CN106784725B - A kind of lithium sulfur battery anode material and its preparation method and application - Google Patents
A kind of lithium sulfur battery anode material and its preparation method and application Download PDFInfo
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- CN106784725B CN106784725B CN201710026650.7A CN201710026650A CN106784725B CN 106784725 B CN106784725 B CN 106784725B CN 201710026650 A CN201710026650 A CN 201710026650A CN 106784725 B CN106784725 B CN 106784725B
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- Prior art keywords
- anode material
- battery anode
- preparation
- sulfur battery
- lithium sulfur
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000010405 anode material Substances 0.000 title claims abstract description 17
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 36
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000005864 Sulphur Substances 0.000 claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 238000005253 cladding Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000004945 emulsification Methods 0.000 claims abstract description 4
- -1 alkyl phenol Chemical compound 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 159000000009 barium salts Chemical class 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004064 cosurfactant Substances 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 claims description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical group [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 125000005227 alkyl sulfonate group Chemical group 0.000 claims description 3
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 3
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 3
- 229910001626 barium chloride Inorganic materials 0.000 claims description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 229920001021 polysulfide Polymers 0.000 claims description 3
- 239000005077 polysulfide Substances 0.000 claims description 3
- 150000008117 polysulfides Polymers 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical group C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 claims description 2
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 claims description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000004816 dichlorobenzenes Chemical class 0.000 claims description 2
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 claims description 2
- 239000001760 fusel oil Substances 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 2
- IEQAICDLOKRSRL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-dodecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO IEQAICDLOKRSRL-UHFFFAOYSA-N 0.000 claims 1
- RKIQXVFUVYXZCD-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCC)C(OS(O)(=O)=O)(CCO)CCCCCCCCCCCCCCCCCC Chemical compound C(CCCCCCCCCCCCCCCCC)C(OS(O)(=O)=O)(CCO)CCCCCCCCCCCCCCCCCC RKIQXVFUVYXZCD-UHFFFAOYSA-N 0.000 claims 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims 1
- 239000004698 Polyethylene Substances 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 125000005909 ethyl alcohol group Chemical group 0.000 claims 1
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 1
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- 239000006210 lotion Substances 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 description 10
- 230000004087 circulation Effects 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- SJGNPMFJYPCPMB-UHFFFAOYSA-N CCCCCCCCCCCCCCCCCCS(C)(CCCCCCCCCCCCCCCCCC)CCO Chemical compound CCCCCCCCCCCCCCCCCCS(C)(CCCCCCCCCCCCCCCCCC)CCO SJGNPMFJYPCPMB-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- CHBCHAGCVIMDKI-UHFFFAOYSA-N [F].C=C Chemical group [F].C=C CHBCHAGCVIMDKI-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000005779 cell damage Effects 0.000 description 1
- 208000037887 cell injury Diseases 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 125000001400 nonyl 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])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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 229960002415 trichloroethylene Drugs 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to electrode material fields, and in particular to a kind of lithium sulfur battery anode material and its preparation method and application.The lithium sulfur battery anode material is that the composite material of barium sulfate cladding sulphur effectively increases the ionic conductivity of positive electrode by barium sulfate to the cladding of sulphur positive electrode；In preparation process, lithium sulphur positive electrode is prepared using soft template method, does not need high temperature and high pressure, can control granular size by adjusting the composition of lotion in emulsion process, evenly dispersed barium sulfate cladding sulphur structure is formed, lithium-sulfur cell chemical property is effectively increased.
Description
Technical field
The invention belongs to electrode material fields, and in particular to a kind of lithium sulfur battery anode material and preparation method thereof and answer
With.
Background technique
Lithium-sulfur cell relies on the advantages such as its high-energy density, pollution-free, at low cost, becomes the best choosing of the following power battery
One of select.Early in 1962, Herbet et al. was put forward for the first time using elementary sulfur as this concept of new positive electrode.Sulphur has
The advantages that theoretical specific capacity is high, storage capacity is abundant, at low cost.But sulphur has the disadvantage in that ionic conducting property is poor, it is unfavorable
In the high rate capability of battery；In charge and discharge process, volume change is larger, be easy to cause cell damage；In charge and discharge process
Form the polysulfide for being soluble in electrolyte；Easily distillation.
Summary of the invention
The present invention is based on the above technical problem, a kind of lithium sulfur battery anode material and its preparation method and application is provided,
The lithium sulfur battery anode material is the composite material that barium sulfate coats sulphur,
Preparation method is preferred are as follows:
(1) oily phase, surfactant, cosurfactant are sufficiently mixed emulsification,
Wherein, oil be mutually hexamethylene, it is benzene,toluene,xylene, pentane, hexane, octane, chlorobenzene, dichloro-benzenes, styrene, complete
The mixing of one or more of vinyl chloride, trichloro ethylene, ethyl acetate, chlorophenol,
Surfactant is triton x-100, alkyl phenol polyoxyethylene ether, alkyl alcohol ether carboxylate, alkyl polyglycoside, alcohol ether
Phosphate monoester, polyoxyethylene aliphatic alcohol ether, octyl phenyl polyoxyethylene ether, 2-Butoxyethyl acetate, dodecyl alcohol polyoxy
Ethylene ether sodium sulfate, α-sodium olefin sulfonate, sodium secondary alkyl sulfonate, aliphatic alcohol polyethenoxy, hydroxyl synthol polyoxyethylene ether, nonyl
Base phenol polyethenoxy ether, dodecyldimethylamine oxide, hexadecyltrimethylammonium chloride, distearyl hydroxyethyl methyl sulphur
The mixing of one or more of sour formicester ammonium, tristerin,
Cosurfactant be ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, n-amyl alcohol, isoamyl alcohol, 1- hexanol,
The mixing of one or more of 2- hexanol, 1- octanol, sec-n-octyl alcohol, fusel oil, n nonylphenol；
(2) sulphur source, sulfuric acid or sulfate, barium salt are added into the system of step (1), reaction forms stable oil-in-water knot
Structure,
Sulphur source be one of elemental sulfur, thiosulfate, the sulfide of alkali or alkaline earth metal and polysulfide or
Several mixing,
Barium salt is the mixing of one or more of barium nitrate, barium chloride, barium acetate, barium sulfate, barium carbonate；
(3) product after step (2) reaction is filtered, washed, dried, finally obtain the composite wood of barium sulfate cladding sulphur
Material.
The present invention also provides a kind of applications of above-mentioned lithium sulfur battery anode material, i.e., the positive electrode are used for lithium ion
In battery.
The beneficial effects of the present invention are: the present invention, to the cladding of sulphur positive electrode, is effectively increased just by barium sulfate
The ionic conductivity of pole material.In preparation process, lithium sulphur positive electrode is prepared using soft template method, does not need high temperature and high pressure,
Reduce the problem of sulphur is easy distillation at high temperature, so that sulphur covering amount increases, improves volumetric properties；Pass through in emulsion process
The composition for adjusting lotion can control granular size, to control the partial size of product, size and dispersibility, is formed and is uniformly divided
Scattered barium sulfate coats sulphur structure, effectively increases lithium-sulfur cell chemical property.
Detailed description of the invention
Fig. 1 is charging and discharging curve figure of the battery under 0.1C multiplying power made from embodiment 1, in figure, two intermediate curves
For the 1st charging and discharging curve, the charging and discharging curve that two articles of curves of upper and lower ends are the 100th time.
Fig. 2 is charging and discharging curve figure of the battery under 0.1C multiplying power made from comparative example 1.
Specific embodiment
The operation of following embodiment is carried out under room temperature (25 DEG C).
Embodiment 1
1, the preparation of the composite material of barium sulfate cladding sulphur
(1) measure 64.68ml hexamethylene, 10.92ml triton x-100,8.4ml 1- hexanol be put on magnetic stirring apparatus
It is sufficiently mixed transparent lotion；
(2) the uniform elemental sulfur ultrasound aqueous dispersions (simple substance of 2.9ml is added into transparency emulsion obtained in step (1)
The weight ratio of sulphur and dispersion liquid is 6:10) and be sufficiently stirred 5 minutes, add the sulfuric acid that 2.8ml Solute mass fraction is 35%
Solution is sufficiently stirred 5 minutes, adds the barium chloride solution that 10.3ml Solute mass fraction is 20% and is sufficiently stirred 5 minutes, mistake
Filter, dry, washing, drying；
2, the preparation of positive electrode
Weigh the composite material of 0.08 gram of barium sulfate obtained above cladding sulphur, 0.01 gram of acetylene black, 0.01 gram gather inclined fluorine
Ethylene is placed in mortar and grinds uniformly, adds 1 milliliter of NMP, and it is uniform to continue grinding；Resulting mixture will be ground and be applied to aluminium
On foil, forced air drying in 50 DEG C of baking ovens, 55 DEG C of vacuum drying 12h are cut into the pole piece having a size of 5mm × 5mm, as anode；
3, using lithium piece as negative electrode material；
4, using PP-PE composite micro porous film as battery diaphragm
The assembling of battery: diaphragm is covered on above lithium piece, electrolyte is added, then cover positive electrode, is assembled into lithium
Sulphur battery.
Electrochemical property test is carried out to lithium-sulfur cell prepared in the present embodiment, voltage window is 1.0V~3.0V,
Charge and discharge electric condition is 0.1C, and the coulombic efficiency after circulation 100 times is 93%, illustrates that utilization efficiency is relatively high.
Attached drawing 1 is charging and discharging curve figure of the prepared battery under 0.1C multiplying power, and it is higher to reflect ionic conductivity.
Embodiment 2
Barium sulfate coats the preparation of the composite material of sulphur
(1) 65.6ml isooctane, 9.5g alkyl alcohol ether carboxylic acid sodium, 4ml normal propyl alcohol is measured to be put on magnetic stirring apparatus sufficiently
Mix transparent lotion；
(2) into transparency emulsion obtained in step (1) be added 4.6ml Solute mass fraction be 60% it is evenly dispersed
Sodium thiosulfate solution is simultaneously sufficiently stirred 5 minutes, adds the ferrum sulfuricum oxydatum solutum that 3.66ml Solute mass fraction is 20% and fills
Divide stirring 5 minutes, add the barium nitrate solution that 11.67ml Solute mass fraction is 20% and be sufficiently stirred 5 minutes, filtering is done
Dry, washing, drying；
Remaining step is the same as embodiment 1.
Electrochemical property test is carried out to lithium-sulfur cell prepared in the present embodiment, voltage window is 1.0V~3.0V,
Charge and discharge electric condition is 0.2C, and the coulombic efficiency after 150 circulations is 86%.
Embodiment 3
Barium sulfate coats the preparation of the composite material of sulphur
(1) measure 62.32ml perchloroethylene, 9.07g sodium secondary alkyl sulfonate, 3.8ml 1- octanol be put into magnetic stirring apparatus
On be sufficiently mixed transparent lotion；
(2) into transparency emulsion obtained in step (1) be added 2.9ml Solute mass fraction be 60% it is evenly dispersed
Sodium sulfide solution is simultaneously sufficiently stirred 5 minutes, adds 2.8ml uniform calcium sulfate ultrasound aqueous dispersions (calcium sulfate and dispersion liquid
Weight ratio be 35:100) be sufficiently stirred 5 minutes, add 10.3ml Solute mass fraction be 20% barium acetate solution it is abundant
Stirring 5 minutes, filtering, dry, washing, drying；
Remaining step is the same as embodiment 1.
Electrochemical property test is carried out to lithium-sulfur cell prepared in the present embodiment, voltage window is 1.0V~3.0V,
Charge and discharge electric condition is 0.2C, and the coulombic efficiency after 200 circulations is 85%.
Embodiment 4
Barium sulfate coats the preparation of the composite material of sulphur
(1) 61.6ml octane, 10.4ml tristerin, 0.8ml isobutanol is measured to be put on magnetic stirring apparatus sufficiently
Mix transparent lotion；
(2) (the vulcanization of the uniform calcium sulfide ultrasound aqueous dispersions of 2.9ml is added into transparency emulsion obtained in step (1)
The weight ratio of calcium and dispersion liquid is 60:100) and be sufficiently stirred 5 minutes, add the sulphur that 3.9ml Solute mass fraction is 30%
Sour aluminum solutions are sufficiently stirred 5 minutes, then the hydrochloric acid solution that 10ml Solute mass fraction is 20% is added dropwise and is sufficiently stirred 5 minutes, then
The uniform barium carbonate ultrasound aqueous dispersions of 12.4ml (weight ratio of barium carbonate and dispersion liquid is 25:100) are added and are sufficiently stirred 5 points
Clock, filtering, dry, washing, drying；
Remaining step is the same as embodiment 1.
Electrochemical property test is carried out to lithium-sulfur cell prepared in the present embodiment, voltage window is 1.0V~3.0V,
Charge and discharge electric condition is 0.2C, and the coulombic efficiency after 200 circulations is 85%.
Embodiment 5
Barium sulfate coats the preparation of the composite material of sulphur
(1) 55.44ml benzene, 4.11g hexadecyltrimethylammonium chloride, 7.2ml n-butanol are measured and is put into magnetic stirring apparatus
On be sufficiently mixed transparent lotion；
(2) evenly dispersed two that 9ml Solute mass fraction is 50% are added into transparency emulsion obtained in step (1)
Sodium sulfide solution is simultaneously sufficiently stirred 5 minutes, adds the Adlerika that 14.5ml Solute mass fraction is 15% and is sufficiently stirred 5
Minute, then the hydrochloric acid solution that 8.5ml Solute mass fraction is 20% is added dropwise and is sufficiently stirred 5 minutes, it adds 0.25g barium carbonate and fills
Divide stirring 5 minutes, filtering, is dried at dry, washing；
Remaining step is the same as embodiment 1.
Electrochemical property test is carried out to lithium-sulfur cell prepared in the present embodiment, voltage window is 1.0V~3.0V,
Charge and discharge electric condition is 0.2C, and the coulombic efficiency after 150 circulations is 87%.
Embodiment 6
Barium sulfate coats the preparation of the composite material of sulphur
(1) 59.04ml toluene, 9.36ml tristerin, 3.6ml n nonylphenol is measured to be put on magnetic stirring apparatus and fill
Divide mixing transparent lotion；
(2) into transparency emulsion obtained in step (1) be added 5.1ml Solute mass fraction be 40% it is evenly dispersed
Thiosulfuric acid aqueous ammonium is simultaneously sufficiently stirred 5 minutes, and it is abundant to add the potassium sulfate solution that 2.6ml Solute mass fraction is 25%
Stirring 5 minutes, then the hydrochloric acid solution that 5.5ml Solute mass fraction is 20% is added dropwise and is sufficiently stirred 5 minutes, add 0.82g carbon
Sour barium is sufficiently stirred 5 minutes, filtering, dry, washing, drying；
Remaining step is the same as embodiment 1.
Electrochemical property test is carried out to lithium-sulfur cell prepared in the present embodiment, voltage window is 1.0V~3.0V,
Charge and discharge electric condition is 0.2C, and the coulombic efficiency after 150 circulations is 85%.
Comparative example 1
Uncoated sulfur materials preparation
(1) measure 64.68ml hexamethylene, 10.92ml triton x-100,8.4ml 1- hexanol be put on magnetic stirring apparatus
It is sufficiently mixed transparent lotion；
(2) the uniform elemental sulfur ultrasound aqueous dispersions (simple substance of 2.9ml is added into transparency emulsion obtained in step (1)
The weight ratio of sulphur and dispersion liquid is 6:10) and be sufficiently stirred 5 minutes, it adds 2.8ml water and is sufficiently stirred 5 minutes, add
10.3ml water is sufficiently stirred 5 minutes, filtering, dry, washing, drying；
The step of positive electrode preparation and battery assembly, is the same as embodiment 1.
Electrochemical property test is carried out to prepared battery, voltage window is 1.0V~3.0V, and charge and discharge electric condition is
0.1C, 100 times circulation after coulombic efficiency be 25%.
Attached drawing 2 is first time charging and discharging curve figure of the prepared battery under 0.1C multiplying power.
Claims (8)
1. a kind of lithium sulfur battery anode material, it is characterised in that: the lithium sulfur battery anode material is that barium sulfate coats answering for sulphur
Condensation material.
2. a kind of preparation method of lithium sulfur battery anode material as described in claim 1, it is characterised in that: the preparation side
Method is,
(1) oily phase, surfactant, cosurfactant are sufficiently mixed emulsification；
(2) sulphur source, sulfuric acid or sulfate, barium salt are sequentially added into the system of step (1), and after being separately added into above-mentioned substance
It is sufficiently stirred, reaction forms stable oil-in-water structure；
(3) product after step (2) reaction is filtered, washed, dried, finally obtain the composite material of barium sulfate cladding sulphur.
3. the preparation method of lithium sulfur battery anode material as claimed in claim 2, it is characterised in that: described in step (1)
Oily is mutually hexamethylene, benzene,toluene,xylene, pentane, hexane, octane, chlorobenzene, dichloro-benzenes, styrene, perchloroethylene, three chloroethenes
The mixing of one or more of alkene, ethyl acetate, chlorophenol.
4. the preparation method of lithium sulfur battery anode material as claimed in claim 2, it is characterised in that: described in step (1)
Surfactant is triton x-100, alkyl phenol polyoxyethylene ether, alkyl alcohol ether carboxylate, alkyl polyglycoside, alcohol ether mono phosphoric acid ester
Ester, polyoxyethylene aliphatic alcohol ether, octyl phenyl polyoxyethylene ether, 2-Butoxyethyl acetate, Brij 35
Sodium sulphate, α-sodium olefin sulfonate, sodium secondary alkyl sulfonate, aliphatic alcohol polyethenoxy, hydroxyl synthol polyoxyethylene ether, nonyl phenol are poly-
Ethylene oxide ether, dodecyldimethylamine oxide, hexadecyltrimethylammonium chloride, distearyl hydroxyethyl methyl sulfuric acid formicester
The mixing of one or more of ammonium, tristerin.
5. the preparation method of lithium sulfur battery anode material as claimed in claim 2, it is characterised in that: described in step (1)
Cosurfactant is ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, n-amyl alcohol, isoamyl alcohol, 1- hexanol, 2- hexanol, 1-
The mixing of one or more of octanol, sec-n-octyl alcohol, fusel oil, n nonylphenol.
6. the preparation method of lithium sulfur battery anode material as claimed in claim 2, it is characterised in that: described in step (2)
Sulphur source is the mixed of elemental sulfur, thiosulfate, the sulfide of alkali or alkaline earth metal and one or more of polysulfide
It closes.
7. the preparation method of lithium sulfur battery anode material as claimed in claim 2, it is characterised in that: described in step (2)
Barium salt is the mixing of one or more of barium nitrate, barium chloride, barium acetate, barium sulfate, barium carbonate.
8. a kind of application of lithium sulfur battery anode material as described in claim 1, it is characterised in that: the application is to incite somebody to action
The positive electrode is in lithium ion battery.
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| CN104701542A (en) * | 2015-02-05 | 2015-06-10 | 中南大学 | All-solid-state lithium-sulfur battery composite positive material, all-solid-state lithium-sulfur battery prepared from composite positive material and preparation method of composite positive material |
| CN105576240A (en) * | 2016-01-20 | 2016-05-11 | 中国科学院过程工程研究所 | Nano barium sulfate carbon composite material and preparation method and application therefor |
| CN105958030A (en) * | 2016-06-28 | 2016-09-21 | 常州大学 | Preparation method of positive electrode material of lithium-sulphur battery |
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| CN105576240A (en) * | 2016-01-20 | 2016-05-11 | 中国科学院过程工程研究所 | Nano barium sulfate carbon composite material and preparation method and application therefor |
| CN105958030A (en) * | 2016-06-28 | 2016-09-21 | 常州大学 | Preparation method of positive electrode material of lithium-sulphur battery |
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