CN113206233A - Bismuth molybdate/sulfur composite material, preparation method thereof and lithium-sulfur battery - Google Patents
Bismuth molybdate/sulfur composite material, preparation method thereof and lithium-sulfur battery Download PDFInfo
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- CN113206233A CN113206233A CN202110470101.5A CN202110470101A CN113206233A CN 113206233 A CN113206233 A CN 113206233A CN 202110470101 A CN202110470101 A CN 202110470101A CN 113206233 A CN113206233 A CN 113206233A
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- bismuth molybdate
- oxygen
- sulfur
- composite material
- vacancy
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- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 title claims abstract description 110
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 56
- 239000011593 sulfur Substances 0.000 title claims abstract description 56
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000001301 oxygen Substances 0.000 claims abstract description 78
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000001354 calcination Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 16
- 150000001621 bismuth Chemical class 0.000 claims description 12
- 239000007774 positive electrode material Substances 0.000 claims description 11
- 150000002751 molybdenum Chemical class 0.000 claims description 9
- 238000004729 solvothermal method Methods 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 239000006258 conductive agent Substances 0.000 claims description 7
- 239000011149 active material Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000002135 nanosheet Substances 0.000 claims description 5
- 125000003158 alcohol group Chemical group 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 239000005077 polysulfide Substances 0.000 abstract description 25
- 229920001021 polysulfide Polymers 0.000 abstract description 25
- 150000008117 polysulfides Polymers 0.000 abstract description 25
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 238000004090 dissolution Methods 0.000 abstract description 15
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 6
- 239000010406 cathode material Substances 0.000 abstract description 5
- 230000005764 inhibitory process Effects 0.000 abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 13
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 12
- -1 sodium fatty alcohol Chemical class 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 7
- 239000011684 sodium molybdate Substances 0.000 description 7
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 7
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- AVBJHQDHVYGQLS-AWEZNQCLSA-N (2s)-2-(dodecanoylamino)pentanedioic acid Chemical compound CCCCCCCCCCCC(=O)N[C@H](C(O)=O)CCC(O)=O AVBJHQDHVYGQLS-AWEZNQCLSA-N 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 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
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000003273 ketjen black 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- 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
- H01M4/38—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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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 provides a bismuth molybdate/sulfur composite material, a preparation method thereof and a lithium-sulfur battery. The preparation method comprises the following steps: step S1, providing oxygen-rich vacancy bismuth molybdate, wherein the oxygen vacancy content of the oxygen-rich vacancy bismuth molybdate is 1-10%; and step S2, mixing the oxygen-rich vacancy bismuth molybdate and the elemental sulfur, and calcining in inert gas to obtain the bismuth molybdate/sulfur composite material. The bismuth molybdate/sulfur composite material prepared by the method can reduce the dissolution of polysulfide from two aspects of physical adsorption inhibition and chemical conversion, has composite stability with elemental sulfur, and can remarkably improve the stability of a battery after being applied to a lithium-sulfur battery cathode material by combining the factors, thereby improving the cycle performance of the battery.
Description
Technical Field
The invention relates to the technical field of energy materials, in particular to a bismuth molybdate/sulfur composite material, a preparation method thereof and a lithium-sulfur battery.
Background
In recent years, the development of new energy automobiles is becoming a national major strategic demand for environmental deterioration and fossil energy shortage, but electric automobiles have a severe demand for energy density of power batteries. The lithium ion battery is limited in the specific capacity of the traditional materials such as lithium cobaltate and lithium manganate, and the current lithium ion battery is difficult to meet the national requirements for new energy automobile scientific and technological planning, so that the seeking of a secondary battery with higher specific capacity is imperative.
The theoretical specific capacity of the lithium-sulfur battery is up to 1675mAh/g, and the lithium-sulfur battery is considered to be a next-generation secondary battery system with high specific energy with great development prospect. However, in practical applications of the lithium-sulfur battery, since the discharge intermediate (lithium polysulfide) is easily dissolved in the ether electrolyte and passes through the separator, the discharge intermediate migrates between the positive electrode and the negative electrode to form a "shuttle effect", which further causes problems such as irreversible loss of the positive electrode active material, damage of the SEI film on the surface of the negative electrode, reduction of the battery life, low coulombic efficiency, and the like, and thus, the cycle performance of the battery is reduced. Therefore, how to suppress the elution of polysulfide into the electrolytic solution is important in the study of the positive electrode of a lithium-sulfur battery.
The conventional solution to the polysulfide dissolution problem is to coat the sulfur surface with a mesoporous carbon material with high specific surface area and high conductivity, thereby limiting the dissolution and diffusion of polysulfide in the electrolyte. Although this method can improve the utilization rate of sulfur to some extent and improve the cycle life, the carbon material belongs to a nonpolar molecule, the action with lithium polysulfide is a physical action, chemical adsorption cannot be formed, and the effect of suppressing the elution of polysulfide ions is not significant.
For the above reasons, it is an urgent need to solve the problem in the development of lithium sulfur batteries to provide a positive electrode active material capable of effectively inhibiting polysulfide elution and thereby effectively improving the performance of lithium sulfur batteries such as cycle.
Disclosure of Invention
The invention mainly aims to provide a bismuth molybdate/sulfur composite material, a preparation method thereof and a lithium-sulfur battery, so as to solve the problem of shuttle effect caused by polysulfide dissolution existing in the positive electrode of the lithium-sulfur battery in the prior art and further improve the cycle performance of the lithium-sulfur battery.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a method for preparing a bismuth molybdate/sulfur composite material, comprising the steps of: step S1, providing oxygen-rich vacancy bismuth molybdate, wherein the oxygen vacancy content of the oxygen-rich vacancy bismuth molybdate is 1-10%; and step S2, mixing the oxygen-rich vacancy bismuth molybdate and the elemental sulfur, and calcining in inert gas to obtain the bismuth molybdate/sulfur composite material.
Further, the oxygen vacancy content of the oxygen-rich vacancy bismuth molybdate is 1-4%.
Further, step S1 includes: dissolving soluble bismuth salt and soluble molybdenum salt in a solvent to form a mixed solution; and carrying out solvothermal reaction on the mixed solution to obtain the oxygen-rich vacancy bismuth molybdate.
Furthermore, the mol ratio of the soluble bismuth salt to the soluble molybdenum salt is (3-5): 2.
Furthermore, the solvent is an alcohol solvent with the boiling point of more than 80 ℃, and each liter of the solvent corresponds to 9-15 g of soluble bismuth salt.
Further, a surfactant is added into the mixed solution, wherein 0.7-1.25 g of the surfactant is added into each liter of the solvent.
In step S2, the weight ratio of the bismuth molybdate and the elemental sulfur in the oxygen-rich vacancy is 0.5 (1-4).
Further, in step S2, the calcination temperature in the calcination process is 150 to 180 ℃, and the calcination time in the calcination process is 12 to 24 hours.
According to another aspect of the invention, a bismuth molybdate/sulfur composite material is also provided, which is prepared by the preparation method, wherein the bismuth molybdate/sulfur composite material is a two-dimensional nanosheet structure.
According to another aspect of the present invention, there is also provided a lithium sulfur battery, wherein the positive electrode comprises a current collector and a positive electrode material on the current collector, the positive electrode material comprises an active material, a conductive agent and a binder, wherein the active material is the bismuth molybdate/sulfur composite material.
The bismuth molybdate/sulfur composite material is prepared by the invention, wherein the bismuth molybdate is ternary metal oxide, has a bimetallic center, has strong adsorption capacity on lithium polysulfide, and can effectively inhibit the dissolution of sulfur. More importantly, the oxygen-rich vacancy bismuth molybdate with the oxygen vacancy content of 1-10% is adopted, and the existence of the oxygen vacancy improves the surface electronic state of the bismuth molybdate, so that the bismuth molybdate has good catalytic activity, and can promote the conversion of lithium polysulfide to lithium sulfide, catalyze the discharge process of a lithium-sulfur battery, and further reduce the dissolution of the lithium polysulfide. In a word, the bismuth molybdate/sulfur composite material prepared by the invention can reduce the dissolution of polysulfide from two aspects of physical adsorption inhibition and chemical conversion, has composite stability with elemental sulfur, and can remarkably improve the stability of a battery after being applied to a lithium-sulfur battery cathode material by combining the factors, thereby improving the cycle performance of the battery.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows an XPS spectrum of bismuth molybdate prepared in example 1 of the present invention;
FIG. 2 shows an SEM photograph of bismuth molybdate prepared in example 1 of the present invention;
fig. 3 shows a first 0.05C charge and discharge curve of the bismuth molybdate/sulfur composite material prepared in example 1 of the present invention after being applied to a lithium sulfur battery; and
fig. 4 shows a 0.05C cycle curve of the bismuth molybdate/sulfur composite material prepared in example 1 of the present invention after being applied to a lithium sulfur battery.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As described in the background section, the prior art lithium sulfur battery positive electrode has a problem of "shuttle effect" caused by polysulfide dissolution, thereby seriously affecting the cycle performance of the lithium sulfur battery.
In order to solve the above problems, the present invention provides a method for preparing a bismuth molybdate/sulfur composite material, comprising the steps of: step S1, providing oxygen-rich vacancy bismuth molybdate, wherein the oxygen vacancy content of the oxygen-rich vacancy bismuth molybdate is 1-10%; and step S2, mixing the oxygen-rich vacancy bismuth molybdate and the elemental sulfur, and calcining in inert gas to obtain the bismuth molybdate/sulfur composite material.
The bismuth molybdate/sulfur composite material is prepared by mixing and calcining the oxygen-rich vacancy, bismuth molybdate and elemental sulfur. Bismuth molybdate is a ternary metal oxide, has a bimetallic center, has strong adsorption capacity on lithium polysulfide, and can effectively inhibit the dissolution of sulfur. More importantly, the oxygen-rich vacancy bismuth molybdate with the oxygen vacancy content of 1-10% is adopted, and the existence of the oxygen vacancy improves the surface electronic state of the bismuth molybdate, so that the bismuth molybdate has good catalytic activity, and can promote the conversion of lithium polysulfide to lithium sulfide, catalyze the discharge process of a lithium-sulfur battery, and further reduce the dissolution of the lithium polysulfide. In a word, the bismuth molybdate/sulfur composite material prepared by the invention can reduce the dissolution of polysulfide from two aspects of physical adsorption inhibition and chemical conversion, has composite stability with elemental sulfur, and can remarkably improve the stability of a battery after being applied to a lithium-sulfur battery cathode material by combining the factors, thereby improving the cycle performance of the battery.
By "oxygen vacancy content" is meant herein the amount of oxygen vacancies as a percentage of the total amount of lattice oxygen and oxygen vacancies.
In order to further improve the catalytic conversion capability of the oxygen-rich vacancy bismuth molybdate to polysulfides and improve the composite stability of the bismuth molybdate and the elemental sulfur, in a preferred embodiment, the oxygen vacancy content of the oxygen-rich vacancy bismuth molybdate is 1-4%.
In a preferred embodiment, the step S1 includes: dissolving soluble bismuth salt and soluble molybdenum salt in a solvent to form a mixed solution; and carrying out solvothermal reaction on the mixed solution to obtain the oxygen-rich vacancy bismuth molybdate. The bismuth molybdate prepared by adopting a solvothermal reaction mode of soluble bismuth salt and soluble molybdenum salt is of a two-dimensional nano flaky structure, and has a better composite effect when being subsequently mixed with a sulfur simple substance and calcined. And the solvothermal reaction can better control the content of oxygen vacancies, and is favorable for further improving the overall performance of the bismuth molybdate/sulfur composite material. In addition, the solvothermal reaction also has the advantages of simple process, clean and environment-friendly preparation process and the like. In the actual reaction process, the oxygen vacancy content of the bismuth molybdate can be regulated and controlled by adjusting the solvothermal reaction process conditions, preferably, the solvothermal reaction temperature is 110-180 ℃, and preferably, the solvothermal reaction time is 12-24 hours.
In a preferred embodiment, the above soluble bismuth salts include, but are not limited to, one or more of bismuth chloride, bismuth sulfate, and bismuth nitrate; preferably, the soluble molybdenum salt includes, but is not limited to, one or more of sodium molybdate, potassium molybdate, and ammonium molybdate. The soluble bismuth salts and the soluble molybdenum salts can be fully dissolved in the solvent to form a more stable reaction system, which is beneficial to improving the stability of the solvent thermal reaction, and the obtained bismuth molybdate with oxygen-rich vacancy has a more uniform overall structure. More preferably, the molar ratio of the soluble bismuth salt to the soluble molybdenum salt is (3-5): 2.
In order to further improve the thermal reaction stability of the solvent, in a preferred embodiment, the solvent is an alcohol solvent with a boiling point of more than 80 ℃, preferably the alcohol solvent is isopropanol and/or ethylene glycol; more preferably, 9-15 g of soluble bismuth salt per liter of solvent.
In a preferred embodiment, a surfactant is also added to the mixed solution; preferably, the surfactant is selected from sodium fatty alcohol polyoxyethylene ether sulfate (AES), ammonium fatty alcohol polyoxyethylene ether sulfate (AESA), sodium lauryl sulfate (SDS), lauroyl glutamic acid, nonylphenol polyoxyethylene ether (TX-10), peregal O, stearic acid monoglyceride, lignosulfonate, heavy alkylbenzene sulfonate, alkylsulfonate (petroleum sulfonate), diffusant NNO, diffusant MF, alkyl polyether (PO-EO copolymer), fatty alcohol polyoxyethylene ether (AEO-3), cetyl trimethyl ammonium bromide CTAB. The addition of the surfactant further contributes to the formation of a two-dimensional nanosheet structure and the formation of oxygen vacancies. Preferably, 0.7-1.25 g of surfactant is added per liter of solvent.
Preferably, in the step S2, the weight ratio of the oxygen-rich vacancy bismuth molybdate to the elemental sulfur is 1 (1-4). By controlling the weight ratio of the two components within the above range, on the one hand, the composite material has good reaction activity when used as a positive electrode active material of a lithium-sulfur battery, on the other hand, the dissolution problem of polysulfide is better solved, and the composite material has better stability and more remarkable improvement on the cycle performance of the battery.
For the purpose of further improving the composite stability of bismuth molybdate and elemental sulfur, in a preferred embodiment, in step S2, the calcination temperature in the calcination process is 150 to 180 ℃, and the calcination time in the calcination process is 12 to 24 hours. The specific calcination process is carried out under the protection of inert gas, including but not limited to nitrogen, argon, etc.
According to another aspect of the invention, a bismuth molybdate/sulfur composite material is also provided, which is prepared by the preparation method. As mentioned above, the method prepares the bismuth molybdate/sulfur composite material by mixing the oxygen-rich vacancies, bismuth molybdate and elemental sulfur and calcining. Bismuth molybdate is a ternary metal oxide, has a bimetallic center, has strong adsorption capacity on lithium polysulfide, and can effectively inhibit the dissolution of sulfur. More importantly, the oxygen-rich vacancy bismuth molybdate with the oxygen vacancy content of 1-10% is adopted, and the existence of the oxygen vacancy improves the surface electronic state of the bismuth molybdate, so that the bismuth molybdate has good catalytic activity, and can promote the conversion of lithium polysulfide to lithium sulfide, catalyze the discharge process of a lithium-sulfur battery, and further reduce the dissolution of the lithium polysulfide. Particularly, the oxygen vacancy content is controlled within the range, so that the bismuth molybdate and sulfur can be combined while the polysulfide is better catalyzed to convert lithium sulfide. In a word, the bismuth molybdate/sulfur composite material prepared by the invention can reduce the dissolution of polysulfide from two aspects of physical adsorption inhibition and chemical conversion, has composite stability with elemental sulfur, and can remarkably improve the stability of a battery after being applied to a lithium-sulfur battery cathode material by combining the factors, thereby improving the cycle performance of the battery.
Preferably, the bismuth molybdate/sulfur composite material is of a two-dimensional nanosheet structure; more preferably, the maximum size of the two-dimensional nanosheet structure is 800nm to 1 μm, and the average thickness is 10 to 25 nm. The bismuth molybdate/sulfur composite material with the structure and the size has better reaction activity as a positive electrode active substance.
According to another aspect of the present invention, there is also provided a lithium sulfur battery, wherein the positive electrode comprises a current collector and a positive electrode material on the current collector, the positive electrode material comprises an active material, a conductive agent and a binder, wherein the active material is the bismuth molybdate/sulfur composite material.
In the actual manufacturing process, the bismuth molybdate/sulfur composite material, a conductive agent and a binder are mixed to prepare slurry, the slurry is coated on a current collector, and the current collector is placed in an oven to be dried at 40-85 ℃ to obtain the lithium-sulfur battery cathode material. The conductive agent and the binder are of the type commonly used in the art, for example, the conductive agent includes, but is not limited to, acetylene black, carbon nanotubes, ketjen black, mesoporous carbon, Super P, graphite conductive agent, etc.; binders include, but are not limited to, CMC-2000, SBR, PVDF.
In a preferred embodiment, the weight percentage of the bismuth molybdate/sulfur composite material in the positive electrode material is 50-80%. By controlling the content within the above range, the positive electrode material has better reactivity and better comprehensive performance in the aspects of conductivity and stability.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
The following oxygen vacancies were tested using XPS spectroscopy.
Example 1
0.45g Bi(NO3)3·5H2O、0.12g Na2MoO4·2H2Dissolving O and 0.04g CTAB in 40ml isopropanol, stirring for 30min, transferring the mixed solution into a 100ml polytetrafluoroethylene reaction kettle, heating the solvent at 110 ℃ for 24h, centrifuging the obtained product, washing for three times by using ethanol, and then drying in vacuum at 60 ℃ to obtain oxygen-rich vacancy bismuth molybdate, wherein an XPS spectrogram of the bismuth molybdateReferring to fig. 1, the oxygen vacancy content is 3% by peak separation calculation; the SEM photograph is shown in FIG. 2.
3g of oxygen-rich vacancy bismuth molybdate and 12g of elemental sulfur are mixed and ground uniformly, and are calcined for 12 hours at 155 ℃ by introducing argon as a protective gas, so that the oxygen-rich vacancy bismuth molybdate/sulfur composite material is obtained.
And (3) performance characterization:
mixing 10g of oxygen-rich vacancy bismuth molybdate/sulfur composite material, 2g of mesoporous carbon, 0.5g of Super P, 10g of CMC-2000 (solid content of 1.5%) and 1g of SBR (solid content of 50%), using water as a solvent to form slurry, stirring for 12h, and coating the slurry on an aluminum foil to serve as a positive electrode; using metallic lithium as a negative electrode; celgard 2400 type separator was used; dissolving 1mol/L LiTFSI in DOL/DME (volume ratio of 1:1) solvent to be used as electrolyte; 1mol/L LiNO3Preparing an additive; and assembling the button cell in the glove box. A blue light test system is adopted to carry out constant current charging and discharging sensing test, and the charging and discharging voltage range is 1.8-2.8V.
The first 0.05C charge-discharge curve of the battery is shown in figure 3; the 0.05C cycle curve is shown in fig. 4. As can be seen from the graph, the capacity retention rate of the lithium-sulfur battery after 250 cycles was 75%.
Example 2
0.36g Bi(NO3)3·5H2O、0.12g Na2MoO4·2H2Dissolving O and 0.05g CTAB in 40ml of isopropanol, stirring for 30min, transferring the mixed solution into a 100ml of polytetrafluoroethylene reaction kettle, heating the solvent at 110 ℃ for 24h, centrifuging the obtained product, washing the product for three times by using ethanol, and then drying the product in vacuum at 60 ℃ to obtain the oxygen-rich vacancy bismuth molybdate.
3g of oxygen-rich vacancy bismuth molybdate and 12g of elemental sulfur are mixed and ground uniformly, and are calcined for 12 hours at 155 ℃ by introducing argon as a protective gas, so that the oxygen-rich vacancy bismuth molybdate/sulfur composite material is obtained.
The properties were characterized as in example 1, and the results of the characterization are shown in Table 1 below.
Example 3
0.6g Bi(NO3)3·5H2O and 0.12g Na2MoO4·2H2O and 0.028g CTAB were dissolved in 40ml of ethylene glycol, stirred for 30min, and the mixed solution was transferred to 100ml of polyIn a tetrafluoroethylene reaction kettle, the solvent is heated for 12 hours at the temperature of 150 ℃, the obtained product is washed for three times by ethanol and then is dried in vacuum at the temperature of 60 ℃, and the bismuth molybdate with oxygen-rich vacancy is obtained.
3g of oxygen-rich vacancy bismuth molybdate and 12g of elemental sulfur are mixed and ground uniformly, and are calcined for 12 hours at 155 ℃ by introducing argon as a protective gas, so that the oxygen-rich vacancy bismuth molybdate/sulfur composite material is obtained.
The properties were characterized as in example 1, and the results of the characterization are shown in Table 1 below.
Example 4
0.6g BiCl3And 0.24g (NH)4)2MoO4And 0.05g of sodium lauryl sulfate (SDS) are dissolved in 60ml of mixed solvent of ethylene glycol and isopropanol (volume ratio is 1:1), the mixture is stirred for 30min, the mixed solution is transferred into a 100ml of polytetrafluoroethylene reaction kettle, the solvent is heated for 12h at 160 ℃, the obtained product is centrifuged, washed with ethanol for three times, and dried in vacuum at 60 ℃ to obtain the oxygen-rich vacancy bismuth molybdate.
3g of oxygen-rich vacancy bismuth molybdate and 12g of elemental sulfur are mixed and ground uniformly, and are calcined for 12 hours at 155 ℃ by introducing argon as a protective gas, so that the oxygen-rich vacancy bismuth molybdate/sulfur composite material is obtained.
The properties were characterized as in example 1, and the results of the characterization are shown in Table 1 below.
Example 5
0.45g Bi(NO3)3·5H2O、0.36g Na2MoO4·2H2Dissolving O and 0.028g CTAB in 40ml of isopropanol, stirring for 30min, transferring the mixed solution into a 100ml of polytetrafluoroethylene reaction kettle, heating the solvent at 110 ℃ for 24h, centrifuging the obtained product, washing the product for three times by using ethanol, and then drying the product in vacuum at 60 ℃ to obtain the oxygen-rich vacancy bismuth molybdate, wherein the oxygen vacancy content is 1%.
And (3) mixing and grinding 2g of oxygen-rich vacancy bismuth molybdate and 16g of elemental sulfur uniformly, introducing argon as a protective gas, and calcining at 155 ℃ for 12 hours to obtain the oxygen-rich vacancy bismuth molybdate/sulfur composite material.
The properties were characterized as in example 1, and the results of the characterization are shown in Table 1 below.
Example 6
0.45g Bi(NO3)3·5H2O、0.36g Na2MoO4·2H2Dissolving O and 0.028g CTAB in 40ml of isopropanol, stirring for 30min, transferring the mixed solution into a 100ml of polytetrafluoroethylene reaction kettle, heating the solvent at 110 ℃ for 24h, centrifuging the obtained product, washing the product for three times by using ethanol, and then drying the product in vacuum at 60 ℃ to obtain the oxygen-rich vacancy bismuth molybdate.
And (3) mixing and grinding 2g of oxygen-rich vacancy bismuth molybdate and 16g of elemental sulfur uniformly, introducing argon as a protective gas, and calcining at 155 ℃ for 12 hours to obtain the oxygen-rich vacancy bismuth molybdate/sulfur composite material.
The properties were characterized as in example 1, and the results of the characterization are shown in Table 1 below.
Comparative example 1
0.45g Bi(NO3)3·5H2O、0.12g Na2MoO4·2H2Dissolving O in 40ml of isopropanol, stirring for 30min, transferring the mixed solution into a 100ml of polytetrafluoroethylene reaction kettle, heating the solvent at 110 ℃ for 24h, centrifuging the obtained product, washing the product for three times by using ethanol, and then drying the product in vacuum at 60 ℃ to obtain oxygen-rich vacancy bismuth molybdate and obtain oxygen-free vacancy bismuth molybdate, wherein an XPS spectrogram of the oxygen-rich vacancy bismuth molybdate is shown in a figure 1, and the content of oxygen vacancies is 0.
And (3) mixing and grinding 2g of oxygen-rich vacancy bismuth molybdate and 12g of elemental sulfur uniformly, introducing argon as a protective gas, and calcining at 155 ℃ for 12h to obtain the oxygen-free vacancy bismuth molybdate/sulfur composite material.
The properties were characterized as in example 1, and the results of the characterization are shown in Table 1 below.
Comparative example 2
And (3) mixing and grinding 6g of acetylene black and 14g of elemental sulfur uniformly, introducing argon as protective gas, and calcining at 155 ℃ for 12h to obtain the acetylene black/sulfur composite material without oxygen vacancies.
The properties were characterized as in example 1, and the results of the characterization are shown in Table 1 below.
The characterization results are shown in table 1 below:
TABLE 1
| Serial number | Oxygen vacancy content | Gram Capacity exertion (mAh/g) | Capacity retention after 0.05C, 250cls cycles |
| Example 1 | 3％ | 1200 | 75％ |
| Example 2 | 4％ | 1108 | 70％ |
| Example 3 | 1％ | 1050 | 65％ |
| Example 4 | 2％ | 1080 | 68％ |
| Example 5 | 3％ | 1120 | 65％ |
| Example 6 | 10％ | 1100 | 63％ |
| Comparative example 1 | 0％ | 1003 | 50％ |
| Comparative example 2 | - | 1002 | 40％ |
As can be seen from the data in table 1, after the bismuth molybdate/sulfur composite materials prepared in the above examples 1 to 6 are applied to the battery, the gram capacity exertion and the cycle retention rate are significantly higher than those of the materials in comparative examples 1 and 2, which indicates that the bismuth molybdate/sulfur composite materials prepared from the oxygen vacancy-rich bismuth molybdate of the present invention have a significant improvement effect on the cycle performance of the lithium-sulfur battery. More particularly, the bismuth molybdate oxygen vacancy content in examples 1 to 5 is 1 to 4%, and the improvement effect on the cycle performance of the lithium-sulfur battery is better.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a bismuth molybdate/sulfur composite material is characterized by comprising the following steps:
step S1, providing oxygen-rich vacancy bismuth molybdate, wherein the oxygen vacancy content of the oxygen-rich vacancy bismuth molybdate is 1-10%;
and step S2, mixing the oxygen-rich vacancy bismuth molybdate and the elemental sulfur, and calcining in inert gas to obtain the bismuth molybdate/sulfur composite material.
2. The method of claim 1, wherein the oxygen vacancy content of the oxygen-vacancy-rich bismuth molybdate is 1-4%.
3. The method for preparing a bismuth molybdate/sulfur composite material as claimed in claim 1 or 2, wherein the step S1 comprises:
dissolving soluble bismuth salt and soluble molybdenum salt in a solvent to form a mixed solution;
and carrying out solvothermal reaction on the mixed solution to obtain the oxygen-rich vacancy bismuth molybdate.
4. The method for preparing a bismuth molybdate/sulfur composite material according to claim 3, wherein the molar ratio of the soluble bismuth salt to the soluble molybdenum salt is (3-5): 2.
5. The method for preparing the bismuth molybdate/sulfur composite material as claimed in claim 3 or 4, wherein the solvent is an alcohol solvent with a boiling point of more than 80 ℃, and 9-15 g of the soluble bismuth salt is used per liter of the solvent.
6. The method of claim 5, wherein a surfactant is further added to the mixed solution, wherein 0.7-1.25 g of the surfactant is added per liter of the solvent.
7. The method of preparing the bismuth molybdate/sulfur composite material according to any one of claims 1 to 4, wherein in the step S2, the weight ratio of the oxygen-rich vacancy bismuth molybdate to the elemental sulfur is 0.5 (1-4).
8. The method of claim 7, wherein in step S2, the calcination temperature is 150-180 ℃ and the calcination time is 12-24 h.
9. A bismuth molybdate/sulfur composite material prepared by the preparation method of any one of claims 1 to 8, wherein the bismuth molybdate/sulfur composite material has a two-dimensional nanosheet structure.
10. A lithium sulfur battery having a positive electrode comprising a current collector and a positive electrode material disposed on said current collector, said positive electrode material comprising an active material, a conductive agent and a binder, wherein said active material is the bismuth molybdate/sulfur composite material of claim 9.
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Effective date of registration: 20220621 Address after: 516100 plants 1, 2, 3, 11, 12, 13, 14, 15a, 15b, 1-3 floors of plant 8, 3 floors of plant 21, and 24 of Xinwangda Industrial Park, Dongpo Avenue, Yuanzhou Town, BOLUO County, Huizhou City, Guangdong Province Applicant after: XINWANGDA HUIZHOU POWER NEW ENERGY Co.,Ltd. Address before: 518107 Xinwangda Industrial Park, No.18, Tangjia south, Gongming street, Guangming New District, Shenzhen City, Guangdong Province Applicant before: SUNWODA ELECTRIC VEHICLE BATTERY Co.,Ltd. |
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| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210803 |