CN114864904A - 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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- 239000011669 selenium Substances 0.000 title claims abstract description 133
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 119
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- ZVSWQJGHNTUXDX-UHFFFAOYSA-N lambda1-selanyllithium Chemical compound [Se].[Li] ZVSWQJGHNTUXDX-UHFFFAOYSA-N 0.000 title claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 229910052963 cobaltite Inorganic materials 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 40
- 239000007774 positive electrode material Substances 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 239000012298 atmosphere Substances 0.000 claims description 27
- 238000001354 calcination Methods 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000011230 binding agent Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- 150000001869 cobalt compounds Chemical class 0.000 claims description 21
- 238000010992 reflux Methods 0.000 claims description 20
- 239000006258 conductive agent Substances 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000011049 filling Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 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
- 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
- 239000007788 liquid 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
- 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
- 239000011268 mixed slurry Substances 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
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 22
- 150000002736 metal compounds Chemical class 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 11
- 239000013543 active substance Substances 0.000 abstract description 10
- 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 21
- 239000010406 cathode material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000004743 Polypropylene Substances 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 239000010405 anode material Substances 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 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 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
- 239000011521 glass Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- -1 Polyethylene Polymers 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000000527 sonication Methods 0.000 description 4
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 3
- 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
- 230000008569 process Effects 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 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
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 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 1
- 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
- 125000003158 alcohol group Chemical group 0.000 description 1
- 230000001476 alcoholic effect Effects 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
- 238000005562 fading 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
- 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
- 238000011068 loading method Methods 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007858 starting material 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
Images
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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a selenium-based composite material, which comprises a cobaltite with a hollow structure and selenium filled in the hollow structure of the cobaltite. The selenium-based composite material with the specific structure is a non-carbon-based selenium composite material, elemental 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 invention inhibits the shuttle effect of the polyselenide and improves the utilization rate of active substances by regulating and controlling the structure (hollow structure) of the metal compound with chemical adsorption and catalytic capability, and the preparation process is simple, mild in condition and strong in controllability, thereby being more suitable for industrial 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-scale energy storage devices, but the problem of low energy density of conventional positive electrode materials has limited further development thereof. The sulfur positive electrode material and the selenium positive electrode material have higher energy density and attract wide attention, and the theoretical volumetric energy density of selenium is equivalent to that of sulfur (sulfur: 3467mAh cm) because the theoretical volumetric energy density of selenium is lower than that of sulfur, but selenium has higher density -3 (ii) a 3240mAh cm Se -3 ). Meanwhile, selenium of a semiconducting nature exhibits better conductivity than almost insulating sulfur, and the volume expansion of selenium and shuttle effect of polyselenide are relatively small, so selenium can exert higher activity and utilization rate even in a battery system of high loading and high area density. Currently, researchers have explored carbon materials with different structures, such as porous carbon, hollow carbon, carbon nanotubes, carbon nanofibers, etc., for selenium cathode materials. For example, in patent CN109360959A, carbon aerogel is used as a substrate to load selenium, and the shuttle effect of polyselenide is inhibited by the active substance confined in the microporous structure, but the nonpolar carbon material has no obvious effect of "capturing" the polyselenide, and cannot promote the conversion of the polyselenide to the final product. Thereby causing an inevitable generation of shuttle effect and thus a continuous fading 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 a plurality of front-line researchers and scientific research enterprises.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a selenium-based composite material and a preparation method thereof, and a lithium selenium battery, in particular, a non-carbon-based selenium positive electrode material and a preparation method thereof, and a lithium selenium battery. The selenium-based composite material with the hollow structure provided by the invention obviously improves the utilization rate of active substances through the synergistic effect of the physical confinement, the chemical adsorption and the catalytic effect, and a lithium selenium battery applying the cathode material has excellent cycling stability and high rate performance.
The invention provides a selenium-based composite material, which comprises a cobaltite with a hollow structure and selenium filled in the hollow structure of the cobaltite.
Preferably, the filling comprises partial filling;
the selenium-based composite material is provided with an inner cavity gap;
the selenium-based composite material is nanoparticles 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 compound 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 positive electrode material;
the positive electrode material comprises a positive electrode material of a lithium selenium secondary battery;
the cobaltite with the hollow structure is obtained by calcining a ZIF-67 metal organic framework material;
the filling is to fill the elemental 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 the ZIF-67 dispersion liquid and a source solution of another element in the cobaltite under a protective atmosphere to obtain a reaction system;
2) calcining the reaction system obtained in the step under a certain atmosphere to obtain a hollow cobalt compound;
3) and mixing the hollow cobalt compound and the selenium solution, drying, and performing heat treatment under a vacuum condition to obtain the selenium-based composite material.
Preferably, the mass concentration of the ZIF-67 dispersion liquid is 1-10 mg/mL;
the solvent of the ZIF-67 dispersion includes 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 cobaltate comprises a soluble salt solution of the other element;
the soluble salt solution comprises a sodium salt solution.
Preferably, the source solution of the other element in the cobaltate comprises a sodium selenide solution, a sodium sulfide solution or a sodium carbonate solution;
the concentration of the source solution of another element in the cobalt compound is 0.1-5M;
the ratio of the ZIF-67 to another element in the cobaltite is (5-15) mg: 1mmol of the active component;
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 calcining time is 2-6 h;
the temperature of the heat treatment is 245-275 ℃;
the heat treatment time is 12-24 h.
The invention also provides a lithium selenium battery, which comprises 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 the above technical schemes or the selenium-based composite material prepared by the preparation method of any one of the above 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 comprises a polyolefin-based separator;
the positive electrode also 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 oil-based binder or a water-based binder;
the content of the binder is 5-20%.
The invention provides a selenium-based composite material, which comprises a cobaltite with a hollow structure and selenium filled in the hollow structure of the cobaltite. Compared with the prior art, the invention aims at the problems that the existing selenium-based material is mainly a selenium-carbon composite material, but the nonpolar carbon material has an unobvious effect of 'capturing' the polyselenide, and can not promote the conversion of the polyselenide to a final product. Thereby causing the problem of an inevitable shuttle effect and thus a continuous capacity fade. The research of the invention considers that the shuttle effect of the polyselenide is inhibited only by regulating the structure of the carbon material at the present stage, but the nonpolar carbon material only plays a role of physical confinement, and the effect is not obvious. Moreover, the reaction kinetics of selenium as the cathode material is slow due to the multi-step redox reaction, and an effective solution for improving the reaction kinetics of the selenium cathode material is not provided. Meanwhile, the preparation of the non-carbon-based selenium anode material is also rarely reported.
Therefore, the invention creatively provides the selenium-based composite material with a specific structure, and the selenium-based composite material is a non-carbon-based selenium positive electrode material. The metal compound with a hollow structure 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 electro-catalytic effect to regulate the oxidation-reduction reaction of the polyselenide, promote the conversion of the polyselenide to a final product and further inhibit the occurrence of a shuttle effect. Meanwhile, the reserved inner cavity gap can buffer the volume expansion of the active material selenium in the discharging process, and the structural stability of the electrode material is ensured. The invention inhibits the shuttle effect of the polyselenide and improves the utilization rate of active substances by regulating and controlling the structure (hollow structure) of the metal compound with chemical adsorption and catalytic capability, and the preparation process is simple, mild in condition and strong in controllability, thereby being more suitable for industrial popularization and application.
The invention abandons the nonpolar carbon material with poor selenium fixation effect, adopts the composite material which has specific structure and composition and is formed by partially filling the selenium with the metal compound with the hollow structure, and obviously improves the utilization rate of the active substance through the synergistic action of the physical confinement, the chemical adsorption and the catalytic effect.
Experimental results show that the lithium-selenium battery obtained by using the non-carbon-based selenium composite material with the specific structure and composition prepared by the invention as the anode material has excellent cycle stability and high rate performance.
Drawings
FIG. 1 is an SEM scanning electron microscope photograph of ZIF-67 powder prepared in accordance with the present invention;
FIG. 2 is a SEM scanning electron microscope photograph of cobalt selenide (H-CoSe) with a hollow structure prepared in example 1 of the present invention;
FIG. 3 shows cobaltosic oxide (Co) having a non-hollow structure prepared in comparative example 1 3 O 4 ) The scanning electron microscope picture of (a);
FIG. 4 is a graph of the cycling performance of the inventive and comparative examples over a 150 cycle period at a current density of 0.5C (1C-678 mA/g);
fig. 5 is a graph of rate performance of selenium cathode material (H-CoSe/Se) prepared in example 1 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the invention are not particularly limited in purity, and the invention preferably adopts the conventional purity used in the field of preparation of analytically pure or lithium selenium battery cathode materials.
The invention provides a selenium-based composite material, which comprises a cobaltite with a hollow structure and selenium filled in the hollow structure of the cobaltite.
In the present invention, the filling of the selenium-based composite material preferably comprises partial filling.
In the present invention, the selenium-based composite material preferably has an intra-cavity void.
In the present invention, the selenium-based composite material is preferably nanoparticles having a petal stacking structure. Or, thought to be, a flower-shaped nanoparticle.
In the invention, the particle size of the selenium-based composite material is preferably 100-800 nm, more preferably 200-700 nm, more preferably 300-600 nm, and more preferably 400-500 nm.
In the present invention, the selenium preferably includes elemental selenium.
In the present invention, the selenium-based composite material is preferably a non-carbon-based selenium-based composite material.
In the present invention, the cobalt compound preferably includes one or more of cobalt selenide, an oxide of cobalt, and a sulfide of cobalt, and more preferably cobalt selenide, an oxide of cobalt, or a sulfide of cobalt.
In the present invention, the mass ratio of the cobaltate to the selenium is preferably 1: (0.5 to 5), more preferably 1: (1.5-4), more preferably 1: (2.5-3).
In the invention, the selenium-based composite material is preferably a non-carbon-based selenium positive electrode 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 hollow cobalt compound is preferably obtained by calcining a ZIF-67 metal organic framework material. The ZIF-67 is a ZIF-67 metal organic framework material which is well known in the field, namely ZIF-67 (Co). The ZIF-67 has a regular dodecahedron structure.
In the present invention, the filling is preferably to fill 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 the ZIF-67 dispersion liquid and a source solution of another element in the cobalt compound in a protective atmosphere to obtain a reaction system;
2) calcining the reaction system obtained in the step under a certain atmosphere to obtain a hollow cobalt compound;
3) and mixing the hollow cobalt compound and the selenium solution, drying, and performing heat treatment under a vacuum condition to obtain the selenium-based composite material.
According to the invention, under a protective atmosphere, a ZIF-67 dispersion liquid and a source solution of another element in a cobalt compound are heated and refluxed to obtain a reaction system.
In the invention, the mass concentration of the ZIF-67 dispersion is preferably 1-10 mg/mL, more preferably 3-8 mg/mL, and more preferably 5-6 mg/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, and more preferably methanol, ethanol, propanol or tert-butanol.
In the present invention, the source solution of the another element in the cobaltate preferably comprises a soluble salt solution of the another 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 cobaltate preferably includes a sodium selenide solution, a sodium sulfide solution, or a sodium carbonate solution.
In the invention, the concentration of the source solution of another element in the cobalt compound is preferably 0.1-5M, more preferably 1-4M, and more preferably 2-3M.
In the invention, the ratio of the ZIF-67 to another element in the cobalt compound is preferably (5-15) mg: 1mmol, more preferably (7-13) mg: 1mmol, more preferably (9-11) mg: 1 mmol.
In the invention, the heating reflux temperature is preferably 60-100 ℃, more preferably 65-95 ℃, more preferably 70-90 ℃, and more preferably 75-85 ℃.
In the invention, the heating reflux time is preferably 1-6 h, more preferably 2-5 h, and more preferably 3-4 h.
In a certain atmosphere, the reaction system obtained in the step is calcined to obtain a hollow cobalt compound.
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 calcining atmospheres based on different cobaltates.
In the invention, the calcination temperature is preferably 300-600 ℃, more preferably 350-550 ℃, and more preferably 400-500 ℃.
In the invention, the calcination time is preferably 2-6 h, more preferably 2.5-5.5 h, more preferably 3-5 h, and more preferably 3.5-4.5 h.
Finally, the cobalt compound with the hollow structure obtained in the step is mixed with selenium solution, and the selenium-based composite material is obtained by drying and then carrying out heat treatment under the vacuum condition.
In the invention, the temperature of the heat treatment is preferably 245-275 ℃, more preferably 250-270 ℃, and more preferably 255-265 ℃.
In the invention, the time of the heat treatment is preferably 12-24 hours, more preferably 14-22 hours, and more preferably 16-20 hours.
The invention is a complete and detailed integral technical scheme, better ensures the structure and the characteristics of the selenium-based composite material, better inhibits the shuttle effect of the polyselenide, and improves the utilization rate of active substances, and the preparation method of the selenium-based composite material preferably comprises the following steps:
ZIF-67 with a regular dodecahedral structure was first synthesized in the solvent phase by dissolving cobalt nitrate hexahydrate and 2-methylimidazole at room temperature. The room temperature can be 10-35 ℃.
Secondly, heating and refluxing the ZIF-67 dispersion liquid, and calcining in different atmospheres to prepare a metal compound with a hollow structure;
and finally, filling the elemental selenium into the hollow structure by a hot melting method.
The selenium anode material provided by the invention is prepared by filling selenium in a metal compound with a hollow structure by a hot melting method, wherein the hollow metal compound is prepared by taking ZIF-67 as a template and performing reflux, drying and calcination.
In the invention, the solvent phase is alcohol substances, such as one or two of methanol and ethanol, and the room-temperature synthesis time is 24 h.
In the invention, the reflux temperature is selected to be 60-100 ℃, the reflux time is selected to be 1-6 h, and the preferred reflux temperature is 75-85 ℃. Preferably, the refluxing time is 2-4 h.
In the invention, the calcining temperature is 300-600 ℃, and the calcining time is 2-6 h. The metal oxide calcination atmosphere is one or more of air and oxygen, and the metal sulfide calcination atmosphere is an inert gas, such as one of nitrogen and argon. The calcination temperature is preferably 400-500 ℃, and the calcination time is preferably 3-4 h.
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 20 h.
In the present invention, the selenium-based composite material includes a metal compound having a hollow structure and an active material selenium filled in the hollow structure. Wherein, the hollow structure is not completely filled, and the reserved inner cavity gap can relieve the volume expansion of the selenium in the discharging process.
The invention also provides a lithium selenium battery, which comprises a positive electrode.
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, and 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 oil-based binder or a water-based binder.
In the present invention, the oily binder preferably comprises 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 more preferably 11% to 14%.
The lithium-selenium battery provided by the steps 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 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 composite separator of both (PP/PE/PP).
The electrolyte is preferably 1mol/LLITFSI (lithium bistrifluoromethanesulfonylimide)/DOL-DME (1:1) and contains 1 percent of LiNO 3 。
In the invention, the conductive agent is one or more of conductive carbon (acetylene black, furnace black, ketjen black), graphene, carbon nanotubes and carbon nanofibers. The content of the conductive agent is 10-30%, and the content of the conductive agent is preferably 15-25%.
In the present invention, the binder is one of an oil-based binder and a water-based binder. The oily binder is preferably one of PVDF and PVDF-HFP; the water-based adhesive is preferably one of PAA, LA132/133 and PTFE. The content of the adhesive is preferably 5-20%, and the content of the adhesive is preferably 8-15%.
The invention provides a non-carbon-based selenium anode material, a preparation method thereof and a lithium selenium battery. The composite material is a selenium-based composite material with a specific structure and is a non-carbon-based selenium positive electrode material. The metal compound with a hollow structure 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 electro-catalytic effect to regulate the oxidation-reduction reaction of the polyselenide, promote the conversion of the polyselenide to a final product and further inhibit the occurrence of a shuttle effect. Meanwhile, the reserved inner cavity gap can buffer the volume expansion of the active material selenium in the discharging process, and the structural stability of the electrode material is ensured. The invention inhibits the shuttle effect of the polyselenide and improves the utilization rate of active substances by regulating and controlling the structure (hollow structure) of the metal compound with chemical adsorption and catalytic capability, and the preparation process is simple, mild in condition and strong in controllability, thereby being more suitable for industrial popularization and application.
The invention abandons the nonpolar carbon material with poor selenium fixation effect, adopts the composite material which has specific structure and composition and is formed by partially filling the selenium with the metal compound with the hollow structure, and obviously improves the utilization rate of the active substance through the synergistic action of the physical confinement, the chemical adsorption and the catalytic effect. The lithium selenium battery using the cathode material has excellent cycling stability and high rate performance.
Experimental results show that the lithium-selenium battery obtained by using the non-carbon-based selenium composite material with the specific structure and composition prepared by the invention as the anode material has excellent cycle stability and high rate performance.
In order to further illustrate the present invention, a selenium-based composite material, a preparation method thereof, and a lithium selenium battery provided by the present invention are described in detail with reference to the following examples, but it should be understood that the examples are implemented on the premise of the technical solution of the present invention, and the detailed embodiments and specific operation procedures are given, only for further illustrating the features and advantages of the present invention, but not for limiting the claims of the present invention, and the scope of the present invention is not limited to the following examples.
Preparation of ZIF-67:
at room temperature, 1.74g of Co (NO) was first introduced 3 ) 2 ·6H 2 O was dissolved in 60mL of methanol to prepare a solution. 40mL of a methanol solution (200mL beaker) containing 3.94g of dimethylimidazole was added, and the mixture was stirred magnetically for 1 hour to be mixed uniformly and allowed to stand at room temperature for 24 hours. Collected by centrifugation, washed several times with methanol and dried overnight under vacuum at 50 ℃. ZIF-67 powder was obtained.
ZIF-67 powder prepared according to the present invention was characterized.
Referring to fig. 1, fig. 1 is an SEM scanning electron microscope 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 dodecahedral structure.
Example 1
360mg of ZIF-67 powder was weighed into 100mL of ethanol, dispersed by sonication, and transferred to a 200mL flask. Refluxing at 80 deg.C for 30min under nitrogen atmosphere, and adding 40mL of 1MNa to the dispersion 2 Se solution is continuously refluxed for 3 hours. The mixture is collected in a centrifugal way and then is treated,the mixture was washed with water and ethanol several times, and dried under vacuum at 60 ℃ overnight. Calcining at 500 ℃ for 4h under the argon atmosphere. Finally obtaining the hollow CoSe material.
The CoSe material prepared in example 1 of the invention was characterized.
Referring to fig. 2, fig. 2 is a SEM scanning electron microscope picture of cobalt selenide (H-CoSe) having a hollow structure prepared in example 1 of the present invention.
After the hollow cobalt selenide is soaked in a carbon disulfide solution containing selenium (according to the mass ratio of CoSe to Se being 1: 2), the carbon disulfide is removed by drying, and the hollow cobalt selenide is transferred into a vacuum glass tube and treated for 20 hours at 260 ℃. Obtaining the selenium cathode material (H-CoSe/Se).
Example 2
360mg of ZIF-67 powder was weighed into 100mL of ethanol, dispersed by sonication, and transferred to a 200mL flask. Refluxing at 80 deg.C for 30min under nitrogen atmosphere, and adding 40mL of 1M Na to the dispersion 2 And continuously refluxing the S solution for 3 h. The mixture was collected by centrifugation, washed several times with water and ethanol, and dried under vacuum at 60 ℃ overnight. Calcining at 500 ℃ for 4h under the argon atmosphere. Finally, the hollow CoS material is obtained. After the hollow cobalt sulfide was immersed in a selenium-containing carbon disulfide solution (mass ratio of CoS: Se is 1: 2), the cobalt sulfide was dried to remove carbon disulfide, and the cobalt sulfide was transferred to a vacuum glass tube and treated at 260 ℃ for 20 hours. Obtaining the selenium cathode material (H-CoS/Se).
Example 3
360mg of ZIF-67 powder was weighed into 100mL of ethanol, dispersed by sonication, and transferred to a 200mL flask. Refluxing at 80 deg.C for 30min under nitrogen atmosphere, and adding 40mL of 1M Na to the dispersion 2 CO 3 The solution was refluxed for 3 h. The mixture was collected by centrifugation, washed several times with water and ethanol, and dried under vacuum at 60 ℃ overnight. Calcining at 500 ℃ for 4h in an air atmosphere. Finally obtaining hollow Co 3 O 4 A material. Soaking hollow cobaltosic oxide in selenium-containing carbon disulfide solution (Co) 3 O 4 Se is 1:2 in mass ratio), drying to remove carbon disulfide, transferring into a vacuum glass tube, and treating at 260 ℃ for 20 h. Obtaining the selenium anode material (H-Co) 3 O 4 /Se)。
Comparative example 1
Weighing 360mg ZIF-67 powderAdded to 100mL of water (accelerated hydrolysis, disruption of structure, FIG. 3), dispersed by sonication, and transferred to a 200mL flask. Refluxing at 80 deg.C for 30min under nitrogen atmosphere, and adding 40mL of 1M Na to the dispersion 2 CO 3 The solution was refluxed for 3 h. The mixture was collected by centrifugation, washed several times with water and ethanol, and dried under vacuum at 60 ℃ overnight. Calcining at 500 ℃ for 4h in an air atmosphere. Finally obtaining non-hollow Co 3 O 4 A material.
For Co prepared in comparative example 1 of the present invention 3 O 4 And (5) characterizing the material.
Referring to fig. 3, fig. 3 is a view illustrating tricobalt tetraoxide (Co) having a non-hollow structure prepared in comparative example 1 3 O 4 ) Scanning electron microscope pictures of (a).
As can be seen from FIG. 3, Co 3 O 4 The structure of the material is destroyed and no longer has a hollow structure.
Soaking non-hollow cobaltosic oxide in selenium-containing carbon disulfide solution (Co) 3 O 4 Se is 1:2 in mass ratio), drying to remove carbon disulfide, transferring into a vacuum glass tube, and treating at 260 ℃ for 20 h. Obtaining the selenium cathode material (Co) 3 O 4 /Se)。
Comparative example 2
After acetylene black was soaked in a selenium-containing carbon disulfide solution (in a mass ratio of acetylene black to Se of 1: 2), carbon disulfide was removed by drying, and the solution was transferred to a vacuum glass tube and treated at 260 ℃ for 20 hours. Obtaining the selenium anode material (C/Se).
Performance detection
The above examples and comparative examples were tested by assembling 2032 button cells, 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 (trifluoromethanesulfonylimide)/DOL-DME (1:1), and the electrolyte contained 1% LiNO 3 (ii) a The test voltage interval is 1.7-3.0V.
Preparing a positive pole piece:
uniformly mixing the selenium positive electrode material, acetylene black, the carbon nano tube and PVDF according to the mass ratio of 75:10:7:8, adding a proper amount of NMP to prepare a 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 plate.
Referring to fig. 4, fig. 4 is a graph of the cycling performance of the inventive and comparative examples over a 150 cycle period at a current density of 0.5C (1C-678 mA/g).
Referring to fig. 5, fig. 5 is a graph of rate performance of a selenium cathode material (H-CoSe/Se) prepared in example 1 of the present invention.
As shown in fig. 4 and 5, the 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 action 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 figure 5).
The foregoing detailed description of a non-carbon based selenium positive electrode material and a method for making the same, and a lithium selenium battery, provided by the present invention, and the principles and embodiments of the present invention are described herein using specific examples, which are provided only to facilitate an understanding of the methods and their core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any combination of the methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention 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 languages of the claims.
Claims (10)
1. A selenium-based composite material, characterized in that the composite material comprises a cobaltate having a hollow structure and selenium filled in the hollow structure of the cobaltate.
2. The selenium-based composite material of 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 nanoparticles with a petal stacking structure;
the particle size of the selenium-based composite material is 100-800 nm.
3. The selenium-based composite material according to claim 1, wherein the selenium comprises elemental selenium;
the selenium-based composite material is a non-carbon-based selenium composite material;
the cobalt compound 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 selenium-based composite material according to claim 1, wherein the selenium-based composite material is a non-carbon-based selenium positive electrode material;
the positive electrode material comprises a positive electrode material of a lithium selenium secondary battery;
the cobaltite with the hollow structure is obtained by calcining a ZIF-67 metal organic framework material;
the filling is to fill the elemental selenium into the hollow structure by a hot melting method.
5. The preparation method of the selenium-based composite material is characterized by comprising the following steps of:
1) heating and refluxing the ZIF-67 dispersion liquid and a source solution of another element in the cobalt compound in a protective atmosphere to obtain a reaction system;
2) calcining the reaction system obtained in the step under a certain atmosphere to obtain a hollow cobalt compound;
3) and mixing the hollow cobalt compound and the selenium solution, drying, and performing heat treatment under a vacuum condition to obtain the selenium-based composite material.
6. The preparation method according to claim 1, wherein the mass concentration of the ZIF-67 dispersion is 1 to 10 mg/mL;
the solvent of the ZIF-67 dispersion includes 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 cobaltate comprises a soluble salt solution of the other element;
the soluble salt solution comprises a sodium salt solution.
7. The production method according to claim 1, wherein the source solution of another element in the cobaltate comprises a sodium selenide solution, a sodium sulfide solution, or a sodium carbonate solution;
the concentration of the source solution of another element in the cobalt compound is 0.1-5M;
the ratio of the ZIF-67 to another element in the cobaltite is (5-15) mg: 1mmol of the active component;
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 certain atmosphere comprises a protective atmosphere, an air atmosphere, an oxygen atmosphere, or a vacuum atmosphere;
the calcining temperature is 300-600 ℃;
the calcining time is 2-6 h;
the temperature of the heat treatment is 245-275 ℃;
the heat treatment time is 12-24 h.
9. A lithium selenium battery, comprising a positive electrode;
the positive electrode comprises a positive electrode material;
the positive electrode material comprises the selenium-based composite material as defined in any one of claims 1 to 4 or the selenium-based composite material prepared by the preparation method as defined in any one of claims 5 to 8.
10. The lithium selenium battery of claim 9, further comprising a negative electrode, a separator, and an electrolyte;
the negative electrode includes a lithium sheet;
the separator comprises a polyolefin-based separator;
the positive electrode also 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 oil-based binder or a water-based binder;
the content of the binder is 5-20%.
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