CN115557537B - MnS nano dot material, ternary sodium-electricity precursor, positive electrode material and preparation method - Google Patents
MnS nano dot material, ternary sodium-electricity precursor, positive electrode material and preparation method Download PDFInfo
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- CN115557537B CN115557537B CN202211044870.XA CN202211044870A CN115557537B CN 115557537 B CN115557537 B CN 115557537B CN 202211044870 A CN202211044870 A CN 202211044870A CN 115557537 B CN115557537 B CN 115557537B
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- 239000000463 material Substances 0.000 title claims abstract description 107
- 239000002096 quantum dot Substances 0.000 title claims abstract description 85
- 239000002243 precursor Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 20
- 239000011734 sodium Substances 0.000 claims abstract description 65
- 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 abstract description 45
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000005245 sintering Methods 0.000 claims abstract description 32
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 12
- 150000002696 manganese Chemical class 0.000 claims abstract description 12
- 238000005530 etching Methods 0.000 claims abstract description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 239000002738 chelating agent Substances 0.000 claims abstract description 9
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 63
- 239000000203 mixture Substances 0.000 claims description 59
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 23
- 239000011159 matrix material Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- 239000003575 carbonaceous material Substances 0.000 claims description 10
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical group [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- JOUIQRNQJGXQDC-AXTSPUMRSA-N namn Chemical compound O1[C@@H](COP(O)([O-])=O)[C@H](O)[C@@H](O)[C@@H]1[N+]1=CC=CC(C(O)=O)=C1 JOUIQRNQJGXQDC-AXTSPUMRSA-N 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 2
- 229940009827 aluminum acetate Drugs 0.000 claims description 2
- ZCLVNIZJEKLGFA-UHFFFAOYSA-H bis(4,5-dioxo-1,3,2-dioxalumolan-2-yl) oxalate Chemical compound [Al+3].[Al+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZCLVNIZJEKLGFA-UHFFFAOYSA-H 0.000 claims description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 239000011572 manganese Substances 0.000 description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 19
- 238000000576 coating method Methods 0.000 description 19
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 17
- 238000001291 vacuum drying Methods 0.000 description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 16
- 239000002033 PVDF binder Substances 0.000 description 16
- 239000006230 acetylene black Substances 0.000 description 16
- 239000002131 composite material Substances 0.000 description 16
- 229960001545 hydrotalcite Drugs 0.000 description 16
- 229910001701 hydrotalcite Inorganic materials 0.000 description 16
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 16
- 239000002002 slurry Substances 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 229910052782 aluminium Inorganic materials 0.000 description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 239000011888 foil Substances 0.000 description 13
- 239000005341 toughened glass Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 239000006258 conductive agent Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 239000003365 glass fiber Substances 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 238000005096 rolling process Methods 0.000 description 8
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 238000004080 punching Methods 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 229910052976 metal sulfide Inorganic materials 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002305 electric material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical group [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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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
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- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a MnS nano-dot material, a ternary sodium electric precursor, a preparation method thereof and a ternary sodium electric positive electrode material, wherein the preparation method of the MnS nano-dot material comprises the following steps: s1, dispersing zinc salt, aluminum salt and graphene oxide in a solvent to obtain a solution A; dissolving a chelating agent, manganese salt and a sulfur-containing additive in a solvent to obtain a solution B; s2, dropwise adding the solution B into the solution A; s3, transferring the precursor into polytetrafluoroethylene to perform a hydrothermal reaction to obtain a nano-dot precursor; and (5) performing high-temperature sintering and etching to obtain the MnS nano-dot material. The nano dots in the material are uniformly distributed, the material structure is complete, the conductivity and the ion transmission rate of the electrode material can be effectively improved, the preparation process is simple, the flow is short, the raw materials are easy to obtain, no toxic or harmful substances are generated, and the large-scale production is easy to realize; the nano dot material is adopted to modify the ternary sodium electric precursor, so that no surface by-product is generated, and the electrochemical performance of the material can be greatly improved.
Description
Technical Field
The invention relates to the technical field of sodium ion battery manufacturing, in particular to a MnS nano-dot material, a ternary sodium-electricity precursor, a preparation method thereof and a ternary sodium-electricity positive electrode material.
Background
Sodium ion batteries have been increasingly studied in recent years, and the types of electrode materials have also been increasing. Similar to lithium ion batteries, sodium-electricity ternary materials have been studied for their advantages of high specific capacity and good stability. Unlike lithium ion batteries, the ionic radius of sodium ions is much larger than that of lithium ions, so that the structural stability of ternary sodium-electric materials in the ion transmission process is much poorer than that of ternary materials in lithium ion batteries, and therefore, the ternary sodium-electric materials still have larger intrinsic defects in the practical application of sodium ion batteries in the future. To overcome the above problems, researchers have generally employed surface coating modification methods. The usual surface coating is largely divided into a conductive layer and an inert protective layer, both of which exhibit different modifying effects.
It is well known that the smaller the particles of the coating, the better the coating, but when the particle size is as small as a nanometer, the particles are very susceptible to agglomeration and maldistribution, which can seriously affect the properties of the material. The nano-dots change the mode of the traditional battery to play a role, have super-strong storage capacity and can greatly improve the charging speed. In order to alleviate the agglomeration phenomenon of the nano-dots, the nano-dot material is generally required to be limited by virtue of a template, so that the nano-dot material is uniformly loaded on the template. The nano-dots loaded in general are mainly of the types of metal particles, metal oxides, metal sulfides and the like. The formation of metal sulfide nanodots is usually accompanied by doping of heteroatoms (S atoms) of the corresponding substrate carbon material, which modifies the substrate carbon material to form a modified heteroatom-modified porous carbon material, which finally improves the structural stability of the material body and provides more stable ion diffusion channels. The metal sulfide nano-dots prepared by the prior method have the following defects: 1. the metal bond bonding capability between the nano-dots and the electrode material is poor due to element selection, so that the composite effect between the nano-dots and the electrode material is influenced; 2. the existing metal sulfide nano-dot structure has weak stability, and the application of the metal sulfide nano-dot in electrode materials is affected.
Disclosure of Invention
The invention provides a MnS nano-dot material, a ternary sodium-electricity precursor, a positive electrode material and a preparation method thereof, which are used for solving the existing technical problems.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a MnS nano-dot material comprises the following steps:
s1, dispersing zinc salt, aluminum salt and graphene oxide in a solvent to obtain a solution A; dissolving a chelating agent, manganese salt and a sulfur-containing additive in a solvent, and adjusting the pH to 5-7 to obtain a solution B;
s2, dropwise adding the solution B into the solution A, and adjusting the pH to 8-10 to obtain a mixed solution;
s3, transferring the mixed solution into polytetrafluoroethylene for hydrothermal reaction, and obtaining a nano-dot precursor after the reaction is completed; and (3) sintering the nano dot precursor at a high temperature, and etching by using an acid solution to obtain the MnS nano dot material.
The design idea of the technical scheme is that firstly, a specific solution A and a specific solution B are subjected to coprecipitation reaction to generate graphene-coated ZnAlMn-based layered hydroxide, then, the completion of the coprecipitation reaction and the complete formation of metal sulfide are further promoted through hydrothermal reaction, meanwhile, the morphology and structure of the hydroxide are adjusted, and finally, the nano dot material with the specific morphology is finally formed through high-temperature sintering. The zinc ion part of the laminate is replaced by aluminum ion in the coprecipitation reaction process, the main laminate is positively charged, the anions between the layers are needed to offset the positive charge so as to achieve charge balance, and in the reaction process, the anions in the chelating agent and the sulfur-containing anions play a role in balancing the charge between the layers. The nano dot material prepared by the method of the technical scheme has hydrotalcite structure, the cations of the main layer plate and the anions between layers of the material are adjustable, the material has topological transformation property, and the intrinsic property of the directionality of the space configuration which is kept unchanged in a continuously-changed space is provided; manganese sulfide has metal elements similar to ternary materials, has better metal bond bonding capability and better composite effect, and meanwhile, manganese plays a main structural supporting role in a main body and a composite layer, so that the structural stability of the material can be effectively improved.
As a further preferable aspect of the above technical solution, in S1, the zinc salt includes at least one of zinc nitrate, zinc acetate and zinc oxalate, the aluminum salt includes at least one of aluminum nitrate, aluminum acetate and aluminum oxalate, and a molar ratio of the zinc salt, aluminum salt and graphene oxide is (2 to 4): 1: (0.01-0.05).
As a further preferable mode of the above technical scheme, in S1, the chelating agent is disodium EDTA, the manganese salt includes at least one of manganese nitrate, manganese acetate and manganese oxalate, and the sulfur-containing additive is SDS or SDBS; the molar ratio of the chelating agent, the manganese salt and the sulfur-containing additive is 1:1: (0.1 to 0.5); the molar ratio of chelating agent, manganese salt and sulfur-containing additive is further preferably 1:1: (0.1-0.2). The proportions of the above components ensure the solubility of the sulfur-containing additive and avoid substantial foaming during stirring.
As a further preferable mode of the technical scheme, the temperature of the hydrothermal reaction in S3 is 140-180 ℃ and the reaction time is 10-14 h; the hydrothermal reaction temperature is further preferably 140 to 160 ℃. The temperature range of the hydrothermal reaction can ensure that the hydrothermal reaction is smoothly carried out, and can ensure that the MnS nanodot precursor has better precursor morphology.
As a further preferable mode of the technical scheme, the high-temperature sintering temperature in S3 is 300-600 ℃ and the sintering time is 2-10 h.
Based on the same technical conception, the invention also provides the MnS nano dot material which is prepared by adopting the preparation method and has a hydrotalcite-like structure, and comprises a carbon material substrate and MnS nano dots loaded on the carbon material substrate.
Based on the same technical conception, the invention also provides a ternary sodium electric precursor material, which comprises a ternary precursor matrix and an MnS nano dot material coated on the surface of the ternary precursor matrix, wherein the MnS nano dot material is the MnS nano dot material or the MnS nano dot material prepared by the preparation method; the mass ratio of the MnS point material to the ternary precursor is (0.1-10): 100.
as a further preferred aspect of the above technical scheme, the ternary precursor matrix has a molecular formula of NaMn (1-m) N m C 6 H 5 O 7 Wherein N comprises at least two of Fe, ni, co and Cu, and x is more than or equal to 0.1 and less than or equal to 0.5.
Based on the same technical conception, the invention also provides a preparation method of the ternary sodium-electricity precursor material, which comprises the following steps:
s1, dissolving manganese salt, sodium salt and doped metal salt in stoichiometric ratio in a solvent, adding citric acid, and fully reacting to form a mixture; the doped metal salt is a salt substance of N, and the N comprises at least two of Fe, ni, co and Cu;
s2, adding the MnS nano-dot material into the mixture, uniformly stirring, and drying to obtain the ternary sodium-electricity precursor material.
As a further preferable mode of the above technical scheme, the ratio of the sum of the molar amounts of the manganese salt, the sodium salt and the doped metal salt to the molar amount of the citric acid in S1 is (1-2): 1.
as a further preferable mode of the above-mentioned technical scheme, the reaction temperature in S1 is 60 to 100 ℃.
Based on the same technical conception, the invention also provides a ternary sodium-electricity positive electrode material, which is prepared by sintering the ternary sodium-electricity precursor material at high temperature.
Further preferably, the high-temperature sintering temperature is 700-1000 ℃ and the sintering time is 2-12 h.
Compared with the prior art, the invention has the advantages that:
(1) According to the invention, hydrotalcite is taken as a template, a carbon material is combined, and then sintering and acid etching are carried out, so that the MnS nano dot material loaded by the carbon material with the hydrotalcite layered structure is prepared. The nano dots in the coating layer material are uniformly distributed, and the structure of the material is complete. The conductivity of the electrode material can be effectively improved by the carbon material, and the ion transmission rate of the material can be promoted by the MnS nano dots;
(2) The preparation method has the advantages of simple preparation process, short flow, readily available raw materials and no generation of toxic and harmful substances in the preparation process. The large-scale production is easy to realize;
(3) The ternary sodium-electricity anode material is subjected to cladding modification based on the ternary sodium-electricity precursor, and nano-dot cladding modified ternary sodium-electricity anode material is synthesized through sintering, so that surface byproducts are not generated, and the electrochemical performance of the material can be greatly improved.
Drawings
Fig. 1 is an SEM image of the ternary sodium-electricity positive electrode material of example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
The MnS nanodot material of the present example is prepared by the following method:
(1) 5mmol Zn (NO) 3 ) 2 、2mmol Al(NO 3 ) 3 And 20mg of graphene oxide are dispersed in 100ml of deionized water to obtain a solution A; 2mmol EDTA-2Na, 2mmol Mn (NO 3 ) 2 And 0.2mmol SDS was dissolved in 50ml deionized water, followed by 2mol L -1 Adjusting the pH value of the NaOH solution to 5.5-6 to obtain a solution B;
(2) Under the protection of nitrogen atmosphere, dropwise adding the solution B into the solution A, and further adjusting the pH value to 9-10 to obtain a mixed solution;
(3) Transferring the mixed solution into polytetrafluoroethylene, performing hydrothermal reaction at 160 ℃ for 12 hours, washing with water and alcohol, and drying to obtain the hydrotalcite layered manganese-based nano-dot precursor. Sintering the nano-dot precursor at high temperature, cooling, and using 2mol L -1 And etching the hydrochloric acid solution for 5 hours to obtain the hydrotalcite-based carbon composite MnS nano dot material.
The ternary sodium electric precursor material of the embodiment comprises a ternary precursor matrix and MnS nano-dot materials coated on the surface of the ternary precursor matrixThe MnS nano dot material is the MnS nano dot material of the embodiment; the molecular formula of the ternary precursor matrix is Na 0.67 Mn 0.7 Ni 0.2 Fe 0.1 C 6 H 5 O 7 The preparation method comprises the following steps:
(1) 0.035mol of Mn (CH 3 COO) 2 ·4H 2 O、0.05mol CH 3 COONa、0.01mol Ni(CH 3 COO) 2 ·4H 2 O、0.005mol Fe(CH 3 COO) 2 ·4H 2 O is dissolved in 100ml deionized water, 0.1mol of citric acid is added, and the mixture is fully stirred at 80 ℃ for reaction until a gel-like mixture is formed; citric acid as a complexing agent can complex effective metal ions to form NaMn (1-m) N m C 6 H 5 O 7 Microgel;
(2) The MnS nanodot material of the embodiment is added into the gel-like mixture, and after the mixture is continuously stirred and reacted for 1h, the mixture is dried for 12h at 120 ℃ to obtain the ternary sodium electric precursor material of the embodiment.
The ternary sodium-electricity positive electrode material of the embodiment is prepared by the following method: the ternary sodium electric precursor material of the embodiment is placed in a muffle furnace to be sintered at high temperature, presintering is carried out for 2 hours at 300 ℃, and then sintering is carried out for 10 hours at 900 ℃ to obtain the ternary sodium electric positive electrode material (expressed as MnS@C composite Na) 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 ). The SEM results are shown in fig. 1.
Na of MnS@C complex 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 Mixing with conductive agent Acetylene Black (AB) and binder polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, taking N-methyl pyrrolidone (NMP) as a solvent, and placing the mixture in a small beaker to stir and mix for 2 hours at the speed of 800r/min to obtain slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, horizontally placing on toughened glass, transferring to a vacuum drying oven at 85 ℃ for drying for 4 hours, preparing a pole piece with the diameter of 12mm by using a punching sheet, drying at 105 ℃ for 4 hours in the vacuum drying oven, and placing in a glove box with the water content and the oxygen content being lower than 0.1ppm and filled with argon atmosphere for 4 hours to reduce the position of the pole piece in the vacuum drying ovenAnd transferring the moisture absorbed in the process, and then assembling the CR2032 type button cell in a glove box. Rolling metal sodium into sheet, blanking into 14mm round sodium sheet to serve as anode, and adding NaClO of 1mol/L 4 The solution was used as an electrolyte and a glass fiber membrane having a diameter of 16mm was used as a separator.
After the battery is assembled and aged for 12 hours, the charge and discharge tests with different potentials are carried out. The discharge specific capacity of the calcined sample after 100 circles under the current density of 1C is 123.7mA h g under the voltage of 2-4V -1 The capacity retention was 86.6%.
Comparative example 1
0.035mol of Mn (CH 3 COO) 2 ·4H 2 O、0.05mol CH 3 COONa、0.01mol Ni(CH 3 COO) 2 ·4H 2 O、0.005mol Fe(CH 3 COO) 2 ·4H 2 O was dissolved in 100ml deionized water, 0.1mol of citric acid was added, and the reaction was stirred well at 80℃until a gel-like mixture was formed. After gel is formed, drying the mixture for 12 hours at 120 ℃, placing the mixture in a muffle furnace for high-temperature sintering, presintering the mixture for 2 hours at 300 ℃, and further sintering the mixture for 10 hours at 900 ℃ to obtain the final Na 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 The product is obtained. Mixing the material with conductive agent Acetylene Black (AB) and binder polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, taking N-methyl pyrrolidone (NMP) as a solvent, and placing the mixture in a small beaker to stir and mix for 2 hours at the rotating speed of 800r/min to obtain slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, horizontally placing the current collector aluminum foil on toughened glass, transferring the toughened glass into a vacuum drying oven at 85 ℃ for drying for 4 hours, preparing a pole piece with the diameter of 12mm by using a punching sheet, then drying the pole piece at 105 ℃ for 4 hours in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content being lower than 0.1ppm and filled with argon atmosphere for 4 hours to reduce the water absorbed by the pole piece in the transferring process, and then assembling the CR2032 button cell in the glove box. Rolling metal sodium into sheet, blanking into 14mm round sodium sheet to serve as anode, and adding NaClO of 1mol/L 4 The solution was used as an electrolyte and a glass fiber membrane having a diameter of 16mm was used as a separator.
After the battery is assembled and aged for 12 hours, different processes are carried outAnd (5) testing the charge and discharge of the potential. The discharge specific capacity of the calcined sample after 100 circles under the current density of 1C is 65.8mA h g under the voltage of 2-4V -1 The capacity retention was 52.2%.
Comparative example 2
(1) 5mmol Zn (NO) 3 ) 2 And 2mmol of Al (NO) 3 ) 3 Dispersing in 100ml deionized water to obtain solution A. Then 2mmol EDTA-2Na, 2mmol Mn (NO) are added 3 ) 2 And 0.2mmol SDS was dissolved in 50ml deionized water, followed by 2mol L -1 And (3) regulating the pH value to 5.5-6 by using NaOH solution to obtain solution B, dropwise adding the solution B into the solution A under the protection of nitrogen atmosphere, further regulating the pH value to 9-10, transferring into polytetrafluoroethylene, performing hydrothermal reaction at 160 ℃ for 12h, washing with water, and drying by alcohol washing to obtain the hydrotalcite layered manganese-based precursor. Sintering the precursor at high temperature, cooling, and using 2mol L -1 And etching the hydrochloric acid solution for 5 hours to obtain the hydrotalcite-based MnS nanodots.
(2) 0.035mol of Mn (CH 3 COO) 2 ·4H 2 O、0.05mol CH 3 COONa、0.01mol Ni(CH 3 COO) 2 ·4H 2 O、0.005mol Fe(CH 3 COO) 2 ·4H 2 O was dissolved in 100ml deionized water, 0.1mol of citric acid was added, and the reaction was stirred well at 80℃until a gel-like mixture was formed. After gel is formed, mnS nano-dots in the step (1) are added into the gel-like mixture, the mixture is continuously stirred and reacts for 1 hour, then the mixture is dried for 12 hours at 120 ℃, then the mixture is placed into a muffle furnace for high-temperature sintering, after presintering for 2 hours at 300 ℃, the mixture is further sintered for 10 hours at 900 ℃ to obtain the final MnS nano-dot composite Na 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 。
Na of MnS nanodot composition 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 Mixing with conductive agent Acetylene Black (AB) and binder polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, taking N-methyl pyrrolidone (NMP) as a solvent, and placing the mixture in a small beaker to stir and mix for 2 hours at the speed of 800r/min to obtain slurry. Coating the slurry on aluminum foil of current collector by using an automatic coating machine, and horizontally placingDrying for 4 hours on toughened glass in a vacuum drying oven at 85 ℃, preparing a pole piece with the diameter of 12mm by punching, drying for 4 hours at 105 ℃ in the vacuum drying oven, placing for 4 hours in a glove box filled with argon atmosphere and having the water content and the oxygen content of lower than 0.1ppm so as to reduce the water absorbed by the pole piece in the transferring process, and then assembling into the CR2032 button cell in the glove box. Rolling metal sodium into sheet, blanking into 14mm round sodium sheet to serve as anode, and adding NaClO of 1mol/L 4 The solution was used as an electrolyte and a glass fiber membrane having a diameter of 16mm was used as a separator.
After the battery is assembled and aged for 12 hours, the charge and discharge tests with different potentials are carried out. The discharge specific capacity of the calcined sample after 100 circles under the current density of 1C is 89.6mA h g under the voltage of 2-4V -1 The capacity retention was 76.3%.
Comparative example 3
(1) 5mmol Zn (NO) 3 ) 2 、2mmol Al(NO 3 ) 3 And 20mg of graphene oxide was dispersed in 100ml of deionized water to obtain solution A. Then 2mmol EDTA-2Na and 2mmol Mn (NO) 3 ) 2 Dissolving in 50ml deionized water, and then 2mol L -1 And (3) regulating the pH value to 5.5-6 by using NaOH solution to obtain solution B, dropwise adding the solution B into the solution A under the protection of nitrogen atmosphere, further regulating the pH value to 9-10, transferring into polytetrafluoroethylene, performing hydrothermal reaction at 160 ℃ for 12h, washing with water, and drying by alcohol washing to obtain the hydrotalcite layered manganese-based precursor. Sintering the precursor at high temperature, cooling, and using 2mol L -1 And etching the hydrochloric acid solution for 5 hours to obtain the hydrotalcite-based carbon composite MnO nano-dots.
(2) 0.035mol of Mn (CH 3 COO) 2 ·4H 2 O、0.05mol CH 3 COONa、0.01mol Ni(CH 3 COO) 2 ·4H 2 O、0.005mol Fe(CH 3 COO) 2 ·4H 2 O was dissolved in 100ml deionized water, 0.1mol of citric acid was added, and the reaction was stirred well at 80℃until a gel-like mixture was formed. After gel formation, mnO nanodots in (1) are added into the gel-like mixture, and after the mixture is stirred and reacted for 1 hour, the mixture is dried at 120 ℃ for 12 hours and then is placed inSintering at high temperature in a muffle furnace for 2h at 300 ℃, and sintering at 900 ℃ for 10h to obtain final MnO@C composite Na 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 。
Coating MnO@C with Na 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 Mixing with conductive agent Acetylene Black (AB) and binder polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, taking N-methyl pyrrolidone (NMP) as a solvent, and placing the mixture in a small beaker to stir and mix for 2 hours at the speed of 800r/min to obtain slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, horizontally placing the current collector aluminum foil on toughened glass, transferring the toughened glass into a vacuum drying oven at 85 ℃ for drying for 4 hours, preparing a pole piece with the diameter of 12mm by using a punching sheet, then drying the pole piece at 105 ℃ for 4 hours in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content being lower than 0.1ppm and filled with argon atmosphere for 4 hours to reduce the water absorbed by the pole piece in the transferring process, and then assembling the CR2032 button cell in the glove box. Rolling metal sodium into sheet, blanking into 14mm round sodium sheet to serve as anode, and adding NaClO of 1mol/L 4 The solution was used as an electrolyte and a glass fiber membrane having a diameter of 16mm was used as a separator.
After the battery is assembled and aged for 12 hours, the charge and discharge tests with different potentials are carried out. The discharge specific capacity of the calcined sample after 100 circles under the current density of 1C is 118.3mA h g under the voltage of 2-4V -1 The capacity retention was 84.9%.
Example 2
The MnS nanodot material of the present example is prepared by the following method:
(1) 5mmol Zn (NO) 3 ) 2 、2mmol Al(NO 3 ) 3 And 10mg of graphene oxide are dispersed in 100ml of deionized water to obtain a solution A; 2mmol EDTA-2Na, 2mmol Mn (NO 3 ) 2 And 0.2mmol SDS was dissolved in 50ml deionized water, followed by 2mol L -1 Adjusting the pH value of the NaOH solution to 5.5-6 to obtain a solution B;
(2) Under the protection of nitrogen atmosphere, dropwise adding the solution B into the solution A, and further adjusting the pH value to 9-10 to obtain a mixed solution;
(3) Transferring the mixed solution into polytetrafluoroethylene, performing hydrothermal reaction at 160 ℃ for 12 hours, washing with water and alcohol, and drying to obtain the hydrotalcite layered manganese-based nano-dot precursor. Sintering the nano-dot precursor at high temperature, cooling, and using 2mol L -1 And etching the hydrochloric acid solution for 5 hours to obtain the hydrotalcite-based carbon composite MnS nano dot material.
The ternary sodium electric precursor material of the embodiment comprises a ternary precursor matrix and MnS nano dot materials coated on the surface of the ternary precursor matrix, wherein the MnS nano dot materials are the MnS nano dot materials of the embodiment; the molecular formula of the ternary precursor matrix is Na 0.67 Mn 0.7 Ni 0.2 Fe 0.1 C 6 H 5 O 7 The preparation method comprises the following steps:
(1) 0.035mol of Mn (CH 3 COO) 2 ·4H 2 O、0.05mol CH 3 COONa、0.01mol Ni(CH 3 COO) 2 ·4H 2 O、0.005mol Fe(CH 3 COO) 2 ·4H 2 O was dissolved in 100ml deionized water, 0.1mol of citric acid was added, and the reaction was stirred well at 80℃until a gel-like mixture was formed.
(2) The MnS nanodot material of the embodiment is added into the gel-like mixture, and after the mixture is continuously stirred and reacted for 1h, the mixture is dried for 12h at 120 ℃ to obtain the ternary sodium electric precursor material of the embodiment.
The ternary sodium-electricity positive electrode material of the embodiment is prepared by the following method: the ternary sodium electric precursor material of the embodiment is placed in a muffle furnace to be sintered at high temperature, presintering is carried out for 2 hours at 300 ℃, and then sintering is carried out for 10 hours at 900 ℃ to obtain the ternary sodium electric positive electrode material (expressed as MnS@C composite Na) 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 )。
Na of MnS@C complex 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 Mixing with conductive agent Acetylene Black (AB) and binder polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, taking N-methyl pyrrolidone (NMP) as a solvent, and placing the mixture in a small beaker to stir and mix for 2 hours at the speed of 800r/min to obtain slurry. Using an automatic coaterThe slurry is coated on a current collector aluminum foil, is horizontally placed on toughened glass and is dried in a vacuum drying oven at 85 ℃ for 4 hours, a punched sheet is prepared into a pole piece with the diameter of 12mm, then the pole piece is dried in the vacuum drying oven at 105 ℃ for 4 hours, the pole piece is placed in a glove box which is filled with argon atmosphere and has the water content and the oxygen content of lower than 0.1ppm for 4 hours so as to reduce the water absorbed by the pole piece in the transferring process, and then the CR2032 button cell is assembled in the glove box. Rolling metal sodium into sheet, blanking into 14mm round sodium sheet to serve as anode, and adding NaClO of 1mol/L 4 The solution was used as an electrolyte and a glass fiber membrane having a diameter of 16mm was used as a separator.
After the battery is assembled and aged for 12 hours, the charge and discharge tests with different potentials are carried out. The discharge specific capacity of the calcined sample after 100 circles under the current density of 1C is 106.8mA h g under the voltage of 2-4V -1 The capacity retention was 82.7%.
Example 3
The MnS nanodot material of the present example is prepared by the following method:
(1) 5mmol Zn (NO) 3 ) 2 、2mmol Al(NO 3 ) 3 And 30mg of graphene oxide are dispersed in 100ml of deionized water to obtain a solution A; 2mmol EDTA-2Na, 2mmol Mn (NO 3 ) 2 And 0.2mmol SDS was dissolved in 50ml deionized water, followed by 2mol L -1 Adjusting the pH value of the NaOH solution to 5.5-6 to obtain a solution B;
(2) Under the protection of nitrogen atmosphere, dropwise adding the solution B into the solution A, and further adjusting the pH value to 9-10 to obtain a mixed solution;
(3) Transferring the mixed solution into polytetrafluoroethylene, performing hydrothermal reaction at 160 ℃ for 12 hours, washing with water and alcohol, and drying to obtain the hydrotalcite layered manganese-based nano-dot precursor. Sintering the nano-dot precursor at high temperature, cooling, and using 2mol L -1 And etching the hydrochloric acid solution for 5 hours to obtain the hydrotalcite-based carbon composite MnS nano dot material.
The ternary sodium electric precursor material of the embodiment comprises a ternary precursor matrix and MnS nano dot materials coated on the surface of the ternary precursor matrix, wherein the MnS nano dot materials are the MnS nano dot materials of the embodiment; ternary precursor matrixHas the molecular formula of Na 0.67 Mn 0.7 Ni 0.2 Fe 0.1 C 6 H 5 O 7 The preparation method comprises the following steps:
(1) 0.035mol of Mn (CH 3 COO) 2 ·4H 2 O、0.05mol CH 3 COONa、0.01mol Ni(CH 3 COO) 2 ·4H 2 O、0.005mol Fe(CH 3 COO) 2 ·4H 2 O is dissolved in 100ml deionized water, 0.1mol of citric acid is added, and the mixture is fully stirred at 80 ℃ for reaction until a gel-like mixture is formed;
(2) The MnS nanodot material of the embodiment is added into the gel-like mixture, and after the mixture is continuously stirred and reacted for 1h, the mixture is dried for 12h at 120 ℃ to obtain the ternary sodium electric precursor material of the embodiment.
The ternary sodium-electricity positive electrode material of the embodiment is prepared by the following method: the ternary sodium electric precursor material of the embodiment is placed in a muffle furnace to be sintered at high temperature, presintering is carried out for 2 hours at 300 ℃, and then sintering is carried out for 10 hours at 900 ℃ to obtain the ternary sodium electric positive electrode material (expressed as MnS@C composite Na) 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 )。
Na of MnS@C complex 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 Mixing with conductive agent Acetylene Black (AB) and binder polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, taking N-methyl pyrrolidone (NMP) as a solvent, and placing the mixture in a small beaker to stir and mix for 2 hours at the speed of 800r/min to obtain slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, horizontally placing the current collector aluminum foil on toughened glass, transferring the toughened glass into a vacuum drying oven at 85 ℃ for drying for 4 hours, preparing a pole piece with the diameter of 12mm by using a punching sheet, then drying the pole piece at 105 ℃ for 4 hours in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content being lower than 0.1ppm and filled with argon atmosphere for 4 hours to reduce the water absorbed by the pole piece in the transferring process, and then assembling the CR2032 button cell in the glove box. Rolling metal sodium into sheet, blanking into 14mm round sodium sheet to serve as anode, and adding NaClO of 1mol/L 4 The solution was used as an electrolyte and a glass fiber membrane having a diameter of 16mm was used as a separator.
After the battery is assembled and aged for 12 hours, the charge and discharge tests with different potentials are carried out. The discharge specific capacity of the calcined sample after 100 circles under the current density of 1C is 120.4mA h g under the voltage of 2-4V -1 The capacity retention was 85.8%.
Example 4
The MnS nanodot material of the present example is prepared by the following method:
(1) 5mmol Zn (NO) 3 ) 2 、2mmol Al(NO 3 ) 3 And 20mg of graphene oxide are dispersed in 100ml of deionized water to obtain a solution A; 2mmol EDTA-2Na, 2mmol Mn (NO 3 ) 2 And 0.2mmol SDS was dissolved in 50ml deionized water, followed by 2mol L -1 Adjusting the pH value of the NaOH solution to 5.5-6 to obtain a solution B;
(2) Under the protection of nitrogen atmosphere, dropwise adding the solution B into the solution A, and further adjusting the pH value to 9-10 to obtain a mixed solution;
(3) Transferring the mixed solution into polytetrafluoroethylene, performing hydrothermal reaction at 160 ℃ for 12 hours, washing with water and alcohol, and drying to obtain the hydrotalcite layered manganese-based nano-dot precursor. Sintering the nano-dot precursor at high temperature, cooling, and using 2mol L -1 And etching the hydrochloric acid solution for 5 hours to obtain the hydrotalcite-based carbon composite MnS nano dot material.
The ternary sodium electric precursor material of the embodiment comprises a ternary precursor matrix and MnS nano dot materials coated on the surface of the ternary precursor matrix, wherein the MnS nano dot materials are the MnS nano dot materials of the embodiment; the molecular formula of the ternary precursor matrix is Na 0.67 Mn 0.7 Ni 0.2 Fe 0.1 C 6 H 5 O 7 The preparation method comprises the following steps:
(1) 0.035mol of Mn (CH 3 COO) 2 ·4H 2 O、0.05mol CH 3 COONa、0.01mol Cu(CH 3 COO) 2 ·4H 2 O、0.005mol Fe(CH 3 COO) 2 ·4H 2 O was dissolved in 100ml deionized water, 0.1mol of citric acid was added, and the reaction was stirred well at 80℃until a gel-like mixture was formed.
(2) The MnS nanodot material of the embodiment is added into the gel-like mixture, and after the mixture is continuously stirred and reacted for 1h, the mixture is dried for 12h at 120 ℃ to obtain the ternary sodium electric precursor material of the embodiment.
The ternary sodium-electricity positive electrode material of the embodiment is prepared by the following method: the ternary sodium electric precursor material of the embodiment is placed in a muffle furnace to be sintered at high temperature, presintering is carried out for 2 hours at 300 ℃, and then sintering is carried out for 10 hours at 900 ℃ to obtain the ternary sodium electric positive electrode material (expressed as MnS@C composite Na) 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 )。
Na of MnS@C complex 0.67 Mn 0.7 Cu 0.2 Fe 0.1 O 2 Mixing with conductive agent Acetylene Black (AB) and binder polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, taking N-methyl pyrrolidone (NMP) as a solvent, and placing the mixture in a small beaker to stir and mix for 2 hours at the speed of 800r/min to obtain slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, horizontally placing the current collector aluminum foil on toughened glass, transferring the toughened glass into a vacuum drying oven at 85 ℃ for drying for 4 hours, preparing a pole piece with the diameter of 12mm by using a punching sheet, then drying the pole piece at 105 ℃ for 4 hours in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content being lower than 0.1ppm and filled with argon atmosphere for 4 hours to reduce the water absorbed by the pole piece in the transferring process, and then assembling the CR2032 button cell in the glove box. Rolling metal sodium into sheet, blanking into 14mm round sodium sheet to serve as anode, and adding NaClO of 1mol/L 4 The solution was used as an electrolyte and a glass fiber membrane having a diameter of 16mm was used as a separator.
After the battery is assembled and aged for 12 hours, the charge and discharge tests with different potentials are carried out. The discharge specific capacity of the calcined sample after 100 circles under the current density of 1C is 103.7mA h g under the voltage of 2-4V -1 The capacity retention was 82.1%.
Example 5
The MnS nanodot material of the present example is prepared by the following method:
(1) 5mmol Zn (NO) 3 ) 2 、2mmol Al(NO 3 ) 3 And 20mg of graphene oxide dispersed in 100ml of deionized waterObtaining a solution A; 2mmol EDTA-2Na, 2mmol Mn (NO 3 ) 2 And 0.2mmol SDS was dissolved in 50ml deionized water, followed by 2mol L -1 Adjusting the pH value of the NaOH solution to 5.5-6 to obtain a solution B;
(2) Under the protection of nitrogen atmosphere, dropwise adding the solution B into the solution A, and further adjusting the pH value to 9-10 to obtain a mixed solution;
(3) Transferring the mixed solution into polytetrafluoroethylene, performing hydrothermal reaction at 160 ℃ for 12 hours, washing with water and alcohol, and drying to obtain the hydrotalcite layered manganese-based nano-dot precursor. Sintering the nano-dot precursor at high temperature, cooling, and using 2mol L -1 And etching the hydrochloric acid solution for 5 hours to obtain the hydrotalcite-based carbon composite MnS nano dot material.
The ternary sodium electric precursor material of the embodiment comprises a ternary precursor matrix and MnS nano dot materials coated on the surface of the ternary precursor matrix, wherein the MnS nano dot materials are the MnS nano dot materials of the embodiment; the molecular formula of the ternary precursor matrix is Na 0.67 Mn 0.7 Ni 0.2 Fe 0.1 C 6 H 5 O 7 The preparation method comprises the following steps:
(1) 0.025mol Mn (CH) 3 COO) 2 ·4H 2 O、0.05mol CH 3 COONa、0.02mol Ni(CH 3 COO) 2 ·4H 2 O、0.005mol Fe(CH 3 COO) 2 ·4H 2 O is dissolved in 100ml deionized water, 0.1mol of citric acid is added, and the mixture is fully stirred at 80 ℃ for reaction until a gel-like mixture is formed;
(2) The MnS nanodot material of the embodiment is added into the gel-like mixture, and after the mixture is continuously stirred and reacted for 1h, the mixture is dried for 12h at 120 ℃ to obtain the ternary sodium electric precursor material of the embodiment.
The ternary sodium-electricity positive electrode material of the embodiment is prepared by the following method: the ternary sodium electric precursor material of the embodiment is placed in a muffle furnace to be sintered at high temperature, presintering is carried out for 2 hours at 300 ℃, and then sintering is carried out for 10 hours at 900 ℃ to obtain the ternary sodium electric positive electrode material (expressed as MnS@C composite Na) 0.67 Mn 0.7 Ni 0.2 Fe 0.1 O 2 )。
Na of MnS@C complex 0.67 Mn 0.5 Ni 0.4 Fe 0.1 O 2 Mixing with conductive agent Acetylene Black (AB) and binder polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, taking N-methyl pyrrolidone (NMP) as a solvent, and placing the mixture in a small beaker to stir and mix for 2 hours at the speed of 800r/min to obtain slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, horizontally placing the current collector aluminum foil on toughened glass, transferring the toughened glass into a vacuum drying oven at 85 ℃ for drying for 4 hours, preparing a pole piece with the diameter of 12mm by using a punching sheet, then drying the pole piece at 105 ℃ for 4 hours in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content being lower than 0.1ppm and filled with argon atmosphere for 4 hours to reduce the water absorbed by the pole piece in the transferring process, and then assembling the CR2032 button cell in the glove box. Rolling metal sodium into sheet, blanking into 14mm round sodium sheet to serve as anode, and adding NaClO of 1mol/L 4 The solution was used as an electrolyte and a glass fiber membrane having a diameter of 16mm was used as a separator.
After the battery is assembled and aged for 12 hours, the charge and discharge tests with different potentials are carried out. The discharge specific capacity of the calcined sample after 100 circles under the current density of 1C is 126.3mA h g under the voltage of 2-4V -1 The capacity retention was 84.9%.
The above description is merely a preferred embodiment of the present invention, and the scope of the present invention is not limited to the above examples. Modifications and variations which would be obvious to those skilled in the art without departing from the spirit of the invention are also considered to be within the scope of the invention.
Claims (13)
1. The preparation method of the MnS nano-dot material is characterized by comprising the following steps of:
s1, dispersing zinc salt, aluminum salt and graphene oxide in a solvent to obtain a solution A; dissolving a chelating agent, manganese salt and a sulfur-containing additive in a solvent, and adjusting the pH to 5-7 to obtain a solution B; the chelating agent is disodium EDTA, and the sulfur-containing additive is SDS or SDBS;
s2, dropwise adding the solution B into the solution A, and adjusting the pH to 8-10 to obtain a mixed solution;
s3, transferring the mixed solution into polytetrafluoroethylene for hydrothermal reaction, and obtaining a nano-dot precursor after the reaction is completed; and (3) sintering the nano dot precursor at a high temperature, and etching by using an acid solution to obtain the MnS nano dot material.
2. The method for preparing the MnS nano dot material according to claim 1, wherein the zinc salt in S1 includes at least one of zinc nitrate, zinc acetate and zinc oxalate, the aluminum salt includes at least one of aluminum nitrate, aluminum acetate and aluminum oxalate, and the molar ratio of the zinc salt, aluminum salt and graphene oxide is (2-4): 1: (0.01 to 0.05).
3. The method for preparing MnS nano-dot material according to claim 1, wherein in S1, the manganese salt includes at least one of manganese nitrate, manganese acetate and manganese oxalate; the molar ratio of the chelating agent, the manganese salt and the sulfur-containing additive is 1:1: (0.1 to 0.5).
4. The method for preparing the MnS nanodot material according to claim 1, wherein the hydrothermal reaction temperature of S3 is 140-180 ℃ and the reaction time is 10-14 h.
5. The method for preparing a MnS nano-dot material according to any one of claims 1 to 4, wherein the high-temperature sintering temperature in S3 is 300 to 600 ℃ and the sintering time is 2 to 10 hours.
6. A MnS nanodot material, characterized in that it is produced by the production method according to any one of claims 1 to 5, and has a hydrotalcite-like structure comprising a carbon material substrate and MnS nanodots supported on the carbon material substrate.
7. A ternary sodium electric precursor material, which is characterized by comprising a ternary precursor matrix and an MnS nano dot material coated on the surface of the ternary precursor matrix, wherein the MnS nano dot material is the MnS nano dot material of claim 6 or the MnS nano dot material prepared by the preparation method of any one of claims 1 to 5; the mass ratio of the MnS nano dot material to the ternary precursor is (0.1-10): 100.
8. the ternary sodium electric precursor material of claim 7, wherein the ternary precursor matrix has a molecular formula of NaMn (1-m) N m C 6 H 5 O 7 Wherein N comprises at least two of Fe, ni, co and Cu, and x is more than or equal to 0.1 and less than or equal to 0.5.
9. A method of preparing a ternary sodalime precursor material according to claim 7 or 8, comprising the steps of:
s1, dissolving manganese salt, sodium salt and doped metal salt in stoichiometric ratio in a solvent, adding citric acid, and fully reacting to form a mixture; the doped metal salt is a salt substance of N, and the N comprises at least two of Fe, ni, co and Cu;
s2, adding the MnS nano-dot material into the mixture, uniformly stirring, and drying to obtain the ternary sodium-electricity precursor material.
10. The preparation method of the ternary sodium electric precursor material according to claim 9, wherein the ratio of the sum of the molar amounts of the manganese salt, the sodium salt and the doped metal salt in the S1 to the molar amount of the citric acid is (1-2): 1.
11. the method for preparing a ternary sodium electric precursor material according to claim 9, wherein the reaction temperature in S1 is 60-100 ℃.
12. A ternary sodium-electricity positive electrode material, characterized in that the ternary sodium-electricity positive electrode material is prepared by high-temperature sintering of the ternary sodium-electricity precursor material according to claim 7 or 8.
13. The ternary sodium electricity positive electrode material according to claim 12, wherein the high-temperature sintering temperature is 700-1000 ℃ and the sintering time is 2-12 h.
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