CN110098396A - A kind of lithium-sulfur battery composite cathode material and preparation method thereof and battery - Google Patents
A kind of lithium-sulfur battery composite cathode material and preparation method thereof and battery Download PDFInfo
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- CN110098396A CN110098396A CN201910371857.7A CN201910371857A CN110098396A CN 110098396 A CN110098396 A CN 110098396A CN 201910371857 A CN201910371857 A CN 201910371857A CN 110098396 A CN110098396 A CN 110098396A
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- metal
- carbon
- anode material
- composite anode
- sulphur
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- 239000002131 composite material Substances 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title abstract description 20
- 239000010406 cathode material Substances 0.000 title abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 163
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 122
- 239000010405 anode material Substances 0.000 claims abstract description 94
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000005864 Sulphur Substances 0.000 claims abstract description 34
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 34
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 34
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 32
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 32
- 239000011258 core-shell material Substances 0.000 claims abstract description 18
- 239000004005 microsphere Substances 0.000 claims description 64
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 19
- 238000003763 carbonization Methods 0.000 claims description 17
- -1 neopelex Chemical group 0.000 claims description 16
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
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- 239000000126 substance Substances 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical group 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229920000136 polysorbate Polymers 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 15
- 150000008117 polysulfides Polymers 0.000 abstract description 15
- 229920001021 polysulfide Polymers 0.000 abstract description 14
- 239000005077 polysulfide Substances 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052744 lithium Inorganic materials 0.000 abstract description 8
- 238000004458 analytical method Methods 0.000 abstract description 5
- 239000013067 intermediate product Substances 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 229910002090 carbon oxide Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 46
- 238000003756 stirring Methods 0.000 description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 35
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- 239000000377 silicon dioxide Substances 0.000 description 27
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- 229910052905 tridymite Inorganic materials 0.000 description 27
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 18
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 17
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 9
- 239000000908 ammonium hydroxide Substances 0.000 description 9
- 229920000573 polyethylene Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229960000935 dehydrated alcohol Drugs 0.000 description 8
- 238000005253 cladding Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 230000003628 erosive effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 239000005030 aluminium foil Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 102000004310 Ion Channels Human genes 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical group [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
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- 230000004927 fusion Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004540 process dynamic Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to lithium sulfur battery anode material technical field more particularly to a kind of lithium-sulfur battery composite cathode material and preparation method thereof and batteries.The present invention provides a kind of battery composite anode material, and battery composite anode material has core-shell structure；Core-shell structure includes metal-carbon shell and the sulphur core that is set in metal-carbon shell；Metal-carbon shell is formed by metal hydroxides and/or metal oxide with carbon, and metal hydroxides and/or metal oxide are coated in carbon；Sulphur core is formed by elemental sulfur.Battery composite anode material of the present invention has core-shell structure, metal-carbon shell can be improved the conductivity of battery composite anode material and can play the role of confinement to sulphur and intermediate product polysulfide, metal hydroxides and/or metal oxide can not only act on absorption polysulfide by " close lithium " or " close sulphur ", inhibit shuttle effect, analysis sulphur site is provided, it can also be catalyzed the conversion of sulphur and polysulfide, improve kinetics of electrode process, improve electrode conversion rate.
Description
Technical field
The invention belongs to lithium sulfur battery anode material technical field more particularly to a kind of lithium-sulfur battery composite cathode material and
Preparation method and battery.
Background technique
Lithium-sulfur cell becomes because of its theoretical energy density high (2600Wh/kg) and theoretical specific capacity high (1675mAh/g)
Increasingly have researching value, also, sulphur has many advantages, such as there are reserves abundant on earth, have it is non-toxic and
Environment friendly, lithium-sulfur cell most promise to be the secondary cell system of next-generation high-energy-density.
But there are some problems to hamper its broad practice for lithium-sulfur cell, and such as: the low electricity of sulphur and discharging product
Conductance causes capacity to be difficult to play；Intermediate product polysulfide is easily dissolved in electrolyte, and coulomb during long circulating is caused to be imitated
The low fast decay with capacity of rate；Volume expansion in charge/discharge process can destroy the electrode structure etc. of lithium-sulfur cell.
There are many methods to be made to solve the above problem in recent years, such as nano carbon-base material since its electric conductivity is high,
Stable structure is widely used and does the carrier of lithium-sulfur cell, however nano carbon-base material is only capable of significantly improving the electric conductivity of electrode,
In the conversion rate for improving lithium sulfur electrode, the effect for limiting shuttle of polysulfide etc. is very limited.
Summary of the invention
In view of this, the present invention provides a kind of battery composite anode material and preparation method thereof and batteries, for solving
Existing lithium sulfur battery anode material has that conversion rate is slow, polysulfide shuttle effect is up for reducing.
The specific technical solution of the present invention is as follows:
A kind of battery composite anode material, the battery composite anode material have core-shell structure；
The core-shell structure includes metal-carbon shell and the sulphur core that is set in the metal-carbon shell；
The metal-carbon shell is formed by metal hydroxides and/or metal oxide with carbon, the metal hydroxides
And/or metal oxide is coated in the carbon；
The sulphur core is formed by elemental sulfur.
Preferably, the metal is transition metal；
The transition metal is selected from one of titanium, iron, nickel, zinc, copper and cobalt or a variety of.
Preferably, the elemental sulfur is 40%~70% in the mass content of the battery composite anode material；
The metal hydroxides and/or metal oxide are 5% in the mass content of the battery composite anode material
~30%；
The carbon is 20%~40% in the mass content of the battery composite anode material.
Preferably, the diameter of the core-shell structure is 100nm~600nm；
The metal-carbon shell with a thickness of 10nm~50nm；
The diameter of the sulphur core is 30nm~200nm；
The partial size of the metal hydroxides and/or metal oxide is 5nm~30nm.
Preferably, cavity is provided between the metal-carbon shell and the sulphur core.
The present invention also provides a kind of preparation methods of battery composite anode material, comprising the following steps:
A) it in the surface deposited metal hydroxide and/or metal oxide of microballoon, obtains to surface and is deposited with metal hydrogen-oxygen
The complex microsphere of compound and/or metal oxide；
B) in complex microsphere surface coated high molecular, then carrying out carbonization treatment makes the macromolecule be carbonized, and obtains carbon
The complex microsphere of cladding；
C) the carbon-coated complex microsphere is performed etching into processing, removes microballoon, obtains metal-carbon shell, then described
Elemental sulfur is loaded in metal-carbon shell, the elemental sulfur forms sulphur core in the metal-carbon shell, obtains cell composite anode material
Material.
Preferably, step c) loads elemental sulfur in the metal-carbon shell and specifically includes:
The metal-carbon shell is mixed with elemental sulfur and is placed in vacuum condition, carrying out heat treatment makes the elemental sulfur
Melting diffuses in the metal-carbon shell.
Preferably, step c) loads elemental sulfur in the metal-carbon shell and specifically includes:
It disperses the metal-carbon shell in sulphur source solution, after surfactant is added, adds precipitating reagent and be stirred
Deposit elemental sulfur to metal-carbon shell.
Preferably, the sulphur source is selected from Na2S2O3、Na2SXWith one of thiocarbamide or a variety of；
The surfactant is selected from cetyl trimethylammonium bromide, neopelex, octyl phenyl polyoxy
One of vinethene and tween are a variety of；
The precipitating reagent is selected from one of hydrochloric acid, oxalic acid, phosphoric acid and acetic acid or a variety of.
The present invention also provides a kind of battery, the positive electrode of the battery includes that battery described in above-mentioned technical proposal is compound
Battery composite anode material made from preparation method described in positive electrode and/or above-mentioned technical proposal.
In conclusion the battery composite anode material has core the present invention provides a kind of battery composite anode material
Shell structure；The core-shell structure includes metal-carbon shell and the sulphur core that is set in the metal-carbon shell；The metal-carbon shell by
Metal hydroxides and/or metal oxide are formed with carbon, and the metal hydroxides and/or metal oxide are coated on described
In carbon；The sulphur core is formed by elemental sulfur.In the present invention, battery composite anode material has core-shell structure, including metal hydrogen-oxygen
Compound and/or metal oxide and carbon the metal-carbon shell formed and the sulphur core being set in metal-carbon shell, metal-carbon shell can
It improves the conductivity of battery composite anode material and confinement, metal-carbon can be played the role of to sulphur and intermediate product polysulfide
On the one hand metal hydroxides and/or metal oxide in shell pass through " close lithium " or " close sulphur " effect absorption polysulfide, suppression
Shuttle effect processed provides analysis sulphur site, on the other hand can also be catalyzed the conversion of sulphur and polysulfide, improves electrode process power
It learns, improves the conversion rate of electrode.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described.
Fig. 1 is a kind of flow diagram of the preparation method of battery composite anode material provided in an embodiment of the present invention；
Fig. 2 is a kind of transmission electron microscope figure for battery composite anode material that the embodiment of the present invention 2 provides；
Fig. 3 is the charge and discharge that a kind of battery composite anode material provided using the embodiment of the present invention 3 makees the battery of anode
Curve graph；
Fig. 4 is the cyclicity that a kind of battery composite anode material provided using the embodiment of the present invention 3 makees the battery of anode
It can curve graph；
Fig. 5 is the cyclicity that a kind of battery composite anode material provided using the embodiment of the present invention 8 makees the battery of anode
It can curve graph；
Fig. 6 is the charge and discharge that a kind of battery composite anode material provided using comparative example 1 of the present invention makees the battery of anode
Curve graph；
Fig. 7 is the cyclicity that a kind of battery composite anode material provided using comparative example 1 of the present invention makees the battery of anode
It can curve graph；
It illustrates: 1. sulphur cores；2. metal hydroxides and/or metal oxide；3. carbon；4. microballoon；5. macromolecule；6.
Complex microsphere；7. the complex microsphere of polymeric PTC materials；8. carbon-coated complex microsphere；9. metal-carbon shell；10. battery is compound just
Pole material.
Specific embodiment
The present invention provides a kind of battery composite anode material and preparation method thereof and batteries, for solving existing lithium sulphur electricity
Pond positive electrode has that conversion rate is slow, polysulfide shuttle effect is up for reducing.
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
A kind of battery composite anode material, battery composite anode material 10 have core-shell structure；
Core-shell structure includes metal-carbon shell 9 and the sulphur core 1 that is set in metal-carbon shell 9；
Metal-carbon shell 9 is formed by metal hydroxides and/or metal oxide 2 with carbon 3, metal hydroxides and/or gold
Belong to oxide 2 to be coated in carbon 3；
Sulphur core 1 is formed by elemental sulfur.
In the embodiment of the present invention, battery composite anode material 10 has core-shell structure, including metal hydroxides and/or gold
Belonging to oxide 2 and the metal-carbon shell 9 formed of carbon 3 and the sulphur core 1 being set in metal-carbon shell 9, metal-carbon shell 9 can be improved
The conductivity of battery composite anode material 10 simultaneously can play the role of confinement, metal-carbon to sulphur core 1 and intermediate product polysulfide
Metal hydroxides and/or 2 one side of metal oxide in shell 9 adsorb polysulfide by " close lithium " or " close sulphur " effect,
Chemical bonding is formed, shuttle effect is inhibited, analysis sulphur site is provided, the conversion of sulphur and polysulfide on the other hand can be also catalyzed, mention
High electrode process dynamics, improves the conversion rate of electrode.
In the embodiment of the present invention, core-shell structure is spherical structure or spherical structure.
In the embodiment of the present invention, the metal in metal hydroxides and/or metal oxide 2 is transition metal；
Transition metal is selected from one of titanium, iron, nickel, zinc, copper and cobalt or a variety of.
Metal hydroxides and/or metal oxide 2 include titanium dioxide, iron hydroxide (Fe (OH)3), nickel oxide, oxygen
Change zinc, Kocide SD (Cu (OH)2) and cobalt hydroxide (Co (OH)3) one of or it is a variety of.
In the embodiment of the present invention, elemental sulfur is 40%~70% in the mass content of battery composite anode material 10；
Metal hydroxides and/or metal oxide 2 the mass content of battery composite anode material 10 be 5%~
30%；
Carbon 3 is 20%~40% in the mass content of battery composite anode material 10.
In the embodiment of the present invention, the diameter of core-shell structure is 100nm~600nm；
Metal-carbon shell 9 with a thickness of 10nm~50nm；
The diameter of sulphur core is 30nm~200nm；
The partial size of metal hydroxides and/or metal oxide 2 is 5nm~30nm, metal hydroxides and/or metal oxygen
Compound 2 is continuously or non-continuously coated on sulphur core 1.
In the embodiment of the present invention, the surface of battery composite anode material 10 has micropore and mesoporous, and the aperture of micropore is 1nm
~2nm, mesoporous aperture are 2nm~30nm.
In the prior art, due to the difference of elemental sulfur and lithium sulfide density, in charge and discharge process, volume can occur for electrode
Expansion, on the one hand, easily in obstruction electrochemical reaction process on the other hand electronics and ion channel easily lead to active material from collection
It falls off and loses activity on fluid, cause lithium-sulfur cell that large-scale application is not yet received.
In the embodiment of the present invention, cavity is provided between metal-carbon shell 9 and sulphur core 1.The volume of lithium reaction of Salmon-Saxl can be alleviated
Fluctuating stress can be avoided the obstruction of electronics and ion channel in electrochemical reaction process, avoid active material from collector
It falls off and loses activity.
In the embodiment of the present invention, cavity is 10%~60% in the volume accounting of battery composite anode material 10, preferably
50%.
It should be noted that sulphur core 1 can be adjusted as needed in 10 load capacity of battery composite anode material, metal-
Cavity may not be present between carbon shell 9 and sulphur core 1.
In the embodiment of the present invention, battery composite anode material 10 has core-shell structure, including metal hydroxides and/or gold
Belong to the metal-carbon shell 9 and sulphur core 1 that oxide 2 and carbon 3 are formed, metal-carbon shell 9 and sulphur core 1 can play synergistic effect, metal-carbon
Shell 9 can be improved the conductivity of battery composite anode material 10 and can play confinement to sulphur core 1 and intermediate product polysulfide
It acts on, the metal hydroxides and/or 2 one side of metal oxide in metal-carbon shell 9 are inhaled by " close lithium " or " close sulphur " effect
Attached polysulfide forms chemical bonding, inhibits shuttle effect, provides analysis sulphur site, on the other hand can also be catalyzed sulphur and more vulcanizations
The conversion of object improves kinetics of electrode process, improves the conversion rate of electrode, sulphur core 1 contains battery composite anode material 10
Amount is high, and cavity is provided between metal-carbon shell 9 and sulphur core 1 can alleviate the volume change of lithium reaction of Salmon-Saxl, have in terms of energy storage huge
Big application prospect.
The present invention also provides a kind of preparation methods of battery composite anode material, comprising the following steps:
A) it in the surface deposited metal hydroxide and/or metal oxide 2 of microballoon 4, obtains to surface and is deposited with metallic hydrogen
The complex microsphere 6 of oxide and/or metal oxide 2；
B) in 6 surface coated high molecular of complex microsphere, then carrying out carbonization treatment makes macromolecule be carbonized, and obtains carbon-coated multiple
Close microballoon 8；
C) carbon-coated complex microsphere 8 is performed etching into processing, removes microballoon 4, obtains metal-carbon shell 9, then in metal-
Elemental sulfur is loaded in carbon shell 9, elemental sulfur forms sulphur core 1 in metal-carbon shell 9, obtains battery composite anode material.
In the embodiment of the present invention, step a) preferably disperses microballoon 4 in metal salt solution and metal salt is hydrolyzed,
It is dry, it obtains to surface and is deposited with the complex microsphere 6 of metal hydroxides and/or metal oxide 2.
The pH value of hydrolysis is 7~10；The temperature of hydrolysis is 25 DEG C~50 DEG C；The time of hydrolysis is 3h~6h.
Step a) microballoon 4 is scattered in metal salt solution specifically: the aqueous solution of microballoon 4 is by ultrasonic disperse in metal salt
In solution；After being hydrolyzed, before dry, further includes: be centrifuged or be separated by filtration, clean.
After step b) preferably disperses Polymer Solution for complex microsphere 6, the complex microsphere 7 of polymeric PTC materials is obtained, then
The complex microsphere 7 of polymeric PTC materials, which is carried out carbonization treatment, makes macromolecule 5 be carbonized, and obtains carbon-coated complex microsphere 8.
The atmosphere of carbonization treatment is nitrogen and/or inert gas；The temperature of carbonization treatment is 600 DEG C~1000 DEG C；Carbonization
The temperature of processing is 1h~6h.
In the embodiment of the present invention, step b) complex microsphere 6 is by ultrasonic disperse in Polymer Solution, the time of ultrasonic disperse
For 1h~3h；After dispersing Polymer Solution for complex microsphere 6, before obtaining the complex microsphere 7 of polymeric PTC materials, further includes: according to
It is secondary be stirred, eccentric cleaning and drying；Carbonization treatment carries out in tube furnace, and the heating rate of carbonization treatment is 2 DEG C/min
~10 DEG C/min.
Step c) preferably performs etching processing in HF or NaOH solution.
In the embodiment of the present invention, microballoon 4 is preferably the SiO of diameter 100nm~300nm2Microballoon；
Metal salt is selected from butyl titanate, FeCl3、AlCl3、ZnCl2、CuSO4With Co (NO3)3One of or it is a variety of；
Macromolecule 5 is preferably phenolic resin.
Microballoon 4 is more preferably the SiO of different-diameter2Microballoon can provide big lithium ion after the microballoon of major diameter etches
Transmission channel can also be such that the load of elemental sulfur increases；And the microballoon of minor diameter, there is bigger specific surface area, can provide more
More reactivity sites.
In the embodiment of the present invention, useMethod prepares the SiO of different-diameter2Microballoon specifically includes: by ethyl alcohol, water
It is sequentially added in beaker with ammonium hydroxide, it is uniform with magnetic stirrer at room temperature, then under stirring conditions by ethyl orthosilicate
(TEOS) it is slowly dropped in uniformly mixed above-mentioned solution and reaction is hydrolyzed, be added dropwise with polyethylene film sealed beaker
Mouthful, there is white precipitate in 1min~5min, stirs, makes end of reaction, using eccentric cleaning, obtain SiO2Microballoon.
In the embodiment of the present invention, step c) can load elemental sulfur in metal-carbon shell 9 by solid phase fusion diffusion method, tool
Body includes:
Metal-carbon shell 9 is mixed with elemental sulfur and is placed in vacuum condition, carrying out heat treatment makes elemental sulfur melting diffusion
To metal-carbon shell.
Further, the volatilization temperature of elemental sulfur is 100 DEG C~300 DEG C, and elemental sulfur is preferably sublimed sulfur；Metal-carbon shell 9
Mass ratio with elemental sulfur is 1:0.25~0.8；Mixing is specially to be fully ground in mortar；Heat treatment is specially at 140 DEG C
Constant temperature handles 2h~10h at~160 DEG C, it is preferred to use oil bath pan is heated.
In the embodiment of the present invention, step c) can also load elemental sulfur in metal-carbon shell 9 by liquid phase deposition, specifically
Include:
It disperses metal-carbon shell 9 in sulphur source solution, after surfactant is added, adding precipitating reagent and being stirred makes
Elemental sulfur is deposited to metal-carbon shell.
Sulphur source is selected from Na2S2O3、Na2SXWith one of thiocarbamide or a variety of, the concentration of sulphur source solution be 0.05mol/L~
0.2mol/L；Surfactant is selected from cetyl trimethylammonium bromide (CTAB), neopelex (SDBS), octyl
One of phenyl polyoxyethylene ether (TX-100) and tween are a variety of；Precipitating reagent is in hydrochloric acid, oxalic acid, phosphoric acid and acetic acid
One or more, the concentration of precipitating reagent is 0.05mol/L~0.2mol/L.
Surfactant is added and then is added before precipitating reagent, further includes: ultrasonic treatment 1h~3h.Precipitating reagent is added
The time being stirred is 1h~3h.After stirring, further includes: be successively filtered, wash and dry, dry temperature is 60
DEG C~120 DEG C.
In order to spread elemental sulfur in metal-carbon shell 9 uniformly, sulphur core is combined closely with metal-carbon shell 9, in metal-carbon
In shell after load elemental sulfur, further includes: be heat-treated, the temperature of heat treatment is 250 DEG C~400 DEG C, preferably 300 DEG C；
The time of heat treatment is 10min~60min, preferably 30min；The heating rate of heat treatment is 2 DEG C/min~10 DEG C/min.
After the heat treatment, the sulphur for removing 10 surface of battery composite anode material, makes 10 table of battery composite anode material
The sulphur in face is 0~10% in the mass content of battery composite anode material.
Preparation method of the present invention usesMethod prepares the SiO of different-diameter2Then microballoon uses SiO2Microballoon conduct
Presoma template, successively coats metal hydroxides and/or metal oxide 2 and macromolecule 5, outside high temperature cabonization macromolecule
Shell, then pass through etching removal SiO2Microballoon obtains metal-carbon shell 9 and the compound obtained battery composite anode material of sulphur.Battery is compound
Positive electrode 10 has core-shell structure, the metal-carbon shell 9 formed including metal hydroxides and/or metal oxide 2 and carbon 3
With the sulphur core 1 being set in metal-carbon shell 9, " conduction ", " absorption ", " confinement " and " catalysis " function of sulfur electrode can be made to obtain
To reinforcing, battery composite anode material load sulfur content is high, electrode reaction dynamics is quick, stability is high.
The present invention also provides a kind of battery, the positive electrode of battery includes above-mentioned technical proposal battery composite anode material
10 and/or above-mentioned technical proposal preparation method made from battery composite anode material 10.
The battery of battery composite anode material by adopting the above technical scheme, positive electrode can realize good captured sulfur result,
The problems such as sulphur volume expansion and dissolution can not only be inhibited, it also can avoid sulphur shuttle effect, sulphur is in cell composite anode in battery
The mass content of material is 40%~70%, and battery may make to show good electrochemical energy storage property.
For a further understanding of the present invention, the present invention will be described in detail combined with specific embodiments below.
Embodiment 1
The preparation of the present embodiment progress battery composite anode material, comprising the following steps:
1) 20mL deionized water, 70mL dehydrated alcohol and 5mL 30wt% ammonium hydroxide are measured respectively, are sequentially added in beaker, room
It is uniform with magnetic stirrer under temperature, it weighs 1.0g ethyl orthosilicate (TEOS) and is slowly dropped to uniformly mixed above-mentioned solution
In, it is added dropwise with polyethylene film sealed beaker mouth, continuously stirs 6h at room temperature, make end of reaction, eccentric cleaning obtains not
With the SiO of diameter2Microballoon, SiO2The diameter of microballoon is 100nm~300nm.
2) 1.0g FeCl is weighed3It is add to deionized water, stirs at room temperature, form metal salt solution A.Separately weigh
1.3g SiO2Microballoon is dissolved in deionized water, obtains solution B.Solution B is instilled dropwise in metal salt solution A, adjusting pH value is
7,3h, FeCl are then persistently stirred at 25 DEG C3Hydrolysis, eccentric cleaning is dry, obtains complex microsphere, i.e. surface is deposited with Fe
(OH)3Microballoon.Wherein, Fe (OH)3With a thickness of 20nm, Fe (OH)3Content is 10%.
3) it weighs 1.5g phenolic resin to be dissolved in deionized water, 1.0g complex microsphere is added, persistently stirs 5h at room temperature, from
Heart cleaning, it is dry, obtain the complex microsphere of polymeric PTC materials；Carbon-coated complex microsphere is put into tube furnace again, in argon gas
In atmosphere, being warming up to 800 DEG C of progress 3h constant temperature carbonization treatments with the heating rate of 2 DEG C/min makes phenolic resin carbonized, obtains carbon
The complex microsphere of cladding, carbon content 20%.
4) obtained carbon-coated complex microsphere is added to concentration is in 2wt% hydrofluoric acid solution, and stirring 10h is carved
Erosion processing, removes SiO2, it is centrifugated, it is cleaned to be dried to obtain Fe (OH)3Metal-carbon shell.Weigh 0.1g Fe (OH)3Metal-
Carbon shell and 0.3g sublimed sulfur, after ground and mixed are uniform, obtained mixture are placed in reactor, is vacuumized, reactor is set
In oil bath pan, 120 DEG C are warming up to, keeps the temperature 10h, sublimed sulfur melting is made to enter Fe (OH)3In the hollow cavity of metal-carbon shell,
Cooled to room temperature, obtains battery composite anode material, and the content of S is 40%, Fe (OH)3Between metal-carbon shell and sulphur core
It is provided with cavity.
Embodiment 2
The preparation of the present embodiment progress battery composite anode material, comprising the following steps:
1) 20mL deionized water, 70mL dehydrated alcohol and 5mL 30wt% ammonium hydroxide are measured respectively, are sequentially added in beaker, room
It is uniform with magnetic stirrer under temperature, it weighs 1.0g ethyl orthosilicate (TEOS) and is slowly dropped to uniformly mixed above-mentioned solution
In, it is added dropwise with polyethylene film sealed beaker mouth, continuously stirs 6h at room temperature, make end of reaction, eccentric cleaning obtains not
With the SiO of diameter2Microballoon, SiO2The diameter of microballoon is 100nm~300nm.
2) 1.2g Co (NO is weighed3)3It is add to deionized water, stirs at room temperature, form metal salt solution A.Separately weigh
1.4g SiO2Microballoon is dissolved in deionized water, obtains solution B.Solution B is instilled dropwise in metal salt solution A, adjusting pH value is
7.5,3.5h, Co (NO are then persistently stirred at 30 DEG C3)3Hydrolysis, eccentric cleaning is dry, obtains complex microsphere, i.e. surface is heavy
Product has Co (OH)3Microballoon.Wherein, Co (OH)3With a thickness of 22nm, Co (OH)3Content is 12%.
3) it weighs 1.5g phenolic resin to be dissolved in deionized water, 1.0g complex microsphere is added, persistently stirs 5h at room temperature, from
Heart cleaning, it is dry, obtain the complex microsphere of polymeric PTC materials；Carbon-coated complex microsphere is put into tube furnace again, in argon gas
In atmosphere, being warming up to 600 DEG C of progress 5h constant temperature carbonization treatments with the heating rate of 2 DEG C/min makes phenolic resin carbonized, obtains carbon
The complex microsphere of cladding, carbon content 22%.
4) obtained carbon-coated complex microsphere is added to concentration is in 2wt% sodium hydroxide solution, and stirring 10h is carried out
Etching processing removes SiO2, it is centrifugated, it is cleaned to be dried to obtain Co (OH)3Metal-carbon shell.Weigh 0.12g Co (OH)3Gold
Category-carbon shell and 0.35g sublimed sulfur, after ground and mixed are uniform, obtained mixture are placed in reactor, is vacuumized, will reacted
Device is placed in oil bath pan, is warming up to 130 DEG C, keeps the temperature 8h, and sublimed sulfur melting is made to enter Co (OH)3The hollow cavity of metal-carbon shell
In, cooled to room temperature obtains battery composite anode material, and the content of S is 45%, Co (OH)3Metal-carbon shell and sulphur core it
Between be provided with cavity.
To the present embodiment Co (OH)3Metal-carbon shell is detected using transmission electron microscope, as a result referring to Fig. 2, result table
Bright Co (OH)3Metal-carbon shell is hollow structure.
Embodiment 3
The preparation of the present embodiment progress battery composite anode material, comprising the following steps:
1) 20mL deionized water, 70mL dehydrated alcohol and 5mL 30wt% ammonium hydroxide are measured respectively, are sequentially added in beaker, room
It is uniform with magnetic stirrer under temperature, it weighs 1.0g ethyl orthosilicate (TEOS) and is slowly dropped to uniformly mixed above-mentioned solution
In, it is added dropwise with polyethylene film sealed beaker mouth, continuously stirs 6h at room temperature, make end of reaction, eccentric cleaning obtains not
With the SiO of diameter2Microballoon, SiO2The diameter of microballoon is 100nm~300nm.
2) it weighs 1.3g butyl titanate to be add to deionized water, stir at room temperature, form solution A.Separately weigh 1.5g
SiO2Microballoon is dissolved in deionized water, obtains solution B.Solution B is instilled in solution A dropwise, adjusting pH value is 8, then 35
4h is persistently stirred at DEG C, tetrabutyl titanate hydrolysis, eccentric cleaning is dry, obtains complex microsphere, i.e. surface is deposited with TiO2It is micro-
Ball.Wherein, TiO2With a thickness of 21nm, TiO2Content is 18%.
3) it weighs 1.5g phenolic resin to be dissolved in deionized water, 1.2g complex microsphere is added, persistently stirs 5h at room temperature, from
Heart cleaning, it is dry, obtain the complex microsphere of polymeric PTC materials；Carbon-coated complex microsphere is put into tube furnace again, in nitrogen
In atmosphere, being warming up to 800 DEG C of progress 3h constant temperature carbonization treatments with the heating rate of 2 DEG C/min makes phenolic resin carbonized, obtains carbon
The complex microsphere of cladding, carbon content 27%.
4) obtained carbon-coated complex microsphere is added to concentration is in 2wt% hydrofluoric acid solution, and stirring 10h is carved
Erosion processing, removes SiO2, it is centrifugated, it is cleaned to be dried to obtain TiO2Metal-carbon shell.Weigh 0.13g TiO2Metal-carbon shell with
0.4g sublimed sulfur after ground and mixed is uniform, obtained mixture is placed in reactor, is vacuumized, reactor is placed in oil bath
In pot, 155 DEG C are warming up to, keeps the temperature 4h, sublimed sulfur melting is made to enter TiO2In the hollow cavity of metal-carbon shell, naturally cool to
Room temperature, obtains battery composite anode material, and the content of S is 52%, TiO2Cavity is provided between metal-carbon shell and sulphur core.
Embodiment 4
The preparation of the present embodiment progress battery composite anode material, comprising the following steps:
1) 20mL deionized water, 70mL dehydrated alcohol and 5mL 30wt% ammonium hydroxide are measured respectively, are sequentially added in beaker, room
It is uniform with magnetic stirrer under temperature, it weighs 1.0g ethyl orthosilicate (TEOS) and is slowly dropped to uniformly mixed above-mentioned solution
In, it is added dropwise with polyethylene film sealed beaker mouth, continuously stirs 6h at room temperature, make end of reaction, eccentric cleaning obtains not
With the SiO of diameter2Microballoon, SiO2The diameter of microballoon is 100nm~300nm.
2) 1.4g CuSO is weighed4It is add to deionized water, stirs at room temperature, form metal salt solution A.Separately weigh
1.7g SiO2Microballoon is dissolved in deionized water, obtains solution B.Solution B is instilled dropwise in metal salt solution A, adjusting pH value is
8,4h, CuSO are then persistently stirred at 40 DEG C4Hydrolysis, eccentric cleaning is dry, obtains complex microsphere, i.e. surface is deposited with Cu
(OH)2Microballoon.Wherein, Cu (OH)2With a thickness of 23nm, Cu (OH)2Content is 22%.
3) it weighs 1.5g phenolic resin to be dissolved in deionized water, 1.0g complex microsphere is added, persistently stirs 5h at room temperature, from
Heart cleaning, it is dry, obtain the complex microsphere of polymeric PTC materials；Carbon-coated complex microsphere is put into tube furnace again, in argon gas
In atmosphere, being warming up to 900 DEG C of progress 2h constant temperature carbonization treatments with the heating rate of 3 DEG C/min makes phenolic resin carbonized, obtains carbon
The complex microsphere of cladding, carbon content 32%.
4) obtained carbon-coated complex microsphere is added to concentration is in 2wt% hydrofluoric acid solution, and stirring 10h is carved
Erosion processing, removes SiO2, it is centrifugated, it is cleaned to be dried to obtain Cu (OH)2Metal-carbon shell.Weigh 0.15g Cu (OH)2Metal-
Carbon shell and 0.35g sublimed sulfur, after ground and mixed are uniform, obtained mixture are placed in reactor, is vacuumized, reactor is set
In oil bath pan, 160 DEG C are warming up to, keeps the temperature 5h, sublimed sulfur melting is made to enter TiO2It is natural in the hollow cavity of metal-carbon shell
It is cooled to room temperature, obtains battery composite anode material, the content of S is 59%, Cu (OH)2It is arranged between metal-carbon shell and sulphur core
There is cavity.
Embodiment 5
The preparation of the present embodiment progress battery composite anode material, comprising the following steps:
1) 20mL deionized water, 70mL dehydrated alcohol and 5mL 30wt% ammonium hydroxide are measured respectively, are sequentially added in beaker, room
It is uniform with magnetic stirrer under temperature, it weighs 1.0g ethyl orthosilicate (TEOS) and is slowly dropped to uniformly mixed above-mentioned solution
In, it is added dropwise with polyethylene film sealed beaker mouth, continuously stirs 6h at room temperature, make end of reaction, eccentric cleaning obtains not
With the SiO of diameter2Microballoon, SiO2The diameter of microballoon is 100nm~300nm.
2) 1.2g ZnCl is weighed2It is add to deionized water, stirs at room temperature, form metal salt solution A.Separately weigh
1.5g SiO2Microballoon is dissolved in deionized water, obtains solution B.Solution B is instilled dropwise in metal salt solution A, adjusting pH value is
8.5,4h, ZnCl are then persistently stirred at 45 DEG C2Hydrolysis, eccentric cleaning is dry, obtains complex microsphere, i.e. surface is deposited with
The microballoon of ZnO.Wherein, ZnO with a thickness of 25nm, ZnO content 27%.
3) it weighs 1.5g phenolic resin to be dissolved in deionized water, 1.3g complex microsphere is added, persistently stirs 5h at room temperature, from
Heart cleaning, it is dry, obtain the complex microsphere of polymeric PTC materials；Carbon-coated complex microsphere is put into tube furnace again, in nitrogen
In atmosphere, being warming up to 900 DEG C of progress 2h constant temperature carbonization treatments with the heating rate of 3 DEG C/min makes phenolic resin carbonized, obtains carbon
The complex microsphere of cladding, carbon content 37%.
4) obtained carbon-coated complex microsphere is added to concentration is in 2wt% sodium hydroxide solution, and stirring 10h is carried out
Etching processing removes SiO2, it is centrifugated, it is cleaned to be dried to obtain ZnO metal-carbon shell.Weigh 0.3g NaS2O3Be dissolved in from
It in sub- water, then weighs 0.2g ZnO metal-carbon shell and is added in above-mentioned solution, add Surfactant CTAB, stir 3h, then
The hydrochloric acid of 0.1mol/L is added dropwise into solution, stirs 1h, eccentric cleaning is dry, obtains battery composite anode material, the content of S
It is 63%, in order to spread elemental sulfur in metal-carbon shell uniformly, sulphur core is combined closely with metal-carbon shell, in metal-carbon shell
After interior load elemental sulfur, battery composite anode material is placed in tube furnace, is that 2 DEG C/min is warming up to 250 DEG C with heating rate
30min heat treatment is carried out, then removes the sulphur of battery composite anode material excess surface.
Embodiment 6
The preparation of the present embodiment progress battery composite anode material, comprising the following steps:
1) 20mL deionized water, 70mL dehydrated alcohol and 5mL 30wt% ammonium hydroxide are measured respectively, are sequentially added in beaker, room
It is uniform with magnetic stirrer under temperature, it weighs 1.0g ethyl orthosilicate (TEOS) and is slowly dropped to uniformly mixed above-mentioned solution
In, it is added dropwise with polyethylene film sealed beaker mouth, continuously stirs 6h at room temperature, make end of reaction, eccentric cleaning obtains not
With the SiO of diameter2Microballoon, SiO2The diameter of microballoon is 100nm~300nm.
2) 1.5g Ni (NO3) is weighed2It is add to deionized water, stirs at room temperature, form metal salt solution A.Separately weigh
1.2g SiO2Microballoon is dissolved in deionized water, obtains solution B.Solution B is instilled dropwise in metal salt solution A, adjusting pH value is
9,4h, Ni (NO are then persistently stirred at 50 DEG C3)2Hydrolysis, eccentric cleaning is dry, obtains complex microsphere, i.e. surface is deposited with
The microballoon of NiO.Wherein, with a thickness of 27nm, NiO content is 30%.
3) it weighs 1.5g phenolic resin to be dissolved in deionized water, 1.5g complex microsphere is added, persistently stirs 5h at room temperature, from
Heart cleaning, it is dry, obtain the complex microsphere of polymeric PTC materials；Carbon-coated complex microsphere is put into tube furnace again, in argon gas
In atmosphere, being warming up to 1000 DEG C of progress 1h constant temperature carbonization treatments with the heating rate of 10 DEG C/min makes phenolic resin carbonized, obtains
Carbon-coated complex microsphere, carbon content 40%.
4) obtained carbon-coated complex microsphere is added to concentration is in 2wt% hydrofluoric acid solution, and stirring 10h is carved
Erosion processing, removes SiO2, it is centrifugated, it is cleaned to be dried to obtain NiO metal-carbon shell.It weighs 0.35g thiocarbamide and is dissolved in deionized water
In, then weigh 0.15gNiO metal-carbon shell and be added in above-mentioned solution, surfactant SDBS is added, 3h is stirred, then to molten
The phosphoric acid of 0.1mol/L is added dropwise in liquid, stirs 1h, eccentric cleaning is dry, obtains battery composite anode material, the content of S is
70%, in order to spread elemental sulfur in metal-carbon shell uniformly, sulphur core is combined closely with metal-carbon shell, in metal-carbon shell
Load elemental sulfur after, battery composite anode material is placed in tube furnace, with heating rate be 5 DEG C/min be warming up to 300 DEG C into
Row 30min heat treatment, then remove the sulphur of battery composite anode material excess surface.
Embodiment 7
The present embodiment is by 3 battery composite anode material of embodiment and Kynoar (PVDF) ratio of 8:1 in mass ratio
It after mixing, being transferred in 5mL beaker, instills suitable NMP (N-Methyl pyrrolidone), magnetic agitation for 24 hours, obtains anode sizing agent,
Slurry is coated on aluminium foil using scraper, dry 12h is put into 60 DEG C of air dry ovens, is rushed above-mentioned aluminium foil using sheet-punching machine
At the disk of 13mm, the quality of each disk is weighed using assay balance, to calculate wherein activity substance content.By battery pack
The liquid-transfering gun used of dress, diaphragm, anode cover, negative electrode casing, gasket, elastic slice, positive plate, lithium piece are placed in glove box.In gloves
According to following assembling sequence in case: negative electrode casing, lithium piece, electrolyte, diaphragm, electrolyte, positive plate, gasket, elastic slice and anode cover
The assembling of battery is carried out, for the amount of electrolyte based on 25 microlitres/mg sulphur, the group of electrolyte becomes LiTFSI containing 1.0M and 1wt%
LiNO3DME:DOL solution (DME:DOL=1:1Vol%), be assembled into 2032 button cells.At 25 DEG C of constant temperature, 1.7V~
In the voltage range of 2.8V, charge-discharge test is carried out with the current density of 0.05C, tests its chemical property.
As a result Fig. 3 and Fig. 4 are please referred to, Fig. 3 is that a kind of battery composite anode material provided using the embodiment of the present invention 3 is made
The charging and discharging curve figure of the battery of anode, Fig. 4 are that a kind of battery composite anode material provided using the embodiment of the present invention 3 is made just
The cycle performance curve graph of the battery of pole.Fig. 3 shows the lithium-sulfur cell prepared using 3 battery composite anode material of embodiment
Initial capacity is 1143mAh/g, and after the circle of circulation 30, capacity relative attenuation is less, is still maintained at 807mAh/g, explanation
Capacity attenuation is slower in its cyclic process.Fig. 4 shows the lithium-sulfur cell prepared using 3 battery composite anode material of embodiment
Efficiency for charge-discharge is close to 100%, and the capacity of preceding 20 circle shows that its capacity attenuation is more slow, and capacity tends to after 20 circles
Stablize.
Embodiment 8
The preparation of the present embodiment progress battery composite anode material, comprising the following steps:
1) 20mL deionized water, 70mL dehydrated alcohol and 5mL 30wt% ammonium hydroxide are measured respectively, are sequentially added in beaker, room
It is uniform with magnetic stirrer under temperature, it weighs 1.0g ethyl orthosilicate (TEOS) and is slowly dropped to uniformly mixed above-mentioned solution
In, it is added dropwise with polyethylene film sealed beaker mouth, continuously stirs 6h at room temperature, make end of reaction, eccentric cleaning obtains not
With the SiO of diameter2Microballoon, SiO2The diameter of microballoon is 100nm~300nm.
2) 1.2g Co (NO is weighed3)3It is add to deionized water, stirs at room temperature, form metal salt solution A.Separately weigh
1.4g SiO2Microballoon is dissolved in deionized water, obtains solution B.Solution B is instilled dropwise in metal salt solution A, adjusting pH value is
7.5,3.5h, Co (NO are then persistently stirred at 30 DEG C3)3Hydrolysis, eccentric cleaning is dry, obtains complex microsphere, i.e. surface is heavy
Product has Co (OH)3Microballoon.Wherein, Co (OH)3With a thickness of 22nm, Co (OH)3Content is 12%.
3) it weighs 1.5g phenolic resin to be dissolved in deionized water, 1.0g complex microsphere is added, persistently stirs 5h at room temperature, from
Heart cleaning, it is dry, obtain the complex microsphere of polymeric PTC materials；Carbon-coated complex microsphere is put into tube furnace again, in argon gas
In atmosphere, being warming up to 600 DEG C of progress 5h constant temperature carbonization treatments with the heating rate of 2 DEG C/min makes phenolic resin carbonized, obtains carbon
The complex microsphere of cladding, carbon content 22%.
4) obtained carbon-coated complex microsphere is added to concentration is in 2wt% sodium hydroxide solution, and stirring 10h is carried out
Etching processing removes SiO2, it is centrifugated, it is cleaned to be dried to obtain Co (OH)3Metal-carbon shell.Weigh 0.12g Co (OH)3Gold
Category-carbon shell and 0.35g sublimed sulfur, after ground and mixed is uniform, obtained mixture is placed in reactor, reactor is placed in oil
In bath, 130 DEG C are warming up to, keeps the temperature 8h, sublimed sulfur melting is made to enter Co (OH)3It is naturally cold in the hollow cavity of metal-carbon shell
But to room temperature, battery composite anode material, Co (OH) are obtained3Cavity is provided between metal-carbon shell and sulphur core.
The assembling of battery is carried out using the present embodiment battery composite anode material with 7 method of embodiment and carries out electrochemistry
The test of energy, as a result referring to Fig. 5, making anode for a kind of battery composite anode material provided using the embodiment of the present invention 8
The cycle performance curve graph of battery.The result shows that using the present embodiment battery composite anode material preparation lithium-sulfur cell it is initial
Capacity is 975mAh/g, and after the circle of circulation 30, capacity relative attenuation is more, and specific discharge capacity 627mAh/g illustrates it
Capacity attenuation is very fast in cyclic process.
Comparative example 1
The preparation of the present embodiment progress battery composite anode material, comprising the following steps:
1) 20mL deionized water, 70mL dehydrated alcohol and 5mL 30wt% ammonium hydroxide are measured respectively, are sequentially added in beaker, room
It is uniform with magnetic stirrer under temperature, it weighs 1.0g ethyl orthosilicate (TEOS) and is slowly dropped to uniformly mixed above-mentioned solution
In, it is added dropwise with polyethylene film sealed beaker mouth, continuously stirs 6h at room temperature, make end of reaction, eccentric cleaning obtains not
With the SiO of diameter2Microballoon, SiO2The diameter of microballoon is 100nm~300nm.
2) it weighs 1.5g phenolic resin to be dissolved in deionized water, 1.0gSiO is added2Microballoon persistently stirs 5h at room temperature, from
Heart cleaning, it is dry, obtain the SiO of polymeric PTC materials2Microballoon；Again by carbon-coated SiO2Microballoon is put into tube furnace, in argon gas gas
In atmosphere, being warming up to 600 DEG C of progress 5h constant temperature carbonization treatments with the heating rate of 2 DEG C/min makes phenolic resin carbonized, obtains carbon packet
The SiO covered2Microballoon.
3) the carbon-coated SiO that will be obtained2It is in 2wt% hydrofluoric acid solution that microballoon, which is added to concentration, and stirring 10h is carved
Erosion processing, removes SiO2, it is centrifugated, it is cleaned to be dried to obtain hollow carbon shell.The hollow carbon shell of 0.1g and 0.3g sublimed sulfur are weighed,
After ground and mixed is uniform, obtained mixture is placed in reactor, is vacuumized, reactor is placed in oil bath pan, is warming up to
120 DEG C, 10h is kept the temperature, enters sublimed sulfur melting in the hollow cavity of carbon shell, it is compound just to obtain battery for cooled to room temperature
Pole material is provided with cavity between hollow carbon shell and sulphur core.
After the ratio of 1 battery composite anode material of comparative example and PVDF 8:1 in mass ratio are mixed, it is transferred in 5mL beaker,
Suitable NMP (N-Methyl pyrrolidone) is instilled, magnetic agitation for 24 hours, obtains anode sizing agent, and slurry is coated on aluminium using scraper
On foil, it is put into 60 DEG C of air dry ovens dry 12h, above-mentioned aluminium foil is washed into the disk of 13mm using sheet-punching machine, uses analysis
Balance weighs the quality of each disk, to calculate wherein activity substance content.Lithium-sulfur cell is assembled by 7 method of embodiment and is surveyed
Try its chemical property.
As a result Fig. 6 and Fig. 7 are please referred to, Fig. 6 is that a kind of battery composite anode material provided using comparative example 1 makees anode
The charging and discharging curve figure of battery, Fig. 7 are that a kind of battery composite anode material provided using comparative example 1 makees following for the battery of anode
Ring performance chart.The initial capacity for the lithium-sulfur cell that Fig. 6 shows to use 1 battery composite anode material of comparative example to prepare for
824mAh/g, after the circle of circulation 30, capacity relative attenuation is more, specific discharge capacity 422mAh/g, holds in cyclic process
Amount decaying is very fast.Fig. 7 shows that the efficiency for charge-discharge of the lithium-sulfur cell prepared using 1 battery composite anode material of comparative example is close
100%, discharge capacity is lower for the first time, and after the circle of circulation 30, capacity attenuation is very fast.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of battery composite anode material, which is characterized in that the battery composite anode material has core-shell structure；
The core-shell structure includes metal-carbon shell and the sulphur core that is set in the metal-carbon shell；
The metal-carbon shell is formed by metal hydroxides and/or metal oxide with carbon, the metal hydroxides and/or
Metal oxide is coated in the carbon；
The sulphur core is formed by elemental sulfur.
2. battery composite anode material according to claim 1, which is characterized in that the metal hydroxides and/or gold
Belonging to the metal in oxide is transition metal；
The transition metal is selected from one of titanium, iron, nickel, zinc, copper and cobalt or a variety of.
3. battery composite anode material according to claim 1, which is characterized in that the elemental sulfur is compound in the battery
The mass content of positive electrode is 40%~70%；
The metal hydroxides and/or metal oxide the mass content of the battery composite anode material be 5%~
30%；
The carbon is 20%~40% in the mass content of the battery composite anode material.
4. battery composite anode material according to claim 1, which is characterized in that the diameter of the core-shell structure is
100nm~600nm；
The metal-carbon shell with a thickness of 10nm~50nm；
The diameter of the sulphur core is 30nm~200nm；
The partial size of the metal hydroxides and/or metal oxide is 5nm~30nm.
5. battery composite anode material according to claim 1, which is characterized in that the metal-carbon shell and the sulphur core
Between be provided with cavity.
6. a kind of preparation method of battery composite anode material, which comprises the following steps:
A) it in the surface deposited metal hydroxide and/or metal oxide of microballoon, obtains to surface and is deposited with metal hydroxides
And/or the complex microsphere of metal oxide；
B) in complex microsphere surface coated high molecular, then carrying out carbonization treatment makes the macromolecule be carbonized, and obtains carbon coating
Complex microsphere；
C) the carbon-coated complex microsphere is performed etching into processing, removes the microballoon, obtain metal-carbon shell, then described
Elemental sulfur is loaded in metal-carbon shell, the elemental sulfur forms sulphur core in the metal-carbon shell, obtains cell composite anode material
Material.
7. preparation method according to claim 6, which is characterized in that step c) loads simple substance in the metal-carbon shell
Sulphur specifically includes:
The metal-carbon shell is mixed with the elemental sulfur and is placed in vacuum condition, carrying out heat treatment makes the elemental sulfur
Melting diffuses in the metal-carbon shell.
8. preparation method according to claim 6, which is characterized in that step c) loads simple substance in the metal-carbon shell
Sulphur specifically includes:
It disperses the metal-carbon shell in sulphur source solution, after surfactant is added, adding precipitating reagent and being stirred makes institute
Elemental sulfur is stated to deposit to the metal-carbon shell.
9. preparation method according to claim 8, which is characterized in that the sulphur source is selected from Na2S2O3、Na2SXIn thiocarbamide
It is one or more；
The surfactant is selected from cetyl trimethylammonium bromide, neopelex, octyl phenyl polyoxyethylene
One of ether and tween are a variety of；
The precipitating reagent is selected from one of hydrochloric acid, oxalic acid, phosphoric acid and acetic acid or a variety of.
10. a kind of battery, which is characterized in that the positive electrode of the battery includes battery described in claim 1 to 5 any one
Battery composite anode material made from preparation method described in composite positive pole and/or claim 6 to 9 any one.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110492071A (en) * | 2019-08-19 | 2019-11-22 | 西京学院 | Inner wall is loaded with the hollow carbon sphere and preparation method and purposes of nickel hydroxide and sulphur |
| CN110931752A (en) * | 2019-12-09 | 2020-03-27 | 华南师范大学 | Nitrogen-doped porous carbon loaded metal nickel lithium-sulfur battery positive electrode material and preparation method and application thereof |
| CN112786856A (en) * | 2021-01-15 | 2021-05-11 | 西安理工大学 | Lithium-sulfur battery positive electrode material and preparation method thereof |
| CN114583165A (en) * | 2020-12-01 | 2022-06-03 | 河南大学 | Metal/metal oxide lithium-sulfur battery positive electrode framework structure |
| CN114583166A (en) * | 2020-12-01 | 2022-06-03 | 河南大学 | Lithium-sulfur battery and preparation method thereof |
| CN114744174A (en) * | 2022-04-14 | 2022-07-12 | 桂林理工大学 | Sulfur/copper hydroxide/graphene oxide composite material for lithium-sulfur battery anode and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104201339A (en) * | 2014-09-18 | 2014-12-10 | 厦门大学 | Battery positive-electrode as well as preparation method and application thereof in lithium-sulfur batteries |
| CN105449209A (en) * | 2016-01-25 | 2016-03-30 | 大连理工大学 | Nitrogen-rich eggshell type lithium sulfur battery anode material and preparation method and application thereof |
| CN107359321A (en) * | 2017-06-09 | 2017-11-17 | 深圳启辰新能源科技有限公司 | Lithium sulfur battery anode material of the nitrogen-doped carbon of spherical structure/titanium oxide bivalve cladding titanium oxide/sulphur and preparation method thereof |
| CN108305997A (en) * | 2017-12-28 | 2018-07-20 | 肇庆市华师大光电产业研究院 | A kind of sulphur/two-layer titanium dioxide composite material and preparation method and application |
| US20180331352A1 (en) * | 2015-11-10 | 2018-11-15 | Grabat Energy S.L. | Carbon composites |
-
2019
- 2019-05-06 CN CN201910371857.7A patent/CN110098396B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104201339A (en) * | 2014-09-18 | 2014-12-10 | 厦门大学 | Battery positive-electrode as well as preparation method and application thereof in lithium-sulfur batteries |
| US20180331352A1 (en) * | 2015-11-10 | 2018-11-15 | Grabat Energy S.L. | Carbon composites |
| CN105449209A (en) * | 2016-01-25 | 2016-03-30 | 大连理工大学 | Nitrogen-rich eggshell type lithium sulfur battery anode material and preparation method and application thereof |
| CN107359321A (en) * | 2017-06-09 | 2017-11-17 | 深圳启辰新能源科技有限公司 | Lithium sulfur battery anode material of the nitrogen-doped carbon of spherical structure/titanium oxide bivalve cladding titanium oxide/sulphur and preparation method thereof |
| CN108305997A (en) * | 2017-12-28 | 2018-07-20 | 肇庆市华师大光电产业研究院 | A kind of sulphur/two-layer titanium dioxide composite material and preparation method and application |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110492071A (en) * | 2019-08-19 | 2019-11-22 | 西京学院 | Inner wall is loaded with the hollow carbon sphere and preparation method and purposes of nickel hydroxide and sulphur |
| CN110931752A (en) * | 2019-12-09 | 2020-03-27 | 华南师范大学 | Nitrogen-doped porous carbon loaded metal nickel lithium-sulfur battery positive electrode material and preparation method and application thereof |
| CN114583165A (en) * | 2020-12-01 | 2022-06-03 | 河南大学 | Metal/metal oxide lithium-sulfur battery positive electrode framework structure |
| CN114583166A (en) * | 2020-12-01 | 2022-06-03 | 河南大学 | Lithium-sulfur battery and preparation method thereof |
| CN112786856A (en) * | 2021-01-15 | 2021-05-11 | 西安理工大学 | Lithium-sulfur battery positive electrode material and preparation method thereof |
| CN112786856B (en) * | 2021-01-15 | 2022-04-22 | 西安理工大学 | Lithium-sulfur battery positive electrode material and preparation method thereof |
| CN114744174A (en) * | 2022-04-14 | 2022-07-12 | 桂林理工大学 | Sulfur/copper hydroxide/graphene oxide composite material for lithium-sulfur battery anode and preparation method thereof |
| CN114744174B (en) * | 2022-04-14 | 2023-10-27 | 桂林理工大学 | Positive electrode composite material of lithium-sulfur battery and preparation method thereof |
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