CN114735750A - Niobium salt material, preparation method and application thereof - Google Patents
Niobium salt material, preparation method and application thereof Download PDFInfo
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- CN114735750A CN114735750A CN202210294369.2A CN202210294369A CN114735750A CN 114735750 A CN114735750 A CN 114735750A CN 202210294369 A CN202210294369 A CN 202210294369A CN 114735750 A CN114735750 A CN 114735750A
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- 239000000463 material Substances 0.000 title claims abstract description 79
- 150000002821 niobium Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000000243 solution Substances 0.000 claims abstract description 74
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 50
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 43
- 238000002156 mixing Methods 0.000 claims abstract description 34
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 33
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002244 precipitate Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 238000004729 solvothermal method Methods 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 14
- 229910019804 NbCl5 Inorganic materials 0.000 claims abstract description 8
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000003792 electrolyte Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000004108 freeze drying Methods 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 6
- 239000007772 electrode material Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 11
- 239000010406 cathode material Substances 0.000 abstract description 2
- 239000010955 niobium Substances 0.000 description 44
- 238000009792 diffusion process Methods 0.000 description 18
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 16
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 229910052758 niobium Inorganic materials 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
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- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 6
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- 230000007246 mechanism Effects 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 5
- IUQLNBKXRLDBEA-UHFFFAOYSA-A [O-]P([O-])(=O)OP(=O)([O-])[O-].[Nb+5].[O-]P([O-])(=O)OP(=O)([O-])[O-].[O-]P([O-])(=O)OP(=O)([O-])[O-].[O-]P([O-])(=O)OP(=O)([O-])[O-].[O-]P([O-])(=O)OP(=O)([O-])[O-].[Nb+5].[Nb+5].[Nb+5] Chemical compound [O-]P([O-])(=O)OP(=O)([O-])[O-].[Nb+5].[O-]P([O-])(=O)OP(=O)([O-])[O-].[O-]P([O-])(=O)OP(=O)([O-])[O-].[O-]P([O-])(=O)OP(=O)([O-])[O-].[O-]P([O-])(=O)OP(=O)([O-])[O-].[Nb+5].[Nb+5].[Nb+5] IUQLNBKXRLDBEA-UHFFFAOYSA-A 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
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- 239000011148 porous material Substances 0.000 description 5
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical group FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
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- 239000013078 crystal Substances 0.000 description 3
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- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 description 3
- 229910000484 niobium oxide Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- 238000005119 centrifugation Methods 0.000 description 2
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- 239000003365 glass fiber Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- NYPFJVOIAWPAAV-UHFFFAOYSA-N sulfanylideneniobium Chemical compound [Nb]=S NYPFJVOIAWPAAV-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 102000020897 Formins Human genes 0.000 description 1
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- 229910004856 P—O—P Inorganic materials 0.000 description 1
- 241000223259 Trichoderma Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
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- 239000003990 capacitor Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- 238000009831 deintercalation Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 235000011226 hei shi Nutrition 0.000 description 1
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- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- CNHRNMLCYGFITG-UHFFFAOYSA-A niobium(5+);pentaphosphate Chemical compound [Nb+5].[Nb+5].[Nb+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O CNHRNMLCYGFITG-UHFFFAOYSA-A 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- -1 phosphate radical Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 238000007086 side reaction Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/38—Condensed phosphates
- C01B25/42—Pyrophosphates
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- C01P2006/40—Electric properties
-
- 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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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of sodium ion batteries, in particular to a niobium salt material, and a preparation method and application thereof. The preparation method comprises the following steps: a) stirring the first solution, the second solution and triethylamine for reaction to obtain a reaction product; the first solution was prepared as follows: reacting NbCl5Uniformly mixing the solution with a hydrochloric acid mixed solution, carrying out solvothermal reaction on the obtained dispersion at 130-150 ℃, and mixing the precipitate obtained by the reaction with methanol to obtain a first solution; the second solution was prepared as follows: mixing hexachlorocyclotriphosphazene, 4' -dihydroxy diphenyl sulfone and methanol to obtain a second solutionLiquid; b) and calcining the reaction product at 600-800 ℃ to obtain the niobium salt material. According to the invention, the niobium salt material is synthesized by adopting a polymer-assisted one-step calcination method, the niobium salt material can be used for preparing a sodium ion battery cathode material, and the finally prepared sodium ion battery has excellent electrochemical performance.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a niobium salt material, and a preparation method and application thereof.
Background
Lithium ion batteries have been widely used in a variety of fields, from electronic devices to electric vehicles to stationary large-scale power grids. The lithium ion battery has the advantages of light weight, high energy and power density, wide electrochemical window and the like. However, the shortage of lithium resources in nature, high cost, and the like have limited the large-scale application of lithium resources in industrial production and daily life to some extent. Because sodium has similar physicochemical characteristics as lithium, sodium ion batteries are used instead of lithium ionsThe pool will be a great trend. In addition, the sodium resource is abundant in nature and low in price. The negative electrode of the sodium ion battery is an important component of the sodium ion battery, and the comprehensive performance of the battery is influenced, so that the search for the negative electrode material of the sodium ion battery with excellent performance is critical. Niobium (Nb) is an important transition metal element with rich oxidation state (Nb)3+、Nb4+And Nb5+) And can be used for electrochemical energy storage. In 2016, a self-assembled Nb was synthesized by hydrothermal synthesis of niobium foil2O5Nanosheets. Using Nb2O5The nano-sheet is a cathode, the pure carbon is an anode, and the sodium ion hybrid capacitor is assembled, and has extremely high energy density and power density, and ultra-long and stable cycle life. Then, Wang et al synthesized a sandwich-type niobium sulfide (NbS) by calcining niobium powder and sulfur powder together2) The catalyst is used for the lithium-sulfur battery to realize high sulfur load, ultrahigh multiplying power and long-period operation life. The figure and the like prepare novel conductive electrode niobium carbide (NbC), and the niobium carbide has a polar characteristic, high conductivity and an ultra-stable structure, can be embedded into a trichoderma spore carbon matrix in the form of nanoparticles, captures soluble polysulfide through chemical action, and can prepare a high-performance lithium-sulfur battery.
The phosphate of metal niobium is difficult to prepare and synthesize, the niobium source is difficult to dissolve, and the general preparation conditions are harsh (hydrofluoric acid is needed). For example, Sanzt et al synthesized layered niobium phosphate in a concentrated hydrofluoric acid system in 1987. However, high-concentration hydrofluoric acid is extremely corrosive and toxic, and not only has strict requirements on reaction vessels and brings difficulties to chemical synthesis, but also generates a large amount of chemical waste and is polluting to the environment. Therefore, it is a challenge to synthesize niobium metal phosphate with high sodium storage capacity by a simple and low-cost method.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a niobium salt material, a preparation method and an application thereof, wherein the prepared niobium salt material can be used for preparing a sodium ion battery negative electrode material, and the finally prepared sodium ion battery has excellent electrochemical performance.
The invention provides a preparation method of a niobium salt material, which comprises the following steps:
a) stirring the first solution, the second solution and triethylamine for reaction to obtain a reaction product;
the first solution was prepared as follows:
reacting NbCl5Uniformly mixing the solution with a hydrochloric acid mixed solution, carrying out solvothermal reaction on the obtained dispersion at 130-150 ℃, and mixing the precipitate obtained by the reaction with methanol to obtain a first solution;
the second solution was prepared as follows:
mixing hexachlorocyclotriphosphazene, 4' -dihydroxydiphenylsulfone and methanol to obtain a second solution;
b) and calcining the reaction product at 600-800 ℃ to obtain the niobium salt material.
Preferably, the hydrochloric acid mixed solution comprises hydrochloric acid, ethylene glycol and deionized water;
in the hydrochloric acid mixed solution, the volume content of hydrochloric acid is 2-3%;
the volume ratio of the ethylene glycol to the deionized water is 7-9: 1 to 3.
Preferably, the solvothermal reaction time is 8-12 h;
after the solvothermal reaction, the method further comprises the following steps:
centrifuging, washing the centrifuged precipitate with deionized water and anhydrous ethanol alternately, and freeze-drying.
Preferably, in the preparation of the first solution, the dosage ratio of the precipitate to the methanol is 0.1-0.2 g: 30-50 mL.
Preferably, the mass ratio of the hexachlorocyclotriphosphazene to the 4, 4' -dihydroxy diphenyl sulfone is 2-4: 2-4;
in the preparation of the second solution, the ratio of the mass sum of hexachlorocyclotriphosphazene and 4, 4' -dihydroxydiphenylsulfone to the amount of methanol is 0.66-0.74 g: 5-15 mL or 3.5-4.5 g: 40-60 mL.
Preferably, the ratio of the mass sum of the hexachlorocyclotriphosphazene and 4, 4' -dihydroxydiphenylsulfone to the mass of the precipitate adopted in the first solution is 0.66-0.74: 0.1 to 0.2 or 3.5 to 4.5: 0.1 to 0.2;
the mass ratio of the sum of the hexachlorocyclotriphosphazene and 4, 4' -dihydroxy diphenyl sulfone to the triethylamine is 0.66-0.74 g: 1-2 mL or 3.5-4.5 g: 6-8 mL;
after the first solution, the second solution and triethylamine are stirred to react, the method further comprises the following steps:
centrifuging, washing the centrifuged precipitate with methanol, and freeze-drying.
The invention also provides a niobium salt material prepared by the preparation method.
The invention also provides an application of the niobium salt material in preparation of a sodium-ion battery electrode material.
The invention also provides a preparation method of the sodium-ion battery, which comprises the following steps:
A) mixing a niobium salt material, a conductive agent and a binder, and uniformly mixing an obtained mixed sample with N-methylpyrrolidone to obtain slurry;
the polyanionic compound is a niobium salt material described above;
B) uniformly coating the slurry on a current collector, and drying in vacuum to obtain an electrode plate;
C) and assembling the electrode plate, the counter electrode sodium plate, the electrolyte and the diaphragm to obtain the sodium-ion battery.
The invention also provides a sodium ion battery prepared by the preparation method.
The invention provides a preparation method of a niobium salt material, which comprises the following steps: a) stirring the first solution, the second solution and triethylamine for reaction to obtain a reaction product; the first solution was prepared as follows: reacting NbCl5Uniformly mixing the solution with a hydrochloric acid mixed solution, carrying out solvothermal reaction on the obtained dispersion at 130-150 ℃, and mixing the precipitate obtained by the reaction with methanol to obtain a first solution; the second solution was prepared as follows: mixing hexachlorocyclotriphosphazene, 4' -dihydroxy diphenyl sulfone and methanol to obtain a second solution; b) calcining the reaction product at 600-800 ℃ to obtain niobiumA salt material. According to the invention, a polymer-assisted one-step calcination method is adopted to synthesize the niobium salt material, the niobium salt material can be used for preparing a sodium ion battery cathode material, and the finally prepared sodium ion battery has excellent electrochemical performance. Meanwhile, the preparation method provided by the invention is simple to operate, the experimental raw materials are environment-friendly, the cost is lower, and the product niobium pyrophosphate NbP1.8O7The electrochemical performance of the niobium-based phosphate material is excellent, and an important reference is provided for synthesizing the niobium-based phosphate material.
Drawings
FIG. 1 is a diagram of the polymerization mechanism of Hexachlorocyclotriphosphazene (HCCP) and 4, 4' -dihydroxydiphenylsulfone (SPO);
FIG. 2 is an XRD pattern of the niobium salt materials prepared in examples 1 and 2 of the present invention;
FIG. 3 is a Nb 3d high resolution XPS plot for the material obtained by varying the ramp rate in example 2;
FIG. 4 is an XPS spectrum of NPO-5;
FIG. 5 shows NbP obtained at three different ramp rates1.8O7SEM picture of (1);
FIG. 6 shows NbP obtained at three different ramp rates1.8O7A TEM image of (D);
FIG. 7 shows NbP obtained at three different ramp rates1.8O7N of (A)2Adsorption and desorption curves and aperture distribution maps;
FIG. 8 shows the cell density at 1000mAg for the button cell obtained in application examples 1-4 and comparative example 1-1A lower constant current long cycle curve;
FIG. 9 shows the current of the button cell battery obtained in application example 2 at 100mA g-1A constant current circulation curve and a constant current charge-discharge curve are obtained;
fig. 10 is a rate performance curve and a capacity-voltage curve of the button cell obtained in application example 2;
fig. 11 is a constant current cycle curve of the button cell obtained in application example 2 under a high current density;
fig. 12 is a cyclic voltammogram of the button cell obtained in application example 2;
fig. 13 is a CV curve of the button cell obtained in application example 2 of the present invention at different scanning rates;
fig. 14 is a curve of b value versus voltage for button cells obtained in application example 2 of the present invention at different voltages;
FIG. 15 is 8mV s-1An original CV curve and a fitted pseudocapacitance curve are obtained;
figure 16 is a graph of pseudocapacitance contributions from button cells obtained in application example 2 of the present invention at different scan rates;
fig. 17 is an ac impedance graph of the button cell obtained in application examples 1 to 4 and comparative example 1 after 30 cycles;
fig. 18 shows the charging and discharging curves and the corresponding sodium ion diffusion coefficients of the GITT test of the button cell obtained in application example 2 at the third and fourth circles.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a niobium salt material, which comprises the following steps:
a) stirring the first solution, the second solution and triethylamine for reaction to obtain a reaction product;
the first solution was prepared as follows:
reacting NbCl5Uniformly mixing the solution with a hydrochloric acid mixed solution, carrying out solvothermal reaction on the obtained dispersion at 130-150 ℃, and mixing the precipitate obtained by the reaction with methanol to obtain a first solution;
the second solution was prepared as follows:
mixing hexachlorocyclotriphosphazene, 4' -dihydroxydiphenylsulfone and methanol to obtain a second solution;
b) and calcining the reaction product at 600-800 ℃ to obtain the niobium salt material.
The first solution, the second solution and triethylamine are stirred to react to obtain a reaction product.
In the present invention, the first solution is prepared according to the following method:
reacting NbCl5And mixing the solution and the mixed solution of hydrochloric acid uniformly, carrying out solvothermal reaction on the obtained dispersion liquid at 130-150 ℃, and mixing the precipitate obtained by the reaction with methanol to obtain a first solution.
In some embodiments of the present invention, the hydrochloric acid mixture comprises hydrochloric acid, ethylene glycol, and deionized water. The hydrochloric acid is concentrated hydrochloric acid, and the mass concentration of the hydrochloric acid is 36-38%. In the hydrochloric acid mixed solution, the volume content of hydrochloric acid is 2-3%. In some embodiments, the hydrochloric acid mixed solution contains 2.5% by volume of hydrochloric acid. The volume ratio of the ethylene glycol to the deionized water is 7-9: 1 to 3. In certain embodiments, the volume ratio of ethylene glycol to deionized water is 8: 2.
in some embodiments of the invention, the uniformly mixing method is magnetic stirring, the uniformly mixing temperature is room temperature, and the uniformly mixing time is 15-25 min. In certain embodiments, the time for homogenization is 20 min.
In certain embodiments of the present invention, the solvothermal reaction time is 8 to 12 hours or 10 hours. The solvothermal reaction was carried out in an autoclave.
In certain embodiments of the present invention, the solvothermal reaction further comprises:
centrifuging, washing the centrifuged precipitate with deionized water and anhydrous ethanol alternately, and freeze-drying.
In certain embodiments of the invention, the number of alternating washes is 3.
In some embodiments of the invention, the freeze-drying time is 10-14 h. In certain embodiments, the freeze-drying time is 12 hours. The freeze-drying is carried out in a freeze-dryer.
In some embodiments of the present invention, the ratio of the precipitate obtained by the solvothermal reaction to the methanol is 0.1-0.2 g: 30-50 mL. In certain embodiments, the solvothermal reaction produces a precipitate with a ratio of 0.15g of methanol: 40 mL.
In certain embodiments of the invention, the mixing of the precipitate from the solvothermal reaction with methanol is performed under ultrasonic and stirring conditions. The method and parameters of the ultrasonic agitation and stirring are not particularly limited in the present invention, and those well known to those skilled in the art can be used.
In the present invention, the second solution is prepared according to the following method:
mixing hexachlorocyclotriphosphazene, 4' -dihydroxydiphenylsulfone and methanol to obtain a second solution.
In certain embodiments of the present invention, the mass ratio of hexachlorocyclotriphosphazene to 4, 4' -dihydroxydiphenylsulfone is 2-4: 2 to 4. In certain embodiments, the mass ratio of hexachlorocyclotriphosphazene to 4, 4' -dihydroxydiphenylsulfone is 3: 4.
in some embodiments of the present invention, the ratio of the sum of the mass of hexachlorocyclotriphosphazene and 4, 4' -dihydroxydiphenylsulfone to the amount of methanol in the preparation of the second solution is 0.66 to 0.74 g: 5-15 mL or 3.5-4.5 g: 40-60 mL. In certain embodiments, the second solution is prepared such that the ratio of the sum of the masses of hexachlorocyclotriphosphazene and 4, 4' -dihydroxydiphenylsulfone to the amount of methanol is 0.7 g: 10mL or 4.1 g: 50 mL.
And after the first solution and the second solution are obtained, stirring the first solution, the second solution and triethylamine for reaction to obtain a reaction product.
Preferably, the method comprises the following steps:
and stirring and mixing the first solution and the second solution, dropwise adding triethylamine into the mixed solution, and stirring for reaction.
In some embodiments of the present invention, the first solution and the second solution are mixed with stirring for 8-12 min.
The dropping can be performed by using a pipette.
In some embodiments of the invention, the stirring reaction is performed at a temperature of 20-30 ℃ for 25-35 min. In certain embodiments, the temperature of the stirred reaction is 25 ℃ for 30 min.
During the stirring reaction, Hexachlorocyclotriphosphazene (HCCP) and 4,4 ' -dihydroxydiphenylsulfone (SPO) are polymerized under the condition of triethylamine to form a poly (cyclotriphosphazene-4, 4 ' -dihydroxydiphenylsulfone) polymer (named PPS, as shown in fig. 1. fig. 1 is a polymerization mechanism diagram of Hexachlorocyclotriphosphazene (HCCP) and 4,4 ' -dihydroxydiphenylsulfone (SPO). under the condition of the polymer PPS, niobium oxide generates niobium pyrophosphate, and the polymer volatilizes and promotes the transformation of the niobium oxide like the niobium pyrophosphate during the calcination process.
In some embodiments of the present invention, after the stirring reaction, the method further comprises:
centrifuging, washing the centrifuged precipitate with methanol, and freeze-drying.
In certain embodiments of the invention, the number of washes with methanol is 3.
In some embodiments of the invention, the freeze-drying time is 10-14 h. In certain embodiments, the freeze-drying time is 12 hours. The freeze-drying is carried out in a freeze-dryer.
The method comprises the step of calcining the freeze-dried precipitate (namely a reaction product) at the temperature of 600-800 ℃ to obtain the niobium salt material.
In certain embodiments of the present invention, prior to the calcining, further comprising:
and heating the reaction product to the calcining temperature at the speed of 1-5 ℃/min.
In certain embodiments of the invention, the rate of temperature increase is 5 deg.C/min, 1 deg.C/min, or 3 deg.C/min, preferably 5 deg.C/min.
In certain embodiments of the invention, the temperature of the calcination is 700 ℃. In certain embodiments of the present invention, the calcination time is 1 to 3 hours. In certain embodiments, the calcination time is 2 hours.
In certain embodiments of the invention, the warming and calcining are both performed under a shielding gas, which may be argon.
The invention also provides a niobium salt material prepared by the preparation method. The niobium salt material prepared by the preparation method is NbP1.8O7/Nb2O5CompoundingMaterials, or NbP1.8O7. The two niobium salt materials can be prepared by changing the dosage of hexachlorocyclotriphosphazene, 4' -dihydroxy diphenyl sulfone and triethylamine.
The invention also provides application of the niobium salt material in preparation of an electrode material of a sodium-ion battery. In particular to the application of the niobium salt material in the preparation of a negative electrode material of a sodium-ion battery.
The invention also provides a preparation method of the sodium-ion battery, which comprises the following steps:
A) mixing a niobium salt material, a conductive agent and a binder, and uniformly mixing an obtained mixed sample with N-methylpyrrolidone to obtain slurry;
the polyanionic compound is a niobium salt material as described above;
B) uniformly coating the slurry on a current collector, and drying in vacuum to obtain an electrode plate;
C) and assembling the electrode plate, the counter electrode sodium plate, the electrolyte and the diaphragm to obtain the sodium-ion battery.
In step A):
in certain embodiments of the present invention, the conductive agent is Super P.
In certain embodiments of the present invention, the binder is polyvinylidene fluoride (PVDF).
In certain embodiments of the present invention, the mass ratio of the polyanionic compound, conductive agent, and binder is 8: 1: 1 or 7: 2: 1.
in certain embodiments of the present invention, the mixing may be a mixed milling in order to mix the niobium salt material, the conductive agent, and the binder.
In certain embodiments of the present invention, mixing the obtained mixed sample with N-methylpyrrolidone comprises:
and dropwise adding N-methyl pyrrolidone into the mixed sample.
The N-methyl pyrrolidone is used as a solvent, and in certain embodiments of the invention, the dosage ratio of the mixed sample to the N-methyl pyrrolidone is 0.4-0.6 g: 0.5-1.5 mL. In certain embodiments, the amount ratio of the mixed sample to N-methylpyrrolidone is 0.5 g: 1 mL.
The blending can be stirring blending.
In step B):
in certain embodiments of the present invention, the current collector is a copper foil.
In some embodiments of the present invention, the temperature of the vacuum drying is 75-85 ℃ and the time is 10-14 h. In certain embodiments, the vacuum drying is at a temperature of 80 ℃ for 12 hours. The vacuum drying is carried out in a vacuum oven.
In some embodiments of the present invention, after the vacuum drying, the method further comprises: and cooling to room temperature.
In some embodiments of the present invention, after cooling to room temperature, the method further comprises: and (6) cutting. A manual sheet punching machine can be adopted for cutting as required. Specifically, the electrode sheet may be cut into a circular piece having a diameter of 12 mm.
In some embodiments of the invention, the electrode sheet is a negative electrode sheet.
In step C):
in certain embodiments of the present invention, the electrolyte comprises NaClO4Solutions and additives; the NaClO4The solvent in the solution comprises Ethylene Carbonate (EC) and diethyl carbonate (DEC), and the volume ratio of the Ethylene Carbonate (EC) to the diethyl carbonate (DEC) is 1: 1. in certain embodiments of the invention, the NaClO4The concentration of the solution is 0.5-1.5 mol/L. In certain embodiments, the NaClO4The concentration of the solution was 1 mol/L. In certain embodiments of the invention, the additive is fluoroethylene carbonate (FEC). In the electrolyte, the mass content of the additive is 4-6 wt%. In certain embodiments, the additive is present in the electrolyte in an amount of 5 wt%.
In certain embodiments of the invention, the membrane is a Whatman GF/A glass fiber membrane.
In certain embodiments of the invention, the assembling is performed in a glove box; in the glove box, the oxygen content is less than 0.1ppm, and the water vapor content is less than 0.1 ppm.
The present invention is not particularly limited to the specific method of assembly, and the assembly method known to those skilled in the art may be used.
In certain embodiments of the invention, the sodium ion battery is a CR2032 button cell battery.
The invention also provides a sodium ion battery prepared by the preparation method.
The source of the above-mentioned raw materials is not particularly limited, and the raw materials may be generally commercially available.
In order to further illustrate the present invention, the following examples are provided to describe the niobium salt material, the preparation method and the application thereof in detail, but the invention should not be construed as being limited to the scope of the present invention.
The starting materials used in the following examples are all commercially available.
Example 1
NbP1.8O7/Nb2O5Preparing a composite material:
1) 1.5g of NbCl5Dispersing in 80mL of mixed solution (solvent comprises ethylene glycol and deionized water, and volume ratio of ethylene glycol to deionized water is 8: 2) containing 2mL of concentrated hydrochloric acid (mass concentration of concentrated hydrochloric acid is 37%), and magnetically stirring at room temperature for 20min to obtain dispersion; then, the dispersion was transferred to an autoclave, subjected to solvothermal reaction for 10 hours in a forced air oven at 140 ℃, and after the reaction was completed, the precipitate was centrifuged, washed alternately 3 times with deionized water and anhydrous ethanol, and dried for 12 hours in a freeze dryer. Weighing 0.15g of dried precipitate, and dispersing in 40mL of methanol under the conditions of ultrasound and stirring to obtain a first solution;
2) dissolving 300mg of Hexachlorocyclotriphosphazene (HCCP) and 400mg of 4, 4' -dihydroxydiphenylsulfone (SPO) in 10mL of methanol to obtain a second solution;
3) after the first solution and the second solution were stirred and mixed for 10min, 1.5mL of triethylamine was added dropwise to the mixed solution using a pipette, and the mixture was stirred and reacted at 25 ℃ for 30 min. Collecting precipitate by centrifugation, washing with methanol for 3 times, and drying in a freeze dryer for 12 hr;
4) in thatUnder the protection of argon, the freeze-dried precipitate is cooled to 5 ℃ for min-1Heating to 700 ℃, and calcining at 700 ℃ for 2h to obtain the niobium salt material niobium pyrophosphate/niobium oxide (NbP)1.8O7/Nb2O5)。
Example 2
NbP1.8O7The preparation of (1):
step 1) same as example 1;
2) dissolving 2g of Hexachlorocyclotriphosphazene (HCCP) and 2.1g of 4, 4' -dihydroxydiphenylsulfone (SPO) in 50mL of methanol to obtain a second solution;
3) and stirring and mixing the first solution and the second solution for 10min, then dropwise adding 7mL of triethylamine into the mixed solution by using a liquid transfer gun, and stirring and reacting for 30min at 25 ℃. Collecting the precipitate by centrifugation, washing with methanol for 3 times, and drying in a freeze dryer for 12 h;
4) under the protection of argon, the freeze-dried precipitate is cooled to 5 ℃ for min-1Heating to 700 ℃, and calcining at 700 ℃ for 2h to obtain niobium pyrophosphate (NbP) as a niobium salt material1.8O7)。
XRD analysis:
the niobium salt materials prepared in examples 1 and 2 were subjected to characterization of crystal structure and analysis of phase using a polycrystalline powder X-ray diffractometer of the MPD type X' Pert PRO, parnacho, the netherlands, and the measured materials were all ground prior to XRD testing.
FIG. 2 is an XRD pattern of the niobium salt materials prepared in examples 1 and 2 of the present invention. Panel a in FIG. 2 is the XRD pattern of the precipitate after drying in step 1) of example 1; as can be seen from FIG. 2, diagram a shows that NbCl5Formation of Nb after hydrothermal treatment2O5Crystal structure and hexagonal system Nb2O5(the spatial group P is a group of spatial groups,
PDF-28-0317). FIG. 2 b shows the Nb salt NbP of example 11.8O7/Nb2O5XRD pattern of (a); as can be seen from FIG. 2, in FIG. b, miscible NbP is obtained by the calcination with the aid of the PPS polymer1.8O7/Nb2O5. FIG. 2C shows the Nb salt NbP of example 21.8O7XRD pattern of (a); as can be seen from FIG. 2, when the amount of PPS polymer is increased, pure-phase NbP is finally obtained1.8O7. To further optimize the properties of the material, only the temperature increase rate of step 4) of example 2 was varied, resulting in a temperature increase of 1 ℃ for min-1，3℃ min-1，5℃ min-1The XRD spectrum of the niobium salt material (NPO-1, NPO-3, NPO-5, respectively, hereinafter all referred to as NPO-1, NPO-3, NPO-5) at the temperature increase rate of (1) is shown in fig. 2, diagram d. FIG. 2, panel d, is an XRD pattern of the material obtained by varying the ramp rate in example 2; as can be seen from fig. 2, at a low temperature rise rate, the crystallinity of the material is better; at a high temperature increase rate, the crystallinity of the material is low, and the material tends to be amorphous. The method is characterized in that the volatilization speeds of the PPS polymer are inconsistent under different heating rates, the volatilization of the PPS polymer is faster under the condition of high heating rate, the rearrangement crystallization behavior among atoms is violent, the crystallinity is gradually reduced, the PPS polymer is converted into an amorphous state, the entropy is increased, and the PPS polymer conforms to the conventional law of thermodynamics.
XPS analysis:
to study NbP1.8O7The chemical valence and the microscopic chemical environment of the Nb element on the surface of the material were analyzed by Escalab 250Xi type X-ray photoelectron spectroscopy of sehmer heishi ltd, usa, and the results are shown in fig. 3. Fig. 3 is a Nb 3d high resolution XPS plot of the material obtained varying the ramp rate in example 2. FIG. 3A is a graph in which the temperature increase rate in example 2 was changed to 1 ℃ for min-1Nb 3d high resolution XPS plot of the resulting material (NPO-1); as can be seen from the graph a in FIG. 3, the high resolution spectrum of the material obtained at this temperature increase rate can be fitted to 3 peaks, and the peaks at 210.49eV and 207.67eV are assigned to Nb 3d of + 5-valent niobium3/2And Nb 3d5/2Furthermore, the peak at 209.61eV is assigned to niobium + 4. FIG. 3 is a view b of a modified example 2The heating rate is 3 ℃ for min-1Nb 3d high resolution XPS plot of the resulting material (NPO-3); as can be seen from the graph b in FIG. 3, the high-resolution spectra of the material obtained at this temperature increase rate can be fit to 4 peaks, and the peaks at 210.6eV and 208.7eV are assigned to Nb 3d of +5 Nb3/2And Nb 3d5/2(ii) a Furthermore, the peaks at 211.33eV and 207.84eV are assigned to Nb 3d of + 4-valent Nb3/2And Nb 3d5/2. FIG. 3 is a graph c showing the temperature increase rate of 5 ℃ for min in example 2-1 Nb 3d high resolution XPS plot of the resulting material (NPO-5); as can be seen from the graph c in FIG. 3, the high-resolution spectra of the material obtained at this temperature increase rate can be fit to 4 peaks, and the peaks at 210.6eV and 208.18eV are assigned to Nb 3d of +5 Nb3/2And Nb 3d5/2(ii) a Furthermore, the peaks at 211.66eV and 207.63eV are assigned to Nb 3d of + 4-valent Nb3/2And Nb 3d5/2. Thus, NbP at three different ramp rates1.8O7The valence states are basically the same, and niobium with +4 valence and +5 valence exists. In addition, NPO-5 contains more + 4-valent Nb than NPO-1, which is probably due to poor crystallinity when the temperature rise rate is high, more crystal defects are generated, and more Nb is reduced to maintain the phase equilibrium in the thermodynamic state.
To confirm NbP1.8O7The chemical valence and the micro-chemical environment of other elements on the surface were analyzed by XPS on NPO-5, as shown in FIG. 4. FIG. 4 is an XPS spectrum of NPO-5 as described above. Panel a in FIG. 4 is an XPS total spectrum of NPO-5; as can be seen from the graph a in fig. 4, the NPO-5 material contains four elements, Nb, P, O, and C, and the atomic contents thereof are 0.48%, 9.13%, 35.99%, and 49.92%, respectively. Panel b in fig. 4 is XPS spectrum of C1 s; as can be seen from panel b in fig. 4, the high resolution profile of C1s can be fit to 3 peaks, C-C (284.8eV), C-O (285.5eV), and C ═ O (287.5eV), respectively. Panel c in figure 4 is the XPS spectrum of P2P; as can be seen from panel c in FIG. 4, the high resolution map of P2P can be fitted to 2 peaks, with peaks at 134.92eV and 134.26eV both ascribed to P-O bonds. Panel d in FIG. 4 is an XPS spectrum of O1 s; as shown in FIG. 4, in the high-resolution map of O1s, it can be seen that the bonding modes of O are P-O-P (133.19eV), P-O-Nb (531.83eV), and C ═O (533.95 eV). This all indicates high purity NbP1.8O7The successful synthesis of the phosphate radical and the strong coordination capacity of the niobium.
SEM analysis:
to observe NbP1.8O7The microstructure and the pore structure of the material are observed by a scanning electron microscope of Japanese Hitachi S4800 model, and are characterized by SEM, as shown in figure 5. FIG. 5 shows NbP obtained at three different ramp rates1.8O7SEM image of (d). In FIG. 5, the first row from top to bottom is an SEM of NPO-1, the second row is an SEM of NPO-3, and the third row is an SEM of NPO-5. It can be seen that as the rate of temperature rise increases, the morphology becomes more porous due to rapid decomposition of the polymer. The loose structure can increase NbP1.8O7The specific surface area of the material enables the electrolyte and the active substance to be better infiltrated, is beneficial to shortening the diffusion distance of sodium ions and improving the specific capacity and the quick charging capacity of the material.
TEM analysis:
to further observe NbP1.8O7The internal micro-topography of the material was observed using a transmission electron microscope of the Japanese Electron JEM-2100UHR model, as shown in FIG. 6. FIG. 6 shows NbP obtained at three different ramp rates1.8O7A TEM image of (a). In FIG. 6, the first row is a TEM image of NPO-1, the second row is a TEM image of NPO-3, and the third row is a TEM image of NPO-5 from top to bottom. As can be seen in FIG. 6, the TEM image substantially corresponds to the SEM image, NbP1.8O7Belongs to micron-sized materials, has smaller specific surface area, and is beneficial to reducing the occurrence of side reactions while meeting the requirement of electrolyte permeation.
And (3) testing a nitrogen adsorption and desorption isothermal curve:
to study NbP1.8O7Specific surface area and porosity characteristics of the material were N-rated using American Michelle instruments ASAP2020 equipment2Adsorption and desorption tests, while NbP was studied1.8O7The pore size distribution of the material is shown in fig. 7. FIG. 7 shows NbP obtained at three different ramp rates1.8O7N of (A)2Adsorption and desorption curves and pore size distribution maps. Panel a of FIG. 7 shows NbP obtained at three different ramp rates1.8O7N of (2)2Adsorption and desorption curves; as can be seen from FIG. 7, a graph a shows that the specific surface area of NPO-1 is 4.6m2 g-1NPO-3 specific surface area of 3.9m2 g-1And the specific surface area of NPO-5 is 7.5m2 g-1. Therefore, when the temperature rise rate is 5 ℃ for min-1Of (2), NbP1.8O7The specific surface area of (a) is the largest. Panel b of FIG. 7 shows NbP obtained at three different ramp rates1.8O7The aperture profile of (a). As can be seen from the graph b in FIG. 7, the interior of the material is of a multi-level pore structure, and compared with the NPO-5, the overall pore structure is richer, so that the permeation of electrolyte is facilitated, the diffusion of sodium ions is accelerated, and the rate capability of the composite material is improved.
Application example 1
Assembling the sodium-ion battery:
1) the NbP of example 11.8O7/Nb2O5The composite material, the Super P and the PVDF binder are mixed according to the mass ratio of 8: 1: 1, fully grinding the mixture until the mixture is uniformly mixed to obtain a mixed sample; dropwise adding N-methylpyrrolidone into the mixed sample (the dosage ratio of the mixed sample to the N-methylpyrrolidone is 0.5 g: 1mL), and uniformly stirring to obtain slurry;
2) uniformly coating the slurry on a copper foil current collector by using a scraper, then putting the copper foil current collector into a vacuum oven, carrying out vacuum drying for 12h at the temperature of 80 ℃, and cutting the copper foil current collector into a wafer with the diameter of 12mm on a manual sheet punching machine to be used as an electrode plate after cooling to the room temperature;
3) the electrode plate is adopted, the sodium plate is taken as a counter electrode, and the electrolyte comprises NaClO4A solution (concentration of 1mol/L, solvent comprising EC and DEC in a volume ratio of 1: 1) and an additive FEC, wherein the additive accounts for 5 wt% of the electrolyte, the diaphragm is a Whatman GF/A glass fiber diaphragm, and the electrolyte is arranged in a glove box (oxygen content)<0.1ppm, water vapor content<0.1ppm) was assembled into a CR2032 button cell 1.
Application example 2
The NbP of example 1 in step 1) of example 1 was applied1.8O7/Nb2O5Composite Material was replaced with NbP of example 21.8O7(NPO-5), and the remaining steps and parameters were carried out as in application example 1 to obtain CR2032 button cell 2.
Application example 3
Will apply the NbP of example 21.8O7(NPO-5) replacement by NbP1.8O7(NPO-1), and the remaining steps and parameters were carried out as in application example 1 to obtain a CR2032 button cell 3.
Application example 4
NbP of application example 21.8O7(NPO-5) replacement by NbP1.8O7(NPO-3), and the remaining steps and parameters were carried out as in application example 1 to obtain a CR2032 button cell 4.
Comparative example 1
The NbP of example 1 in step 1) of example 1 was applied1.8O7/Nb2O5The composite material was replaced with the precipitated Nb from example 1, step 1) after drying2O5And the rest steps and parameters are carried out according to application example 1 to prepare the CR2032 button cell 5.
Testing of electrochemical performance:
the button cell obtained in application examples 1-4 and comparative example 1 was subjected to constant current charge and discharge test in a voltage range of 0.01-3V, and long cycle stability under a large current density was studied, as shown in fig. 8. FIG. 8 shows the results of applying 1000mA g to the button cell obtained in examples 1 to 4 and comparative example 1-1Lower constant current long cycle curve. FIG. 8, panel a, shows the button cell obtained in application examples 1-2 and comparative example 1 at 1000mA g-1A lower constant current long cycle curve; as can be seen from diagram a in FIG. 8, Nb2O5The reversible discharge specific capacity is only 70mAh g after 750 cycles of circulation-1Mixed phase NbP1.8O7/Nb2O5The reversible discharge specific capacity reaches 147mAh g after 750 cycles of circulation-1. In contrast, pure phase NbP1.8O7The reversible discharge specific capacity reaches 204mAh g after 750 cycles of circulation-1Coulombic efficiency close to 100%, indicating pure phase NbP1.8O7Has high specific capacity and stable cycling performance, which is probably due to pure phase NbP1.8O7Has more excellent sodium ion transmission kinetics. FIG. 8, panel b, shows the button cell batteries obtained in application examples 2-4 at 1000mA g-1Constant current long cycle curve, i.e. NbP at the same calcination temperature and different heating rates1.8O7At 1000mA g-1Lower constant current circulation curve; as can be seen from the graph b in FIG. 8, the button cell obtained in application example 3 (NPO-1 corresponding to the graph b in FIG. 8) has a specific reversible discharge capacity of 177.2mAh g after 700 cycles-1Coulomb efficiency approaches 100%; the button cell obtained in application example 4 (corresponding to NPO-3 in the graph b in FIG. 8) reached a reversible specific discharge capacity of 183.7mAh g after 700 cycles-1Coulombic efficiency approaches 100%; the button cell obtained in application example 2 (corresponding to NPO-5 in a graph b in figure 8) has the reversible discharge specific capacity of 206.6mAh g after 700 cycles-1Coulombic efficiency approaches 100%. It can be seen from this that NbP1.8O7Under the same calcining temperature, if the heating rates are different, the specific capacities are different, and the material with high heating rate has better electrochemical performance. This can be attributed to the higher the temperature rise rate (5 ℃ C. min.)-1) The more amorphous the material tends to be. The amorphous structure has isotropy and short-range order, and the long-range disorder shows lower entropy energy when sodium ions are embedded, so that more sodium ions can be embedded.
In view of the optimal long-cycle performance of the button cell obtained in application example 2 in different heating rates, the current cell is subjected to 100mA g-1Next, a constant current cycle test was performed, and the results are shown in FIG. 9. FIG. 9 shows the current of the button cell battery obtained in application example 2 at 100mA g-1A constant current cycle curve and a constant current charge-discharge curve. Fig. 9, panel a, shows the button cell at 100mAg obtained in application example 2-1Lower constant current circulation curve; as can be seen from the graph a in fig. 9, the specific discharge capacity of the button cell obtained in application example 2 after the first cycle is 646.7mAh g-1The coulombic efficiency of the first circle is 41.01 percent, and the specific capacity after 100 cycles is 228.5mAh g-1The capacity retention based on the first charge specific capacity was 86.2%. Good electricityThe chemical properties are mainly attributed to the polyanion NbP1.8O7Has a large framework structure, and isotropically promotes the diffusion kinetics of sodium ions as it tends to an amorphous structure. FIG. 9, panel b shows the button cell obtained in application example 2 at 100mA g-1Constant current charge and discharge curve. As can be seen from the graph b in FIG. 9, the button cell obtained in application example 2 was operated at 100mA g-1The first discharge and charge specific capacities of the constant-current charge-discharge curves of the lower three previous circles are 646.7mAh g respectively-1And 265.2mAh g-1. The initial slightly lower coulombic efficiency was due to decomposition of the electrolyte to form a Solid Electrolyte Interface (SEI), and then after three cycles, the coulombic efficiency gradually increased to over 90% because irreversible decomposition of the electrolyte was relieved and the active materials in the electrode were gradually activated.
Since the button cell obtained in application example 2 has excellent long-cycle properties at low current density, it was studied again at 0.1A g-1、0.2A g-1、0.5A g-1、1A g-1、2A g-1、3A g-1And 4A g-1The rate capability of the following test results are shown in fig. 10. Fig. 10 is a rate performance curve and a capacity-voltage curve of the button cell obtained in application example 2. The graph a in fig. 10 is the rate performance curve of the button cell obtained in application example 2, and it can be seen from the graph a in fig. 10 that the current density is from 0.1Ag-1To 4A g-1In the variation (2), the average specific charge-discharge capacities thereof are 320.2, 275.6, 230.6, 186.8, 143.1, 120.1 and 105.3mAh g, respectively-1. When the temperature is restored to 0.1A g-1The average charge-discharge specific capacity can reach 298.9mAh g when the current density is high-1. This indicates that the NPO-5 material has good reversibility during sodium intercalation and sodium deintercalation. The graph b in fig. 10 is a capacity-voltage curve of the button cell obtained in application example 2 under different current densities, and as can be seen from the graph b in fig. 10, the capacity-voltage curve is consistent with the rate performance, and meanwhile, the electrochemical polarization of the composite material is small under different rates.
The button cell obtained in application example 2 was also studied because of its excellent rate capabilityThe long cycling stability at current density is shown in fig. 11. Fig. 11 is a constant current cycle curve of the button cell obtained in application example 2 at high current density. FIG. 11A is a graph of the button cell battery obtained in application example 2 at 1000mA g-1Lower constant current circulation curve; as can be seen from the graph a in fig. 11, the specific discharge capacity and the specific charge capacity of the button cell obtained in application example 2 in the first cycle are respectively 301.6mAh g-1And 144.5mAh g-1The first turn coulombic efficiency was 47.9%. The reversible discharge specific capacity can reach 164.6mAh g after 5000 cycles-1The coulombic efficiency is close to 100%, which shows that NPO-5 has excellent long-cycle performance. FIG. 11, panel b, shows the button cell obtained in application example 2 at 2000mA g-1Lower constant current circulation curve; the button cell obtained in application example 2 was first charged at 100mA g-1The first discharge capacity and the first charge specific capacity of the activated carbon are 489mAh g respectively-1And 216.5mAh g-1The first turn coulombic efficiency was 44.27%. At 2000mA g-1101.37mAh g still remained after 5000 cycles of circulation at the current density-1The high reversible specific capacity of the composite material indicates the research on the quick charging performance of the composite material.
To study NbP1.8O7The specific electrochemical sodium storage mechanism of the electrode was tested in CV at 0.2mV s for the button cell obtained in example 2-1The scanning rate and the cyclic voltammetry curve of the button cell obtained in application example 2 measured under a voltage window of 0.01-3V are shown in fig. 12. Fig. 12 is a cyclic voltammogram of the button cell obtained in application example 2. As can be seen from fig. 12, a broad peak appears at around 1V during the first discharge, disappearing in the following cycles, due to decomposition of the organic electrolyte and formation of the SEI film. In the following second and third scans, no significant oxidation peaks occurred, probably due to the rapid sodium-removal reaction of the sodium ions at the surface of the negative electrode material. In addition, the two cyclic curves almost completely overlap, indicating that NbP1.8O7The electrode (NPO-5) has high reversibility of sodium storage.
To study NbP1.8O7Dynamic behavior of electrodes, to applicationsThe button cell obtained in example 2 has a charge of 0.2-12 mV s-1Next, CV tests at different scan rates were performed as shown in fig. 13. Fig. 13 is a CV curve of the button cell obtained in application example 2 of the present invention at different scanning rates. Fig. 14 is a curve of b value as a function of voltage for button cells obtained in application example 2 of the present invention at different voltages. As can be seen from FIG. 14, the b value is between 0.4 and 1, which indicates that the sodium storage mechanism of the NPO-5 material is controlled by the diffusion and the pseudocapacitance. FIG. 15 is 8mV s-1The pseudocapacitance curve and the original CV curve were subjected to area integration using the original CV curve (blue region) and the fitted pseudocapacitance curve (red region), respectively, and the pseudocapacitance contribution was calculated to be 45.6% by area ratio, as shown in fig. 16. Figure 16 is a graph of pseudocapacitance contributions from button cells obtained in example 2 of the present invention at different scan rates. As can be seen from FIG. 16, the general trend is to increase from 0.2 to 12mV s with the scan rate-1The pseudocapacitance contribution gradually increased from 16.5% to 56.4%. At 8mV s-1At the following scan rates, the contribution of pseudocapacitance is small, which is indicated at 8mV s-1The following scan rates are primarily diffusion-controlled sodium storage mechanisms; when increasing to 12mV s-1At a scanning rate of (3), the contribution of the pseudocapacitance can reach 56.4%, which indicates that the NPO-5 material is mainly a sodium storage mechanism controlled by the pseudocapacitance at a large scanning rate.
And (3) testing alternating current impedance:
to compare the reaction kinetics of the electrode materials, an ac impedance test was performed. Fig. 17 is an ac impedance graph of the button cells obtained in application examples 1 to 4 and comparative example 1 after 30 cycles. FIG. 17A is an AC impedance diagram of the button cell obtained by applying examples 1-2 and comparative example 1 after 30 cycles; from graph a in fig. 17, the semi-circle of the high frequency region of the curve represents the charge transfer resistance at the electrolyte/cathode interface; the straight line of the curve low-frequency region represents the resistance of sodium ions diffusing into the electrode material body phase; nb2O5，NbP1.8O7/Nb2O5And NbP1.8O7The impedance values of the electrodes decreased in order, indicating NbP1.8O7The electronic conductivity of the material is the highest, which is opposite to the excellent rate capabilityShould be used. Fig. 17 b is an ac impedance diagram of the button cell obtained in application examples 2 to 4 after 30 cycles; as can be seen from the graph b in FIG. 17, the impedance values of the NPO-1, NPO-3 and NPO-5 electrodes decrease in sequence, indicating that the electronic conductivity of NPO-5 is higher, which may be attributed to the higher degree of graphitization and better conductivity of the carbon material in the composite material at high temperature-rising rates. The crystallinity becomes lower at a high temperature rising rate, and the material forms a special diffusion path in a low-crystallization state, which is beneficial to promoting the rapid diffusion of sodium ions.
To further understand NbP1.8O7The diffusion rate of sodium ions in the material was evaluated by GITT for NPO-5 material. Fig. 18 shows the charging and discharging curves and the corresponding sodium ion diffusion coefficients of the GITT test of the button cell obtained in application example 2 in the third and fourth circles. As can be seen from FIG. 18, the NPO-5 electrode exhibited a diffusion coefficient variation range of 5.1X 10 during the third discharge-8cm2 s-1To 2.1X 10-6cm2 s-1(ii) a The diffusion coefficient of the NPO-5 electrode in the third charging process is varied in a range of 1.5X 10-8cm2 s-1To 2.4X 10-7cm2 s-1(ii) a The diffusion coefficient of the NPO-5 electrode in the fourth discharge process is changed in a range of 3.4 x 10-8cm2 s-1To 2.0X 10-6cm2 s-1(ii) a In the fourth charging process, the diffusion coefficient of the NPO-5 electrode is changed in a range of 1.7 x 10-8cm2 s-1To 1.7X 10-7cm2 s-1. As described above, the NPO-5 electrode has a high sodium ion diffusion coefficient. The special diffusion channels towards amorphous materials and the large framework structure of phosphate may promote the rapid diffusion of sodium ions. The high sodium ion diffusion coefficient ensures that the NPO-5 electrode has excellent rate capability and long cycle performance.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of a niobium salt material comprises the following steps:
a) stirring the first solution, the second solution and triethylamine for reaction to obtain a reaction product;
the first solution was prepared as follows:
reacting NbCl5Uniformly mixing the solution with a hydrochloric acid mixed solution, carrying out solvothermal reaction on the obtained dispersion at 130-150 ℃, and mixing the precipitate obtained by the reaction with methanol to obtain a first solution;
the second solution was prepared as follows:
mixing hexachlorocyclotriphosphazene, 4' -dihydroxy diphenyl sulfone and methanol to obtain a second solution;
b) and calcining the reaction product at 600-800 ℃ to obtain the niobium salt material.
2. The method according to claim 1, wherein the hydrochloric acid mixture comprises hydrochloric acid, ethylene glycol, and deionized water;
in the hydrochloric acid mixed solution, the volume content of hydrochloric acid is 2-3%;
the volume ratio of the ethylene glycol to the deionized water is 7-9: 1 to 3.
3. The preparation method according to claim 1, wherein the solvothermal reaction time is 8-12 h;
after the solvothermal reaction, the method further comprises the following steps:
centrifuging, washing the centrifuged precipitate with deionized water and anhydrous ethanol alternately, and freeze-drying.
4. The method according to claim 1, wherein the first solution is prepared such that the ratio of the amount of the precipitate to methanol is 0.1 to 0.2 g: 30-50 mL.
5. The preparation method according to claim 1, wherein the mass ratio of hexachlorocyclotriphosphazene to 4, 4' -dihydroxydiphenylsulfone is 2-4: 2-4;
in the preparation of the second solution, the ratio of the mass sum of hexachlorocyclotriphosphazene and 4, 4' -dihydroxydiphenylsulfone to the amount of methanol is 0.66-0.74 g: 5-15 mL or 3.5-4.5 g: 40-60 mL.
6. The method according to claim 1, wherein the ratio of the sum of the masses of hexachlorocyclotriphosphazene and 4, 4' -dihydroxydiphenylsulfone to the mass of precipitate taken from the first solution is 0.66 to 0.74: 0.1 to 0.2 or 3.5 to 4.5: 0.1 to 0.2;
the mass ratio of the sum of the hexachlorocyclotriphosphazene and 4, 4' -dihydroxy diphenyl sulfone to the triethylamine is 0.66-0.74 g: 1-2 mL or 3.5-4.5 g: 6-8 mL;
after the first solution, the second solution and triethylamine are stirred to react, the method further comprises the following steps:
centrifuging, washing the centrifuged precipitate with methanol, and freeze-drying.
7. A niobium salt material obtained by the production method according to any one of claims 1 to 6.
8. Use of the niobium salt material of claim 7 in the preparation of a sodium ion battery electrode material.
9. A preparation method of a sodium ion battery comprises the following steps:
A) mixing a niobium salt material, a conductive agent and a binder, and uniformly mixing an obtained mixed sample with N-methylpyrrolidone to obtain slurry;
the polyanionic compound is the niobium salt material of claim 7;
B) uniformly coating the slurry on a current collector, and drying in vacuum to obtain an electrode plate;
C) and assembling the electrode plate, the counter electrode sodium plate, the electrolyte and the diaphragm to obtain the sodium-ion battery.
10. The sodium ion battery prepared by the preparation method of claim 9.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107925075A (en) * | 2015-08-20 | 2018-04-17 | 日本电气硝子株式会社 | Negative electrode active material for electricity storage device |
| CN109698326A (en) * | 2017-10-23 | 2019-04-30 | 中国石油大学(华东) | A kind of organic phosphorization tin/oxidized graphite composite material for sodium-ion battery cathode |
| CN110190270A (en) * | 2019-06-28 | 2019-08-30 | 中国石油大学(华东) | A kind of preparation method and its performance test methods of the titanium composite material for sodium ions to potassium ions battery cathode |
| CN111082040A (en) * | 2019-12-19 | 2020-04-28 | 上海交通大学 | Core-shell structure T-Nb2O5Preparation method and application of @ C composite material |
| CN111470535A (en) * | 2020-04-17 | 2020-07-31 | 扬州大学 | Niobium pentoxide yolk structure nano material with controllable core volume and preparation method thereof |
| CN111717902A (en) * | 2020-05-08 | 2020-09-29 | 中山大学 | Nitrogen, phosphorus and sulfur co-doped porous carbon loaded metal phosphide nano composite material and preparation method and application thereof |
-
2022
- 2022-03-24 CN CN202210294369.2A patent/CN114735750B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107925075A (en) * | 2015-08-20 | 2018-04-17 | 日本电气硝子株式会社 | Negative electrode active material for electricity storage device |
| CN109698326A (en) * | 2017-10-23 | 2019-04-30 | 中国石油大学(华东) | A kind of organic phosphorization tin/oxidized graphite composite material for sodium-ion battery cathode |
| CN110190270A (en) * | 2019-06-28 | 2019-08-30 | 中国石油大学(华东) | A kind of preparation method and its performance test methods of the titanium composite material for sodium ions to potassium ions battery cathode |
| CN111082040A (en) * | 2019-12-19 | 2020-04-28 | 上海交通大学 | Core-shell structure T-Nb2O5Preparation method and application of @ C composite material |
| CN111470535A (en) * | 2020-04-17 | 2020-07-31 | 扬州大学 | Niobium pentoxide yolk structure nano material with controllable core volume and preparation method thereof |
| CN111717902A (en) * | 2020-05-08 | 2020-09-29 | 中山大学 | Nitrogen, phosphorus and sulfur co-doped porous carbon loaded metal phosphide nano composite material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| ZHONGTAO LI ET AL.: "Controllably Enriched Oxygen Vacancies through Polymer Assistance in Titanium Pyrophosphate as a Super Anode for Na/K-Ion Batteries", ACS NANO, vol. 13, pages 9227 * |
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