CN114864904B - Selenium-based composite material, preparation method thereof and lithium-selenium battery - Google Patents
Selenium-based composite material, preparation method thereof and lithium-selenium battery Download PDFInfo
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- CN114864904B CN114864904B CN202210588645.6A CN202210588645A CN114864904B CN 114864904 B CN114864904 B CN 114864904B CN 202210588645 A CN202210588645 A CN 202210588645A CN 114864904 B CN114864904 B CN 114864904B
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- positive electrode
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- 239000011669 selenium Substances 0.000 title claims abstract description 128
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 118
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- ZVSWQJGHNTUXDX-UHFFFAOYSA-N lambda1-selanyllithium Chemical compound [Se].[Li] ZVSWQJGHNTUXDX-UHFFFAOYSA-N 0.000 title claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 38
- 239000007774 positive electrode material Substances 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 239000012298 atmosphere Substances 0.000 claims description 27
- 239000011230 binding agent Substances 0.000 claims description 27
- 238000001354 calcination Methods 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- 238000010992 reflux Methods 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 15
- 239000006258 conductive agent Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 10
- 239000010405 anode material Substances 0.000 claims description 9
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 9
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 8
- QVYIMIJFGKEJDW-UHFFFAOYSA-N cobalt(ii) selenide Chemical compound [Se]=[Co] QVYIMIJFGKEJDW-UHFFFAOYSA-N 0.000 claims description 8
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000002134 carbon nanofiber Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000012621 metal-organic framework Substances 0.000 claims description 4
- 239000011268 mixed slurry Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 22
- 150000002736 metal compounds Chemical class 0.000 abstract description 13
- 239000013543 active substance Substances 0.000 abstract description 12
- 238000001179 sorption measurement Methods 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000002195 synergetic effect Effects 0.000 abstract description 7
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 abstract description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 7
- 239000010406 cathode material Substances 0.000 description 7
- -1 methanol and ethanol Chemical class 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000006230 acetylene black Substances 0.000 description 5
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000000527 sonication Methods 0.000 description 3
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 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
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000006232 furnace black Substances 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 1
- 239000004966 Carbon aerogel Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- MBLUWALPEKUVHJ-UHFFFAOYSA-N [Se].[C] Chemical compound [Se].[C] MBLUWALPEKUVHJ-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- 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
- H01M10/052—Li-accumulators
-
- 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
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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
Abstract
The invention provides a selenium-based composite material, which comprises cobalt compounds with a hollow structure and selenium filled in the hollow structure of the cobalt compounds. The selenium-based composite material with a specific structure is a non-carbon-based selenium composite material, simple substance selenium is partially filled in a metal compound with a hollow structure, and the utilization rate of active substances is obviously improved through the synergistic effect of physical confinement, chemical adsorption and catalytic effect. The method provided by the invention can inhibit the shuttle effect of the polyselenide by regulating and controlling the structure (hollow structure) of the metal compound with chemical adsorption and catalytic capability, and improve the utilization rate of the active substances, and the method is simple in preparation process, mild in condition, strong in controllability and more suitable for industrialized popularization and application.
Description
Technical Field
The invention belongs to the technical field of lithium-selenium battery positive electrode materials, relates to a selenium-based composite material and a preparation method thereof, and a lithium-selenium battery, and particularly relates to a non-carbon-based selenium positive electrode material and a preparation method thereof, and a lithium-selenium battery.
Background
In recent years, lithium ion batteries have been widely used in electric vehicles, portable electronic devices, and large-sized energy storage devices, but the problem of low energy density of conventional cathode materials has limited their further development. Sulfur cathode material and selenium cathode material have higher energy density, and draw a great deal of attention, and compared with sulfur, selenium has lower theoretical mass specific capacity but higher density, so the theoretical volumetric energy density of selenium is equivalent to that of sulfur (sulfur: 3467mAh cm) -3 The method comprises the steps of carrying out a first treatment on the surface of the Selenium 3240mAh cm -3 ). Meanwhile, selenium of semiconductor nature exhibits better conductivity than almost insulating sulfur, and volume expansion of selenium and shuttle effect of polyselenide are relatively small, thus, even in high-loadSelenium also exhibits higher activity and utilization in high surface density battery systems. Currently, researchers have explored carbon materials of different structures, such as porous carbon, hollow carbon, carbon nanotubes, carbon nanofibers, etc., for selenium cathode materials. As in patent CN109360959a, the carbon aerogel is used as a substrate to carry selenium, and the shuttle effect of the polyselenide is inhibited by the microporous structure domain-limiting active substance, but the effect of "capturing" the polyselenide by the nonpolar carbon material is not obvious, and the transformation of the polyselenide into the final product cannot be promoted. Thereby causing unavoidable shuttling effects and thus a constant decay of capacity.
Therefore, how to provide a more excellent selenium-based composite material as a positive electrode material of a lithium series battery, and to better improve the existing positive electrode material, has become one of the problems to be solved by many first-line researchers and scientific enterprises.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a selenium-based composite material, a preparation method thereof and a lithium-selenium battery, in particular to a non-carbon-based selenium positive electrode material, a preparation method thereof and a lithium-selenium battery. The selenium-based composite material with the hollow structure provided by the invention has the advantages that the utilization rate of active substances is obviously improved through the synergistic effect of physical confinement, chemical adsorption and catalytic effect, and the lithium-selenium battery using the positive electrode material has excellent cycle stability and high rate capability.
The invention provides a selenium-based composite material, which comprises cobalt compounds with a hollow structure and selenium filled in the hollow structure of the cobalt compounds.
Preferably, the filling comprises partial filling;
the selenium-based composite material is provided with an inner cavity gap;
the selenium-based composite material is a nanoparticle with a petal stacking structure;
the particle size of the selenium-based composite material is 100-800 nm.
Preferably, the selenium comprises elemental selenium;
the selenium-based composite material is a non-carbon-based selenium composite material;
the cobalt oxide comprises one or more of cobalt selenide, cobalt oxide and cobalt sulfide;
the mass ratio of the cobalt compound to the selenium is 1: (0.5-5).
Preferably, the selenium-based composite material is a non-carbon-based selenium anode material;
the positive electrode material comprises a positive electrode material of a lithium selenium secondary battery;
the cobalt compound with the hollow structure is obtained by calcining ZIF-67 metal organic framework material;
the filling is specifically to fill simple substance selenium into the hollow structure by a hot melting method.
The invention provides a preparation method of a selenium-based composite material, which comprises the following steps:
1) Heating and refluxing ZIF-67 dispersion liquid and a source solution of another element in cobalt compound in a protective atmosphere to obtain a reaction system;
2) Calcining the reaction system obtained in the steps under a certain atmosphere to obtain cobalt compounds with hollow structures;
3) And mixing the cobalt compound with the hollow structure obtained by the steps with the selenium solution, drying, and performing heat treatment under vacuum conditions to obtain the selenium-based composite material.
Preferably, the ZIF-67 dispersion has a mass concentration of 1-10 mg/mL;
the solvent of the ZIF-67 dispersion liquid comprises an alcohol solvent;
the alcohol solvent comprises one or more of methanol, ethanol, propanol and tert-butanol;
the source solution of the other element in the cobalt compound comprises a soluble salt solution of the other element;
the soluble salt solution includes a sodium salt solution.
Preferably, the source solution of another element in the cobalt compound comprises a sodium selenide solution, a sodium sulfide solution or a sodium carbonate solution;
the concentration of the source solution of the other element in the cobalt compound is 0.1-5M;
the ratio of ZIF-67 to the other element in the cobalt compound is (5-15) mg:1mmol;
the temperature of the heating reflux is 60-100 ℃;
the heating reflux time is 1-6 h.
Preferably, the certain atmosphere comprises a protective atmosphere, an air atmosphere, an oxygen atmosphere or a vacuum atmosphere;
the calcining temperature is 300-600 ℃;
the calcination time is 2-6 h;
the temperature of the heat treatment is 245-275 ℃;
the heat treatment time is 12-24 hours.
The invention also provides a lithium selenium battery, which comprises an anode;
the positive electrode comprises a positive electrode material;
the positive electrode material comprises the selenium-based composite material prepared by any one of the technical schemes or the preparation method of any one of the technical schemes.
Preferably, the lithium selenium battery further comprises a negative electrode, a separator and an electrolyte;
the negative electrode includes a lithium sheet;
the separator includes a polyolefin-based separator;
the positive electrode further comprises a current collector, a conductive agent and a binder;
the positive electrode material, the conductive agent and the binder form mixed slurry to be coated on the current collector;
the conductive agent comprises one or more of conductive carbon, graphene, carbon nanotubes and carbon nanofibers;
the content of the conductive agent is 10% -30%;
the binder comprises an oily binder or an aqueous binder;
the content of the binder is 5% -20%.
The invention provides a selenium-based composite material, which comprises cobalt compounds with a hollow structure and selenium filled in the hollow structure of the cobalt compounds. Compared with the prior art, the invention aims at the existing selenium-based material, mainly selenium-carbon composite material, but the nonpolar carbon material has no obvious effect of capturing the polyselenide and can not promote the transformation of the polyselenide into a final product. Thereby causing unavoidable shuttling effects and further causing the problem of continuous capacity decay. According to the invention, the shuttle effect of the polyselenide is inhibited only by regulating the structure of the carbon material, but the nonpolar carbon material only plays a role of physical confinement, so that the effect is not obvious. And the multi-step oxidation-reduction reaction causes the reaction kinetics of selenium as a positive electrode material to be slower, and an effective solution for improving the reaction kinetics of the selenium positive electrode material is not available. Meanwhile, there are few reports on the preparation of non-carbon-based selenium anode materials.
In this regard, the invention creatively provides a selenium-based composite material with a specific structure, and the selenium-based composite material is a non-carbon-based selenium anode material. The metal compound with the hollow structure of the non-carbon-based selenium composite material can inhibit the shuttle effect of the polyselenide through the synergistic effect of physical confinement and chemical adsorption; and the metal compound can provide an electrocatalytic effect to regulate the oxidation-reduction reaction of the polyselenide, promote the transformation of the polyselenide into a final product, and further inhibit the occurrence of a shuttle effect. Meanwhile, the reserved cavity gap can buffer the volume expansion of active substance selenium in the discharging process, and the structural stability of the electrode material is ensured. The method provided by the invention can inhibit the shuttle effect of the polyselenide by regulating and controlling the structure (hollow structure) of the metal compound with chemical adsorption and catalytic capability, and improve the utilization rate of the active substances, and the method is simple in preparation process, mild in condition, strong in controllability and more suitable for industrialized popularization and application.
According to the invention, a nonpolar carbon material with a poor selenium fixing effect is abandoned, and a composite material with a hollow structure and a specific structure and a hollow structure and partially filled with selenium is adopted, so that the utilization rate of active substances is obviously improved through the synergistic effect of physical confinement, chemical adsorption and catalytic effect.
Experimental results show that the lithium selenium battery prepared by adopting the non-carbon-based selenium composite material with specific structure and composition as the positive electrode material has excellent cycle stability and high rate capability.
Drawings
FIG. 1 is a SEM image of ZIF-67 powder prepared according to the present invention;
FIG. 2 is a SEM image of cobalt selenide (H-CoSe) having a hollow structure prepared in example 1 of the present invention;
FIG. 3 is a non-hollow tricobalt tetraoxide (Co) prepared in comparative example 1 3 O 4 ) Scanning electron microscope pictures of (a);
FIG. 4 is a graph of cycle performance of 150 cycles at a current density of 0.5C (1C=678 mA/g) for examples of the present invention and comparative examples;
FIG. 5 is a graph showing the rate performance of the selenium positive electrode material (H-CoSe/Se) prepared in example 1 of the present invention.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention and are not limiting of the invention claims.
All the raw materials of the present invention are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in purity, and the present invention preferably adopts analytically pure or conventional purity used in the field of preparation of lithium selenium battery cathode materials.
The invention provides a selenium-based composite material, which comprises cobalt compounds with a hollow structure and selenium filled in the hollow structure of the cobalt compounds.
In the present invention, the selenium-based composite material preferably comprises a partial filling.
In the present invention, the selenium-based composite preferably has an intra-cavity void.
In the present invention, the selenium-based composite is preferably a nanoparticle having a petal stacking structure. Or nanoparticles having a flower shape.
In the present invention, the particle diameter of the selenium-based composite is preferably 100 to 800nm, more preferably 200 to 700nm, still more preferably 300 to 600nm, still more preferably 400 to 500nm.
In the present invention, the selenium preferably includes elemental selenium.
In the present invention, the selenium-based composite is preferably a non-carbon-based selenium-based composite.
In the present invention, the cobalt oxide preferably includes one or more of cobalt selenide, cobalt oxide, and cobalt sulfide, and more preferably cobalt selenide, cobalt oxide, or cobalt sulfide.
In the present invention, the mass ratio of the cobalt compound to the selenium is preferably 1: (0.5 to 5), more preferably 1: (1.5 to 4), more preferably 1: (2.5-3).
In the present invention, the selenium-based composite material is preferably a non-carbon-based selenium cathode material.
In the present invention, the positive electrode material preferably includes a positive electrode material of a lithium selenium secondary battery.
In the present invention, the cobalt compound having a hollow structure is preferably obtained by calcining a ZIF-67 metal organic framework material. The ZIF-67 is a ZIF-67 metal-organic framework material known in the art, namely ZIF-67 (Co). The ZIF-67 has a regular dodecahedron structure.
In the present invention, the filling is particularly preferably filling the elemental selenium into the hollow structure by a hot-melt method.
The invention provides a preparation method of a selenium-based composite material, which comprises the following steps:
1) Heating and refluxing ZIF-67 dispersion liquid and a source solution of another element in cobalt compound in a protective atmosphere to obtain a reaction system;
2) Calcining the reaction system obtained in the steps under a certain atmosphere to obtain cobalt compounds with hollow structures;
3) And mixing the cobalt compound with the hollow structure obtained by the steps with the selenium solution, drying, and performing heat treatment under vacuum conditions to obtain the selenium-based composite material.
The invention firstly heats and reflows ZIF-67 dispersion liquid and source solution of another element in cobalt compound under protective atmosphere to obtain a reaction system.
In the present invention, the ZIF-67 dispersion preferably has a mass concentration of 1 to 10mg/mL, more preferably 3 to 8mg/mL, and still more preferably 5 to 6mg/mL.
In the present invention, the solvent of the ZIF-67 dispersion preferably includes an alcohol solvent.
In the present invention, the alcoholic solvent preferably includes one or more of methanol, ethanol, propanol and tert-butanol, more preferably methanol, ethanol, propanol or tert-butanol.
In the present invention, the source solution of the other element in the cobalt compound preferably includes a soluble salt solution of the other element.
In the present invention, the soluble salt solution preferably includes a sodium salt solution.
In the present invention, the source solution of another element in the cobalt compound preferably includes a sodium selenide solution, a sodium sulfide solution, or a sodium carbonate solution.
In the present invention, the concentration of the source solution of the other element in the cobalt compound is preferably 0.1 to 5M, more preferably 1 to 4M, and still more preferably 2 to 3M.
In the present invention, the ratio of ZIF-67 to the other element in the cobalt compound is preferably (5-15) mg:1mmol, more preferably (7 to 13) mg:1mmol, more preferably (9 to 11) mg:1mmol.
In the present invention, the temperature of the heating reflux is preferably 60 to 100 ℃, more preferably 65 to 95 ℃, still more preferably 70 to 90 ℃, still more preferably 75 to 85 ℃.
In the present invention, the heating reflux time is preferably 1 to 6 hours, more preferably 2 to 5 hours, and still more preferably 3 to 4 hours.
The cobalt compound with the hollow structure is obtained by calcining the reaction system obtained in the steps under a certain atmosphere.
In the present invention, the certain atmosphere preferably includes a protective atmosphere, an air atmosphere, an oxygen atmosphere, or a vacuum atmosphere. The invention selects different calcination atmospheres based on different cobalt compounds.
In the present invention, the temperature of the calcination is preferably 300 to 600 ℃, more preferably 350 to 550 ℃, and still more preferably 400 to 500 ℃.
In the present invention, the calcination time is preferably 2 to 6 hours, more preferably 2.5 to 5.5 hours, still more preferably 3 to 5 hours, still more preferably 3.5 to 4.5 hours.
Finally, the cobalt compound with the hollow structure obtained in the steps is mixed with the selenium solution, and after drying, the selenium-based composite material is obtained through heat treatment under the vacuum condition.
In the present invention, the temperature of the heat treatment is preferably 245 to 275 ℃, more preferably 250 to 270 ℃, and still more preferably 255 to 265 ℃.
In the present invention, the time of the heat treatment is preferably 12 to 24 hours, more preferably 14 to 22 hours, and still more preferably 16 to 20 hours.
The invention is a complete and refined whole technical proposal, better ensures the structure and the characteristics of the selenium-based composite material, better inhibits the shuttle effect of the polyselenide, improves the utilization rate of active substances, and the preparation method of the selenium-based composite material preferably comprises the following steps:
firstly, dissolving cobalt nitrate hexahydrate and 2-methylimidazole in a solvent phase at room temperature to synthesize ZIF-67 with a regular dodecahedron structure. The room temperature may be 10 to 35 ℃.
Secondly, heating and refluxing the ZIF-67 dispersion liquid, and calcining under different atmospheres to prepare a metal compound with a hollow structure;
and finally, filling the simple substance selenium into the hollow structure by a hot melting method.
According to the selenium positive electrode material provided by the invention, selenium is filled in a metal compound with a hollow structure by a hot melting method, and the hollow metal compound is obtained by taking ZIF-67 as a template and carrying out reflux, drying and calcination.
In the invention, the solvent phase is one or two of alcohols such as methanol and ethanol, and the room temperature synthesis time is 24 hours.
In the present invention, the reflux temperature is selected to be 60 to 100 ℃, the reflux time is selected to be 1 to 6 hours, and the reflux temperature is preferably 75 to 85 ℃. Preferably, the reflux time is 2 to 4 hours.
In the invention, the calcination temperature is 300-600 ℃, and the calcination time is 2-6 h. The metal oxide calcining atmosphere is one or more of air and oxygen, and the metal sulfide calcining atmosphere is an inert gas, such as one of nitrogen and argon. The calcination temperature is preferably 400 to 500 ℃, and the calcination time is preferably 3 to 4 hours.
In the present invention, the hot-melting conditions are: heating for 12-24 h at 245-275 ℃ under vacuum condition. The heating temperature is preferably 260℃and the heating time is preferably 20h.
In the present invention, the selenium-based composite material includes a metal compound having a hollow structure and selenium as an active material filled in the hollow structure. The hollow structure is not completely filled, and the reserved cavity gaps can relieve the volume expansion of selenium in the discharging process.
The invention also provides a lithium selenium battery, which comprises an anode.
In the present invention, the positive electrode preferably includes a positive electrode material.
In the present invention, the positive electrode material preferably includes the selenium-based composite material according to any one of the above technical schemes or the selenium-based composite material prepared by the preparation method according to any one of the above technical schemes.
In the present invention, the lithium selenium battery preferably includes a negative electrode, a separator, and an electrolyte.
In the present invention, the negative electrode preferably includes a lithium sheet.
In the present invention, the separator preferably includes a polyolefin-based separator. Specifically, the polyolefin-based separator preferably includes one of Polyethylene (PE), polypropylene (PP), or a composite separator of both (PP/PE/PP).
In the present invention, the positive electrode preferably includes a current collector, a conductive agent, and a binder.
In the present invention, the conductive agent preferably includes one or more of conductive carbon, graphene, carbon nanotubes, and carbon nanofibers, more preferably conductive carbon, graphene, carbon nanotubes, or carbon nanofibers. Specifically, the conductive carbon preferably includes one or more of acetylene black, furnace black, and ketjen black.
In the present invention, the content of the conductive agent is preferably 10% to 30%, more preferably 14% to 26%, and still more preferably 18% to 22%.
In the present invention, the binder preferably includes an oily binder or an aqueous binder.
In the present invention, the oily binder preferably includes PVDF and/or PVDF-HFP, more preferably PVDF or PVDF-HFP. The aqueous binder preferably comprises one or more of PAA, LA132/133 and PTFE, more preferably PAA, LA132/133 or PTFE.
In the present invention, the content of the binder is preferably 5% to 20%, more preferably 8% to 17%, and still more preferably 11% to 14%.
The lithium selenium battery provided by the invention comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode comprises a current collector and mixed slurry of a selenium-based positive electrode material, a conductive agent and a binder, wherein the mixed slurry is coated on the current collector.
Wherein the negative electrode is a lithium sheet. The separator is preferably a polyolefin-based separator, such as one of Polyethylene (PE), polypropylene (PP), or a two-component separator (PP/PE/PP).
The electrolyte is preferably 1mol/LLiTFSI (lithium bis (trifluoromethanesulfonyl imide))/DOL-DME (1:1), containing 1% LiNO 3 。
In the invention, the conductive agent is one or more of conductive carbon (acetylene black, furnace black and ketjen black), graphene, carbon nanotubes and carbon nanofibers. The content of the conductive agent is 10-30%, preferably 15-25%.
In the present invention, the binder is one of an oily binder and an aqueous binder. The oily binder is preferably one of PVDF and PVDF-HFP; the aqueous binder is preferably one of PAA, LA132/133 and PTFE. The binder content is preferably 5% -20%, and the binder content is preferably 8% -15%.
The invention provides a non-carbon-based selenium positive electrode material, a preparation method thereof and a lithium selenium battery. The selenium-based composite material with a specific structure is a non-carbon-based selenium anode material. The metal compound with the hollow structure of the non-carbon-based selenium composite material can inhibit the shuttle effect of the polyselenide through the synergistic effect of physical confinement and chemical adsorption; and the metal compound can provide an electrocatalytic effect to regulate the oxidation-reduction reaction of the polyselenide, promote the transformation of the polyselenide into a final product, and further inhibit the occurrence of a shuttle effect. Meanwhile, the reserved cavity gap can buffer the volume expansion of active substance selenium in the discharging process, and the structural stability of the electrode material is ensured. The method provided by the invention can inhibit the shuttle effect of the polyselenide by regulating and controlling the structure (hollow structure) of the metal compound with chemical adsorption and catalytic capability, and improve the utilization rate of the active substances, and the method is simple in preparation process, mild in condition, strong in controllability and more suitable for industrialized popularization and application.
According to the invention, a nonpolar carbon material with a poor selenium fixing effect is abandoned, and a composite material with a hollow structure and a specific structure and a hollow structure and partially filled with selenium is adopted, so that the utilization rate of active substances is obviously improved through the synergistic effect of physical confinement, chemical adsorption and catalytic effect. The lithium selenium battery using the positive electrode material has excellent cycle stability and high rate capability.
Experimental results show that the lithium selenium battery prepared by adopting the non-carbon-based selenium composite material with specific structure and composition as the positive electrode material has excellent cycle stability and high rate capability.
For further explanation of the present invention, the following detailed description is given of a selenium-based composite material, a preparation method thereof and a lithium-selenium battery according to the present invention by referring to the examples, but it should be understood that these examples are implemented on the premise of the technical scheme of the present invention, and detailed implementation and specific operation procedures are given only for further explanation of the features and advantages of the present invention, and not limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Preparation of ZIF-67:
at room temperature, 1.74g of Co (NO 3 ) 2 ·6H 2 O was dissolved in 60mL of methanol to prepare a solution. To 40mL of a methanol solution (200 mL beaker) in which 3.94g of dimethylimidazole was dissolved was added, and the mixture was stirred magnetically for 1 hour to mix the mixture uniformly, and allowed to stand at room temperature for 24 hours. The mixture was collected by centrifugation, washed with methanol several times, and dried overnight at 50℃under vacuum. ZIF-67 powder was obtained.
The ZIF-67 powder prepared by the invention is characterized.
Referring to FIG. 1, FIG. 1 is a SEM image of ZIF-67 powder prepared according to the present invention.
As can be seen from FIG. 1, the ZIF-67 organometallic framework material prepared by the invention has a regular dodecahedron structure.
Example 1
360mg of ZIF-67 powder was weighed into 100mL of ethanol, dispersed by sonication, and transferred into a 200mL flask. Reflux at 80deg.C for 30min under nitrogen atmosphere, adding 40mL1MNA to the dispersion 2 The Se solution is refluxed for 3 hours. The mixture was collected by centrifugation, washed with water and ethanol, and dried overnight at 60℃under vacuum. Calcining for 4 hours at 500 ℃ under argon atmosphere. Finally, the hollow CoSe material is obtained.
The CoSe material prepared in example 1 of the present invention was characterized.
Referring to fig. 2, fig. 2 is an SEM scanning electron microscope image of cobalt selenide (H-CoSe) having a hollow structure prepared in example 1 of the present invention.
After soaking the hollow cobalt selenide in a selenium-containing carbon disulfide solution (according to the mass ratio of CoSe: se=1:2), drying to remove carbon disulfide, transferring the carbon disulfide into a vacuum glass tube, and treating the cobalt selenide at 260 ℃ for 20 hours. And obtaining the selenium anode material (H-CoSe/Se).
Example 2
Weighing 360mg ZIF-67 powder, adding into 100mL ethanol, ultrasonic dispersing, and transferring toIn a 200mL flask. Reflux at 80℃for 30min under nitrogen, 40mL of 1M Na was added to the dispersion 2 The solution S was refluxed for 3h. The mixture was collected by centrifugation, washed with water and ethanol, and dried overnight at 60℃under vacuum. Calcining for 4 hours at 500 ℃ under argon atmosphere. Finally, the hollow CoS material is obtained. After soaking the hollow cobalt sulfide in a selenium-containing carbon disulfide solution (according to the mass ratio of CoS: se=1:2), drying to remove carbon disulfide, transferring the carbon disulfide into a vacuum glass tube, and treating the carbon disulfide for 20 hours at 260 ℃. And obtaining the selenium positive electrode material (H-CoS/Se).
Example 3
360mg of ZIF-67 powder was weighed into 100mL of ethanol, dispersed by sonication, and transferred into a 200mL flask. Reflux at 80℃for 30min under nitrogen, 40mL of 1M Na was added to the dispersion 2 CO 3 The solution was refluxed for 3h. The mixture was collected by centrifugation, washed with water and ethanol, and dried overnight at 60℃under vacuum. Calcining for 4 hours at 500 ℃ in an air atmosphere. Finally, hollow Co is obtained 3 O 4 A material. Soaking hollow cobaltosic oxide in selenium-containing carbon disulfide solution (according to Co 3 O 4 Se=1:2 mass ratio), drying to remove carbon disulfide, transferring into a vacuum glass tube, and treating at 260 ℃ for 20h. Obtaining selenium anode material (H-Co) 3 O 4 /Se)。
Comparative example 1
360mg of ZIF-67 powder was weighed into 100mL of water (accelerating hydrolysis, breaking structure, shown in FIG. 3), dispersed by sonication, and transferred into a 200mL flask. Reflux at 80℃for 30min under nitrogen, 40mL of 1M Na was added to the dispersion 2 CO 3 The solution was refluxed for 3h. The mixture was collected by centrifugation, washed with water and ethanol, and dried overnight at 60℃under vacuum. Calcining for 4 hours at 500 ℃ in an air atmosphere. Finally, non-hollow Co is obtained 3 O 4 A material.
Co prepared in comparative example 1 of the present invention 3 O 4 The material was characterized.
Referring to fig. 3, fig. 3 is a non-hollow tricobalt tetraoxide (Co) prepared in comparative example 1 3 O 4 ) Is a scanning electron microscope picture of (c).
As can be seen from FIG. 3, co 3 O 4 The structure of the material has been destroyed and no longer has a hollow structure.
After non-hollow cobaltosic oxide is soaked in a selenium-containing carbon disulfide solution (according to Co 3 O 4 Se=1:2 mass ratio), drying to remove carbon disulfide, transferring into a vacuum glass tube, and treating at 260 ℃ for 20h. Obtaining selenium cathode material (Co) 3 O 4 /Se)。
Comparative example 2
After immersing acetylene black in a selenium-containing carbon disulfide solution (according to the mass ratio of acetylene black: se=1:2), drying to remove carbon disulfide, transferring into a vacuum glass tube, and treating at 260 ℃ for 20h. And obtaining the selenium positive electrode material (C/Se).
Performance detection
The above examples and comparative examples were tested by assembling 2032 button cell batteries, the positive electrode was the selenium positive electrode material prepared in the above examples and comparative examples, the negative electrode was lithium metal, the electrolyte was 1mol/L LiTFSI (lithium bis (trifluoromethanesulfonyl imide)/DOL-DME (1:1), and the electrolyte contained 1% LiNO 3 The method comprises the steps of carrying out a first treatment on the surface of the The test voltage interval is 1.7-3.0V.
Preparing a positive electrode plate:
and uniformly mixing the selenium anode material, the acetylene black, the carbon nano tube and the PVDF according to the mass ratio of 75:10:7:8, adding a proper amount of NMP to prepare slurry, uniformly coating the slurry on an aluminum foil, placing the aluminum foil in a vacuum drying oven at 60 ℃ for 24 hours, and finally punching to prepare the electrode slice.
Referring to fig. 4, fig. 4 is a graph showing cycle performance of 150 cycles at a current density of 0.5C (1c=678 mA/g) for the examples of the present invention and the comparative examples.
Referring to fig. 5, fig. 5 is a graph showing the rate performance of the selenium positive electrode material (H-CoSe/Se) prepared in example 1 of the present invention.
As shown in fig. 4 and 5, comparison of the experimental results of the comparative example and each example shows that: the metal compound with the hollow structure provided by the invention can obviously improve the utilization rate of active substances through the synergistic effect of physical confinement, chemical adsorption and catalytic effect, inhibit the shuttle effect of the polyselenide and further improve the cycle performance of the battery. While having excellent rate capability (shown in fig. 5).
The foregoing has outlined rather broadly the principles and embodiments of the present invention by providing a non-carbon based selenium anode material and method of making and using the same, and lithium selenium battery, wherein the foregoing examples are provided to facilitate an understanding of the principles and embodiments of the present invention, including the best mode, and further to enable any person skilled in the art to practice the invention, including making and using any devices or systems, and performing any incorporated methods. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (10)
1. The preparation method of the selenium-based composite material is characterized by comprising the following steps of:
1) Heating and refluxing ZIF-67 dispersion liquid and a source solution of another element in cobalt compound in a protective atmosphere to obtain a reaction system;
2) Calcining the reaction system obtained in the steps under a certain atmosphere to obtain cobalt compounds with hollow structures;
3) Mixing cobalt compound with a hollow structure obtained in the above step with selenium solution, drying, and then carrying out heat treatment under vacuum condition to obtain selenium-based composite material;
the composite material includes cobalt oxide having a hollow structure and selenium filled in the hollow structure of the cobalt oxide.
2. The method of manufacturing according to claim 1, wherein the filling comprises partial filling;
the selenium-based composite material is provided with an inner cavity gap;
the selenium-based composite material is a nanoparticle with a petal stacking structure;
the particle size of the selenium-based composite material is 100-800 nm.
3. The method of claim 1, wherein the selenium comprises elemental selenium;
the selenium-based composite material is a non-carbon-based selenium composite material;
the cobalt oxide comprises one or more of cobalt selenide, cobalt oxide and cobalt sulfide;
the mass ratio of the cobalt compound to the selenium is 1: (0.5-5).
4. The method of claim 1, wherein the selenium-based composite material is a non-carbon-based selenium anode material;
the positive electrode material comprises a positive electrode material of a lithium selenium secondary battery;
the cobalt compound with the hollow structure is obtained by calcining ZIF-67 metal organic framework material;
the filling is specifically to fill simple substance selenium into the hollow structure by a hot melting method.
5. The preparation method according to claim 1, wherein the mass concentration of the ZIF-67 dispersion is 1-10 mg/mL;
the solvent of the ZIF-67 dispersion liquid comprises an alcohol solvent;
the alcohol solvent includes one or more of methanol, ethanol, propanol and tert-butanol.
6. The method according to claim 1, wherein the source solution of another element in the cobalt compound comprises a soluble salt solution of another element;
the soluble salt solution includes a sodium salt solution.
7. The production method according to claim 1, wherein the source solution of another element in the cobalt compound comprises a sodium selenide solution, a sodium sulfide solution, or a sodium carbonate solution;
the concentration of the source solution of the other element in the cobalt compound is 0.1-5M;
the ratio of ZIF-67 to the other element in the cobalt compound is (5-15) mg:1mmol;
the temperature of the heating reflux is 60-100 ℃;
the heating reflux time is 1-6 h.
8. The method of claim 1, wherein the atmosphere comprises a protective atmosphere, an air atmosphere, an oxygen atmosphere, or a vacuum atmosphere;
the calcining temperature is 300-600 ℃;
the calcination time is 2-6 h;
the temperature of the heat treatment is 245-275 ℃;
the heat treatment time is 12-24 hours.
9. A lithium selenium battery, characterized by comprising a positive electrode;
the positive electrode comprises a positive electrode material;
the positive electrode material comprises the selenium-based composite material prepared by the preparation method of any one of claims 1-8.
10. The lithium selenium battery of claim 9, wherein the lithium selenium battery further comprises a negative electrode, a separator, and an electrolyte;
the negative electrode includes a lithium sheet;
the separator includes a polyolefin-based separator;
the positive electrode further comprises a current collector, a conductive agent and a binder;
the positive electrode material, the conductive agent and the binder form mixed slurry to be coated on the current collector;
the conductive agent comprises one or more of conductive carbon, graphene, carbon nanotubes and carbon nanofibers;
the content of the conductive agent is 10% -30%;
the binder comprises an oily binder or an aqueous binder;
the content of the binder is 5% -20%.
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| CN109092331A (en) * | 2018-08-04 | 2018-12-28 | 安徽师范大学 | A kind of hollow tubular cobalt selenium compound/molybdenum selenium compound composite nano materials and its preparation method and application |
| CN113410440A (en) * | 2021-05-14 | 2021-09-17 | 华南理工大学 | Cobalt diselenide @ porous nitrogen-doped carbon nanocomposite, potassium ion battery and preparation method of cobalt diselenide @ porous nitrogen-doped carbon nanocomposite |
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| CN109092331A (en) * | 2018-08-04 | 2018-12-28 | 安徽师范大学 | A kind of hollow tubular cobalt selenium compound/molybdenum selenium compound composite nano materials and its preparation method and application |
| CN113410440A (en) * | 2021-05-14 | 2021-09-17 | 华南理工大学 | Cobalt diselenide @ porous nitrogen-doped carbon nanocomposite, potassium ion battery and preparation method of cobalt diselenide @ porous nitrogen-doped carbon nanocomposite |
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