CN113422032A - Negative electrode material NiSe of sodium ion battery2Preparation method and application of @ C microspheres - Google Patents
Negative electrode material NiSe of sodium ion battery2Preparation method and application of @ C microspheres Download PDFInfo
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- CN113422032A CN113422032A CN202110752560.2A CN202110752560A CN113422032A CN 113422032 A CN113422032 A CN 113422032A CN 202110752560 A CN202110752560 A CN 202110752560A CN 113422032 A CN113422032 A CN 113422032A
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- ion battery
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- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 45
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 38
- 239000004005 microsphere Substances 0.000 title abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 46
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000011259 mixed solution Substances 0.000 claims abstract description 33
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 25
- 239000011669 selenium Substances 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 18
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 150000007524 organic acids Chemical class 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010406 cathode material Substances 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 3
- 238000007789 sealing Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- 238000001035 drying Methods 0.000 claims description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- 239000000047 product Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 23
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 16
- 239000012265 solid product Substances 0.000 claims description 12
- 239000008139 complexing agent Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000011889 copper foil Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 24
- 238000007599 discharging Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000012621 metal-organic framework Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 238000004146 energy storage Methods 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 230000002441 reversible effect Effects 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 230000002427 irreversible effect Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000013099 nickel-based metal-organic framework Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000013132 MOF-5 Substances 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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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- 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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Abstract
The invention provides a preparation method of a negative electrode material in a sodium ion battery, which comprises the following steps: dissolving a nickel source, organic acid and polyvinylpyrrolidone in the mixed solution, sealing, carrying out hydrothermal reaction, and centrifuging to obtain a metal organic framework material; then, the mixture is mixed with selenium powder by a simple one-step method and then sintered in a weak reducing atmosphere to obtain NiSe with selenium vacancy2@ C composite material. The prepared material is hollow microspheres formed by particles with the particle size of 50-200 nm, and the diameter of the microspheres is 1.3-2.5 mu m. The carbon skeleton can improve the conductivity of the materialThe hollow microspheres can relieve volume expansion in the charging and discharging process. The method for synthesizing the material is simple, energy-saving and time-saving, the product purity is high, the material source is wide, the price is low, the mixed solution used in the synthesis process can be repeatedly utilized for many times, the requirements of low cost and environmental protection of the sodium ion battery cathode material are met, and the material shows higher rate performance and better cycle stability when being used as the sodium ion battery cathode material.
Description
Technical Field
The invention belongs to the technical field of chemical power sources, and particularly relates to a preparation method and application of a sodium-ion battery cathode material.
Background
The current renewable energy sources such as solar energy, wind energy, tidal energy and the like draw more and more attention of researchers due to the advantages of environmental friendliness, wide distribution range, continuous renewable and the like. However, the new energy source is limited by natural factors such as uneven distribution and strong weather dependence while having the above advantages, so that an energy storage link with higher energy conversion efficiency and high stability needs to be added between the links of energy production and energy consumption and utilization. On the other hand, most products have good compatibility with electric power energy, so that the global scale of a power grid and the supply of electric power are increased year by year, and a large-scale power grid energy storage system needs to be established for more effectively utilizing the generated electric energy and realizing peak shifting operation of the power grid. The energy storage system has multiple types such as mechanical energy storage, electromagnetic energy storage, phase change energy storage, chemical energy storage and the like according to different energy storage modes, wherein the electrochemical energy storage is the energy storage mode with the highest expandability and working environment friendliness. In addition, electrochemical energy storage, particularly lithium ion batteries with higher energy density than lead acid batteries, has rapidly evolved due to the rapid spread of the early 3C products (computer, communications, consumer electronics). With the technology becoming more mature at present, the cost gap between the lithium ion battery and the traditional battery systems such as lead-acid batteries is gradually closed, and the installation scale of the lithium ion battery is also rapidly increased. Through the development expectation of the power battery in the future, the rapid popularization of the current electric vehicles can drive the demand of the power battery to be further increased. However, the problems of cost increase of raw materials, reduction of exploitable lithium resources and the like all bring new challenges to the lithium ion battery system, and a novel battery system with lower cost, more abundant raw materials and high enough energy density is urgently needed at present.
Sodium is one of the most abundant elements in the earth crust, the distribution of the sodium is wider, and the exploitation cost is low enough; the sodium ions do not form alloy with the aluminum current collector in the process of charging and discharging, so the negative current collector can adopt aluminum materials to further reduce the cost and the weight of the battery. The above factors make sodium ion batteries possible for alternative lithium ion battery applications. In addition, the atomic weight and the ionic radius of sodium in alkali metal are second to those of lithium, sodium element and lithium element have similar physicochemical properties, and a plurality of mechanisms which are proved in lithium ion batteries can be applied to a sodium ion battery system; sodium ion batteries are allowed to discharge to zero volts due to their no over-discharge characteristics in order to provide higher energy densities. The above advantages make sodium ion batteries a strong competitor for lithium ion batteries. The sodium ion battery mainly comprises a positive electrode material, a negative electrode material, a diaphragm, electrolyte, a battery shell and the like, wherein the negative electrode material is widely concerned by researchers as one of the current main research directions. At present, research on negative electrode materials mainly focuses on materials based on reaction mechanisms such as intercalation reaction, alloying reaction and conversion reaction, wherein the negative electrode materials based on the conversion reaction mechanism mainly comprise metal oxides, sulfides, phosphides and the like, the materials realize energy storage through valence change in the charging and discharging processes, and the materials have the advantages of high specific capacity caused by multi-electron reaction and the disadvantages of low conductivity, large volume expansion and poor cycle stability and rate capability of the materials.
Because of phase-pure NiSe2The crystal can cause material pulverization due to large volume change in the charge and discharge processes, so that the loss of reactive active substances is caused, and the reversible capacity of the material is reduced in the circulation process; lower electronic conductivity limited materialRate capability of the material. Therefore, the development of a novel negative electrode material with long service life, high energy density and high safety is the central importance of the development of sodium ion batteries. Aiming at the problems, the invention provides a negative electrode material NiSe for a sodium-ion battery2A process for the preparation of @ C.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made keeping in mind the above problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a negative electrode material NiSe for a sodium-ion battery2A process for the preparation of @ C.
To solve the above technical problem, according to an aspect of the present invention, the present invention provides the following technical solutions: NiSe serving as negative electrode material of sodium-ion battery2A method of preparing @ C, comprising:
dissolving a nickel source, a complexing agent and a dispersing agent in a mixed solvent, uniformly stirring, sealing, carrying out hydrothermal reaction, taking out a solid-liquid mixture, centrifuging to obtain a solid product, washing with ethanol, and drying.
Mixing the dried sample with selenium powder, sintering in the atmosphere, taking out and cooling to obtain NiSe2@ C composite material.
NiSe serving as the negative electrode material of the sodium-ion battery2A preferred embodiment of the process for the preparation of @ C, wherein: the nickel source comprises one or more of nickel sulfate, nickel acetate and nickel nitrate; the complexing agent is organic acid and comprises one or more of trimesic acid, isophthalic acid, phthalic acid and terephthalic acid; the dispersing agent is polyvinylpyrrolidone.
The negative electrode material of the sodium-ion batteryNiSe material2A preferred embodiment of the process for the preparation of @ C, wherein: the method comprises the steps of dissolving a nickel source, a complexing agent and a dispersing agent, wherein the nickel source, the complexing agent and the dispersing agent comprise, by mass, 10-45% of the nickel source, 3-50% of the complexing agent and 10-80% of the dispersing agent
NiSe serving as the negative electrode material of the sodium-ion battery2A preferred embodiment of the process for the preparation of @ C, wherein: the mixed solvent is a mixed solution of water, ethanol and N, N-dimethylformamide, and the mixing ratio of the mixed solvent is 1: 1:1, the concentration of the prepared nickel nitrate mixed solution is 0.05 mol/L.
NiSe serving as the negative electrode material of the sodium-ion battery2A preferred embodiment of the process for the preparation of @ C, wherein: the stirring is uniform, wherein the stirring mode is one or more of manual stirring, magnetic stirring and mechanical stirring, and the stirring time is 3-6 h.
NiSe serving as the negative electrode material of the sodium-ion battery2A preferred embodiment of the process for the preparation of @ C, wherein: the hydrothermal reaction is carried out, wherein the reaction temperature is 120-180 ℃, and the reaction time is 3-42 h.
NiSe serving as the negative electrode material of the sodium-ion battery2A preferred embodiment of the process for the preparation of @ C, wherein: washing and drying, wherein the washing mode is that ethanol is mixed and then centrifugally separated, the volume ratio of the ethanol to the original mixed solution is 1: 6-1: 3, and the washing times are 3-5 times; and drying at the drying temperature of 50-100 ℃ for 10 h.
NiSe serving as the negative electrode material of the sodium-ion battery2A preferred embodiment of the process for the preparation of @ C, wherein: and mixing the sample with selenium powder, wherein the molar ratio of the nickel source to the selenium source is 1: 3-1: 5. The mixing mode is one or more of manual grinding, mechanical ball milling and mechanical stirring, and the mixing time is 0.5-24 h.
NiSe serving as the negative electrode material of the sodium-ion battery2A preferred embodiment of the process for the preparation of @ C, wherein: the sintering is carried out under an atmosphere, wherein the atmosphere is a reducing atmosphere, and the atmosphere comprises but is not limited to hydrogen and argon mixed gas; the above-mentionedAnd sintering, wherein the heating rate is 1-20 ℃/min, the sintering temperature is 100-1200 ℃, and the sintering time is 1-72 h.
NiSe serving as the negative electrode material of the sodium-ion battery2The product obtained by the preparation method of @ C, wherein: the use of said composition, comprising,
mixing NiSe2Uniformly mixing the material of @ C, a conductive agent and a binder to form slurry, coating the slurry on a copper foil, and then drying the copper foil in an oven at 80 ℃ for 12 hours to obtain the negative electrode material of the sodium-ion battery; wherein,
the conductive agent comprises acetylene black;
the binder comprises sodium carboxymethylcellulose;
wherein, by mass percentage, comprises NiSe250-95% of @ C material, 8-25% of conductive agent and 5-15% of binder.
The invention has the beneficial effects that:
(1) the invention mainly provides a negative electrode material NiSe for a sodium ion battery2The @ C microsphere and the preparation method have the advantages that the material is uniform in appearance, the particle size is 50-200 nm, the crystallinity is good, and the diameter of the formed microsphere is 1.3-2.5 mu m; the electrochemical performance is excellent, the initial specific capacity is higher, the rate capability is excellent, and compared with the prior material or technology, the method has the advantages of simple synthesis method, uniform product appearance and generated NiSe2The @ C material has the advantages of less energy consumption source, high material purity and the like, and meets the requirements of high specific capacity, low cost, environmental protection and the like of the negative electrode material of the sodium-ion battery.
(2) NiSe prepared by the invention2@ C412 mAhg for the negative electrode material of sodium-ion battery-1The specific discharge capacity of the first circle is 206.6mAhg when the first circle is circulated for 100, 150 and 200 circles under the current density of 500mA/g-1、209.7mAhg-1And 215.7mAhg-1The material has a stable reversible capacity starting at 100 cycles; and comparative pure phase NiSe2937mAhg of the first turn-1The discharge specific capacity is mainly due to irreversible capacity generated by a large amount of SEI films in the initial charge-discharge process, and the discharge ratio of the SEI films under the same conditions and the same turnsThe capacities were 160.6, 151.1 and 147.0mAhg, respectively-1Starting after 100 cycles with a stable reversible capacity of less than 160mAhg-1. NiSe finally prepared by using the method2@ C vs. pure phase NiSe2The method reduces a large amount of irreversible capacity and electrolyte consumption generated by a large amount of SEI films in the early circulation process, and improves the circulation reversible capacity of the material.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 shows NiSe obtained in example 12XRD pattern of the @ C material.
FIG. 2 shows NiSe obtained in example 12Raman plots of the @ C material.
FIG. 3 shows NiSe obtained in example 12XPS plot of the @ C material.
FIG. 4 shows NiSe obtained in example 12SEM image of @ C material.
FIG. 5 shows NiSe obtained in example 12Charge-discharge curves for the @ C material.
FIG. 6 shows NiSe obtained in example 12Graph of rate capability for @ C material.
FIG. 7 is a graph of rate performance of button cells prepared in example 1 at different current densities
FIG. 8 is an XRD pattern of Ni-MOF-1 and selenium powder preparation products with different molar ratios.
FIG. 9 is an SEM image of Ni-MOF prepared at different ethanol addition levels.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Scanning the prepared material by using an SEM (scanning electron microscope) to observe the appearance.
The electrochemical performance test method adopted by the invention comprises the following steps:
NiSe synthesized by the method of the invention2Uniformly mixing the @ C negative electrode material, acetylene black and sodium hydroxymethyl cellulose in a mass ratio of 70:20:10, coating the mixture on a copper foil, drying the mixture, pressing the dried mixture into a wafer with the diameter of 14mm, and drying the wafer in a forced air oven at 80 ℃ for 8 hours to obtain the sodium-ion battery negative electrode material.
Sodium ion batteries are prepared by means conventional in the art. Using metallic sodium as counter electrode, adding NaCF3SO3Dissolving the solution in a diglyme solution to form a solution with the concentration of 1mol/L as an electrolyte; and assembling the button cell in a glove box protected by argon atmosphere. Adopting a BST-5V type Newcastle (NEWARE) battery tester to carry out electrochemical performance test, wherein the charge-discharge voltage range is 0.3V-3.0V (vs. Na)+Na), the test temperature was 25 ℃.
Example 1:
preparing a mixed solution by taking 20mL of deionized water, 20mL of ethanol and 20mL of N, N-Dimethylformamide (DMF), and magnetically stirring for 5 min; 0.864gNi (NO) in turn3)2·6H2Dissolving 0.300g of trimesic acid and 3.000g of polyvinylpyrrolidone (PVP) in the mixed solution, and stirring for 3 hours until the solution is clear; then transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction for 10 hours at 150 ℃, cooling and passing throughCentrifuging to obtain a solid product, washing and drying the solid product by ethanol, and finally drying the solid product in a drying oven at 80 ℃ for 10 hours to obtain the product Ni-MOF-1.
0.4420gNi-MOF-1 and 0.6236g selenium powder were mixed and ground for 30min, and then transferred to a tube furnace under hydrogen argon (H) gas 25%) at a rate of 5 ℃/min to 400 ℃ and held for 4h, the final product obtained being recorded as NiSe2@C-1。
Comparative example 1:
preparing a mixed solution by taking 20mL of deionized water, 20mL of ethanol and 20mL of N, N-Dimethylformamide (DMF), and magnetically stirring for 5 min; 0.864gNi (NO) in turn3)2·6H2Dissolving 0.300g of trimesic acid and 3.000g of polyvinylpyrrolidone (PVP) in the mixed solution, and stirring for 3 hours until the solution is clear; and then transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction for 10h at 150 ℃, cooling, centrifuging to obtain a solid product, washing and drying by using ethanol, and finally drying in a drying oven at 80 ℃ for 10h to obtain a product Ni-MOF-1.
Heating 0.4420gNi-MOF-1 to 500 deg.C at a heating rate of 5 deg.C/min in a muffle furnace under air atmosphere, maintaining for 10min, mixing the product with 0.6236g selenium powder, grinding for 30min, transferring into a tube furnace, and mixing with hydrogen and argon (H)25%) was heated to 400 ℃ at a heating rate of 5 ℃/min and held for 4 h. The product NiSe2-1 is obtained in a pure phase.
Example 2:
preparing a mixed solution from 40mL of N, N-dimethylformamide and 40mL of acetone, and mixing 0.2326gNi (NO)3)2·6H2Adding O and 0.1330g of isophthalic acid into the mixed solution in sequence and stirring for 6 hours until the solution is clear; then transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction for 4h at 160 ℃, cooling, centrifuging to obtain a solid product, washing and drying with ethanol, and finally drying in a drying oven at 80 ℃ for 10h to obtain a product Ni-MOF-2;
0.2574gNi-MOF-2 and 0.3124g selenium powder were mixed and ground for 30min, and then transferred to a tube furnace under hydrogen argon (H) gas 25%) at 5 deg.c/min under an atmosphereThe temperature is raised to 400 ℃ at the temperature raising rate and is kept for 4 hours, and the obtained final product is recorded as NiSe2@C-2；。
Example 3:
preparing a mixed solution from 40mL of N, N-dimethylformamide and 40mL of acetone, and mixing 0.2326gNi (NO)3)2·6H2O and 0.1330g of terephthalic acid are sequentially added into the mixed solution and stirred for 6 hours until the solution is clear; then transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction for 4h at 160 ℃, cooling, centrifuging to obtain a solid product, washing and drying with ethanol, and finally drying in a drying oven at 80 ℃ for 10h to obtain a product Ni-MOF-3;
0.2574gNi-MOF-3 and 0.3124g selenium powder were mixed and ground for 30min, and then transferred to a tube furnace under hydrogen argon (H) gas 25%) at a rate of 5 ℃/min to 400 ℃ and held for 4h, the final product obtained being recorded as NiSe2@C-3。
Example 4:
preparing a mixed solution by taking 20mL of deionized water, 20mL of ethanol and 20mL of N-Dimethylformamide (DMF), and magnetically stirring for 5 min; 0.864gNi (NO) in turn3)2·6H2Dissolving 0.300g of trimesic acid and 3.000g of polyvinylpyrrolidone (PVP) in the mixed solution, and stirring for 3 hours until the solution is clear; and then transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction at 150 ℃ for 30h, cooling, centrifuging to obtain a solid product, washing and drying by using ethanol, and finally drying in a drying oven at 80 ℃ for 10h to obtain a product Ni-MOF-4.
0.4420gNi-MOF-4 and 0.6236g selenium powder were mixed and ground for 30min, and then transferred to a tube furnace under hydrogen argon (H) gas 25%) at a rate of 5 ℃/min to 400 ℃ and held for 4h, the final product obtained being recorded as NiSe2@C-4。
Example 5:
preparing a mixed solution by taking 20mL of deionized water, 20mL of ethanol and 20mL of N-Dimethylformamide (DMF), and magnetically stirring for 5 min; 0.7465gNi (CH)3COO)2·4H2O, 0.300g of trimesic acid and 3.000g of polyethyleneDissolving pyrrolidone (PVP) in the mixed solution, and stirring for 3h until the solution is clear; and then transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction for 10h at 150 ℃, cooling, centrifuging to obtain a solid product, washing and drying by using ethanol, and finally drying in a drying oven at 80 ℃ for 10h to obtain a product Ni-MOF-5.
0.2574gNi-MOF-5 and 0.3124g selenium powder were mixed and ground for 30min, and then transferred to a tube furnace under hydrogen argon (H) gas 25%) at a rate of 5 ℃/min to 400 ℃ and held for 4h, the final product obtained being recorded as NiSe2@C-5。
Example 6:
preparing a mixed solution by taking 20mL of deionized water, 20mL of ethanol and 20mL of N-Dimethylformamide (DMF), and magnetically stirring for 5 min; taking Ni (CH) in sequence3COO)2·4H2Dissolving O, trimesic acid and 3.000g of polyvinylpyrrolidone (PVP) in the mixed solution, and stirring for 3h until the solution is clear; and then transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction at 150 ℃ for 10h, cooling, centrifuging to obtain a solid product, washing and drying by using ethanol, and finally drying in a drying oven at 80 ℃ for 10h to obtain the product. The amounts of the nickel source and trimesic acid added are shown in table 1.
TABLE 1 addition amounts of nickel source and trimesic acid
The yield of the Ni-MOFs obtained by the molar ratio of the nickel source to the organic acid is the highest at 2.1: 1.
Example 7
Deionized water, ethanol and N, N-Dimethylformamide (DMF) are taken to prepare a mixed solution. Wherein the volume ratio of the deionized water to the N, N-dimethylformamide is 1:1, the volume ratio of the added amount of the ethanol is 0 percent20%, 30%, 40%. Magnetically stirring for 5 min; 0.864gNi (NO) in turn3)2·6H2Dissolving 0.300g of trimesic acid and 3.000g of polyvinylpyrrolidone (PVP) in the mixed solution, and stirring for 3 hours until the solution is clear; and then transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction at 150 ℃ for 10h, cooling, centrifuging to obtain a solid product, washing and drying by using ethanol, and finally drying in a drying oven at 80 ℃ for 10h to obtain four products. And performing SEM electron microscopy characterization on the product. The results are shown in FIG. 8.
Example 8
Respectively taking the molar ratio of 1: 2.1: 3. 1: 4. 1:5 Ni-MOF-1 and selenium powder were mixed and ground for 30min, and then transferred to a tube furnace under hydrogen argon (H) gas 25%) to 400 ℃ at a heating rate of 5 ℃/min and maintaining the temperature for 4h to obtain the final product. And XRD characterization was performed on the four products. As shown in fig. 9.
In the synthesis process of Ni-MOFs, different organic acids are selected to influence the growth orientation and unit structure of the metal organic framework material, so that the metal organic framework materials with different pore size distributions and specific surface areas are generated, the irreversible loss of active substances caused by material pulverization of the materials in the charging and discharging processes is relieved to different degrees, and the higher specific surface area obviously improves the rate capability of the materials.
Example 1a microsphere shell structure with a columnar interior is formed; example 2a multi-shell layer was formed; example 3 a spherical polyhedral structure was formed; example 4 formed a radial microsphere structure and example 5a microsphere structure. Electrochemical tests were carried out for examples 1 to 5, and the test results are shown in Table 2. The microsphere shell structure synthesized in example 1 has more uniform size distribution, so the NiSe is obtained2The @ C cycle stability is more excellent.
TABLE 2 results of electrochemical test of examples 1 to 5
FIG. 1 shows the NiSe obtained2The XRD pattern of @ C shows the diffraction pattern of the material and NiSe2The standard cards are completely matched, the crystallinity of the material is higher, and the NiSe is not influenced by the in-situ coating of the carbon2The crystal structure of (1). NiSe in material prepared by the method2Belong to
Space group, cubic system (PDF No. 65-5016).
The Raman test results in FIG. 2 demonstrate the presence of carbon material at 1380cm-1And 1561cm -1 shows a D peak and a G peak of the carbon material, respectively.
As shown in FIG. 3, NiSe was confirmed from the XPS spectrum2The existence of nickel in 0 and +2 in @ C, and the XRD pattern of the binding material can confirm that NiSe is2Presence of selenium vacancies in @ C.
The SEM image of FIG. 4 shows that the obtained material has a particle size of 50-200 nm, good crystallinity, and a diameter of the formed microsphere of 1.3-2.5 μm.
FIGS. 5 and 6 are NiSe, respectively2@ C and pure phase NiSe2The charge-discharge curve of the material shows that the NiSe prepared by the invention2@ C412 mAhg for the negative electrode material of sodium-ion battery-1The specific discharge capacity of the first circle is 206.6mAhg when the first circle is circulated for 100, 150 and 200 circles under the current density of 500mA/g-1、209.7mAhg-1And 215.7mAhg-1The material has a stable reversible capacity starting at 100 cycles; and comparative pure phase NiSe2937mAhg of the first turn-1The discharge specific capacity is mainly due to irreversible capacity generated by a large amount of SEI films in the initial charge-discharge process, and the discharge specific capacities under the same conditions and the same turns are respectively 160.6 mAhg, 151.1 mAhg and 147.0mAhg-1Starting after 100 cycles with a stable reversible capacity of less than 160mAhg-1. NiSe finally prepared by using the method2@ C vs. pure phase NiSe2The method reduces a large amount of irreversible capacity and electrolyte consumption generated by a large amount of SEI films in the early circulation process, and improves the circulation reversible capacity of the material.
FIG. 7 is a graph showing the rate performance of button cell at different current densities, wherein 293.8mAhg is maintained at current densities of 0.5A/g, 1A/g and 2A/g, respectively-1、253.2mAhg-1And 232.8mAhg-1When the current density returns to 0.5A/g, the discharge specific capacity is restored to 239.3mAhg-1. Illustrating the NiSe with selenium vacancy defects prepared by the process2The @ C material exhibits excellent rate capability.
As shown in FIG. 8, the volume ratio of the mixed solution added with ethanol is most uniform and smooth in the surface topography of the product microspheres at about 30%. The structure stability is higher, and the utilization rate of raw materials is higher.
As shown in FIG. 9, when the molar ratio of Ni-MOF to selenium powder in the solid phase reaction is 1:4, the obtained product has better crystallinity and the lowest impurity content. Wherein, when the molar ratio of Ni to Se is 1:2, the product is mainly NiSe and a small amount of Ni is simultaneously present7Se5(ii) a As the selenium content increases, i.e. the Ni-Se molar ratio is 1:3, part of the Ni will be present in the product3Se4Impurities; when the molar ratio of Ni to Se is about 1:4, XRD diffraction peak and NiSe in the calcined product2One to one correspondence, which indicates the NiSe in the product2The impurity content is low; when the molar ratio of Ni to Se is 1:5, NiSe is removed from the product2There is also a characteristic peak of partial selenium simple substance.
Because the selenium powder is easy to dissipate at high temperature, a certain excessive selenium source can ensure the full reaction, the impurity content in the product obtained when the molar ratio of the nickel source to the selenium source is about 1:4 in the solid-phase reaction process is the lowest, and Ni can be generated when the selenium source is less7Se5、NiSe、Ni3Se4And the product has partial elemental selenium due to excessive selenium sources, the elemental selenium is generally used as a positive electrode material in a sodium ion battery, and a reaction platform and a voltage window with high elemental selenium are not favorable for the electrochemical performance of the material as a negative electrode in the charge-discharge process.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. NiSe serving as negative electrode material of sodium-ion battery2A preparation method of @ C is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
dissolving a nickel source, a complexing agent and a dispersing agent in a mixed solvent, uniformly stirring, sealing, carrying out hydrothermal reaction, taking out a solid-liquid mixture, centrifuging to obtain a solid product, washing with ethanol, and drying.
Mixing the dried sample with selenium powder, sintering and cooling in the atmosphere, and taking out to obtain NiSe2@ C composite material.
2. NiSe as the negative electrode material of sodium-ion battery in claim 12A preparation method of @ C is characterized by comprising the following steps: the nickel source comprises one or more of nickel sulfate, nickel acetate and nickel nitrate; the complexing agent is organic acid and comprises one or more of trimesic acid, isophthalic acid, phthalic acid and terephthalic acid; the dispersing agent is polyvinylpyrrolidone.
3. NiSe as the negative electrode material of sodium-ion battery as in claim 1 or 22A preparation method of @ C is characterized by comprising the following steps: the method comprises the steps of dissolving a nickel source, a complexing agent and a dispersing agent, wherein the nickel source, the complexing agent and the dispersing agent comprise, by mass, 10-45% of the nickel source, 3-50% of the complexing agent and 10-80% of the dispersing agent.
4. NiSe as the negative electrode material of sodium-ion battery in claim 12A preparation method of @ C is characterized by comprising the following steps: the mixed solvent is a mixed solution of water, ethanol and N, N-dimethylformamide, and the mixing volume ratio of the mixed solvent is 1: 1:1, the concentration of the prepared nickel nitrate mixed solution is 0.05 mol/L.
5. Such asNiSe as the negative electrode material of sodium-ion battery in claim 12A preparation method of @ C is characterized by comprising the following steps: the stirring is uniform, wherein the stirring mode is one or more of manual stirring, magnetic stirring and mechanical stirring, and the stirring time is 3-6 h.
6. NiSe as the negative electrode material of sodium-ion battery in claim 12A preparation method of @ C is characterized by comprising the following steps: the hydrothermal reaction is carried out, wherein the reaction temperature is 120-180 ℃, and the reaction time is 3-42 h.
7. NiSe as the negative electrode material of sodium-ion battery in claim 12A preparation method of @ C is characterized by comprising the following steps: washing and drying, wherein the washing mode is that ethanol is mixed and then centrifugally separated, the volume ratio of the ethanol to the original mixed solution is 1: 6-1: 3, and the washing times are 3-5 times; and drying at the drying temperature of 50-100 ℃ for 10 h.
8. NiSe as the negative electrode material of sodium-ion battery in claim 12A preparation method of @ C is characterized by comprising the following steps: and mixing the sample with selenium powder, wherein the molar ratio of the nickel source to the selenium source is 1: 3-1: 5. The mixing mode is one or more of manual grinding, mechanical ball milling and mechanical stirring, and the mixing time is 0.5-24 h.
9. NiSe as the negative electrode material of sodium-ion battery in claim 12A preparation method of @ C is characterized by comprising the following steps: the sintering is carried out under an atmosphere, wherein the atmosphere is a reducing atmosphere, and the atmosphere comprises but is not limited to hydrogen and argon mixed gas; and sintering, wherein the heating rate is 1-20 ℃/min, the sintering temperature is 100-1200 ℃, and the sintering time is 1-72 h.
10. The NiSe as claimed in claim 1-9 for negative electrode material of sodium-ion battery2The application of the product prepared by the preparation method of @ C in the cathode material of the sodium-ion battery is characterized in that: the application comprises
Mixing NiSe2Uniformly mixing the material of @ C, a conductive agent and a binder to form slurry, coating the slurry on a copper foil, and then drying the copper foil in an oven at 80 ℃ for 12 hours to obtain the negative electrode material of the sodium-ion battery; wherein,
the conductive agent comprises acetylene black;
the binder comprises sodium carboxymethylcellulose;
according to the mass percentage, wherein, NiSe250-95% of @ C material, 8-25% of conductive agent and 5-15% of binder.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114464465A (en) * | 2022-03-14 | 2022-05-10 | 安阳工学院 | Carbon hollow sphere coated metal selenide composite material and preparation method and application thereof |
| CN114665080A (en) * | 2022-04-18 | 2022-06-24 | 齐鲁工业大学 | SnSe2-NiSe2Negative electrode material of/CNT (carbon nanotube) sodium ion battery and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108486605A (en) * | 2018-03-14 | 2018-09-04 | 济南大学 | A kind of carbon coating selenizing nickel cobalt nano material and preparation method thereof with excellent electrolysis water performance |
| CN110085834A (en) * | 2019-04-29 | 2019-08-02 | 齐鲁工业大学 | A kind of preparation method of two nickelous selenide high-performance anode material of lithium-ion batteries of Fe2O3 doping |
| CN110931777A (en) * | 2019-10-29 | 2020-03-27 | 肇庆市华师大光电产业研究院 | Preparation method of sodium ion battery negative electrode material |
| CN111463418A (en) * | 2020-04-24 | 2020-07-28 | 江苏科技大学 | Carbon-coated nickel selenide ultrathin nanosheet composite material and preparation method thereof |
| CN112010360A (en) * | 2020-07-29 | 2020-12-01 | 北京理工大学 | Universal preparation method for synthesizing carbon-coated nickel metal compounds with various morphologies |
| CN112058297A (en) * | 2020-08-27 | 2020-12-11 | 中国石油大学(华东) | Nickel-based electro-catalytic material and preparation method and application thereof |
-
2021
- 2021-07-02 CN CN202110752560.2A patent/CN113422032A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108486605A (en) * | 2018-03-14 | 2018-09-04 | 济南大学 | A kind of carbon coating selenizing nickel cobalt nano material and preparation method thereof with excellent electrolysis water performance |
| CN110085834A (en) * | 2019-04-29 | 2019-08-02 | 齐鲁工业大学 | A kind of preparation method of two nickelous selenide high-performance anode material of lithium-ion batteries of Fe2O3 doping |
| CN110931777A (en) * | 2019-10-29 | 2020-03-27 | 肇庆市华师大光电产业研究院 | Preparation method of sodium ion battery negative electrode material |
| CN111463418A (en) * | 2020-04-24 | 2020-07-28 | 江苏科技大学 | Carbon-coated nickel selenide ultrathin nanosheet composite material and preparation method thereof |
| CN112010360A (en) * | 2020-07-29 | 2020-12-01 | 北京理工大学 | Universal preparation method for synthesizing carbon-coated nickel metal compounds with various morphologies |
| CN112058297A (en) * | 2020-08-27 | 2020-12-11 | 中国石油大学(华东) | Nickel-based electro-catalytic material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| MEI HAO等: "Conversion of MOF into carbon-coated NiSe2 yolk-shell microspheres as advanced battery-type electrodes", 《ELECTROCHIMICA ACTA》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114464465A (en) * | 2022-03-14 | 2022-05-10 | 安阳工学院 | Carbon hollow sphere coated metal selenide composite material and preparation method and application thereof |
| CN114464465B (en) * | 2022-03-14 | 2023-08-25 | 安阳工学院 | Carbon hollow sphere coated metal selenide composite material and preparation method and application thereof |
| CN114665080A (en) * | 2022-04-18 | 2022-06-24 | 齐鲁工业大学 | SnSe2-NiSe2Negative electrode material of/CNT (carbon nanotube) sodium ion battery and preparation method thereof |
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Application publication date: 20210921 |