CN109546139B - Metal sulfide/carbon composite material, preparation method and application thereof in battery cathode material - Google Patents
Metal sulfide/carbon composite material, preparation method and application thereof in battery cathode material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 108
- 239000002131 composite material Substances 0.000 title claims abstract description 103
- 229910052976 metal sulfide Inorganic materials 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000010406 cathode material Substances 0.000 title abstract description 16
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 20
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 74
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 65
- 239000000243 solution Substances 0.000 claims description 52
- 238000010438 heat treatment Methods 0.000 claims description 48
- 238000005406 washing Methods 0.000 claims description 36
- 239000010902 straw Substances 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 20
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 241000609240 Ambelania acida Species 0.000 claims description 15
- 239000010905 bagasse Substances 0.000 claims description 15
- 239000012535 impurity Substances 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 230000002378 acidificating effect Effects 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 239000007773 negative electrode material Substances 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 10
- 239000011684 sodium molybdate Substances 0.000 claims description 10
- 235000015393 sodium molybdate Nutrition 0.000 claims description 10
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical group [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- XUKVMZJGMBEQDE-UHFFFAOYSA-N [Co](=S)=S Chemical compound [Co](=S)=S XUKVMZJGMBEQDE-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims description 8
- 244000276331 Citrus maxima Species 0.000 claims description 7
- 241000209140 Triticum Species 0.000 claims description 7
- 235000021307 Triticum Nutrition 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 235000001759 Citrus maxima Nutrition 0.000 claims description 6
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 6
- 229920005610 lignin Polymers 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004201 L-cysteine Substances 0.000 claims description 3
- 235000013878 L-cysteine Nutrition 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 3
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 240000008042 Zea mays Species 0.000 claims description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 235000005822 corn Nutrition 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000005083 Zinc sulfide Substances 0.000 claims description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 15
- 238000012360 testing method Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 description 20
- 238000001035 drying Methods 0.000 description 17
- 229910052961 molybdenite Inorganic materials 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 238000001994 activation Methods 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- -1 Transition metal sulfide Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002060 nanoflake Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 238000007792 addition Methods 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
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
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- 239000003658 microfiber Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
-
- 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
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- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- 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
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- H—ELECTRICITY
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- 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
- H01M2004/027—Negative electrodes
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Abstract
A metal sulfide/carbon composite material, a preparation method and application thereof in a battery cathode material relate to the technical field of battery electrode material preparation. The nanometer metal sulfide in the structure of the composite material is uniformly loaded in the carbon net. With the different proportion of the metal sulfide in the composite material, the shape of the metal sulfide in the product also shows different. The composite material with the structure has high ionic and electronic conductivity and excellent structural stability, and is beneficial to improving the rate capability and prolonging the cycle life of the material. The metal sulfide/carbon composite material is used as a sodium ion battery cathode material and assembled into a battery for testing, and the composite material shows outstanding high-current rapid charge and discharge performance, has an ultra-long cycle life, has high charge and discharge capacity, and is an ideal sodium ion battery cathode material with an application prospect.
Description
Technical Field
The invention relates to the technical field of battery electrode material preparation, in particular to a metal sulfide/carbon composite material, a preparation method and application thereof in a battery cathode material.
Background
With the widespread use of lithium ion batteries in electric vehicles, the cost and the reserves of the relevant raw materials are facing serious problems. Sodium is abundant in the earth, and accounts for 2.36% of the earth's crust, and is more than 1000 times of the lithium resource (0.0017%). The relatively inexpensive sodium ion battery (NIB) is gradually drawing a great deal of attention in the global industry. And lithium and sodium belong to the first main group and have similar physicochemical properties, and NIB is a novel energy storage system which is most hopeful to replace the traditional lithium ion battery at present. Transition metal sulfide as a type of NIB negative electrode material is a promising candidate negative electrode material due to the fact that the transition metal sulfide has high theoretical specific discharge capacity.
Among the various metal sulfides, molybdenum disulfide (MoS)2) The material has a two-dimensional layered structure of Na+Provide a good transmission channel, and MoS2Has high theoretical specific capacity (670mAh/g) and is a sodium-ion battery cathode material with wide application prospect. But pure MoS2Low conductivity and the structure tends to collapse and agglomerate during charge/discharge cycling, resulting in poor long-range cycling performance. Research finds that molybdenum disulfide/carbon (MoS) is adopted2the/C) composite material can effectively improve pure MoS2Has a problem that it is an excellent battery negative electrode material.
In recent years, various MoS2The synthesis method of the/C composite negative electrode material is developed. For example, the hydrothermal synthesis of MoS using sodium molybdate and thiourea as precursors2Material, then MoS2Mixing the material with carbon-containing organic substance (such as glucose), performing hydrothermal reaction to realize carbon coating, and performing hydrothermal reaction on the mixture in Ar/H2(5%) annealing at 800 ℃ for 2h in a mixed gas to obtain MoS2the/C composite material can stably circulate for 300 circles at a current density of 0.67A/g, and has a discharge capacity of 400mAh/g (Wang J, Luo C, Gao T, et al.Small 2015,11,4,473 and 481). Carbon coated MoS synthesized by the technology2Composite material, surface-coated carbon layer capable of bearing MoS2The charge and discharge volume strain force is limited, so the cycle life of the lithium ion battery can be only improved in a limited way. MoS growth by taking graphene, carbon nano tube and carbon fiber as carbon carriers2To prepare MoS2the/C composite is also a common synthetic route. E.g. water, from Zhao Hailei et alPerforming a thermal method, performing ultrasonic dispersion on the graphene aqueous solution for 1h, adding polyvinylpyrrolidone, thiourea, ammonium molybdate and oxalic acid, performing hydrothermal reaction for 12h at 180 ℃, cleaning, drying and adding the mixture to C2H2Calcining the mixture in an Ar mixed gas at 500 ℃ for 30min to obtain MoS2The graphene composite material has good high-current charge and discharge performance, can circulate 200 circles under the high-current density of 5A/g, and has the capacity of 304mAh/g (Teng Y, ZHao H, Zhang Z, et al. carbon 2017,119, 91-100). MoS prepared by this technique2The performance of the/C composite material is better improved, but the synthesis cost is very expensive, and the yield is less. There are also methods for preparing MoS using biomass as a carbon source2the/C composite material, such as LiuGuilinong et al, is prepared by cleaning, drying and calcining palm fiber in argon at 800 ℃ to obtain palm fiber carbon, dispersing the palm fiber carbon in aqueous solution, adding sodium molybdate, thiourea and glucose, carrying out hydrothermal reaction at 200 ℃ for 24h, further calcining the product at 600 ℃ in argon atmosphere for 2h, and finally obtaining MoS2the/C composite material is used as a negative electrode material of the sodium-ion battery, and the discharge capacity of 223mAh/g is kept for 100 circles under the current density of 0.05A/g. According to the technical scheme, the biomass is carbonized at high temperature and then used as a carbon substrate to carry MoS through hydrothermal reaction with a molybdenum source and a sulfur source2And further calcined at high temperature to obtain the final product (LiuG, Cui J, Luo R, et al. applied Surface science2019,469, 854-863). The scheme has more steps, increases the cost by multiple high-temperature calcinations, and carbonizes the carbon base and the loaded MoS2The binding force is limited, and the long cycle performance and the large-current charge and discharge performance are not good.
The metal sulfide/carbon composite material obtained by the methods generally has the limitations of high cost, complex operation or poor electrochemical performance as a battery cathode material, and the like, and the cost, the environmental protection and the high performance cannot be considered at the same time, so that the practical application of the metal sulfide/carbon composite material is limited. Therefore, a green and low-cost synthesis method of the high-performance metal sulfide/carbon composite material is developed, and the method has important significance for scale preparation of the metal sulfide/carbon composite material and practical application of the metal sulfide/carbon composite material as a high-performance battery cathode material.
Disclosure of Invention
Aiming at the technical problem that the metal sulfide/carbon composite material in the prior art cannot simultaneously take two important industrialization indexes of low cost, environment-friendly preparation route and high electrochemical performance into consideration, the invention firstly provides a metal sulfide/carbon net composite material with a novel structure, which has high ionic and electronic conductivity and strong structural stability. Meanwhile, the invention also provides a preparation method of the composite material, and a high-temperature calcination pretreatment process of biomass is not needed. The composite material is applied to a sodium ion battery cathode material, shows outstanding high-current rapid charge and discharge performance, has an ultra-long cycle life, and has high charge and discharge capacity.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a metal sulfide/carbon composite material, which consists of metal sulfide and carbon, wherein in the structure, the nano-scale metal sulfide in a flower shape or a sheet shape is uniformly loaded in a carbon net. With the different proportion of the metal sulfide in the composite material, the shape of the metal sulfide in the product also shows different.
In the metal sulfide/carbon composite material, when the metal sulfide is preferably molybdenum disulfide, tungsten disulfide, cobalt disulfide or zinc sulfide, the beneficial effects of high ionic conductivity, high structural stability and the like can be further achieved.
The invention provides a preparation method of a metal sulfide/carbon composite material, which comprises the steps of activating straws by a delignification solution to prepare a straw precursor, mixing the straw precursor with a metal source for preparing metal sulfide and a sulfur source for carrying out hydrothermal reaction, and carrying out oxygen-free high-temperature treatment on a prepared product to obtain the metal sulfide/carbon composite material.
As a preferred technical scheme of the preparation method, the preparation method specifically comprises the following steps:
1) crushing the straw raw material, adding an acidic reaction solution for impurity removal, and adding a lignin removal solution for activation to obtain a straw precursor; the straw is selected from bagasse, corn cob, pomelo peel, rice straw and wheat straw;
2) mixing the straw precursor with a metal source and a sulfur source solution, and carrying out hydrothermal reaction; the metal source is selected from sodium molybdate, sodium tungstate, cobalt sulfate and zinc chloride, and the sulfur source is selected from thiourea, L-cysteine and elemental sulfur;
3) heating the hydrothermal reaction product in an oxygen-free atmosphere to prepare a metal sulfide/carbon composite material; the mass fraction of the metal sulfide in the composite material is 5 wt% -95 wt%, preferably 30 wt% -90 wt%.
As a further preferable technical scheme of the preparation method of the invention:
the process of adding the acidic reaction solution into the acidic reaction solution, mixing, heating and removing impurities and the process of adding the delignification solution, mixing, heating and activating are carried out in the step 1), and the two processes are not limited in sequence; meanwhile, the method can be used for only activating without removing impurities. The preferable steps are firstly adding the acidic reaction solution, mixing, heating and removing impurities, then adding the lignin-removing solution, mixing, heating and activating.
In the step 1), the acidic reaction solution is one or more of hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, preferably a sulfuric acid solution; the concentration of the acidic reaction solution is 0.1-15 mol/L, preferably 1-5 mol/L; the delignification solution is one or more of sodium hydroxide, potassium hydroxide, hydrogen peroxide, sodium sulfite and sodium hypochlorite, and is preferably sodium hydroxide solution; the solute content of the delignification solution is 0.1 wt% -40 wt%, preferably 1 wt% -15 wt%; the ratio of the straw powder to the delignification solution is 1 g: 5mL to 400mL, preferably 1 g: 20mL to 100 mL.
The mixing mode among the straw powder, the acidic reaction solution and the delignification solution in the step 1) comprises stirring and mixing and ultrasonic mixing; the heating temperature for the impurity removal and lignin removal solution activation treatment is between 10 and 300 ℃, and preferably between 50 and 120 ℃; the treatment time is between 30 minutes and 3 days, preferably between 2 hours and 20 hours.
In the step 1) and the step 2), washing and drying treatment needs to be carried out on the product, wherein the washing comprises water washing and alcohol washing.
The pH value of the mixed solution in the step 2) is 1-9, preferably 5-8; the temperature of the heating reaction is 140-300 ℃, preferably 160-220 ℃; the reaction time is from 30 minutes to 3 days, preferably from 6 hours to 24 hours.
The oxygen-free atmosphere in the step 3) comprises one or more of argon, nitrogen and argon/hydrogen mixed gas, preferably nitrogen; the heating temperature is between 200 and 1000 ℃, preferably between 400 and 800 ℃; the heating time is 30 minutes to 3 days, preferably 30 minutes to 5 hours.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention provides a method for preparing a metal sulfide/carbon composite material by taking straws as precursors, wherein in the synthesized metal sulfide/carbon mesh composite material taking molybdenum disulfide as an example, molybdenum disulfide flakes (nano flower balls assembled by nano flakes) and the nano flakes are embedded between carbon meshes. The molybdenum disulfide is in a layer expanding structure, the interlayer spacing of the molybdenum disulfide is increased (reaching 0.98nm), the interlayer spacing of the traditional molybdenum disulfide material is only 0.64nm, the composite material with the structure has high ionic and electronic conductivity, and the metal sulfide and carbon have strong bonding force and excellent structural stability, so that the rate capability and the cycle life of the material are improved, and the material is an ideal sodium ion battery cathode material with an application prospect.
2) The preparation process is simple and efficient, uses cheap raw materials, is environment-friendly, has low production cost, and solves the problems that the existing preparation method of the molybdenum disulfide/carbon composite material has low cost and high electrochemical performance and the like. The preparation method can effectively solve the key problem of mass production of the molybdenum disulfide/carbon composite material as the cathode material of the high-performance sodium-ion battery. The adopted raw materials are straws, so that the method is low in cost and environment-friendly, and can realize resource utilization of wastes. Compared with the prior art for preparing the metal sulfide/carbon composite material based on the biomass, the preparation method has simple and unique preparation process, does not need the high-temperature calcination pretreatment process of the biomass, and does not have carbon-based and loaded MoS2The binding force is limited, and the obtained product has unique appearance and structure and outstanding electrochemical performance.
3) The metal sulfide/carbon composite material is used as a negative electrode material of a sodium ion battery and assembled into the battery for testing as the application of the composite material in the aspect of electrochemical energy storage. Compared with the international reported molybdenum disulfide/carbon composite cathode material, the molybdenum disulfide/carbon composite cathode material has the advantages of superior cycle stability, excellent high-current rapid charge and discharge performance, stable cycle of 8000 circles under the high-current density of 5A/g, high discharge specific capacity of 194mAh/g, capacity retention rate of 80.2 percent of the capacity after activation (low-current density activation of the first 20 circles), and coulombic efficiency of 99.8 percent. Therefore, the composite material has excellent high-current charge and discharge performance, an ultra-long cycle life and excellent charge and discharge capacity, and is an ideal sodium ion battery negative electrode material with application prospect.
Drawings
FIGS. 1a and b are scanning electron micrographs of the molybdenum disulfide/carbon composite material obtained in example 1 at different angles, and FIGS. 1c to f are selected-area electron spectrum images of a sample;
FIG. 2a is the X-ray diffraction spectrum of the molybdenum disulfide/carbon composite material obtained in example 1, and FIG. 2b is the high-resolution transmission electron micrograph of the material;
FIG. 3 is a charge-discharge curve diagram of the molybdenum disulfide/carbon composite material obtained in example 1 as a negative electrode material of a sodium ion battery at a current density of 0.2A/g;
FIG. 4 is a graph of the rate capability of the molybdenum disulfide/carbon composite obtained in example 1 as a negative electrode material of a sodium ion battery;
FIG. 5 is a graph of the cycle performance of the cathode material of the sodium ion battery made of the molybdenum disulfide/carbon composite material obtained in example 1 at a large current density of 5A/g;
FIG. 6a is the X-ray diffraction spectrum of the molybdenum disulfide/carbon composite material obtained in example 2, and FIGS. 6b and c are the scanning electron micrographs of the material at different angles;
FIG. 7 is a scanning electron microscope image of the molybdenum disulfide/carbon composite obtained in example 3;
FIG. 8 is a scanning electron micrograph of a molybdenum disulfide/carbon composite obtained in example 4;
FIG. 9 is a scanning electron micrograph of a molybdenum disulfide/carbon composite obtained in example 5;
FIG. 10a is the X-ray diffraction spectrum of the tungsten disulfide/carbon composite material obtained in example 6, and FIG. 10b is the scanning electron microscope image of the material;
FIG. 11a is the X-ray diffraction spectrum of the cobalt disulfide/carbon composite material obtained in example 7, and FIG. 11b is the scanning electron micrograph of the material.
Detailed Description
The metal sulfide/carbon composite material, the preparation method and the application thereof in the battery negative electrode material of the present invention are further described in detail below with reference to the examples and the accompanying drawings.
Example 1
A preparation method of a molybdenum disulfide/carbon composite material comprises the following steps:
(1) pretreating bagasse: crushing 5g of bagasse raw material, adding 250mL of sulfuric acid with the concentration of 1mol/L to remove impurities, heating at 80 ℃ for 2h, washing with water, filtering, adding 250mL of sodium hydroxide solution with the concentration of 10 wt%, uniformly mixing, heating at 90 ℃ for 3h, washing with water, washing with alcohol, filtering, and drying to obtain the bagasse precursor.
(2) And (2) adding 1g of bagasse precursor prepared in the step (1) into 60mL of water for dispersion, adding 2mmol of sodium molybdate and 8mmol of thiourea, adjusting the pH value to 7, stirring and mixing uniformly, carrying out hydrothermal reaction at the reaction temperature of 200 ℃ for 24h, washing the product with water and alcohol, filtering, and drying.
(3) And (3) placing the mixture prepared in the step (2) in a tubular furnace, and heating the mixture in the nitrogen atmosphere at 700 ℃ for 2 hours to obtain the molybdenum disulfide/carbon mesh composite material.
Fig. 1a and b are scanning electron micrographs of the molybdenum disulfide/carbon composite material obtained in this example, and fig. 1c to f are selected area electron spectrum images of the sample. As can be seen from the figure, the molybdenum disulfide flower chips are embedded in the carbon net structure, and the carbon net tightly wraps the molybdenum disulfide flower chips with the diameter of about 300 nanometers, and the molybdenum disulfide flower chips are uniformly distributed, so that the structural stability of the material is improved. As shown in FIG. 2a, the X-ray diffraction spectrum of the molybdenum disulfide/carbon network composite material obtained in this example is hexagonal phase molybdenum disulfide (JCPDS 00-024-9.0 degrees, and d is 0.98nm, which shows that the molybdenum disulfide (002) crystal face interlayer spacing of the embodiment is increased, and the molybdenum disulfide (002) crystal face interlayer spacing is of an expanded layer structure and is beneficial to Na+Fast transmission of (2). No obvious carbon diffraction peak, indicating that the carbon in the product is amorphous carbon. As shown in fig. 2b, a high-resolution transmission electron microscope image of the molybdenum disulfide/carbon mesh composite material obtained in this embodiment further verifies that the gap between the molybdenum disulfide layers is 0.98 nm.
And (3) testing the performance of the sodium-ion battery:
the molybdenum disulfide/carbon mesh composite material obtained in example 1 was mixed with 10 wt% of polyvinylidene fluoride (PVDF) binder, 10 wt% of conductive carbon black, and methyl pyrrolidone (NMP) to form a slurry, coated on a metal copper foil, and dried in a vacuum drying oven at 110 ℃ for 10 hours to obtain a molybdenum disulfide/carbon mesh composite material electrode.
Assembly of CR2025 coin cells using the working electrode: sodium sheet as counter electrode, glass microfiber (Whatman, GF/A) as diaphragm, and NaClO4The assembly of the CR2025 cell was completed in a glove box under argon atmosphere using a 1.0mol/L solution of Propylene Carbonate (PC) as the electrolyte.
The cycling performance was tested by the Land CT2001A battery test system (0.01V-3.0V) at 25 ℃.
FIG. 3 is a charge-discharge curve diagram of the molybdenum disulfide/carbon mesh composite material prepared in example 1, and FIG. 3 shows that the first-turn discharge and charge specific capacities of the material under the voltage range of 0.01-3.0V and the current density of 0.2A/g under the 1 st turn, the 2 nd turn and the 3 rd turn are 743mA h/g and 395mA h/g respectively, and the first-turn coulombic efficiency reaches 53.2%.
Fig. 4 is a graph of the rate capability of the molybdenum disulfide/carbon network composite material prepared in example 1, and fig. 4 shows that the rate capability of the composite material at different current densities of 0.2, 0.5, 1, 3, 5, 7, 10, 15 and 20A/g super-large current can still maintain higher specific discharge capacity, which shows that the composite material has excellent electrochemistry.
In addition, after the test of the super-large current density of 20A/g is finished and the small current of 0.2A/g is recovered again, the reversible specific capacity can still be recovered to the original specific capacity, and the specific capacity is not obviously attenuated in 10 cycles under each current density, which shows that the molybdenum disulfide/carbon mesh composite material has excellent reversibility and rate capability.
Fig. 5 is a graph of the large current cycle performance of the molybdenum disulfide/carbon mesh composite material prepared in example 1 of the present invention, and fig. 5 shows that the molybdenum disulfide/carbon mesh composite material can stably cycle 8000 cycles at a large current density of 5A/g (the battery has completed the cycle activation process at a low current density of 0.2A/g for the first 20 cycles) as the negative electrode of the sodium ion battery, and the capacity after 8000 cycles still reaches mA 194 h/g, which is 80.2% of the capacity after activation, and the coulombic efficiency reaches 99.8%. The material is fully shown to have superior structural stability, ultra-long cycle life and high specific discharge capacity, and is an excellent high-performance sodium ion battery cathode material.
Example 2
A preparation method of a molybdenum disulfide/carbon composite material comprises the following steps:
(1) pretreating bagasse: crushing 5g of bagasse raw material, adding 250mL of sulfuric acid with the concentration of 1mol/L to remove impurities, heating at 80 ℃ for 2h, washing with water, filtering, adding 250mL of sodium hydroxide solution with the concentration of 10 wt%, uniformly mixing, heating at 90 ℃ for 3h, washing with water, washing with alcohol, filtering, and drying to obtain the bagasse precursor.
(2) And (2) adding 1g of bagasse precursor prepared in the step (1) into 60mL of water for dispersion, adding 1mmol of sodium molybdate and 4mmol of thiourea, adjusting the pH value to 7, stirring and mixing uniformly, carrying out hydrothermal reaction at the reaction temperature of 200 ℃ for 24h, washing the product with water and alcohol, filtering, and drying.
(3) And (3) placing the mixture prepared in the step (2) in a tubular furnace, and heating the mixture in the nitrogen atmosphere at 700 ℃ for 2 hours to obtain the molybdenum disulfide/carbon composite material.
As shown in FIG. 6a, the X-ray diffraction spectrum of the molybdenum disulfide/carbon network composite material obtained in this example is hexagonal phase molybdenum disulfide (JCPDS 00-024-The shift was 8.8 ° for 2 θ and 1.05nm for d, indicating that the molybdenum disulfide (002) interplanar spacing of the present example was increased (up to 1.05nm) for an extended layer structure in favor of Na+Fast transmission of (2). Fig. 6b-c are scanning electron micrographs of the molybdenum disulfide/carbon composite material obtained in this example. As can be seen from the figure, the molybdenum disulfide sheets are embedded in the carbon mesh, and the carbon mesh tightly wraps the molybdenum disulfide sheets with the diameter of about 200nm, and the molybdenum disulfide sheets are uniformly distributed, so that the structural stability of the material is improved.
Example 3
A preparation method of a molybdenum disulfide/carbon composite material comprises the following steps:
(1) pretreating corncobs: crushing 5g of corncob raw materials, adding the crushed corncob raw materials into 300mL of 5 wt% potassium hydroxide solution, uniformly mixing, heating at 100 ℃ for 2h, washing with water, washing with alcohol, filtering, and drying to obtain the corncob precursor.
(2) And (2) adding 1.5g of the corncob precursor prepared in the step (1) into 60mL of water for dispersion, adding 2mmol of sodium molybdate and 8mmol of L-cysteine, adjusting the pH value to 6, stirring and mixing uniformly, carrying out hydrothermal reaction at the reaction temperature of 160 ℃ for 24h, washing the product with water and alcohol, filtering and drying.
(3) And (3) placing the mixture prepared in the step (2) in a tubular furnace, and heating the mixture in argon at 500 ℃ for 5 hours to obtain the molybdenum disulfide/carbon mesh composite material.
Fig. 7 is a scanning electron microscope image of the molybdenum disulfide/carbon composite material obtained in this embodiment, which is a molybdenum disulfide/carbon mesh composite structure.
Example 4
A preparation method of a molybdenum disulfide/carbon composite material comprises the following steps:
(1) pretreating shaddock peel: crushing 5g of shaddock peel raw material, adding 250mL of hydrochloric acid with the concentration of 2mol/L to remove impurities, heating at 100 ℃ for 5h, washing with water, filtering, adding 500mL of hydrogen peroxide solution with the concentration of 12 wt%, uniformly mixing, heating at 120 ℃ for 3h, washing with water, washing with alcohol, filtering, and drying to obtain a shaddock peel precursor.
(2) And (2) taking 0.5g of the shaddock peel precursor prepared in the step (1), adding into 60mL of water for dispersion, adding 1mmol of sodium molybdate and 4mmol of L-cysteine, adjusting the pH value to 8, stirring and mixing uniformly, carrying out hydrothermal reaction at 220 ℃ for 8h, washing with alcohol, filtering and drying the product.
(3) And (3) placing the mixture prepared in the step (2) in a tubular furnace, and heating the mixture in the presence of argon/hydrogen mixed gas at the heating temperature of 800 ℃ for 1h to obtain the molybdenum disulfide/carbon mesh composite material.
Fig. 8 is a scanning electron microscope image of the molybdenum disulfide/carbon composite material obtained in this embodiment, which is a molybdenum disulfide/carbon mesh composite structure.
Example 5
A preparation method of a molybdenum disulfide/carbon composite material comprises the following steps:
(1) pre-treating wheat straws: crushing 5g of wheat straw raw material, adding 250mL of nitric acid with the concentration of 3mol/L to remove impurities, heating at 90 ℃ for 3h, washing with water, filtering, adding 100mL of sodium sulfite solution with the concentration of 15 wt%, uniformly mixing, heating for 10h at the heating temperature of 110 ℃, washing with water, washing with alcohol, filtering, and drying to obtain the wheat straw precursor.
(2) And (2) adding 2g of the wheat straw precursor prepared in the step (1) into 120mL of water for dispersion, adding 2mmol of sodium molybdate and 8mmol of thiourea, adjusting the pH value to 5, stirring and mixing uniformly, carrying out hydrothermal reaction at the reaction temperature of 210 ℃ for 10h, washing with alcohol, filtering and drying the product.
(3) And (3) placing the mixture prepared in the step (2) in a tubular furnace, and heating the mixture in the nitrogen atmosphere at the heating temperature of 1000 ℃ for 1h to obtain the molybdenum disulfide/carbon mesh composite material.
Fig. 9 is a scanning electron microscope image of the molybdenum disulfide/carbon composite material obtained in this embodiment, which is a molybdenum disulfide/carbon mesh composite structure.
Example 6
A preparation method of a tungsten disulfide/carbon composite material comprises the following specific steps:
(1) pretreating bagasse: crushing 5g of bagasse raw material, adding 250mL of phosphoric acid with the concentration of 4mol/L to remove impurities, heating at 80 ℃ for 2h, washing with water, filtering, adding 250mL of 10 wt% sodium hydroxide solution, uniformly mixing, heating at 90 ℃ for 3h, washing with water, washing with alcohol, filtering, and drying to obtain the bagasse precursor.
(2) And (2) taking 1g of the bagasse precursor prepared in the step (1), adding 60mL of water for dispersion, adding 1mmol of sodium tungstate and 4mmol of thiourea, adjusting the pH value to 7, stirring and mixing uniformly, carrying out hydrothermal reaction at the reaction temperature of 190 ℃ for 20h, washing the product with water, washing with alcohol, filtering, and drying.
(3) And (3) placing the mixture prepared in the step (2) in a tubular furnace, and heating the mixture in the nitrogen atmosphere at the heating temperature of 500 ℃ for 5 hours to obtain the tungsten disulfide/carbon mesh composite material.
Fig. 10a-b are the X-ray diffraction spectrum and the scanning electron microscope image of the tungsten disulfide/carbon mesh composite material obtained in this example, respectively. Diffraction spectrum analysis shows that the product of the embodiment is hexagonal phase tungsten disulfide (JCPDS 01-087-2417), and carbon is amorphous carbon. As can be seen from fig. 10b, the product of this embodiment is a tungsten disulfide/carbon mesh composite material.
Example 7
A preparation method of a cobalt disulfide/carbon composite material comprises the following specific steps:
(1) pretreating corncobs: crushing 5g of corncob raw material, adding 250mL of sulfuric acid with the concentration of 5mol/L to remove impurities, heating at 80 ℃ for 3h, washing with water, filtering, adding 250mL of potassium hydroxide solution with the concentration of 10 wt%, uniformly mixing, heating at 100 ℃ for 5h, washing with water, washing with alcohol, filtering, and drying to obtain the corncob precursor.
(2) And (2) adding 1g of the corncob precursor prepared in the step (1) into 60mL of water for dispersion, adding 1mmol of cobalt sulfate and 4mmol of L-cysteine, adjusting the pH to 7, stirring and mixing uniformly, carrying out hydrothermal reaction at 190 ℃ for 24h, washing the product with water, washing with alcohol, filtering and drying.
(3) And (3) placing the mixture prepared in the step (2) in a tubular furnace, and heating the mixture in the nitrogen atmosphere at the heating temperature of 750 ℃ for 2 hours to obtain the cobalt disulfide/carbon composite material.
Fig. 11a-b are the X-ray diffraction spectrum and the scanning electron microscope image of the cobalt disulfide/carbon network composite material obtained in this example, respectively. Diffraction spectrum analysis shows that the product of the embodiment is cubic phase cobalt disulfide (JCPDS 03-06503322), and carbon is amorphous carbon. As can be seen from fig. 11b, the product of this example is a cobalt disulfide/carbon mesh composite.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (10)
1. A metal sulfide/carbon composite material is composed of metal sulfides and carbon, and is characterized in that the flake-shaped nanoscale metal sulfides are uniformly loaded in a carbon net, the carbon net tightly wraps the metal sulfides, the metal sulfides are molybdenum disulfide, tungsten disulfide, cobalt disulfide or zinc sulfide, and the mass fraction of the metal sulfides in the composite material is 5-95 wt%;
the preparation method of the metal sulfide/carbon composite material comprises the following steps:
1) crushing the straw raw material, adding an acidic reaction solution for impurity removal, and adding a lignin removal solution for activation to obtain a straw precursor;
the straw is selected from bagasse, corn cob, shaddock peel, rice straw or wheat straw; the acid reaction solution is sulfuric acid solution, and the delignification solution is sodium hydroxide solution; the concentration of the acidic reaction solution is 0.1-15 mol/L, the solute content of the delignification solution is 0.1-40 wt%, and the ratio of the straw powder to the delignification solution is 1 g: 5 mL-400 mL; the heating temperature for the impurity removal and lignin removal solution activation treatment is 10-300 ℃; the treatment time is 30 minutes to 3 days;
2) mixing the straw precursor with a metal source and a sulfur source solution, and carrying out hydrothermal reaction;
the metal source is selected from sodium molybdate, sodium tungstate, cobalt sulfate or zinc chloride, and the sulfur source is selected from thiourea, L-cysteine or elemental sulfur; the pH value of the mixed solution is 1-9; the temperature of the heating reaction is 140-300 ℃; the reaction time is 30 minutes to 3 days;
3) heating the hydrothermal reaction product in an oxygen-free atmosphere to prepare a metal sulfide/carbon composite material;
the heating temperature is 200-1000 ℃; the heating time is 30 minutes to 3 days.
2. A method of preparing the metal sulfide/carbon composite of claim 1, comprising the steps of:
1) crushing the straw raw material, adding an acidic reaction solution for impurity removal, and adding a lignin removal solution for activation to obtain a straw precursor;
the straw is selected from bagasse, corn cob, shaddock peel, rice straw or wheat straw; the acid reaction solution is sulfuric acid solution, and the delignification solution is sodium hydroxide solution; the concentration of the acidic reaction solution is 0.1-15 mol/L, the solute content of the delignification solution is 0.1-40 wt%, and the ratio of the straw powder to the delignification solution is 1 g: 5 mL-400 mL; the heating temperature for the impurity removal and lignin removal solution activation treatment is 10-300 ℃; the treatment time is 30 minutes to 3 days;
2) mixing the straw precursor with a metal source and a sulfur source solution, and carrying out hydrothermal reaction;
the metal source is selected from sodium molybdate, sodium tungstate, cobalt sulfate or zinc chloride, and the sulfur source is selected from thiourea, L-cysteine or elemental sulfur; the pH value of the mixed solution is 1-9; the temperature of the heating reaction is 140-300 ℃; the reaction time is 30 minutes to 3 days;
3) heating the hydrothermal reaction product in an oxygen-free atmosphere to prepare a metal sulfide/carbon composite material;
the heating temperature is 200-1000 ℃; the heating time is 30 minutes to 3 days.
3. The method as claimed in claim 2, wherein the concentration of the acidic reaction solution in the step 1) is 1mol/L to 5mol/L, the solute content of the delignification solution is 1 wt% to 15 wt%, and the ratio of the straw powder to the delignification solution is 1 g: 20mL to 100 mL.
4. The method as claimed in claim 2, wherein the mixing manner of the straw powder, the acidic reaction solution and the delignification solution in the step 1) comprises stirring and mixing and ultrasonic mixing.
5. The method of claim 2, wherein the heating temperature for the de-doping and delignification solution activation treatment is 50 ℃ to 120 ℃; the treatment time is 2-20 hours.
6. The method as claimed in claim 2, wherein the product is washed and dried in step 1) and step 2), and the washing comprises water washing and alcohol washing.
7. The method according to claim 2, wherein the pH value of the mixed solution in the step 2) is 5 to 8; the temperature of the heating reaction is 160-220 ℃; the reaction time is 6-24 hours.
8. The method of claim 2, wherein the oxygen-free atmosphere in step 3) comprises one or more of argon, nitrogen, and argon/hydrogen mixture; the heating temperature is 400-800 ℃; the heating time is 30 minutes to 5 hours.
9. The method of claim 2, wherein the mass fraction of metal sulfide in the composite material prepared in step 3) is 30 wt% to 90 wt%.
10. Use of the metal sulfide/carbon composite material according to claim 1 in a negative electrode material of a sodium ion battery.
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| CN112289982B (en) * | 2019-07-22 | 2023-01-06 | 比亚迪股份有限公司 | Positive electrode material, preparation method thereof and solid-state lithium battery |
| CN110416527A (en) * | 2019-08-16 | 2019-11-05 | 济南大学 | A kind of method that plant Zea mays stalk prepares combination electrode material as template growth |
| CN112758985B (en) * | 2019-10-21 | 2022-03-22 | 中国科学院福建物质结构研究所 | WS (WS)2Nitrogen-doped carbon composite material, preparation method and application thereof |
| CN110844939B (en) * | 2019-11-12 | 2022-03-01 | 杭州电子科技大学 | Molybdenum sulfide carbon nanosphere carbon nanofiber composite electrode material and preparation method thereof |
| CN112086640A (en) * | 2020-08-13 | 2020-12-15 | 广州大学 | Material for lithium/sodium ion battery electrode and preparation method thereof |
| CN112397699B (en) * | 2020-11-16 | 2021-08-13 | 西北大学 | Transition metal chalcogenide/carbon composite material rich in anion vacancies and preparation method and application thereof |
| CN114291807B (en) * | 2022-01-19 | 2023-10-31 | 合肥学院 | Preparation method and application of single-layer carbon nano-network material |
| CN115069177B (en) * | 2022-06-16 | 2023-09-08 | 中国科学院福建物质结构研究所 | Metal sulfide-carbon composite material with yolk-eggshell structure and preparation method and application thereof |
| CN115924960B (en) * | 2023-01-09 | 2024-06-21 | 楚能新能源股份有限公司 | Metal sulfide/carbon composite anode material with three-dimensional network structure, preparation method thereof and lithium ion battery |
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