CN106783201B - 一种硫化钼/三氧化二铁复合材料及其制备方法和应用 - Google Patents
一种硫化钼/三氧化二铁复合材料及其制备方法和应用 Download PDFInfo
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- molybdenum sulfide
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 title 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000006185 dispersion Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011733 molybdenum Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000012546 transfer Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 9
- 235000013877 carbamide Nutrition 0.000 claims description 9
- 239000008139 complexing agent Substances 0.000 claims description 9
- 229910052961 molybdenite Inorganic materials 0.000 claims description 9
- 238000002604 ultrasonography Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- -1 dihydroxymethyl ethyl carbamide Chemical compound 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- WPPOGHDFAVQKLN-UHFFFAOYSA-N N-Octyl-2-pyrrolidone Chemical compound CCCCCCCCN1CCCC1=O WPPOGHDFAVQKLN-UHFFFAOYSA-N 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 230000000536 complexating effect Effects 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 abstract description 26
- 239000002086 nanomaterial Substances 0.000 abstract description 10
- 239000003990 capacitor Substances 0.000 abstract description 8
- 239000007772 electrode material Substances 0.000 abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 6
- 238000004073 vulcanization Methods 0.000 abstract description 6
- 238000000224 chemical solution deposition Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 4
- 239000002073 nanorod Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 239000013078 crystal Substances 0.000 description 12
- 239000010410 layer Substances 0.000 description 11
- 239000002243 precursor Substances 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000013401 experimental design Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 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 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- 239000007787 solid Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910016874 Fe(NO3) Inorganic materials 0.000 description 1
- 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- RFHAOTPXVQNOHP-UHFFFAOYSA-N fluconazole Chemical compound C1=NC=NN1CC(C=1C(=CC(F)=CC=1)F)(O)CN1C=NC=N1 RFHAOTPXVQNOHP-UHFFFAOYSA-N 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
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- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical compound [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
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- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compounds Of Iron (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明涉及一种硫化钼/三氧化二铁复合材料及其制备方法和应用,所述复合材料的结构为:三氧化二铁纳米棒生长于硫化钼纳米片上。制备方法包括:通过液相法剥离硫化钼矿石得到硫化钼纳米片,然后通过溶剂转移法将其转移到水中并超声分散得到硫化钼纳米片水相分散液;通过化学浴沉积法在硫化钼纳米片上生长三氧化二铁前驱体纳米结构,后通过高温热处理得到硫化钼/三氧化二铁复合材料。本发明的复合材料具有良好均匀性和一致性,材料电化学活性好、导电性好,使用该复合材料作为超级电容器电极材料时,具有较好的充放电倍率及循环稳定性;而且制备过程方便环保,反应温度低,安全系数高,易于工业化生产。
Description
技术领域
本发明属于过渡金属硫族化合物-过渡金属氧化物材料及其制备领域,特别涉及一种硫化钼/三氧化二铁复合材料及其制备方法和应用。
背景技术
铁氧化物纳米材料作为金属氧化物的一员,是非常重要的无机纳米材料。由其化学性质稳定,合成简单容易得到,且成本低廉,环境友好,又其有良好的抗腐烛性、磁学性能等特性,因而被广泛应用在磁性涂料、精细陶瓷、塑料制品、电子材料、油墨、微电子学、传感器、催化剂、废水处理等工业方而及生物医学方面,并且在未来有望开发新的用途,所以铁氧化物纳米材料的性质以及形貌已经成为科学研究的重要内容。高比表面积和孔隙率对于高性能电极材料是很重要的,其不仅通过缩短扩散路径促进离子传输,而且通过在广范围的活性位点中插入离子而增加电化学活性表面积。具有富集多孔结构的晶体由于不均匀的纳米晶体或纳米晶体的非紧密堆积是有前途的能量存储材料。具有可控结构的介观晶体在能量存储和转换中拥有显着增强的化学和物理性质。不幸的是,氧化铁晶体的合成被聚合物添加剂困扰,它能短时稳定初级纳米颗粒,但是会导致严重的问题,例如对合成方法敏感的不同添加剂,后处理(高温煅烧)后表面活性位点会显著降低。因此,非常需要开发一种具有足够孔隙的赤铁矿晶相的简单且无添加剂的纳米材料。
MoS2是具有层状结构的过渡金属硫化物,最近被发现作为用于超级电容器和锂离子电池(LIB)的常见电极材料。该材料由通过范德华相互作用堆叠在一起的S-Mo-S原子层组成。这种分层结构允许小半径的离子,例如锂离子,可逆地插入层之间的通道中,而在其整个尺寸上没有大的体积膨胀。由于MoS2作为石墨的类层状结构,已经有许多相应的方法被设计出来制备少层的MoS2纳米片。由于2D结构产生的大的有效表面积,以及与石墨烯相比拥有更高的容量,MoS2纳米片具有巨大的替代石墨烯的潜力,并且成为一个的下一个在能量储存领域受重视的材料。
发明内容
本发明所要解决的技术问题是提供一种硫化钼/三氧化二铁复合材料及其制备方法和应用,该方法易于操作,反应温度低,制备过程环保、产品质量好,性能稳定,工艺简单、重现性好、易于实施。制备得到具有优异电化学性能的硫化钼/三氧化二铁复合材料。
通过将MoS2与铁氧化物纳米材料复合,可以有效的发挥两者材料的优势所在,而客服了单一材料面临的一些缺点。硫化钼/三氧化二铁复合结构增加了电极/电解液的接触,提供了更多的电化学活性位点,并且这种结构还能有效缓解充放电过程中的体积变化;引入三氧化二铁纳米棒有效的阻止了硫化钼纳米片的重新堆叠,使得该材料运用到超级电容器或者锂离子电池电极材料中具有优异的性能。
本发明的一种硫化钼/三氧化二铁复合材料,所述复合材料的结构为:三氧化二铁纳米棒生长于硫化钼纳米片上;其中,硫化钼纳米片的横向尺寸为200~400nm。
所述三氧化二铁纳米棒的尺寸为80~120nm。
所述的硫化钼/三氧化二铁复合材料的制备方法,包括:
(1)将辉钼矿加入到有机溶剂中,超声5~30h,沉降,抽滤,得到硫化钼纳米片;然后通过溶剂转移法将硫化钼纳米片转移至低沸点溶剂中,超声分散,得到硫化钼纳米片分散液;其中,硫化钼纳米片分散液的浓度为0.5~0.8mg/mL。
(2)将铁盐溶于步骤(1)中的硫化钼纳米片分散液中,得到悬浮液,置于油浴锅中;然后加入络合剂和形貌控制剂,升温至80~100℃反应6~24h,洗涤,干燥,得到硫化钼/三氧化二铁前驱体复合材料;
(3)将步骤(2)中的硫化钼/三氧化二铁前驱体复合材料进行程序升温热处理,得到硫化钼/三氧化二铁复合材料。
所述步骤(1)中有机溶剂为二甲基甲酰胺、二羟甲基乙基脲和N-辛基-2-吡咯烷酮中的至少一种;低沸点溶剂为乙二醇、乙醇、甲醇和去离子水中的至少一种。
所述步骤(1)中超声后得到硫化钼纳米片分散液;其浓度为0.5~0.8mg/mL。
所述步骤(1)中硫化钼纳米薄片为单层或者少层(2~10层)。
所述步骤(2)中铁盐为硝酸铁、醋酸铁和氯化铁中的一种。
所述步骤(2)中铁盐与硫化钼纳米片的摩尔比为6.2:1~6:1。
所述步骤(2)的悬浮液中铁盐的浓度为0.015~0.06mol/L。
所述步骤(2)中络合剂为氨水或尿素;当络合剂为氨水时,氨水与铁盐的摩尔比为3:1~1:1;当络合剂为尿素时,尿素与铁盐的摩尔比为4:1~3:1。
所述步骤(2)中形貌控制剂为六亚甲基四胺或硫酸钠;当形貌控制剂为六亚甲基四胺时,六亚甲基四胺与络合剂的摩尔比为0.2:1~0.4:1;当形貌控制剂为硫酸钠时,硫酸钠与络合剂的摩尔比为0.1:1~0.3:1。
所述步骤(3)中程序升温热处理的条件为:将硫化钼/三氧化二铁前驱体复合材料置于管式炉或双管CVD系统中,在氮气或者氩气气氛下,控制升温程序为:从室温升温到180~220℃保温90~270min;优选温度为200℃,优选分段保温加热,即在100℃、150℃、200℃,分别保温30-90min在氮气或者氩气气氛下,从室温升温到。
所述的硫化钼/三氧化二铁复合材料的应用,所述复合材料应用于高性能超级电容器电极材料以及锂离子电池、太阳能电池的电极材料。
本发明所提供的硫化钼/三氧化二铁复合材料,是由铁盐通过化学浴沉积法在具有层状结构的硫化钼纳米片上原位生长前驱体纳米结构后,高温热处理得到硫化钼/三氧化二铁复合材料;其制备原料组成包括:硫化钼(辉钼矿)、氯化铁、氨水(尿素)、六亚甲基四胺(硫酸钠)、二甲基甲酰胺以及去离子水。制备方法,包括:通过液相法剥离硫化钼矿石(辉钼矿)得到单层或少层硫化钼纳米片;通过化学浴沉积法在硫化钼纳米片上生长三氧化二铁前驱体纳米结构,后通过高温热处理得到硫化钼/三氧化二铁复合材料。
本发明用过一种简单的实验设计,制备得到硫化钼/三氧化二铁复合材料;该复合材料具有如下优势:通过液相剥离的硫化钼纳米片具有独特的类石墨烯单片层结构以及很高的比表面积,可以为三氧化二铁提供更多的成核位点,有效地分散了三氧化二铁纳米结构,形成的介孔晶体结构有效储存电解液,有利于提高倍率性能;这种独特的结构提供了以下优点:首先,由于自组装过程产生的α-Fe2O3晶体的介孔性质减少了赝电容材料中离子的扩散路径,确保活性材料的有效利用;第二,在混合电极中具有许多单层结构的硫化钼提供极高的表面积,从而有助于电解质离子有效地接近电极表面,并且基本上克服了α-Fe2O3差的导电性;第三,通过使用形貌控制剂来引导纳米结构金属氧化物的自组装,这种合成方法是便捷和经济的;最后,通过调整实验参数(反应温度,时间,前体等)更能控制所制备的杂化物。而且硫化钼/三氧化二铁复合材料形成范德华异质结构,由于层间弱的范德华作用力,相邻的层间不再受晶格必须相匹配的限制;并且,由于没有成分过渡,所形成的异质结具有原子级陡峭的载流子(势场)梯度;这种能级阶梯式交错有利于电子空穴分离,由于以过渡金属硫族化合物为代表的非石墨烯二维层状材料通常可以形成二类能带关系,因此以它们为基础搭建的异质结具有非常强的载流子分离能力,比单独材料的电荷迁移效率高。
有益效果
(1)本发明的方法简单温和,绿色无污染,重复性好,易于操作,反应温度低,不存在高温或者化学试剂可能引起的爆炸抑或是有毒有害物质释放等危险因素,是一种有效快捷的制备方法,有望在工业生产领域得到应用;
(2)本发明的实验设计巧妙:通过简单的液相体系超声剥离后通过溶剂交换法,简单有效的制备出了高浓度水相硫化钼纳米片分散液,这种单分子层的纳米片拥有最大化的比表面积,可以提供很大的界面接触;同时采用温和条件化学浴沉积法和随后的热处理可以很方便得到复合材料,纳米棒状的三氧化二铁与硫化钼纳米片存在协同作用,并且通过奥斯瓦尔德熟化和溶解再结晶过程紧密结合,使其复合材料结构可控;
(3)本发明中三氧化二铁的引入与硫化钼纳米片形成了范德华异质结构,异质结构的硫化钼/三氧化二铁具有低尺寸晶体结构和原子性尖锐界面,并且由于电子和空穴对被有效地分离为自由电子和空穴,因此在硫化钼/三氧化二铁异质结构中有效地发生超快电荷转移,这极大地改善了其导电性;其次,由于与高比面积的硫化钼纳米片作为衬底的集成,异质结构的硫化钼/三氧化二铁复合物的自团聚体已经大大减少,这可以充分保持活性材料和电解质之间的有效接触;最后,垂直堆叠或网状纳米结构的界面之间的基本间隔使得电解质离子容易接近电极/电解质界面处的异质结构,这将容易促进氧化还原反应以用于提高电化学电容性能;
(4)本发明制备的硫化钼/三氧化二铁复合材料具有微介孔多级结构,更是针对其利用单一材料电化学活性较差以及难大规模化生产等缺点而发明的;这种复合材料拥有很大的比容量值、很稳定的倍率性能和出色的循环稳定性,研究成果能广泛应用于高性能超级电容器、锂离子电池等新能源器件的电极材料。
附图说明
图1是实施例1中硫化钼/三氧化二铁复合材料的SEM图;其中,a,b分别为低倍和高倍的电镜照片;
图2是实施例1中硫化钼/三氧化二铁复合材料的XRD图;其中a,b分别为热处理前后的样品XRD图;
图3是实施例1中硫化钼/三氧化二铁复合材料作为超级电容器电极由电化学工作站三电极测试系统得到的电化学性能图;其中,(a)(b)(c)(d)分别是三个样品5mV/s的循环伏安法CV曲线图、硫化钼/三氧化二铁在5~50mV/s的CV曲线图、恒电流充放电曲线图和循环性能图;
图4为实施例2中硫化钼/三氧化二铁复合材料的SEM图。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
(1)将2g硫化钼矿(辉钼矿)加入到500g二甲基甲酰胺中,用实验用细胞粉碎机连续超声10小时(超声程序为工作8s,间歇2s循环进行),取上层清液离心,得到均匀分散液,即为硫化钼纳米片分散液,浓度为0.2mg/ml;
(2)取上述分散液,抽滤,获得硫化钼纳米片固体,用30mL乙醇和30mL去离子水交替洗涤三次后干燥保存;
(3)将60mg上述硫化钼纳米片分散于100mL去离子水中,超声,得到硫化钼纳米片稳定分散液;其中,分散液的浓度为0.6mg/ml;
(4)取337.5mg六水合氯化铁加入到上述分散液中,机械搅拌使之分散均匀;
(5)将上述分散液置于100摄氏度油浴锅中,恒温30分钟后加入227.25mg尿素和157.5mg六亚甲基四胺,恒温反应过夜(12h),即可得到复合材料前驱体,称之为硫化钼/三氧化二铁前驱体复合材料;
(6)将制备得到的复合材料前驱体用去离子水和乙醇反复洗涤多次,干燥,备用;
(7)取上述干燥的复合材料前驱体放置于瓷方舟中,放入管式炉在氮气保护下进行程序升温,从室温升温到200℃,分段保温加热,即在100℃、150℃、200℃,分别保温1h,得到硫化钼/三氧化二铁复合材料;
(8)将制备得到的复合材料用去离子水和乙醇反复洗多次,干燥,最终命名为硫化钼/三氧化二铁复合材料。
同时,将步骤(3)中硫化钼分散液替换成同等体积的去离子水,重复后续步骤,制备对照组前驱体以及三氧化二铁样品。
使用扫描电子显微镜(SEM)、X射线衍射仪(XRD)来表征上述得到的硫化钼/三氧化二铁复合材料的结构形貌,其结果如下:
(1)SEM测试结果表明:纯三氧化二铁显示具有均匀尺寸的纳米颗粒形态。另外,图1揭示了当硫化钼纳米片复合到该体系中时,三氧化二铁纳米颗粒自组装成纳米棒结构。这种现象可能是由于硫化钼纳米片的存在,其可以为三氧化二铁的成核和晶体生长提供大的表面积。该方法可以描述为溶解-再结晶机理,其中,前体颗粒逐渐溶解到反应溶液中,然后随着前体颗粒的消耗产生三氧化二铁核物质。然后在硫化钼纳米片的表面上形成三氧化二铁纳米棒附聚物,这是由于在硫化钼纳米片上通过取向附着和奥斯瓦尔德熟化机理的连续生长三氧化二铁纳米棒;参见图1。其中,图1a和1b分别为硫化钼/三氧化二铁杂化物低倍和高倍电镜照片。
(2)硫化钼/三氧化二铁杂化物通过这种简单的溶液工艺生长和后续退火工艺制造。通过XRD测量检查所获得的硫化钼/三氧化二铁杂化物的晶体结构。XRD测试结果表明,硫化钼纳米片在2θ=14.7,32.8,33.7,36.2,39.9,44.4,50.1,56.1,58.6,和60.5°有对应的衍射峰存在,其分别归属于硫化钼的(002),(100),(101),(102),(103),(006),(105),(106),(110)和(008)晶面。如图2所示,通过化学浴沉积得到的复合材料前驱体和后处理之后的复合材料在2θ=23.5,32.7,35.2,40.3,48.9,53.7,62.3和63.5o有对应的衍射峰存在,分别对应三氧化二铁的(012),(104),(110),(113),(024),(116),(214)和(300)晶面。退火前后的混合物的XRD图案都与单斜晶三氧化二铁(JCPDS no.33-0664)的XRD图案很好的符合。这可能是由于三氧化二铁前驱体(Fe(OH)3)的不稳定性,其在反应过程中将直接转化为三氧化二铁,但是后退火过程使得具有更高结晶度的三氧化二铁纳米材料。该结果表明三氧化二铁已经成功负载到硫化钼纳米片上。
通过电化学工作站来表征上述得到的硫化钼/三氧化二铁复合材料的电化学性能,其结果如下:
(1)循环伏安法CV曲线(图3a)可以看到硫化钼/三氧化二铁复合材料显示出最大的环面积,表明与纯的硫化钼和三氧化二铁相比它具有优异的电容性能。此外,硫化钼/三氧化二铁复合物在不同扫描速率下的CV曲线如图3b所示。硫化钼纳米片具有矩形形状,而在三氧化二铁和硫化钼/三氧化二铁复合电极中分别具有约-0.6和-1.05V的一对阳极和阴极峰。氧化还原对可以分别归属于可逆的氧化还原过程,表明法拉第赝电容反应是这种复合材料容量的主要贡献。随着电流密度的升高,即使高达50mV/s时,CV曲线仍保持与低电流密度的形状大致相同,这表明这种材料作为超级电容器电极使用拥有良好的倍率性能;参见图3。
(2)测试不同电流密度下的恒电流充电/放电数据,以进一步评价硫化钼/三氧化二铁复合物的电化学性能(图3c)。与CV结果一致,硫化钼/三氧化二铁呈现具有高非线性放电曲
线的典型赝电容行为。计算的硫化钼/三氧化二铁电极的比电容可以通过如下公式计算:
其中Cm是比容量,I是充放电电流,t是放电时间,ΔV电位窗口(此实验中是1.2V),m是电极中活性材料的质量。在电流密度为1,2,5,7,10和20A g-1时,MoS2-Fe2O3电极的比电容分别为647.8,606.0,537.1,472.8,419.6和362.5F g-1,显示出超过单一采用三氧化二铁和硫化钼电极的优异倍率性能,证明了本发明在超级电容器中的实用性;参见图3c。
(3)由实施例1中得到的材料组装成对称电容器,在两电极测试系统下表征其在2Ag-1电流密度下,0~1V电位窗口下循环充放电使用的情况。绘制曲线可知使用纯三氧化二铁作为电极材料几乎不能实现令人满意的循环稳定性,但是将硫化钼纳米片和和三氧化二铁合理组合成独特的复合材料可以显着增强循环稳定性。,经过6000次充放电循环测试,三氧化二铁电极容量衰减到了54%;对于硫化钼/三氧化二铁复合材料,电容从1至500次循环时有略微增加(达到106%),这可能归因于电极/电解质的接触逐渐增强。在6000次循环后,电极的循环稳定性缓慢降低至硫化钼/三氧化二铁复合材料的轻微结构破坏可能是电容降低的原因。该测试表明该材料有很好的实用前景;参见图3d。
实施例2
(1)将1g硫化钼矿(辉钼矿)加入到200g二羟甲基乙基脲中,用实验用超声清洗机连续超声20小时,取上层清液离心,得到均匀分散液,即为硫化钼纳米片分散液,分散液的浓度为0.5mg/ml;
(2)取100mL上述分散液,抽滤,获得硫化钼纳米片固体,用30mL乙醇和30mL去离子水交替洗涤三次后用150mL去离子水洗涤。
(3)将上述硫化钼纳米片80mg分散于100mL去离子水中,超声得到硫化钼纳米片稳定分散液;
(4)取302.9mg九水合硝酸铁加入到上述分散液中,机械搅拌使之分散均匀;
(5)将上述三组分散液置于90摄氏度油浴锅中,恒温30分钟后加入60mL氨水和106.5mg硫酸钠,恒温反应12小时,即可得到复合材料前驱体,称之为硫化钼/三氧化二铁前驱体复合材料;
(6)将制备得到的复合材料前驱体用去离子水和乙醇反复洗涤多次,干燥,备用;
(7)取上述干燥的复合材料前驱体放置于瓷方舟中,放入双管CVD系统中在氩气保护下进行程序升温,从室温升温到200℃,分段保温加热,即在100℃、150℃、200℃,分别保温30min,得到硫化钼/三氧化二铁复合材料;
将制备得到的复合材料用去离子水和乙醇反复洗多次,干燥,最终命名为硫化钼/三氧化二铁-2复合材料。
通过扫描电子显微镜表征硫化钼/三氧化二铁-2复合材料,其结果如图4所示,可以在硫化钼纳米片表面得到均匀的三氧化二铁纳米棒,长度为100nm左右,直径为10-20nm。
Claims (6)
1.一种硫化钼/三氧化二铁复合材料的制备方法,包括:
(1)将辉钼矿加入到有机溶剂中,超声5~30h,沉降,抽滤,得到硫化钼纳米片;然后通过溶剂转移法将硫化钼纳米片转移至低沸点溶剂中,超声分散,得到硫化钼纳米片分散液;其中,硫化钼纳米片分散液的浓度为0.5~0.8mg/mL;
(2)将铁盐溶于步骤(1)中的硫化钼纳米片分散液中,得到悬浮液,然后加入络合剂和形貌控制剂,升温至80~100℃反应6~24h,洗涤,干燥,得到硫化钼/三氧化二铁前驱体复合材料;
(3)将步骤(2)中的硫化钼/三氧化二铁前驱体复合材料进行程序升温热处理,得到硫化钼/三氧化二铁复合材料,其中程序升温热处理的条件为:在氮气或者氩气气氛下,从室温升温到180~220℃保温90~270min。
2.根据权利要求1所述的一种硫化钼/三氧化二铁复合材料的制备方法,其特征在于,所述步骤(1)中有机溶剂为二甲基甲酰胺、二羟甲基乙基脲和N-辛基-2-吡咯烷酮中的至少一种;低沸点溶剂为乙二醇、乙醇、甲醇和去离子水中的至少一种。
3.根据权利要求1所述的一种硫化钼/三氧化二铁复合材料的制备方法,其特征在于,所述步骤(2)中铁盐为硝酸铁、醋酸铁和氯化铁中的一种。
4.根据权利要求1所述的一种硫化钼/三氧化二铁复合材料的制备方法,其特征在于,所述步骤(2)中铁盐与硫化钼纳米片的摩尔比为6.2:1~6:1。
5.根据权利要求1所述的一种硫化钼/三氧化二铁复合材料的制备方法,其特征在于,所述步骤(2)中络合剂为与铁盐的摩尔比为3:1~1:1的氨水或与铁盐的摩尔比为4:1~3:1的尿素。
6.根据权利要求1所述的一种硫化钼/三氧化二铁复合材料的制备方法,其特征在于,所述步骤(2)中形貌控制剂为与络合剂的摩尔比为0.2:1~0.4:1的六亚甲基四胺或与络合剂的摩尔比为0.1:1~0.3:1的硫酸钠。
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