSon; Making porosity is 88%, and aperture is the diatomite thin slice that 5um structure contains carbon; Thin slice is inserted containing many lithium sulfides, first ammoniaIn the nmp solution of base butyric acid lithium, lithium perchlorate, lithium phosphate 33%wt, through dipping 33min take out after, will contain many lithium sulfides,It is the high temperature furnace of 240 DEG C that the block diatomite of methylamino butyric acid lithium, lithium perchlorate, lithium phosphate and nmp solvent is placed in temperature,Suitably extracting under the condition of the vacuum that negative pressure is 0.068Mpa, after the processing time is 36min, through the normal temperature air of anhydrous steamChamber is cooled to normal temperature, so just obtains flooding for the first time the diatomite of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphateThin slice; And then insert contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, nmp solution in, dipping18min, then to insert temperature be in the high temperature furnace of 266 DEG C, suitably extracting under the condition of the vacuum that negative pressure is 0.088Mpa, processesTime is cooled to normal temperature through the normal temperature air chamber of anhydrous steam after being 33min, so flooded for the second time many lithium sulfides,The diatomite thin slice of methylamino butyric acid lithium, lithium perchlorate, lithium phosphate; Through dipping and the high temperature evaporation of 8 times go out repeatedly like thisNMP, the lithium-sulfur cell that makes to contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 21%wt in block diatomite is completeSolid electrolyte; 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 3.6molIndustry one-level NMP, 1.0mol industry one-level vulcanized sodium and 0.003mol industry one sodium hydroxide, at 370rpm stirring conditionUnder, slowly the temperature of reaction system is elevated to 110 DEG C, then add 1.003mol industry top grade lithium chloride, continue to raise anti-Answer the temperature to 188 DEG C of system, and under this temperature conditions, make reaction system insulation 21min, until have tiny in reaction systemWhite crystal while separating out, the water evaporates in reaction system is removed simultaneously, and stops heating; And filter while hot, will reactWhite crystal in system filters out, and filtrate rejoins reaction system, and the stirring intensity of reactor is 370rpm, adds and joinsSublimed sulfur in side and deionization anaerobic water, treat temperature rise to 112 DEG C, and the insulation 5h that refluxes under this temperature conditions, untilIn reaction system, during without sublimed sulfur powder, stop, to reaction system heating, the temperature of reaction system being dropped to chamber slowly simultaneouslyTemperature, now, separates out a small amount of light yellow or white pressed powder in reaction system; From reaction system, filter out separate out pale yellowLook or white solid powder, measure the mass concentration of many lithium sulfides, then adds methylamino butyric acid lithium, perchloric acid according to recipe ratioLithium, lithium phosphate, and temperature is heated to 113 DEG C, under this temperature conditions, be incubated 44min, then, be cooled to room temperature stand-by; FromAnd obtain wherein many lithium sulfides, the methylamino butyric acid of nmp solution containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphateLithium, lithium perchlorate, lithium phosphate are dissolved in nmp solvent with the mass ratio of 60:30:7:3, form containing many lithium sulfides, methylamino butyric acidThe nmp solution of 18～33%wt of 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, be uniformly mixed into viscose glue mud, after homogenizer fully mixes, be pressed into 210 μ m thickThin slice; It is in the high temperature furnace of 243 DEG C 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, then thin slice is inserted in the high temperature furnace of 1310 DEG C, under the condition that is 0.0991Mpa in negative pressure, process168min, is cooled to normal temperature in the normal temperature air chamber of anhydrous steam; Former to deviate from hydrogen, oxygen on the fine molecular resin chain of polypropyleneSon; Making porosity is 68%, and aperture is the diatomite thin slice that 4um structure contains carbon; Thin slice is inserted containing many lithium sulfides, first ammoniaIn the nmp solution of base butyric acid lithium, lithium perchlorate, lithium phosphate 31%wt, through dipping 34min take out after, will contain many lithium sulfides,It is the high temperature furnace of 223 DEG C that the block diatomite of methylamino butyric acid lithium, lithium perchlorate, lithium phosphate and nmp solvent is placed in temperature,Suitably extracting under the condition of the vacuum that negative pressure is 0.071Mpa, after the processing time is 38min, through the normal temperature air of anhydrous steamChamber is cooled to normal temperature, so just obtains flooding for the first time the diatomite of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphateThin slice; And then insert contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, nmp solution in, dipping21min, then to insert temperature be in the high temperature furnace of 261 DEG C, suitably extracting under the condition of the vacuum that negative pressure is 0.089Mpa, processesTime is cooled to normal temperature through the normal temperature air chamber of anhydrous steam after being 34min, so flooded for the second time many lithium sulfides,The diatomite thin slice of methylamino butyric acid lithium, lithium perchlorate, lithium phosphate; Through dipping and the high temperature evaporation of 7 times go out repeatedly like thisNMP, the lithium-sulfur cell that makes to contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 19%wt in block diatomite is completeSolid electrolyte; 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 3.9molIndustry one-level NMP, 1.0mol industry one-level vulcanized sodium and 0.003mol industry one sodium hydroxide, at 380rpm stirring conditionUnder, slowly the temperature of reaction system is elevated to 114 DEG C, then add 1.003mol industry top grade lithium chloride, continue to raise anti-Answer the temperature to 178 DEG C of system, and under this temperature conditions, make reaction system insulation 24min, until have tiny in reaction systemWhite crystal while separating out, the water evaporates in reaction system is removed simultaneously, and stops heating; And filter while hot, will reactWhite crystal in system filters out, and filtrate rejoins reaction system, and the stirring intensity of reactor is 380rpm, adds and joinsSublimed sulfur in side and deionization anaerobic water, treat temperature rise to 114 DEG C, and the insulation 4.8h that refluxes under this temperature conditions, straightTo in reaction system during without sublimed sulfur powder, stop, to reaction system heating, the temperature of reaction system being dropped to slowly simultaneouslyRoom temperature, now, separates out a small amount of light yellow or white pressed powder in reaction system; From reaction system, filter out separate out shallowYellow or white solid powder, measure the mass concentration of many lithium sulfides, then adds methylamino butyric acid lithium, high chlorine according to recipe ratioAcid lithium, lithium phosphate, and temperature is heated to 113 DEG C, 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, methylaminoButyric acid lithium, lithium perchlorate, lithium phosphate are dissolved in nmp solvent with the mass ratio of 62:22:8:8, form containing many lithium sulfides, methylaminoThe nmp solution of the 21%wt of 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, be uniformly mixed into viscose glue mud, after homogenizer fully mixes, be pressed into 430 μ m thickThin slice; It is in the high temperature furnace of 253 DEG C 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, then thin slice is inserted in the high temperature furnace of 1364 DEG C, under the condition that is 0.0994Mpa in negative pressure, process171min, is cooled to normal temperature in the normal temperature air chamber of anhydrous steam; Former to deviate from hydrogen, oxygen on the fine molecular resin chain of polypropyleneSon; 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, firstIn the nmp solution of aminobutyric acid lithium, lithium perchlorate, lithium phosphate 30%wt, after dipping 36min takes out, will contain many sulfurationsIt is the high temperature furnace of 234 DEG C that the block diatomite of lithium, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate and nmp solvent is placed in temperatureIn, suitably extracting under the condition of the vacuum that negative pressure is 0.075Mpa, after the processing time is 41min, through the normal temperature of anhydrous steamAir chamber is cooled to normal temperature, so just obtains flooding for the first time the silicon of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphateAlgae soil thin slice; And then insert contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, nmp solution in, dipping29min, then to insert temperature be in the high temperature furnace of 262 DEG C, suitably extracting under the condition of the vacuum that negative pressure is 0.090Mpa, processesTime is cooled to normal temperature through the normal temperature air chamber of anhydrous steam after being 35min, so flooded for the second time many lithium sulfides,The diatomite thin slice of methylamino butyric acid lithium, lithium perchlorate, lithium phosphate; Through dipping and the high temperature evaporation of 6 times go out repeatedly like thisNMP, the lithium-sulfur cell that makes to contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 20%wt in block diatomite is completeSolid electrolyte; 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 4.4molIndustry one-level NMP, 1.0mol industry one-level vulcanized sodium and 0.003mol industry one sodium hydroxide, at 384rpm stirring conditionUnder, slowly the temperature of reaction system is elevated to 108～118 DEG C, then add 1.003mol industry top grade lithium chloride, continue to riseThe temperature to 174 of high reaction system DEG C, and under this temperature conditions, make reaction system insulation 26min, until have in reaction systemWhen tiny white crystal is separated out, the water evaporates in reaction system is removed simultaneously, and stop heating; And filter while hot, willWhite crystal in reaction system filters out, and filtrate rejoins reaction system, and the stirring intensity of reactor is 384rpm, addsEnter sublimed sulfur and deionization anaerobic water in formula, treat temperature rise to 116 DEG C, and the insulation that refluxes under this temperature conditions5.1h, until in reaction system during without sublimed sulfur powder, stop to reaction system heating, simultaneously by slow the temperature of reaction systemDrop to room temperature, now, in reaction system, separate out a small amount of light yellow or white pressed powder; From reaction system, filter out and analyseLight yellow or the white solid powder going out, measures the mass concentration of many lithium sulfides, then adds methylamino butyric acid according to recipe ratioLithium, lithium perchlorate, lithium phosphate, and temperature is heated to 117 DEG C, under this temperature conditions, be incubated 51min, then, be cooled to chamberTemperature is 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 containing many lithium sulfides,The nmp solution of the 26%wt of 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, be uniformly mixed into viscose glue mud, after homogenizer fully mixes, be pressed into 540 μ m thickThin slice; It is in the high temperature furnace of 254 DEG C 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, then thin slice is inserted in the high temperature furnace of 1384 DEG C, under the condition that is 0.0996Mpa in negative pressure, process184min, is cooled to normal temperature in the normal temperature air chamber of anhydrous steam; Former to deviate from hydrogen, oxygen on the fine molecular resin chain of polypropyleneSon; 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, firstIn the nmp solution of aminobutyric acid lithium, lithium perchlorate, lithium phosphate 32%wt, after dipping 34min takes out, will contain many sulfurationsIt is the high temperature furnace of 237 DEG C that the block diatomite of lithium, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate and nmp solvent is placed in temperatureIn, suitably extracting under the condition of the vacuum that negative pressure is 0.086Mpa, after the processing time is 44min, through the normal temperature of anhydrous steamAir chamber is cooled to normal temperature, so just obtains flooding for the first time the silicon of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphateAlgae soil thin slice; And then insert contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, nmp solution in, dipping29min, then to insert temperature be in the high temperature furnace of 264 DEG C, suitably extracting under the condition of the vacuum that negative pressure is 0.089Mpa, processesTime is cooled to normal temperature through the normal temperature air chamber of anhydrous steam after being 34min, so flooded for the second time many lithium sulfides,The diatomite thin slice of methylamino butyric acid lithium, lithium perchlorate, lithium phosphate; Through dipping and the high temperature evaporation of 8 times go out repeatedly like thisNMP, makes the lithium-sulfur cell that contains many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 19.0%wt in block diatomiteAll solid state electrolyte; 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 4.6molIndustry one-level NMP, 1.0mol industry one-level vulcanized sodium and 0.003mol industry one sodium hydroxide, at 374rpm stirring conditionUnder, slowly the temperature of reaction system is elevated to 117 DEG C, then add 1.003mol industry top grade lithium chloride, continue to raise anti-Answer the temperature to 183 DEG C of system, and under this temperature conditions, make reaction system insulation 32min, until have tiny in reaction systemWhite crystal while separating out, the water evaporates in reaction system is removed simultaneously, and stops heating; And filter while hot, will reactWhite crystal in system filters out, and filtrate rejoins reaction system, and the stirring intensity of reactor is 374rpm, adds and joinsSublimed sulfur in side and deionization anaerobic water, treat temperature rise to 115 DEG C, and the insulation 5.8h that refluxes under this temperature conditions, straightTo in reaction system during without sublimed sulfur powder, stop, to reaction system heating, the temperature of reaction system being dropped to slowly simultaneouslyRoom temperature, now, separates out a small amount of light yellow or white pressed powder in reaction system; From reaction system, filter out separate out shallowYellow or white solid powder, measure the mass concentration of many lithium sulfides, then adds methylamino butyric acid lithium, high chlorine according to recipe ratioAcid lithium, lithium phosphate, and temperature is heated to 115 DEG C, 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, methylaminoButyric acid lithium, lithium perchlorate, lithium phosphate are dissolved in nmp solvent with the mass ratio of 66:18:8:8, form containing many lithium sulfides, methylaminoThe nmp solution of the 28%wt of 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, be uniformly mixed into viscose glue mud, after homogenizer fully mixes, be pressed into 380 μ m thickThin slice; It is in the high temperature furnace of 246 DEG C 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, then thin slice is inserted in the high temperature furnace of 1386 DEG C, under the condition that is 0.0994Mpa in negative pressure, process188min, is cooled to normal temperature in the normal temperature air chamber of anhydrous steam; Former to deviate from hydrogen, oxygen on the fine molecular resin chain of polypropyleneSon; 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, firstIn the nmp solution of aminobutyric acid lithium, lithium perchlorate, lithium phosphate 32%wt, after dipping 37min takes out, will contain many sulfurationsIt is the high temperature furnace of 238 DEG C that the block diatomite of lithium, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate and nmp solvent is placed in temperatureIn, suitably extracting under the condition of the vacuum that negative pressure is 0.086Mpa, after the processing time is 46min, through the normal temperature of anhydrous steamAir chamber is cooled to normal temperature, so just obtains flooding for the first time the silicon of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphateAlgae soil thin slice; And then insert contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, nmp solution in, dipping29min, then to insert temperature be in the high temperature furnace of 265 DEG C, suitably extracting under the condition of the vacuum that negative pressure is 0.091Mpa, processesTime is cooled to normal temperature through the normal temperature air chamber of anhydrous steam after being 35min, so flooded for the second time many lithium sulfides,The diatomite thin slice of methylamino butyric acid lithium, lithium perchlorate, lithium phosphate; Through dipping and the high temperature evaporation of 6 times go out repeatedly like thisNMP, makes the lithium-sulfur cell that contains many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 20.4%wt in block diatomiteAll solid state electrolyte; 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, add3.94mol industry one-level NMP, 1.0mol industry one-level vulcanized sodium and 0.003mol industry one sodium hydroxide, stir at 379rpmMix under condition, slowly the temperature of reaction system is elevated to 111 DEG C, then add 1.003mol industry top grade lithium chloride, continueThe temperature to 181 DEG C of rising reaction system, and under this temperature conditions, make reaction system insulation 27min, until in reaction systemWhile having tiny white crystal to separate out, the 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 temperature rise to 113 DEG C, and the insulation that refluxes under this temperature conditions5.6h, until in reaction system during without sublimed sulfur powder, stop to reaction system heating, simultaneously by slow the temperature of reaction systemDrop to room temperature, now, in reaction system, separate out a small amount of light yellow or white pressed powder; From reaction system, filter out and analyseLight yellow or the white solid powder going out, measures the mass concentration of many lithium sulfides, then adds methylamino butyric acid according to recipe ratioLithium, lithium perchlorate, lithium phosphate, and temperature is heated to 115 DEG C, under this temperature conditions, be incubated 63min, then, be cooled to chamberTemperature is 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 containing many lithium sulfides,The nmp solution of the 30%wt of 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, be uniformly mixed into viscose glue mud, after homogenizer fully mixes, be pressed into 260 μ m thickThin slice; It is in the high temperature furnace of 244 DEG C 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, then thin slice is inserted in the high temperature furnace of 1344 DEG C, under the condition that is 0.0997Mpa in negative pressure, process179min, is cooled to normal temperature in the normal temperature air chamber of anhydrous steam; Former to deviate from hydrogen, oxygen on the fine molecular resin chain of polypropyleneSon; Making porosity is 86.3%, and aperture is the diatomite thin slice that 4.8um structure contains carbon; By thin slice insert containing many lithium sulfides,In the nmp solution of methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 29%wt, after dipping 36min takes out, will contain many sulphurIt is the high temperature of 235 DEG C that the block diatomite of changing lithium, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate and nmp solvent is placed in temperatureIn stove, suitably extracting under the condition of the vacuum that negative pressure is 0.079Mpa, after the processing time is 43min, normal through anhydrous steamWarm air chamber is cooled to normal temperature, so just obtains flooding for the first time many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphateDiatomite thin slice; And then insert contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, nmp solution in, soakStain 21min, then to insert temperature be in the high temperature furnace of 261 DEG C, suitably extracting under the condition of the vacuum that negative pressure is 0.088Mpa, locatesThe reason time is cooled to normal temperature through the normal temperature air chamber of anhydrous steam after being 35min, is so flooded for the second time many sulfurationsThe diatomite thin slice of lithium, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate; Through dipping and the high temperature evaporation of 7 times go out repeatedly like thisNMP, makes the lithium-sulfur cell that contains many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 19.8%wt in block diatomiteAll solid state electrolyte; 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 4.5molIndustry one-level NMP, 1.0mol industry one-level vulcanized sodium and 0.003mol industry one sodium hydroxide, at 381rpm stirring conditionUnder, slowly the temperature of reaction system is elevated to 114 DEG C, then add 1.003mol industry top grade lithium chloride, continue to raise anti-Answer the temperature to 188 DEG C of system, and under this temperature conditions, make reaction system insulation 32min, until have tiny in reaction systemWhite crystal while separating out, the water evaporates in reaction system is removed simultaneously, and stops heating; And filter while hot, will reactWhite crystal in system filters out, and filtrate rejoins reaction system, and the stirring intensity of reactor is 381rpm, adds and joinsSublimed sulfur in side and deionization anaerobic water, treat temperature rise to 116 DEG C, and the insulation 5.5h that refluxes under this temperature conditions, straightTo in reaction system during without sublimed sulfur powder, stop, to reaction system heating, the temperature of reaction system being dropped to slowly simultaneouslyRoom temperature, now, separates out a small amount of light yellow or white pressed powder in reaction system; From reaction system, filter out separate out shallowYellow or white solid powder, measure the mass concentration of many lithium sulfides, then adds methylamino butyric acid lithium, high chlorine according to recipe ratioAcid lithium, lithium phosphate, and temperature is heated to 117 DEG C, 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, methylaminoButyric acid lithium, lithium perchlorate, lithium phosphate are dissolved in nmp solvent with the mass ratio of 63:21:8:8, form containing many lithium sulfides, methylaminoThe nmp solution of the 31%wt of 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, be uniformly mixed into viscose glue mud, after homogenizer fully mixes, be pressed into 630 μ m thickThin slice; It is in the high temperature furnace of 256 DEG C 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, then thin slice is inserted in the high temperature furnace of 1388 DEG C, under the condition that is 0.0998Mpa in negative pressure, process184min, is cooled to normal temperature in the normal temperature air chamber of anhydrous steam; Former to deviate from hydrogen, oxygen on the fine molecular resin chain of polypropyleneSon; Making porosity is 84.1%, and aperture is the diatomite thin slice that 4.67um structure contains carbon; Thin slice is inserted containing many sulfurationsIn the nmp solution of lithium, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 30.8%wt, after dipping 36min takes out, will containIt is 229 DEG C that the block diatomite of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate and nmp solvent is placed in temperatureIn high temperature furnace, suitably extracting under the condition of the vacuum that negative pressure is 0.085Mpa, after the processing time is 45min, through anhydrous steamNormal temperature air chamber be cooled to normal temperature, so just obtain flooding for the first time many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, phosphoric acidThe diatomite thin slice of lithium; And then insert contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, nmp solutionIn, dipping 18～33min, then to insert temperature be in the high temperature furnace of 263 DEG C, is suitably extracting vacuum that negative pressure is 0.089MpaUnder condition, the processing time is cooled to normal temperature through the normal temperature air chamber of anhydrous steam after being 35min, is just soaked for the second time like thisSteep the diatomite thin slice of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate; Through such dipping and the height of 7 times repeatedlyTemperature evaporates NMP, makes to contain in block diatomite many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 20.69%wtLithium-sulfur cell all solid state electrolyte; 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 4.7molIndustry one-level NMP, 1.0mol industry one-level vulcanized sodium and 0.003mol industry one sodium hydroxide, at 389rpm stirring conditionUnder, slowly the temperature of reaction system is elevated to 117 DEG C, then add 1.003mol industry top grade lithium chloride, continue to raise anti-Answer the temperature to 187 DEG C of system, and under this temperature conditions, make reaction system insulation 19min, until have tiny in reaction systemWhite crystal while separating out, the water evaporates in reaction system is removed simultaneously, and stops heating; And filter while hot, will reactWhite crystal in system filters out, and filtrate rejoins reaction system, and the stirring intensity of reactor is 389rpm, adds and joinsSublimed sulfur in side and deionization anaerobic water, treat temperature rise to 116 DEG C, and the insulation 4.3h that refluxes under this temperature conditions, straightTo in reaction system during without sublimed sulfur powder, stop, to reaction system heating, the temperature of reaction system being dropped to slowly simultaneouslyRoom temperature, now, separates out a small amount of light yellow or white pressed powder in reaction system; From reaction system, filter out separate out shallowYellow or white solid powder, measure the mass concentration of many lithium sulfides, then adds methylamino butyric acid lithium, high chlorine according to recipe ratioAcid lithium, lithium phosphate, and temperature is heated to 116 DEG C, 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, methylaminoButyric acid lithium, lithium perchlorate, lithium phosphate are dissolved in nmp solvent with the mass ratio of 65:19:8:8, form containing many lithium sulfides, methylaminoThe nmp solution of the 29%wt of 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, be uniformly mixed into viscose glue mud, after homogenizer fully mixes, be pressed into 590 μ m thickThin slice; It is in the high temperature furnace of 247 DEG C that thin slice is inserted to temperature, is suitably extracting vacuum that negative pressure is 0.078～0.084MpaUnder condition, after the processing time is 64min, then thin slice is inserted in the high temperature furnace of 1387 DEG C to the condition that is 0.0998Mpa in negative pressureUnder, process 186min, be cooled to normal temperature in the normal temperature air chamber of anhydrous steam; To deviate from the fine molecular resin chain of polypropyleneHydrogen, oxygen atom; Making porosity is 87.3%, and aperture is the diatomite thin slice that 3～5um structure contains carbon; Thin slice is inserted and containedIn the nmp solution of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 29%wt, after dipping 37min takes out, willIt is 238 that the block diatomite that contains many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate and nmp solvent is placed in temperatureDEG C high temperature furnace in, suitably extracting under the condition of the vacuum that negative pressure is 0.083Mpa, after the processing time is 47min, through anhydrousThe normal temperature air chamber of 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, NMPIn solution, dipping 24min, then to insert temperature be in the high temperature furnace of 261 DEG C, is suitably extracting vacuum that negative pressure is 0.091MpaUnder condition, the processing time is cooled to normal temperature through the normal temperature air chamber of anhydrous steam after being 36min, is just soaked for the second time like thisSteep the diatomite thin slice of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate; Through such dipping and the height of 8 times repeatedlyTemperature evaporates NMP, makes to contain in block diatomite many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 20.4%wtLithium-sulfur cell all solid state electrolyte; Wherein the thickness of lithium-sulfur cell all solid state electrolyte thin slice is 0.590mm.
Claims (2)
1. a manufacture method for lithium-sulfur cell all solid state electrolyte, is characterized in that, by fine polypropylene resin micropowder and diatomSoil, with mass ratio 46～56:54～44, adds in high-speed mixing agitator, and adding nmp solvent to make diatomaceous quality is 18～24wt%, under well-beaten condition, is uniformly mixed into viscosity viscose glue mud, then that viscose glue mud is entirely solid according to lithium-sulfur cellThe electrolytical bulk material that need to be made into respective shapes of state, is placed in the high temperature furnace through nitrogen replacement by bulk material,Under the condition of extracting vacuum, make block viscose glue mud become the block diatomite that only contains carbon composition, then by many lithium sulfides, firstAminobutyric acid lithium, lithium perchlorate, lithium phosphate are dissolved in nmp solvent with the mass ratio of 58～66:33～18:6～8:3～8, formContain the nmp solution of 18～33wt% of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, then will be through high temperature placeBlock diatomite after reason immerses in the nmp solution that contains many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate, dipping13～18min, after taking-up, will contain the bulk silicon of many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate and nmp solventAlgae soil is placed in another high temperature furnace through nitrogen replacement, under the condition of extracting vacuum, makes the nmp solvent in block diatomiteFully evaporate, 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 and lithium phosphate totally 18～21wt%, obtain lithium-sulfur cell all solid state electrolyte.
2. the manufacture method of lithium-sulfur cell all solid state electrolyte according to claim 1, is characterized in that, comprises followingConcrete 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, 360～Under 390rpm stirring condition, slowly the temperature of reaction system is elevated to 108～118 DEG C, then adds 1.003mol industry excellentLevel lithium chloride, temperature to 160～190 DEG C of continuing 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, the moisture evaporation in reaction system is removed, simultaneouslyAnd stop heating;
2) by 1) the anhydrous response system that obtains under the protection of nitrogen, filter while hot, by the white crystal mistake in reaction systemLeach, filtrate is under 360～390rpm condition in the mixing speed of reactor, add sublimed sulfur in formula and deionization withoutOxygen water, treats temperature rise to 108～118 DEG C, and the insulation 4～6h that refluxes under this temperature conditions, until nothing rises in reaction systemWhen magnificent sulphur powder, stop, to reaction system heating, the temperature of reaction system being dropped to room temperature slowly simultaneously, now, reaction bodyIn 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, and the quality of measuring many lithium sulfides is denseDegree, then adds methylamino butyric acid lithium, lithium perchlorate, lithium phosphate according to recipe ratio, and temperature is heated to 108～118 DEG C,Under this temperature conditions, be incubated 33～66min, then, be cooled to room temperature stand-by; Thereby obtain containing many lithium sulfides, methylamino butyric acidThe nmp solution of lithium, lithium perchlorate, lithium phosphate;
4), by formula in the fine resin micropowder powder of polypropylene and diatomite, adding nmp solvent to make diatomaceous quality is 18～24wt%, under well-beaten condition, is uniformly mixed into viscose glue mud, after homogenizer fully mixes, pressesBecome the thick diatomite thin slice of 180～660 μ m;
5), by 4) to insert temperature be in the high temperature furnace of 240～260 DEG C for the diatomite thin slice of gained, suitably extracting negative pressure beUnder the condition of the vacuum of 0.078～0.084MPa, after the processing time is 48～68min, then diatomite thin slice is inserted to 1280～In the high temperature furnace of 1390 DEG C, under the condition that is 0.098～0.0999MPa in negative pressure, process 166～188min, at anhydrous steamNormal temperature air chamber be cooled to normal temperature; To deviate from hydrogen, the oxygen atom on the fine molecular resin chain of polypropylene; Make porosity and be 66～88%, aperture is the diatomite thin slice that 3～5um structure contains carbon;
6), by 5) the diatomite thin slice that obtains inserts 3) containing many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate 28～In the nmp solution of 33wt%, through flooding after 33～38min taking-up, will contain many lithium sulfides, methylamino butyric acid lithium, perchloric acidIt is the high temperature furnace of 220～240 DEG C that the block diatomite of lithium, lithium phosphate and nmp solvent is placed in temperature, is suitably extracting negative pressureBe under the condition of vacuum of 0.068～0.088MPa, after the processing time is 36～48min, through the normal temperature air chamber of anhydrous steamBe cooled to normal temperature, the diatomite that so just obtains flooding for the first time many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate is thinSheet;
7) by 6) the diatomite thin slice that obtains insert again contain many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate,In nmp solution, dipping 18～33min, then to insert temperature be in the high temperature furnace of 260～266 DEG C, suitably extracting negative pressure isUnder the condition of the vacuum of 0.088～0.091MPa, after the processing time is 33～36min, cold through the normal temperature air chamber of anhydrous steamBut to normal temperature, the diatomite that is so flooded for the second time many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate, lithium phosphate is thinSheet;
8) by 7) the diatomite thin slice that obtains adopts 7) process conditions in step, through dipping and the high temperature of 6～8 times steam repeatedlySend NMP, make to contain in block diatomite thin slice many lithium sulfides, methylamino butyric acid lithium, lithium perchlorate and lithium phosphate totally 18～21wt%, obtains lithium-sulfur cell all solid state electrolyte; Wherein the thickness of lithium-sulfur cell all solid state electrolyte thin slice be 0.1～0.664mm。
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| CN103730632A (en) * | 2013-12-18 | 2014-04-16 | 湘潭大学 | Bergmeal-based lithium sulphur battery cathode material as well as preparation and application methods thereof |
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