CN110265633A - A kind of micro-nano structure lithium-sulfur battery composite cathode material and preparation method thereof and battery - Google Patents
A kind of micro-nano structure lithium-sulfur battery composite cathode material and preparation method thereof and battery Download PDFInfo
- Publication number
- CN110265633A CN110265633A CN201910372455.9A CN201910372455A CN110265633A CN 110265633 A CN110265633 A CN 110265633A CN 201910372455 A CN201910372455 A CN 201910372455A CN 110265633 A CN110265633 A CN 110265633A
- Authority
- CN
- China
- Prior art keywords
- carbon
- metal
- anode material
- sulphur
- shell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title abstract description 13
- 239000002086 nanomaterial Substances 0.000 title abstract description 4
- 239000010406 cathode material Substances 0.000 title abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 197
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 140
- 239000010405 anode material Substances 0.000 claims abstract description 83
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 81
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000005864 Sulphur Substances 0.000 claims abstract description 38
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 30
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 27
- 239000011258 core-shell material Substances 0.000 claims abstract description 18
- 239000004005 microsphere Substances 0.000 claims description 83
- 238000010438 heat treatment Methods 0.000 claims description 29
- 238000003763 carbonization Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 18
- 238000011282 treatment Methods 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 239000011593 sulfur Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000005530 etching Methods 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 229920002521 macromolecule Polymers 0.000 claims description 12
- -1 neopelex Chemical group 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 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
- 239000000126 substance Substances 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229920000136 polysorbate Polymers 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 229920001021 polysulfide Polymers 0.000 abstract description 22
- 239000005077 polysulfide Substances 0.000 abstract description 22
- 150000008117 polysulfides Polymers 0.000 abstract description 22
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052744 lithium Inorganic materials 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 11
- 239000013067 intermediate product Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 238000004458 analytical method Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 38
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 30
- 238000003756 stirring Methods 0.000 description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- 229910052681 coesite Inorganic materials 0.000 description 18
- 229910052906 cristobalite Inorganic materials 0.000 description 18
- 239000000377 silicon dioxide Substances 0.000 description 18
- 229910052682 stishovite Inorganic materials 0.000 description 18
- 229910052905 tridymite Inorganic materials 0.000 description 18
- 238000004140 cleaning Methods 0.000 description 16
- 238000010792 warming Methods 0.000 description 16
- 229910052786 argon Inorganic materials 0.000 description 15
- 239000007789 gas Substances 0.000 description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 8
- 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 8
- 239000005011 phenolic resin Substances 0.000 description 8
- 229920001568 phenolic resin Polymers 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000005253 cladding Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 239000011149 active material Substances 0.000 description 5
- 239000004202 carbamide Substances 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- 238000010129 solution processing Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000003487 electrochemical reaction Methods 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 102000004310 Ion Channels Human genes 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 239000011805 ball Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000011806 microball Substances 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
- 238000012360 testing method Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 210000002700 urine Anatomy 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide 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
- 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
- 238000005259 measurement Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004540 process dynamic Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M4/366—Composites as layered products
-
- 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
- H01M4/625—Carbon or graphite
-
- 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
Abstract
The invention belongs to lithium sulfur battery anode material technical field more particularly to a kind of micro-nano structure lithium-sulfur battery composite cathode material and preparation method thereof and batteries.The present invention provides a kind of battery composite anode material, 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 titanium dioxide and Heteroatom doping carbon, and coated by titanium dioxide is in Heteroatom doping 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, titanium dioxide in metal-carbon shell can not only act on absorption polysulfide by " close lithium " or " close sulphur ", inhibit shuttle effect, analysis sulphur site is provided, it can be also catalyzed the conversion of sulphur and polysulfide, kinetics of electrode process is improved, improve the conversion rate of electrode.
Description
Technical field
The invention belongs to lithium sulfur battery anode material technical field more particularly to a kind of micro-nano structure lithium-sulfur cell are compound just
Pole material and preparation method thereof and battery.
Background technique
Energy storage technology is that the new century mankind solve the problems, such as one of key technology of energy and environment.By the hair of many decades
Exhibition, traditional performance of lithium ion battery have had evolved to theoretical limit, therefore find the secondary lithium of next-generation high-energy density
Ion battery is particularly important.Lithium-sulfur cell has high theoretical specific capacity (1675mAh g-1) and energy density
(2600Whkg-1), it is 3-5 times of conventional lithium ion battery, and elemental sulfur rich reserves, environmental-friendly, low in cost, therefore have
Hope the electrochemical energy storage system for becoming a new generation.
However, current lithium-sulfur cell has the following problems: (1) positive electrode elemental sulfur and lithium sulfide conductivity are low, cause
Active material is difficult to make full use of；(2) the conversion reaction dynamics between sulfur component is slower, causes electrochemical process to exist serious
Polarization, reduce the energy efficiency of battery；(3) intermediate product of the soluble polysulfide as electrochemical reaction is high
Rank product dissolves diffusion in the electrolytic solution, and side reaction on the one hand occurs with lithium anode, leads to the loss and appearance of active material
The rapid decay of amount, on the other hand, the intermediate product as electrochemical reaction is dissolved in electrolyte, influences and change electrolyte
The conversion reaction of composition and active material.The above problem causes lithium-sulfur cell that large-scale application is not yet received.
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 conductivity is low, 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 titanium dioxide and Heteroatom doping carbon, and the coated by titanium dioxide is in the miscellaneous original
In sub- doped carbon；
The sulphur core is formed by elemental sulfur.
Preferably, the Heteroatom doping carbon includes one of nitrogen-doped carbon, sulfur doping carbon and phosphorus doping carbon or a variety of.
Preferably, the elemental sulfur is 40%~70% in the mass content of the battery composite anode material；
The titanium dioxide is 5%~30% in the mass content of the battery composite anode material；
The Heteroatom doping 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 titanium dioxide 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 deposition of titanium oxide of microballoon, obtains to surface and is deposited with the complex microsphere of titanium dioxide；
B) in complex microsphere surface coated high molecular, the complex microsphere of polymeric PTC materials is obtained, then by the high score
The complex microsphere that attached bag is covered carries out carbonization treatment under mixed atmosphere makes the macromolecule be carbonized, and obtains Heteroatom doping carbon coating
Complex microsphere；
C) the carbon-coated complex microsphere of the Heteroatom doping is performed etching into processing, removes microballoon, obtains metal-carbon
Shell, then elemental sulfur is loaded in the metal-carbon shell, the elemental sulfur forms sulphur core in the metal-carbon shell, obtains battery
Composite positive pole；
It wherein, include one of ammonia, hydrogen sulfide and hydrogen phosphide or a variety of in the mixed atmosphere.
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.
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
Titanium dioxide is formed with Heteroatom doping carbon, and the coated by titanium dioxide is in the Heteroatom doping carbon；The sulphur core is by list
Matter sulphur is formed.In the present invention, battery composite anode material has core-shell structure, including titanium dioxide is formed with Heteroatom doping carbon
Metal-carbon shell and the sulphur core that is set in metal-carbon shell, metal-carbon shell can be improved the conductance of battery composite anode material
Rate simultaneously can play the role of confinement to sulphur and intermediate product polysulfide, on the one hand the titanium dioxide in metal-carbon shell passes through " parent
Lithium " or " close sulphur " effect absorption polysulfide capture polysulfide with polysulfide linkages, and inhibition shuttle effect provides analysis sulphur
On the other hand the active site of sulphur and polysulfide conversion reaction can also be provided in site, realize electrocatalysis, improves electrode mistake
Journey dynamics 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 thermal multigraph for battery composite anode material that the embodiment of the present invention 3 provides；
Fig. 3 is that a kind of battery composite anode material provided using the embodiment of the present invention 2 makees the permanent for the first time of the battery of anode
Flow charging and discharging curve figure；
It illustrates: 1. sulphur cores；2. titanium dioxide；3. Heteroatom doping carbon；4. microballoon；5. macromolecule；6. complex microsphere；
7. the complex microsphere of polymeric PTC materials；8. the carbon-coated complex microsphere of Heteroatom doping；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 conductivity is low, 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 by titanium dioxide
Titanium 2 and the formation of Heteroatom doping carbon 3, titanium dioxide 2 are coated in Heteroatom doping carbon 3；Sulphur core 1 is formed by elemental sulfur.
In the embodiment of the present invention, battery composite anode material has core-shell structure, including titanium dioxide 2 and Heteroatom doping
The metal-carbon shell 9 and sulphur core 1 that carbon 3 is formed, metal-carbon shell 9 can be improved the conductivity of battery composite anode material 10 and can
Play the role of confinement to sulphur and intermediate product polysulfide, 2 one side of titanium dioxide in metal-carbon shell 9 by " close lithium " or
" close sulphur " effect absorption polysulfide captures polysulfide with polysulfide linkages, inhibits shuttle effect, provides analysis sulphur site,
On the other hand the active site of sulphur and polysulfide conversion reaction can also be provided, realize electrocatalysis, it is dynamic to improve electrode process
Mechanics 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, Heteroatom doping carbon 3 include one of nitrogen-doped carbon, sulfur doping carbon and phosphorus doping carbon or
It is a variety of.
In the embodiment of the present invention, elemental sulfur is 60%~70% in the mass content of battery composite anode material 10；
Titanium dioxide 2 is 5%~10% in the mass content of battery composite anode material 10；
Heteroatom doping carbon 3 is 30%~50% 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 1 is 30nm~200nm；
The partial size of titanium dioxide 2 is 5nm~30nm, and titanium dioxide 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 is 2nm~30nm, preferably 5nm~10nm.
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 elemental sulfur 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 titanium dioxide 2 is mixed with hetero atom
The metal-carbon shell 9 that miscellaneous carbon 3 is formed and the sulphur core 1 being set in metal-carbon shell 9, metal-carbon shell 9 and sulphur core 1 can play collaboration
Effect, metal-carbon shell 9 can be improved the conductivity of battery composite anode material 10 and can be to sulphur and intermediate product polysulfides
Playing the role of confinement, 2 one side of titanium dioxide in metal-carbon shell 9 adsorbs polysulfide by " close lithium " or " close sulphur ",
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, and sulphur is high in the content of battery composite anode material 10；Metal-carbon shell 9
Cavity is provided between sulphur core 1 can alleviate the volume change of lithium reaction of Salmon-Saxl, there is huge application prospect in terms of energy storage.
The present invention also provides a kind of preparation methods of battery composite anode material, comprising the following steps:
A) it in the surface deposition of titanium oxide 2 of microballoon 4, obtains to surface and is deposited with the complex microsphere 6 of titanium dioxide 2；
B) in 6 surface coated high molecular 5 of complex microsphere, the complex microsphere 6 of the cladding of macromolecule 5 is obtained, then macromolecule 5 is wrapped
The complex microsphere 6 covered carries out carbonization treatment under mixed atmosphere makes macromolecule 5 be carbonized, and it is carbon-coated compound to obtain Heteroatom doping
Microballoon 8；
C) the carbon-coated complex microsphere 8 of Heteroatom doping is performed etching into processing, removes microballoon, obtains metal-carbon shell 9,
Elemental sulfur is loaded in metal-carbon shell 9 again, elemental sulfur forms sulphur core 1 in metal-carbon shell 9, obtains battery composite anode material
10；
It wherein, include one of ammonia, hydrogen sulfide and hydrogen phosphide or a variety of in mixed atmosphere.
In the embodiment of the present invention, step a) preferably disperses microballoon 4 in solution of tetrabutyl titanate and makes butyl titanate
It is hydrolyzed, it is dry, complex microsphere 6 is obtained, complex microsphere 6 is the microballoon 4 that surface is deposited with titanium dioxide 2.
The pH value of step a) hydrolysis is 7~10, and preferably pH value is 8；
The temperature of step a) hydrolysis is 25 DEG C~50 DEG C, preferably 30 DEG C；
The time of step a) hydrolysis is 3h~6h, preferably 5h；
Step a) microballoon 4 is scattered in solution of tetrabutyl titanate specifically: the aqueous solution of microballoon 4 is by ultrasonic disperse in titanium
In sour four butyl acetate solutions；After being hydrolyzed, before dry, further includes: be centrifuged or be separated by filtration, clean.Hydrolyze four fourth of metatitanic acid
After ester, the cladding titanium dioxide 2 on microballoon 4, the cladding time is preferably 30min.
The SiO of the preferred different-diameter of step a) microballoon 42Microballoon, SiO2The diameter of microballoon is 80nm~300nm.Major diameter
After microballoon 4 etches, big lithium ion transport channel can be provided, the load of elemental sulfur can also be made to increase；And minor diameter is micro-
Ball 4 has bigger specific surface area, can provide 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.
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 is carried out to carbonization treatment under mixed atmosphere makes macromolecule 5 be carbonized, and obtains Heteroatom doping carbon
The complex microsphere 8 of cladding.
Step b) carbonization treatment is constant temperature carbonization treatment, and the temperature of carbonization treatment is 500 DEG C~1000 DEG C；
The time of step b) carbonization treatment is 1h~6h.
Macromolecule 5 in phenolic resin, polyacrylic acid, polymethyl methacrylate, polyaniline and polyvinyl alcohol one
Kind is a variety of, preferably phenolic resin；
Mixed atmosphere is the atmosphere that ammonia, hydrogen sulfide and/or hydrogen phosphide are mixed in nitrogen and/or inert gas；
The flow velocity of nitrogen and/or inert gas is 30mL/min~80mL/min.
In the complex microsphere 7 of step b) polymeric PTC materials, the mass ratio of complex microsphere 6 and macromolecule 5 is 0.5~1:0.5
~1；For complex microsphere 6 by ultrasonic disperse in Polymer Solution, the time of ultrasonic disperse is 0.5h~3h；Complex microsphere 6 is divided
It dissipates after Polymer Solution, before obtaining the complex microsphere 7 of polymeric PTC materials, further includes: be successively stirred, eccentric cleaning and dry
It is dry；Carbonization treatment carries out in tube furnace, and the heating rate of carbonization treatment is 2 DEG C/min~10 DEG C/min.When carbonization treatment,
The uptake of tube furnace puts one of urea, melamine, thiocarbamide and phosphorus powder or a variety of, so that being mixed in mixed atmosphere
Ammonia, hydrogen sulfide and/or hydrogen phosphide.
Step c) performs etching processing in HF or NaOH solution, the mass concentration of HF or NaOH solution be 1wt%~
6wt%, the time of etching processing are 10h~20h.
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 9.
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 2~8:5~10；Mixing is specially to be fully ground in mortar；Heat treatment be specially 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 cladding titanium dioxide 2 and macromolecule 5, then macromolecule layer is carbonized by carbonization treatment in tube furnace,
The structure and composition of carbon outer shell are adjusted by the type of control carbonization treatment condition, mixed atmosphere and macromolecule 5, then is adopted
SiO is removed with etching method2Microballoon kernel obtains hollow metal-carbon shell, then compound with sulphur source, obtains including metal-carbon shell
9 with the battery composite anode material 10 of sulphur core 1, the battery composite anode material 10 can make " conduction " of sulfur electrode, " absorption ",
" confinement " and " catalysis " function is strengthened, and the load sulfur content of battery composite anode material 10 is high, electronics and ion transport are fast, electrode
Kinetics is quick, effectively polysulfide can be inhibited to shuttle, and also can be relieved bulk strain, the stability of lithium-sulfur cell reaction
It is high.
The battery composite anode material 10 that the present invention is prepared has core-shell structure, and material can be improved in metal-carbon shell 9
Conductivity, and play the role of confinement to the more lithium sulfides of intermediate product；And the present invention is carried out by the carbon-coating to metal-carbon shell 9
The doping of non-carbon element, is interacted by polar-polar, realizes the inhibition migrated to polysulfide；Metal-carbon shell 9 has
Strengthen absorption sulphur and polysulfide and is catalyzed the difunctional of lithium reaction of Salmon-Saxl；Gap between metal-carbon shell 9 and sulphur core 1 can be with
Alleviate the volume change of lithium-sulfur cell charge and discharge process.In battery composite anode material 10 of the present invention the load capacity of elemental sulfur it is high,
Energy efficiency is high, high rate performance is high, 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, elemental sulfur is compound in battery in battery
The mass content of positive electrode is 60%~70%, and battery may make to show good electrochemical energy storage property.
The result shows that for the first time charge and discharge of the battery of battery composite anode material 10 at 0.05C by adopting the above technical scheme
Electric specific capacity reaches 1089mAhg-1, there is high specific discharge capacity and good cyclical stability.
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) it weighs 0.5g butyl titanate to be add to deionized water, stir at room temperature, form solution of tetrabutyl titanate.Separately
Weigh 0.2g SiO2Microballoon is dissolved in deionized water, obtains SiO2Microspheres solution.By SiO2Microspheres solution instills metatitanic acid four dropwise
In butyl acetate solution, adjusting pH value is 8, and 5h is then persistently stirred at 30 DEG C, and tetrabutyl titanate hydrolysis, eccentric cleaning is dry, obtains
To complex microsphere, i.e. surface is deposited with TiO2Microballoon.Wherein, TiO2With a thickness of 30nm, TiO2Content is 12%.
3) it weighs 1.2g phenolic resin to be dissolved in deionized water, 0.8g complex microsphere is added, persistently stirs 8h 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, and will urine
Element is placed on the uptake of tube furnace, decomposes urea with the argon gas that flow velocity is 30mL/min heating, is full of argon in tube furnace at this time
The mixed atmosphere of gas and ammonia, being warming up to 600 DEG C of progress 2h constant temperature carbonization treatments with the heating rate of 2 DEG C/min makes phenolic resin
Carbonization obtains the carbon-coated complex microsphere of N doping, and nitrogen-doped carbon content is 20%, the carbon-coated complex microsphere surface of N doping
Micropore and mesoporous aperture be 1nm~20nm.
4) the carbon-coated complex microsphere of obtained N doping is added to concentration is to stir 10h in 1wt% hydrofluoric acid solution
Processing is performed etching, SiO is removed2, centrifuge separation is cleaned to be dried to obtain metal-carbon shell, metal-carbon shell with a thickness of 20nm.
0.15g metal-carbon shell and 0.45g sublimed sulfur are weighed, after ground and mixed is uniform, obtained mixture is placed in reactor, is taken out
Reactor is placed in oil bath pan by vacuum, is warming up to 135 DEG C, keeps the temperature 12h, and sublimed sulfur melting is made to enter the hollow of metal-carbon shell
In inner cavity, cooled to room temperature obtains battery composite anode material, and the content of S is 40.3%, metal-carbon shell and sulphur core it
Between be provided with cavity.
Embodiment 2
The preparation of the present embodiment progress battery composite anode material, comprising the following steps:
1) it weighs 1.3g polyacrylic acid to be dissolved in deionized water, complex microsphere prepared by 1.0g embodiment 1 is added, at room temperature
10h is persistently stirred, eccentric cleaning is dry, obtains the complex microsphere of polymeric PTC materials；Carbon-coated complex microsphere is put into pipe again
In formula furnace, and thiocarbamide is placed on to the uptake of tube furnace, thiocarbamide is decomposed with the argon gas that flow velocity is 35mL/min heating, is managed at this time
It is full of the mixed atmosphere of argon gas and hydrogen sulfide in formula furnace, 650 DEG C of progress 2.5h constant temperature carbon are warming up to the heating rate of 3 DEG C/min
Change processing makes polyacrylic acid be carbonized, and obtains the carbon-coated complex microsphere of sulfur doping, and sulfur doping carbon content is 27%, sulfur doping carbon packet
The mesoporous aperture on the complex microsphere surface covered is 5nm~25nm.
2) the carbon-coated complex microsphere of obtained sulfur doping is added to concentration is stirring in 2wt% sodium hydroxide solution
11h performs etching processing, removes SiO2, centrifuge separation is cleaned to be dried to obtain metal-carbon shell, metal-carbon shell with a thickness of
25nm.0.16g metal-carbon shell and 0.50g sublimed sulfur are weighed, after ground and mixed is uniform, obtained mixture is placed in reactor
In, it vacuumizes, reactor is placed in oil bath pan, be warming up to 140 DEG C, keep the temperature 10h, sublimed sulfur melting is made to enter metal-carbon shell
Hollow cavity in, cooled to room temperature obtains battery composite anode material, and the content of S is 46.7%, metal-carbon shell with
Cavity is provided between sulphur core.
Embodiment 3
The preparation of the present embodiment progress battery composite anode material, comprising the following steps:
1) it weighs 1.5g polymethyl methacrylate to be dissolved in deionized water, the compound micro- of the preparation of 1.3g embodiment 1 is added
Ball persistently stirs 6h at room temperature, and eccentric cleaning is dry, obtains the complex microsphere of polymeric PTC materials；It again will be carbon-coated compound micro-
Ball is put into tube furnace, and melamine is placed on to the uptake of tube furnace, with the argon gas that flow velocity is 40mL/min heating by three
Poly cyanamid decomposes, and is full of the mixed atmosphere of argon gas and ammonia in tube furnace at this time, is warming up to 700 with the heating rate of 4 DEG C/min
DEG C carry out 3h constant temperature carbonization treatment so that polymethyl methacrylate is carbonized, obtain the carbon-coated complex microsphere of N doping, N doping
Carbon content is 29%, and the surface mesoporous aperture of the carbon-coated complex microsphere of N doping is 10nm~30nm.
2) the carbon-coated complex microsphere of obtained N doping is added to concentration is to stir 12h in 3wt% hydrofluoric acid solution
Processing is performed etching, SiO is removed2, centrifuge separation is cleaned to be dried to obtain metal-carbon shell, metal-carbon shell with a thickness of 30nm.
0.18g metal-carbon shell and 0.60g sublimed sulfur are weighed, after ground and mixed is uniform, obtained mixture is placed in reactor, is taken out
Reactor is placed in oil bath pan by vacuum, is warming up to 145 DEG C, keeps the temperature 8h, and sublimed sulfur melting is made to enter the hollow of metal-carbon shell
In inner cavity, cooled to room temperature obtains battery composite anode material, and the content of S is 69.5%, metal-carbon shell and sulphur core it
Between be provided with cavity.
Thermogravimetric analysis is carried out to the present embodiment battery composite anode material, thermogravimetric analysis measurement carries out on thermal analyzer,
In N2The content of elemental sulfur is measured from room temperature to 700 DEG C with the rate of heat addition of 10 DEG C/min under atmosphere.As a result figure is please referred to
2, the results showed that the content of sulphur is 69.5% in composite positive pole.
Embodiment 4
The preparation of the present embodiment progress battery composite anode material, comprising the following steps:
1) it weighs 1.6g polyaniline to be dissolved in deionized water, complex microsphere prepared by 1.2g embodiment 1 is added, holds at room temperature
Continuous stirring 8h, eccentric cleaning is dry, obtains the complex microsphere of polymeric PTC materials；Carbon-coated complex microsphere is put into tubular type again
In furnace, and phosphorus powder is placed on to the uptake of tube furnace, phosphorus powder is gasified with the argon gas that flow velocity is 40mL/min heating, at this time tubular type
It is full of the mixed atmosphere of argon gas and hydrogen phosphide in furnace, 750 DEG C of progress 3.5h constant temperature carbonizations are warming up to the heating rate of 5 DEG C/min
Processing makes polyaniline be carbonized, and obtains the carbon-coated complex microsphere of phosphorus doping, and phosphorus doping carbon content is 33%, and phosphorus doping is carbon-coated
The surface mesoporous aperture of complex microsphere is 20nm~30nm.
2) the carbon-coated complex microsphere of obtained phosphorus doping is added to concentration is stirring in 4wt% sodium hydroxide solution
13h performs etching processing, removes SiO2, centrifuge separation is cleaned to be dried to obtain metal-carbon shell, metal-carbon shell with a thickness of
35nm.0.20g metal-carbon shell and 0.55g sublimed sulfur are weighed, after ground and mixed is uniform, obtained mixture is placed in reactor
In, it vacuumizes, reactor is placed in oil bath pan, be warming up to 155 DEG C, keep the temperature 5h, sublimed sulfur melting is made to enter metal-carbon shell
In hollow cavity, cooled to room temperature obtains battery composite anode material, and the content of S is 59%, metal-carbon shell and sulphur core
Between be provided with cavity.
Embodiment 5
The preparation of the present embodiment progress battery composite anode material, comprising the following steps:
1) it weighs 1.7g polyvinyl alcohol to be dissolved in deionized water, complex microsphere prepared by 1.0g embodiment 1 is added, at room temperature
8h is persistently stirred, eccentric cleaning is dry, obtains the complex microsphere of polymeric PTC materials；Carbon-coated complex microsphere is put into pipe again
In formula furnace, and urea is placed on to the uptake of tube furnace, urea is decomposed with the argon gas that flow velocity is 45mL/min heating, is managed at this time
It is full of the mixed atmosphere of argon gas and ammonia in formula furnace, is warming up at 800 DEG C of progress 4h constant temperature carbonizations with the heating rate of 6 DEG C/min
Reason makes polyvinyl alcohol be carbonized, and obtains the carbon-coated complex microsphere of N doping, and nitrogen-doped carbon content is 35%, and N doping is carbon-coated
The surface mesoporous aperture of complex microsphere is 40nm~50nm,.
2) the carbon-coated complex microsphere of obtained N doping is added to concentration is to stir 14h in 5wt% hydrofluoric acid solution
Processing is performed etching, SiO is removed2, centrifuge separation is cleaned to be dried to obtain metal-carbon shell, metal-carbon shell with a thickness of 40nm.
It weighs 0.60g thiocarbamide to be dissolved in deionized water, stir at room temperature, form clear solution, then weigh 0.16g metal-carbon shell ultrasound
It is dispersed in clear solution, adds surface active agent tween, stir 4h, the hydrochloric acid of 0.1mol/L is then added dropwise into solution, stirs
2h is mixed, centrifuge washing is dry, obtains battery composite anode material, the content of S is 63%, in order to make elemental sulfur in metal-carbon shell
Uniformly, sulphur core is combined closely with metal-carbon shell for interior diffusion, after loading elemental sulfur in metal-carbon shell, by cell composite anode
Material is placed in tube furnace, is that 2 DEG C/min is warming up to 250 DEG C of progress 30min second heat treatments, then removes battery and answer with heating rate
Close the sulphur of positive electrode excess surface.
Embodiment 6
The preparation of the present embodiment progress battery composite anode material, comprising the following steps:
1) it weighs 1.8g polymethyl methacrylate to be dissolved in deionized water, the compound micro- of the preparation of 1.2g embodiment 1 is added
Ball persistently stirs 10h at room temperature, and eccentric cleaning is dry, obtains the complex microsphere of polymeric PTC materials；It again will be carbon-coated compound
Microballoon is put into tube furnace, and thiocarbamide is placed on to the uptake of tube furnace, with the argon gas that flow velocity is 50mL/min heating by thiocarbamide
It decomposes, is full of the mixed atmosphere of argon gas and hydrogen sulfide in tube furnace at this time, is warming up to 1000 DEG C with the heating rate of 10 DEG C/min
Carrying out 2h constant temperature carbonization treatment makes polymethyl methacrylate be carbonized, and obtains the carbon-coated complex microsphere of sulfur doping, sulfur doping carbon
Content is 40%, and the surface mesoporous aperture with macropore of the carbon-coated complex microsphere of sulfur doping is 40nm~60nm.
2) the carbon-coated complex microsphere of obtained sulfur doping is added to concentration is to stir 15h in 5wt% hydrofluoric acid solution
Processing is performed etching, SiO is removed2, centrifuge separation is cleaned to be dried to obtain metal-carbon shell, metal-carbon shell with a thickness of 50nm.
Weigh 0.80g Na2S2O3It is dissolved in deionized water, stirs at room temperature, form clear solution, then weigh 0.20g metal-carbon shell and surpass
Sound is dispersed in clear solution, adds Surfactant CTAB, stirs 5h, and the acetic acid of 0.15mol/L is then added dropwise into solution,
1h is stirred, centrifuge washing is dry, obtains battery composite anode material, the content of S is 70%, in order to make elemental sulfur in metal-carbon
Uniformly, sulphur core is combined closely with metal-carbon shell for diffusion in shell, after loading elemental sulfur in metal-carbon shell, battery is compound just
Pole material is placed in tube furnace, is that 5 DEG C/min is warming up to 300 DEG C of progress 30min second heat treatments, then removes battery with heating rate
The sulphur of composite positive pole excess surface.
Embodiment 7
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 0.5g butyl titanate to be add to deionized water, stir at room temperature, form solution of tetrabutyl titanate.Separately
Weigh 0.2g SiO2Microballoon is dissolved in deionized water, obtains SiO2Microspheres solution.By SiO2Microspheres solution instills metatitanic acid four dropwise
In butyl acetate solution, adjusting pH value is 8, and 5h is then persistently stirred at 30 DEG C, and tetrabutyl titanate hydrolysis, eccentric cleaning is dry, obtains
To complex microsphere, i.e. surface is deposited with TiO2Microballoon.Wherein, TiO2With a thickness of 30nm, TiO2Content is 12%.
3) it weighs 1.2g phenolic resin to be dissolved in deionized water, 0.8g complex microsphere is added, persistently stirs 8h 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, and will urine
Element is placed on the uptake of tube furnace, decomposes urea with the argon gas that flow velocity is 30mL/min heating, is full of argon in tube furnace at this time
The mixed atmosphere of gas and ammonia, being warming up to 600 DEG C of progress 2h constant temperature carbonization treatments with the heating rate of 2 DEG C/min makes phenolic resin
Carbonization obtains the carbon-coated complex microsphere of N doping, and nitrogen-doped carbon content is 20%, the carbon-coated complex microsphere surface of N doping
Micropore and mesoporous aperture be 1nm~20nm.
4) the carbon-coated complex microsphere of obtained N doping is added to concentration is to stir 10h in 1wt% hydrofluoric acid solution
Processing is performed etching, SiO is removed2, centrifuge separation is cleaned to be dried to obtain metal-carbon shell, metal-carbon shell with a thickness of 20nm.
0.15g metal-carbon shell and 0.45g sublimed sulfur are weighed, after ground and mixed is uniform, obtained mixture is placed in reactor, it will
Reactor is placed in oil bath pan, is warming up to 135 DEG C, keeps the temperature 12h, enters sublimed sulfur melting in the hollow cavity of metal-carbon shell,
Cooled to room temperature obtains battery composite anode material, and the content of S is 30%, is arranged between metal-carbon shell and sulphur core free
Chamber.
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 0.5g butyl titanate to be add to deionized water, stir at room temperature, form solution of tetrabutyl titanate.Separately
Weigh 0.2g SiO2Microballoon is dissolved in deionized water, obtains SiO2Microspheres solution.By SiO2Microspheres solution instills metatitanic acid four dropwise
In butyl acetate solution, adjusting pH value is 8, and 5h is then persistently stirred at 30 DEG C, and tetrabutyl titanate hydrolysis, eccentric cleaning is dry, obtains
To complex microsphere, i.e. surface is deposited with TiO2Microballoon.Wherein, TiO2With a thickness of 30nm, TiO2Content is 12%.
3) it weighs 1.5g phenolic resin to be dissolved in deionized water, 0.8g complex microsphere is added, persistently stirs 8h 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 2h 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%, the micropore on the carbon-coated complex microsphere surface of N doping and mesoporous aperture are 1nm
~20nm.
4) obtained carbon-coated complex microsphere is added to concentration is in 1wt% hydrofluoric acid solution, and stirring 10h is carved
Erosion processing, removes SiO2, centrifuge separation is cleaned to be dried to obtain metal-carbon shell, metal-carbon shell with a thickness of 20nm.It weighs
0.15g metal-carbon shell and 0.45g sublimed sulfur, after ground and mixed are uniform, obtained mixture are placed in reactor, is vacuumized,
Reactor is placed in oil bath pan, is warming up to 135 DEG C, keeps the temperature 12h, sublimed sulfur melting is made to enter the hollow cavity of metal-carbon shell
In, cooled to room temperature obtains battery composite anode material, and the content of S is 45%, is arranged between metal-carbon shell and sulphur core
There is cavity.
Embodiment 8
The present embodiment is by embodiment or comparative example battery composite anode material and Kynoar (PVDF) 8:1 in mass ratio
Ratio mixing after, be transferred in 5mL beaker, instill suitable NMP (N-Methyl pyrrolidone), magnetic agitation for 24 hours, obtains anode
Slurry is coated on aluminium foil by slurry using scraper, is put into 60 DEG C of air dry ovens dry 12h, will be above-mentioned using sheet-punching machine
Aluminium foil is washed into the disk of 13mm, and the quality of each disk is weighed using assay balance, to calculate wherein activity substance content.It will
The liquid-transfering gun used of battery assembly, diaphragm, anode cover, negative electrode casing, gasket, elastic slice, positive plate, lithium piece are placed in glove box.
According to following assembling sequence in glove box: negative electrode casing, lithium piece, electrolyte, diaphragm, electrolyte, positive plate, gasket, elastic slice and
Anode cover carries out the assembling of battery, the amount of electrolyte by 25 microlitres/mg sulphur based on, the group of electrolyte become LiTFSI containing 1.0M with
1wt%LiNO3DME:DOL solution (DME:DOL=1:1Vol%), be assembled into 2032 button cells.At 25 DEG C of constant temperature,
In the voltage range of 1.7V~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 table 1 are please referred to, Fig. 3 is that a kind of battery composite anode material provided using the embodiment of the present invention 2 is made
The charging and discharging curve figure of the battery of anode, table 1 are to make anode using the embodiment of the present invention or comparative example battery composite anode material
Battery electrochemical performance data.Fig. 3 shows that two platforms of the curve of constant current charge-discharge for the first time of battery are located at 2.1 Hes
2.3V or so, specific discharge capacity 1089mAhg-1.Table 1 shows that composite positive pole of the invention imitates battery capacity and coulomb
Rate is significantly improved.
Table 1 makees the electrochemical performance data of the battery of anode using battery composite anode material of the embodiment of the present invention
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 titanium dioxide and Heteroatom doping carbon, and the coated by titanium dioxide is mixed in the hetero atom
In miscellaneous carbon；
The sulphur core is formed by elemental sulfur.
2. battery composite anode material according to claim 1, which is characterized in that the Heteroatom doping carbon includes that nitrogen is mixed
One of miscellaneous carbon, sulfur doping carbon and phosphorus doping carbon are 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 titanium dioxide is 5%~30% in the mass content of the battery composite anode material；
The Heteroatom doping 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 titanium dioxide 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 deposition of titanium oxide of microballoon, obtains to surface and is deposited with the complex microsphere of the titanium dioxide；
B) in complex microsphere surface coated high molecular, the complex microsphere of polymeric PTC materials is obtained, then by the high score attached bag
The complex microsphere covered carries out carbonization treatment under mixed atmosphere makes the macromolecule be carbonized, and it is carbon-coated multiple to obtain Heteroatom doping
Close microballoon；
C) the carbon-coated complex microsphere of the Heteroatom doping is performed etching into processing, removes the microballoon, obtains metal-carbon
Shell, then elemental sulfur is loaded in the metal-carbon shell, the elemental sulfur forms sulphur core in the metal-carbon shell, obtains battery
Composite positive pole；
It wherein, include one of ammonia, hydrogen sulfide and hydrogen phosphide or a variety of in the mixed atmosphere.
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 list
Matter sulphur is deposited to 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910372455.9A CN110265633A (en) | 2019-05-06 | 2019-05-06 | A kind of micro-nano structure lithium-sulfur battery composite cathode material and preparation method thereof and battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910372455.9A CN110265633A (en) | 2019-05-06 | 2019-05-06 | A kind of micro-nano structure lithium-sulfur battery composite cathode material and preparation method thereof and battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110265633A true CN110265633A (en) | 2019-09-20 |
Family
ID=67914305
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910372455.9A Pending CN110265633A (en) | 2019-05-06 | 2019-05-06 | A kind of micro-nano structure lithium-sulfur battery composite cathode material and preparation method thereof and battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110265633A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110697678A (en) * | 2019-09-28 | 2020-01-17 | 上海应用技术大学 | Sulfur atom doped carbon material taking waste lithium sulfur or magnesium sulfur battery as raw material and preparation and application thereof |
| CN111525119A (en) * | 2020-04-14 | 2020-08-11 | 北京理工大学 | Lithium-sulfur battery positive electrode material and preparation method thereof |
| CN113097458A (en) * | 2021-03-29 | 2021-07-09 | 清华大学 | Ternary cathode material @ titanium nitride core-shell structure composite material and preparation method thereof |
| CN117293321A (en) * | 2023-11-22 | 2023-12-26 | 江苏中兴派能电池有限公司 | Silicon anode material, preparation method thereof, anode and battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107221666A (en) * | 2017-06-28 | 2017-09-29 | 深圳市贝特瑞纳米科技有限公司 | Combination electrode material of Heteroatom doping graphene coated and preparation method 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 |
| JP2019036505A (en) * | 2017-08-21 | 2019-03-07 | 株式会社クラレ | Negative electrode for lithium sulfur battery and lithium sulfur battery |
-
2019
- 2019-05-06 CN CN201910372455.9A patent/CN110265633A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107221666A (en) * | 2017-06-28 | 2017-09-29 | 深圳市贝特瑞纳米科技有限公司 | Combination electrode material of Heteroatom doping graphene coated and preparation method thereof |
| JP2019036505A (en) * | 2017-08-21 | 2019-03-07 | 株式会社クラレ | Negative electrode for lithium sulfur battery and lithium sulfur battery |
Non-Patent Citations (2)
| Title |
|---|
| WEIQI YAO等: ""Pea-pod-like" nitrogen-doped hollow porous carbon cathode hosts decorated with polar titanium dioxide nanocrystals as efficient polysulfide reservoirs for advanced lithium–sulfur batteries", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| 陈玉华等 知识产权出版社: "《新型清洁能源技术》", 31 January 2019 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110697678A (en) * | 2019-09-28 | 2020-01-17 | 上海应用技术大学 | Sulfur atom doped carbon material taking waste lithium sulfur or magnesium sulfur battery as raw material and preparation and application thereof |
| CN111525119A (en) * | 2020-04-14 | 2020-08-11 | 北京理工大学 | Lithium-sulfur battery positive electrode material and preparation method thereof |
| CN111525119B (en) * | 2020-04-14 | 2022-03-25 | 北京理工大学 | Lithium-sulfur battery positive electrode material and preparation method thereof |
| CN113097458A (en) * | 2021-03-29 | 2021-07-09 | 清华大学 | Ternary cathode material @ titanium nitride core-shell structure composite material and preparation method thereof |
| CN117293321A (en) * | 2023-11-22 | 2023-12-26 | 江苏中兴派能电池有限公司 | Silicon anode material, preparation method thereof, anode and battery |
| CN117293321B (en) * | 2023-11-22 | 2024-01-30 | 江苏中兴派能电池有限公司 | Silicon anode material, preparation method thereof, anode and battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105742635B (en) | A kind of tin ash/graphene/carbon composite material and preparation method thereof | |
| CN110265633A (en) | A kind of micro-nano structure lithium-sulfur battery composite cathode material and preparation method thereof and battery | |
| CN102694155B (en) | Silicon-carbon composite material, preparation method thereof and lithium ion battery employing same | |
| CN105810914B (en) | A kind of sodium-ion battery sulfur doping porous carbon materials and preparation method thereof | |
| CN106450195B (en) | A kind of positive material for lithium-sulfur battery and preparation method thereof and the lithium-sulfur cell containing the positive electrode | |
| CN103193263B (en) | Preparation method and application of hollow SnO2@C nanosphere in lithium ion battery | |
| CN108539171B (en) | Preparation method of zinc sulfide and graphene oxide compound and application of compound in positive electrode material of lithium-sulfur battery | |
| CN106229498B (en) | Cathode material suitable for water-based metal ion battery and preparation method thereof | |
| CN103066265B (en) | Sodium ion battery negative pole active substance and preparation method and application thereof | |
| CN103035879B (en) | Positive pole piece for lithium-sulfur batteries and preparation method thereof | |
| CN110098396A (en) | A kind of lithium-sulfur battery composite cathode material and preparation method thereof and battery | |
| CN106159234B (en) | Manganese dioxide carbon coated sulphur composite material and preparation method, lithium-sulfur cell | |
| CN112952047B (en) | Preparation method of carbon-loaded potassium vanadate and application of carbon-loaded potassium vanadate in potassium ion battery | |
| CN104900862A (en) | P2 phase layered electrode material of symmetric sodium ion secondary battery and preparation method thereof | |
| CN108493425A (en) | A kind of preparation method of the Sn4P3 nano particle anode material of lithium-ion batteries of mesoporous carbon nanotube cladding | |
| CN105789615A (en) | Modified lithium nickel cobalt manganese cathode material and preparation method thereof | |
| CN109950487A (en) | A kind of lithium sulfur battery anode material and preparation method thereof | |
| CN115763717A (en) | Sodium ion battery positive electrode material, preparation method thereof, sodium ion battery positive electrode piece and sodium ion battery | |
| CN105895871B (en) | A kind of porous Si-C composite material and preparation method and application | |
| CN105552336A (en) | Hydrothermal method synthesized MnO2/NCNTs nanocomposite and preparation method thereof | |
| CN109896524A (en) | A kind of preparation method and applications of two dimensional crystal MXene nano material | |
| CN111613784A (en) | Organic-inorganic composite lithium-selenium battery positive electrode material and preparation method and application thereof | |
| CN105185978A (en) | Manganese-containing oxygen compound used as negative active substance, and preparation method and use thereof | |
| CN112028123A (en) | Preparation method of manganese vanadate material and energy storage application thereof | |
| CN110649263A (en) | Nickel-ion battery lithium vanadium phosphate positive electrode material, sol-gel preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190920 |
|
| RJ01 | Rejection of invention patent application after publication |