CN115224286A - Hollow cubic cage-shaped nickel disulfide/nickel diselenide lithium oxygen battery anode catalyst and preparation method thereof - Google Patents
Hollow cubic cage-shaped nickel disulfide/nickel diselenide lithium oxygen battery anode catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN115224286A CN115224286A CN202211007269.3A CN202211007269A CN115224286A CN 115224286 A CN115224286 A CN 115224286A CN 202211007269 A CN202211007269 A CN 202211007269A CN 115224286 A CN115224286 A CN 115224286A
- Authority
- CN
- China
- Prior art keywords
- nickel
- diselenide
- disulfide
- hollow cubic
- cubic cage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 224
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 113
- NKHCNALJONDGSY-UHFFFAOYSA-N nickel disulfide Chemical compound [Ni+2].[S-][S-] NKHCNALJONDGSY-UHFFFAOYSA-N 0.000 title claims abstract description 69
- XIMIGUBYDJDCKI-UHFFFAOYSA-N diselenium Chemical compound [Se]=[Se] XIMIGUBYDJDCKI-UHFFFAOYSA-N 0.000 title claims abstract description 68
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 57
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 25
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 20
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 238000005987 sulfurization reaction Methods 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 150000002815 nickel Chemical class 0.000 claims abstract description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 230000035484 reaction time Effects 0.000 claims abstract description 4
- 238000004073 vulcanization Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 13
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical group O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 11
- -1 nickel selenide lithium oxygen Chemical compound 0.000 claims description 4
- 239000010406 cathode material Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 102000020897 Formins Human genes 0.000 claims description 2
- 108091022623 Formins Proteins 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 29
- 238000001816 cooling Methods 0.000 description 18
- 238000001291 vacuum drying Methods 0.000 description 11
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 9
- 238000001132 ultrasonic dispersion Methods 0.000 description 9
- 238000007599 discharging Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004771 selenides Chemical class 0.000 description 1
- VIDTVPHHDGRGAF-UHFFFAOYSA-N selenium sulfide Chemical compound [Se]=S VIDTVPHHDGRGAF-UHFFFAOYSA-N 0.000 description 1
- 229960005265 selenium sulfide Drugs 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a hollow cubic cage-shaped nickel disulfide/nickel diselenide lithium oxygen battery anode catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: dispersing nickel salt and polyvinylpyrrolidone in a solvent to obtain a uniform mixed solution; carrying out hydrothermal reaction on the mixed solution, wherein the hydrothermal reaction temperature is 100-150 ℃, and the hydrothermal reaction time is 4-8h; obtaining a dodecahedral nickel-based acetate precursor; simultaneously carrying out vulcanization and selenization treatment on a dodecahedron nickel-based acetate precursor in a protective atmosphere to obtain a hollow cubic cage; in the sulfuration and selenization processes, adding sublimed sulfur and selenium powder, and calcining for 4-4h at 370-440 ℃ to obtain the hollow cubic cage-shaped nickel disulfide/nickel diselenide material. The hollow cubic cage-shaped structure can effectively store discharge products, reduce volume expansion in the charge-discharge process and provide a three-dimensional space and a channel for electron and ion transfer.
Description
Technical Field
The invention belongs to the technical field of electrochemistry and new energy, and particularly relates to a hollow cubic cage-shaped nickel disulfide/nickel diselenide lithium oxygen battery anode catalyst and a preparation method thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
Currently, lithium ion batteries are widely used in small portable electronic devices due to their advantages such as long cycle life, high output voltage, and slow self-discharge. However, the lithium ion battery has low theoretical energy density and cannot meet the use requirements of remote electric vehicles and large-scale intelligent power grids.
The lithium oxygen battery is a novel power supply system directly using oxygen as an electrode active material, and the theoretical energy density of the lithium oxygen battery is higher and is 5-10 times of that of the existing lithium ion battery. The lithium oxygen battery has simple charge and discharge reaction mechanism, but has many challenges in industrialization, such as poor rate performance, limited cycle life, low specific capacity, high overpotential of charge and discharge processes, and the like.
The positive electrode of the lithium-oxygen battery is a main place for forming and decomposing discharge products, so the performance of the lithium-oxygen battery can be effectively improved by reasonably designing the microstructure of the positive electrode material. Currently, noble metals and alloys, carbon composites, metal nitrides, oxides, sulfides, carbides, and the like have been widely studied as lithium oxygen battery positive electrode catalysts. Among numerous transition metal chalcogen compounds, nickel sulfide and nickel selenide have rich valence states, have the advantages of easy synthesis, controllable structure, excellent redox catalytic activity and the like, and are widely applied to the field of catalysis.
Research shows that single-phase nickel sulfide and nickel selenide are applied to the lithium oxygen battery, but the effect is not ideal. For example, the prior art uses metal sulfides as a dual-function catalyst for nonaqueous lithium oxygen batteries to obtain 6733mAh g -1 The first discharge specific capacity and the cycle life of more than 30 times. But its low conductivity seriously hinders the catalytic activity from being exerted. In recent years, researchers find that the construction of a heterojunction can significantly improve the electrical conductivity of the material and expose a large number of active sites, thereby improving the catalytic performance of the material. However, the current research on the heterointerface composite material mainly focuses on the bimetallic chalcogenide compound composed of two different metal cations, and mostly adopts the strategy of epitaxial growth in solution, and because the process is complicated, the method cannot be widely applied in actual production.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a hollow cubic cage-shaped nickel disulfide/nickel diselenide lithium oxygen battery anode catalyst and a preparation method thereof. The obtained high-lattice matched nickel disulfide/nickel diselenide heterostructure has the advantages that due to the difference of Fermi energy levels of different materials, electrons can be transferred from a region with high Fermi energy level to a region with low Fermi energy level through a heterogeneous interface, and therefore the conductivity of the material is improved. Meanwhile, the constructed heterostructure can trigger slight lattice distortion to introduce disordered atomic arrangement through Jahn-Teller effect to provide additional electrochemical reaction active sites, so as to promote the performance of the lithium-oxygen battery. And the hollow cubic structure can effectively solve the volume expansion caused by the accumulation of discharge products, so that the discharge product shows excellent cycling stability. The surface has abundant holes, which is beneficial to the soaking of electrolyte in the charging and discharging process, thereby being beneficial to the promotion of capacity and cycling stability.
In order to realize the purpose, the invention is realized by the following technical scheme:
in a first aspect, the invention provides a preparation method of a hollow cubic cage-shaped nickel disulfide/nickel diselenide lithium oxygen battery anode catalyst, which comprises the following steps:
dispersing nickel salt and polyvinylpyrrolidone in a solvent to obtain a uniform mixed solution;
carrying out hydrothermal reaction on the mixed solution, wherein the hydrothermal reaction temperature is 100-150 ℃, and the hydrothermal reaction time is 4-8h; obtaining a dodecahedral nickel-based acetate precursor;
simultaneously vulcanizing and selenizing a dodecahedron nickel-based acetate precursor in a protective atmosphere to obtain a hollow cubic cage-shaped nickel disulfide/nickel diselenide material;
adding sublimed sulfur and selenium powder in the sulfuration and selenization processes, and calcining for 4-4h at 370-440 ℃ to obtain the selenium-rich sulfur-rich selenium-rich material.
In a second aspect, the invention provides a hollow cubic cage-shaped nickel disulfide/nickel diselenide lithium oxygen battery anode catalyst, which is prepared by the preparation method.
In a third aspect, the invention provides a lithium oxygen battery, wherein a cathode material of the lithium oxygen battery comprises the hollow cubic cage-shaped nickel disulfide/nickel diselenide cathode catalyst of the lithium oxygen battery.
The beneficial effects achieved by one or more of the embodiments of the invention described above are as follows:
(1) The addition amount of PVP can change the growth morphology of the material, so that the morphology of the precursor is uniform and loose. The heating temperature and heating time can affect the particle size and tap density of the precursor. The hollow structure is related to the temperature and time of selenization by sulfide, mainly due to the Kendall effect, and the hollow cubic cage-like structure is caused by different diffusion speeds of S, se and Ni ions inwards and outwards caused by different radiuses of the S, se and Ni ions.
The invention adopts a simple hydrothermal method and a synchronous sulfuration/selenization mode under a protective atmosphere to construct the nickel disulfide/nickel diselenide with a hollow cubic cage-shaped structure, which has a three-dimensional porous structure and is Li + /O 4 The transmission of (2) provides a three-dimensional transmission channel, and slow reaction kinetics in the charging and discharging process are accelerated; it should be noted that, in selenization and sulfidization, the proportion of the selenium powder and the sublimed sulfur is changed to adjust the proportion of the nickel selenide and the nickel sulfide, thereby influencing the catalytic performance of the lithium oxygen battery;
(4) The synchronous sulfurization and selenization method adopted by the invention can be applied to the construction of other transition metal heterostructures, such as any two-phase heterojunction construction of sulfide, selenide, phosphide and the like. The strategy has simple process and high yield, can be applied on a large scale, and provides effective driving force for the industrial production and the large-scale application of the lithium-oxygen battery;
(3) The cubic structure prepared by the method is micron-sized, and compared with a nano structure, the cubic structure is not easy to agglomerate in the charging and discharging process; the hollow cubic cage-shaped structure can effectively store discharge products, reduce volume expansion in the charge and discharge process and provide a three-dimensional space and a channel for electron and ion transfer.
(4) The heterostructure with rich interfaces, which is constructed by the invention, has a large number of additional active sites and a built-in electric field, is beneficial to the transmission of electrons and ions, and can effectively improve the cycling stability and specific capacity of the material;
(5) The lithium oxygen battery anode catalyst prepared by the invention endows the lithium oxygen battery with good electrochemical performance and repeatability in application, has high cycle stability and specific capacity, and is verified by experiments to be 100mA g -1 The specific capacity of the first charge and discharge can reach 10695.5/11718.5mAh g under the current density of the lithium secondary battery -1 (ii) a The charge-discharge terminal voltage has good rate performance, and the charge-discharge terminal voltage has small change along with the increase of current density; at a fixed specific capacity of 600mAh g -1 The current density is 400mA g -1 The cycle performance of more than 400 times can be obtained by charging and discharging in time.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention without limiting the invention to the proper forms disclosed herein.
FIG. 1 is an XRD pattern of hollow cubic cage nickel disulfide/nickel diselenide prepared in example 1;
fig. 2 is a FESEM image of hollow cubic cage nickel disulfide/nickel diselenide prepared in example 1 at 50000 magnification;
fig. 3 is a TEM image of hollow cubic cage-shaped nickel disulfide/nickel diselenide prepared in example 1 at 50000 magnification;
FIG. 4 is a first cycle of performance graph of the hollow cubic cage-shaped nickel disulfide/nickel diselenide prepared in example 1 for testing of lithium oxygen batteries;
fig. 5 is a graph of performance of the rate test of the hollow cubic cage-shaped nickel disulfide/nickel diselenide for a lithium oxygen battery prepared in example 1;
fig. 6 is a cycle performance diagram of the hollow cubic cage-shaped nickel disulfide/nickel diselenide prepared in example 1 for a lithium oxygen battery test, where the test conditions are as follows: current density 400mA g -1 Cutoff capacity of 600mAh g -1 。
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In a first aspect, the invention provides a preparation method of a hollow cubic cage-shaped nickel disulfide/nickel diselenide lithium oxygen battery anode catalyst, which comprises the following steps:
dispersing nickel salt and polyvinylpyrrolidone in a solvent to obtain a uniform mixed solution;
carrying out hydrothermal reaction on the mixed solution, wherein the hydrothermal reaction temperature is 100-150 ℃, and the hydrothermal reaction time is 4-8h; obtaining a dodecahedral nickel-based acetate precursor;
simultaneously carrying out vulcanization and selenylation treatment on a dodecahedron nickel-based acetate precursor in a protective atmosphere to obtain a hollow cubic cage-shaped nickel disulfide/nickel diselenide material;
in the process of sulfuration and selenization, sublimed sulfur and selenium powder are added, and calcinations is carried out for 4-4h at 370-440 ℃, thus obtaining the selenium sulfide.
In some embodiments, the nickel salt is nickel acetate tetrahydrate, the nickel salt belongs to a soluble salt, is low in cost and easy to dissolve in ethanol, and the main component is easy to remove, so that the influence of deposition of impurity atoms on the product quality is avoided.
Preferably, the mass ratio of the nickel acetate tetrahydrate to the polyvinylpyrrolidone is 1:0.8 to 1.4.
The polyvinylpyrrolidone is a surface stabilizer and a morphology control agent, and the hydrophobic carbon chain in the PVP has strong repulsion effect (steric hindrance) in water, so that the mutual aggregation among nanoparticles can be prevented, and the effect of stabilizing a reaction system is achieved. Meanwhile, mutually exclusive PVP molecules can be subjected to hydrogen bonding on solvent molecules due to the existence of hydroxyl groups, so that the PVP molecules are combined with the crystal and wrapped around the crystal, and the crystal is grown in a certain shape.
Preferably, the solvent is absolute ethyl alcohol.
In some embodiments, the method further comprises the step of purifying the prepared dodecahedral nickel-based acetate precursor.
Preferably, the purification comprises centrifugal separation, washing and drying, wherein the washing is to wash the dodecahedron nickel-based acetate precursor by using absolute ethyl alcohol.
More preferably, the rotation speed of the centrifugal separation is 3000-5000 rpm min -1 。
Further preferably, the drying is vacuum drying, the temperature of the vacuum drying is 50-70 ℃, and the heat preservation time is 10-14 h.
In some embodiments, the mass ratio of sublimed sulfur to selenium powder to dodecahedral nickel-based acetate precursor is 1-3: 1.5 to 3:1.
in some embodimentsIn the process of sulfuration and selenization, the heating rate is 1 to 5 ℃ for min -1 Preferably 1 to 4min -1 . The heating rate is slow, so that the reaction can be carried out on the whole material, the two phases are uniformly distributed, and the product with uniform and stable structure is prepared. If the temperature is too fast, the sulfurization/selenization process is fast, so that the inner pore diameter and the hollow size of the material become large and loose, and the structure of the catalyst material is greatly influenced. And raw materials can be fully utilized, and the waste of the raw materials is reduced.
In some embodiments, the specific methods of sulfurization and selenization are: and placing the obtained dodecahedral nickel-based acetate precursor in the downstream of a nitrogen atmosphere tube furnace, placing sublimed sulfur and selenium powder in the upstream of the tube furnace, simultaneously vulcanizing and selenizing, calcining at 370-440 ℃ for 4-4h, and finishing the reaction to obtain the hollow cubic cage-shaped nickel disulfide/nickel diselenide material.
In a second aspect, the invention provides a hollow cubic cage-shaped nickel disulfide/nickel diselenide lithium oxygen battery cathode catalyst, which is prepared by the preparation method.
In a third aspect, the invention provides a lithium oxygen battery, wherein a cathode material of the lithium oxygen battery comprises the hollow cubic cage-shaped nickel disulfide/nickel diselenide cathode catalyst of the lithium oxygen battery.
The present invention is further illustrated by the following examples.
Example 1
The preparation method of the hollow cubic cage-shaped nickel disulfide/nickel diselenide comprises the following steps:
s1, preparing a reaction solution: adding 450mg of nickel acetate tetrahydrate and 450mg of PVP (K30) into 30mL of absolute ethyl alcohol, and performing ultrasonic dispersion at room temperature for 40min to obtain a clear and transparent solution;
s4, preparing a dodecahedron nickel-based acetate precursor: and S1, adding the uniform solution obtained in the step S1 into a hydrothermal kettle, carrying out heat treatment at 140 ℃ for 6h, naturally cooling to room temperature, centrifugally collecting a precursor, and washing with absolute ethyl alcohol for five times. Vacuum drying at 60 ℃ for 14h, and naturally cooling to room temperature to obtain a required dodecahedral nickel-based acetate precursor;
s3, preparing a hollow cubic cage-shaped nickel disulfide/nickel diselenide material: and S4, respectively placing the dodecahedral nickel-based acetate precursor and the sublimed sulfur/selenium powder prepared in the step S4 at the lower end and the upper end of a nitrogen atmosphere tube furnace, reacting for 3 hours at 400 ℃, and obtaining the hollow cubic cage-shaped nickel disulfide/nickel diselenide material after heat treatment is finished.
FIG. 1 shows XRD test, diffraction data and NiS of hollow cubic cage-shaped nickel disulfide/nickel diselenide material synthesized by the present embodiment 4 (JCPDS No. 89-3058) and NiSe 4 (JCPDS No. 11-0554) is consistent with the method but has some deviation, mainly because the two-phase structure is similar to generate solid solution, no impurity phase appears, and the product is the high-purity nickel disulfide/nickel diselenide composite material; fig. 4 is an FESEM view of the hollow cubic cage-shaped nickel disulfide/nickel diselenide material synthesized in this embodiment, and fig. 3 is a TEM view of the hollow cubic cage-shaped nickel disulfide/nickel diselenide material synthesized in this embodiment, which shows that the hollow cubic cage-shaped nickel disulfide/nickel diselenide material is in a micron level.
An electrode was prepared from the hollow cubic cage-like nickel disulfide/nickel diselenide material obtained in example 1 by the following method:
weighing a cubic cage-shaped nickel disulfide/nickel diselenide material, carbon black and PTFE according to the mass ratio of 4. The 4034 type button cell with the hole is used for the electrochemical test of the lithium-oxygen battery, an active metal lithium sheet is used as a negative electrode, and 1mol L of electrolyte is used -1 LiTFSI/TEGDME solution, and the membrane is a glass fiber membrane. All cell assemblies were performed in a glove box filled with argon atmosphere and then electrochemical tests were performed on a LAND CT 4001A multichannel cell tester in a pure oxygen environment at room temperature.
FIG. 4 shows the results of the present example when the material is used as a positive electrode catalyst of a lithium oxygen battery at 100mA g -1 The current density of the battery is 4.35 to 4.5V of cutoff voltage, and the charging and discharging specific capacity is 10695.5/11718.5mAh g -1 (ii) a FIG. 5 shows the material obtained in this example as a positive electrode of a lithium oxygen batteryThe multiplying power performance test chart during the polar catalysis has small change of the charge-discharge terminal voltage along with the increase of the current density and good multiplying power performance; FIG. 5 is a graph showing the cycling performance of the material obtained in this example when used as a lithium oxygen battery cathode catalyst at a fixed specific capacity of 600mAh g -1 The current density is 400mA g -1 The cycle performance of 404 times was achieved by charging and discharging under the condition of (1).
Example 2
The preparation method of the hollow cubic cage-shaped nickel disulfide/nickel diselenide comprises the following steps:
s1, preparing a reaction solution: adding 450mg of nickel acetate tetrahydrate and 400mg of PVP (K30) into 30mL of absolute ethyl alcohol, and performing ultrasonic dispersion at room temperature for 40min to obtain a clear and transparent solution;
s4, preparing a dodecahedron nickel-based acetate precursor: and (4) adding the uniform solution obtained in the step S1 into a hydrothermal kettle, carrying out heat treatment at 140 ℃ for 6h, naturally cooling to room temperature, centrifugally collecting a precursor, and washing with absolute ethyl alcohol for five times. Vacuum drying at 60 deg.C for 14h, and naturally cooling to room temperature to obtain required dodecahedral nickel-based acetate precursor;
s3, preparing a hollow cubic cage-shaped nickel disulfide/nickel diselenide material: and S4, respectively placing the dodecahedral nickel-based acetate precursor prepared in the step S4 and sublimed sulfur/selenium powder at the lower end and the upper end of a nitrogen atmosphere tube furnace, reacting for 3 hours at 400 ℃, and obtaining the hollow cubic cage-shaped nickel disulfide/nickel diselenide material after heat treatment is finished.
Example 3
The preparation method of the hollow cubic cage-shaped nickel disulfide/nickel diselenide comprises the following steps:
s1, preparing a reaction solution: adding 450mg of nickel acetate tetrahydrate and 300mg of PVP (K30) into 30mL of absolute ethyl alcohol, and performing ultrasonic dispersion at room temperature for 40min to obtain a clear and transparent solution;
s4, preparing a dodecahedron nickel-based acetate precursor: and (4) adding the uniform solution obtained in the step S1 into a hydrothermal kettle, carrying out heat treatment for 6 hours at 140 ℃, naturally cooling to room temperature, centrifugally collecting a precursor, and washing the precursor with absolute ethyl alcohol for five times. Vacuum drying at 60 deg.C for 14h, and naturally cooling to room temperature to obtain required dodecahedral nickel-based acetate precursor;
s3, preparing a hollow cubic cage-shaped nickel disulfide/nickel diselenide material: and S4, respectively placing the dodecahedral nickel-based acetate precursor prepared in the step S4 and sublimed sulfur/selenium powder at the lower end and the upper end of a nitrogen atmosphere tube furnace, reacting for 3 hours at 400 ℃, and obtaining the hollow cubic cage-shaped nickel disulfide/nickel diselenide material after heat treatment is finished.
Example 4
The preparation method of the hollow cubic cage-shaped nickel disulfide/nickel diselenide comprises the following steps:
s1, preparing a reaction solution: adding 450mg of nickel acetate tetrahydrate and 450mg of PVP (K30) into 30mL of absolute ethyl alcohol, and performing ultrasonic dispersion at room temperature for 40min to obtain a clear and transparent solution;
s4, preparing a dodecahedron nickel-based acetate precursor: and (4) adding the uniform solution obtained in the step S1 into a hydrothermal kettle, carrying out heat treatment at 100 ℃ for 6h, naturally cooling to room temperature, centrifugally collecting a precursor, and washing with absolute ethyl alcohol for five times. Vacuum drying at 60 ℃ for 14h, and naturally cooling to room temperature to obtain the required dodecahedral nickel-based acetate precursor;
s3, preparing a hollow cubic cage-shaped nickel disulfide/nickel diselenide material: and (5) respectively placing the dodecahedral nickel-based acetate precursor prepared in the step (S4) and sublimed sulfur/selenium powder at the lower end and the upper end of a nitrogen atmosphere tube furnace, reacting for 3 hours at 400 ℃, and obtaining the hollow cubic cage-shaped nickel disulfide/nickel diselenide material after heat treatment.
Example 5
The preparation method of the hollow cubic cage-shaped nickel disulfide/nickel diselenide comprises the following steps:
s1, preparing a reaction solution: adding 450mg of nickel acetate tetrahydrate and 450mg of PVP (K30) into 30mL of absolute ethyl alcohol, and performing ultrasonic dispersion at room temperature for 40min to obtain a clear and transparent solution;
s4, preparing a dodecahedron nickel-based acetate precursor: and (4) adding the uniform solution obtained in the step S1 into a hydrothermal kettle, carrying out heat treatment for 6 hours at 140 ℃, naturally cooling to room temperature, centrifugally collecting a precursor, and washing the precursor with absolute ethyl alcohol for five times. Vacuum drying at 60 deg.C for 14h, and naturally cooling to room temperature to obtain required dodecahedral nickel-based acetate precursor;
s3, preparing a hollow cubic cage-shaped nickel disulfide/nickel diselenide material: and S4, respectively placing the dodecahedral nickel-based acetate precursor prepared in the step S4 and sublimed sulfur/selenium powder at the lower end and the upper end of a nitrogen atmosphere tube furnace, reacting for 3 hours at 400 ℃, and obtaining the hollow cubic cage-shaped nickel disulfide/nickel diselenide material after heat treatment is finished.
Example 6
The preparation method of the hollow cubic cage-shaped nickel disulfide/nickel diselenide comprises the following steps:
s1, preparing a reaction solution: adding 450mg of nickel acetate tetrahydrate and 450mg of PVP (K30) into 30mL of absolute ethyl alcohol, and performing ultrasonic dispersion at room temperature for 40min to obtain a clear and transparent solution;
s4, preparing a dodecahedron nickel-based acetate precursor: and (4) adding the uniform solution obtained in the step S1 into a hydrothermal kettle, carrying out heat treatment at 140 ℃ for 4h, naturally cooling to room temperature, centrifugally collecting a precursor, and washing with absolute ethyl alcohol for five times. Vacuum drying at 60 deg.C for 14h, and naturally cooling to room temperature to obtain required dodecahedral nickel-based acetate precursor;
s3, preparing a hollow cubic cage-shaped nickel disulfide/nickel diselenide material: and S4, respectively placing the dodecahedral nickel-based acetate precursor prepared in the step S4 and sublimed sulfur/selenium powder at the lower end and the upper end of a nitrogen atmosphere tube furnace, reacting for 3 hours at 400 ℃, and obtaining the hollow cubic cage-shaped nickel disulfide/nickel diselenide material after heat treatment is finished.
Example 7
The preparation method of the hollow cubic cage-shaped nickel disulfide/nickel diselenide comprises the following steps:
s1, preparing a reaction solution: adding 450mg of nickel acetate tetrahydrate and 450mg of PVP (K30) into 30mL of absolute ethyl alcohol, and performing ultrasonic dispersion at room temperature for 40min to obtain a clear and transparent solution;
s4, preparing a dodecahedron nickel-based acetate precursor: and (4) adding the uniform solution obtained in the step S1 into a hydrothermal kettle, carrying out heat treatment at 140 ℃ for 8h, naturally cooling to room temperature, centrifugally collecting a precursor, and washing with absolute ethyl alcohol for five times. Vacuum drying at 60 deg.C for 14h, and naturally cooling to room temperature to obtain required dodecahedral nickel-based acetate precursor;
s3, preparing a hollow cubic cage-shaped nickel disulfide/nickel diselenide material: and S4, respectively placing the dodecahedral nickel-based acetate precursor prepared in the step S4 and sublimed sulfur/selenium powder at the lower end and the upper end of a nitrogen atmosphere tube furnace, reacting for 3 hours at 400 ℃, and obtaining the hollow cubic cage-shaped nickel disulfide/nickel diselenide material after heat treatment is finished.
Example 8
The preparation method of the hollow cubic cage-shaped nickel disulfide/nickel diselenide comprises the following steps:
s1, preparing a reaction solution: adding 450mg of nickel acetate tetrahydrate and 450mg of PVP (K30) into 30mL of absolute ethyl alcohol, and performing ultrasonic dispersion at room temperature for 40min to obtain a clear and transparent solution;
s4, preparing a dodecahedron nickel-based acetate precursor: and (4) adding the uniform solution obtained in the step S1 into a hydrothermal kettle, carrying out heat treatment for 6 hours at 140 ℃, naturally cooling to room temperature, centrifugally collecting a precursor, and washing the precursor with absolute ethyl alcohol for five times. Vacuum drying at 60 ℃ for 14h, and naturally cooling to room temperature to obtain a required dodecahedral nickel-based acetate precursor;
s3, preparing a hollow cubic cage-shaped nickel disulfide/nickel diselenide material: and (4) respectively placing the dodecahedral nickel-based acetate precursor prepared in the step (4) and sublimed sulfur/selenium powder at the lower end and the upper end of a nitrogen atmosphere tube furnace, reacting for 3.5 hours at 400 ℃, and obtaining the hollow cubic cage-shaped nickel disulfide/nickel diselenide material after heat treatment is finished.
Example 9
The preparation method of the hollow cubic cage-shaped nickel disulfide/nickel diselenide comprises the following steps:
s1, preparing a reaction solution: adding 450mg of nickel acetate tetrahydrate and 450mg of PVP (K30) into 30mL of absolute ethyl alcohol, and performing ultrasonic dispersion at room temperature for 40min to obtain a clear and transparent solution;
s4, preparing a dodecahedron nickel-based acetate precursor: and (4) adding the uniform solution obtained in the step S1 into a hydrothermal kettle, carrying out heat treatment at 100 ℃ for 6h, naturally cooling to room temperature, centrifugally collecting a precursor, and washing with absolute ethyl alcohol for five times. Vacuum drying at 60 deg.C for 14h, and naturally cooling to room temperature to obtain required dodecahedral nickel-based acetate precursor;
s3, preparing a hollow cubic cage-shaped nickel disulfide/nickel diselenide material: and (5) respectively placing the dodecahedral nickel-based acetate precursor prepared in the step (S4) and sublimed sulfur/selenium powder at the lower end and the upper end of a nitrogen atmosphere tube furnace, reacting for 4 hours at 400 ℃, and obtaining the hollow cubic cage-shaped nickel disulfide/nickel diselenide material after heat treatment.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a hollow cubic cage-shaped nickel disulfide/nickel diselenide lithium oxygen battery anode catalyst is characterized by comprising the following steps: the method comprises the following steps:
dispersing nickel salt and polyvinylpyrrolidone in a solvent to obtain a uniform mixed solution;
carrying out hydrothermal reaction on the mixed solution, wherein the hydrothermal reaction temperature is 100-150 ℃, and the hydrothermal reaction time is 4-8h; obtaining a dodecahedral nickel-based acetate precursor;
simultaneously carrying out vulcanization and selenization treatment on a dodecahedron nickel-based acetate precursor in a protective atmosphere to obtain a hollow cubic cage;
in the sulfuration and selenization processes, adding sublimed sulfur and selenium powder, and calcining for 2-4h at 370-420 ℃ to obtain the hollow cubic cage-shaped nickel disulfide/nickel diselenide material.
2. The preparation method of the hollow cubic cage-shaped nickel disulfide/nickel diselenide lithium oxygen battery anode catalyst according to claim 1, characterized by comprising the following steps: the nickel salt is nickel acetate tetrahydrate.
3. The preparation method of the hollow cubic cage-shaped nickel disulfide/nickel diselenide lithium oxygen battery anode catalyst according to claim 2, characterized by comprising the following steps: the mass ratio of the nickel acetate tetrahydrate to the polyvinylpyrrolidone is 1:0.8 to 1.2.
4. The preparation method of the hollow cubic cage-shaped nickel disulfide/nickel diselenide lithium oxygen battery cathode catalyst according to claim 1, is characterized in that: the method also comprises a step of purifying the prepared dodecahedral nickel-based acetate precursor.
5. The preparation method of the hollow cubic cage-shaped nickel disulfide/nickel diselenide lithium oxygen battery anode catalyst according to claim 4, characterized by comprising the following steps: the purification comprises centrifugal separation, washing and drying, wherein the washing is to wash a dodecahedron nickel-based acetate precursor by adopting absolute ethyl alcohol.
6. The preparation method of the hollow cubic cage-shaped nickel disulfide/nickel diselenide lithium oxygen battery anode catalyst according to claim 1, characterized by comprising the following steps: the mass ratio of sublimed sulfur to selenium powder to the dodecahedral nickel-based acetate precursor is 1-3: 1.5 to 3:1.
7. the preparation method of the hollow cubic cage-shaped nickel disulfide/nickel diselenide lithium oxygen battery anode catalyst according to claim 1, characterized by comprising the following steps: the heating rate in the sulfuration and selenization process is 1-5 ℃ for min -1 。
8. The preparation method of the hollow cubic cage-shaped nickel disulfide/nickel diselenide lithium oxygen battery cathode catalyst according to claim 1, is characterized in that: the specific method for sulfuration and selenization comprises the following steps: and placing the obtained dodecahedral nickel-based acetate precursor in the downstream of a nitrogen atmosphere tube furnace, placing sublimed sulfur and selenium powder in the upstream of the tube furnace, simultaneously vulcanizing and selenizing, calcining at 370-420 ℃ for 2-4h, and finishing the reaction to obtain the hollow cubic cage-shaped nickel disulfide/nickel diselenide material.
9. The utility model provides a cavity cubic cage form nickel disulfide/two nickel selenide lithium oxygen battery positive pole catalyst which characterized in that: prepared by the preparation method of any one of claims 1 to 8.
10. A lithium oxygen battery, characterized by: the cathode material comprises the hollow cubic cage-shaped nickel disulfide/nickel diselenide lithium oxygen battery cathode catalyst of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211007269.3A CN115224286A (en) | 2022-08-22 | 2022-08-22 | Hollow cubic cage-shaped nickel disulfide/nickel diselenide lithium oxygen battery anode catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211007269.3A CN115224286A (en) | 2022-08-22 | 2022-08-22 | Hollow cubic cage-shaped nickel disulfide/nickel diselenide lithium oxygen battery anode catalyst and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115224286A true CN115224286A (en) | 2022-10-21 |
Family
ID=83616669
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211007269.3A Pending CN115224286A (en) | 2022-08-22 | 2022-08-22 | Hollow cubic cage-shaped nickel disulfide/nickel diselenide lithium oxygen battery anode catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115224286A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116864714A (en) * | 2023-08-16 | 2023-10-10 | 山东大学 | Bimetal selenide/carbon composite conductive powder material, and preparation method and application thereof |
| CN117486264A (en) * | 2023-12-29 | 2024-02-02 | 洛阳理工学院 | Carbon nano-sheet loaded cobalt-based heterojunction material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120115048A1 (en) * | 2010-11-04 | 2012-05-10 | Samsung Electronics Co., Ltd. | Positive electrode for lithium air battery, method of preparing the positive electrode, and lithium air battery including the positive electrode |
| CN111659436A (en) * | 2020-05-19 | 2020-09-15 | 中国科学院山西煤炭化学研究所 | Electronegative heteroatom-transition metal co-doped carbon-based non-noble metal electrocatalyst and preparation method thereof |
| CN113078328A (en) * | 2021-03-17 | 2021-07-06 | 浙江大学 | Co-FPOH microsphere material for water system zinc-air battery and preparation method thereof |
| CN113957474A (en) * | 2020-07-03 | 2022-01-21 | 中国科学院大连化学物理研究所 | Water electrolysis material with heterojunction structure and preparation method and application thereof |
| KR20220090596A (en) * | 2020-12-21 | 2022-06-30 | 동국대학교 산학협력단 | Air electrode for Lithium Air Battery and Method of manufacturing the same |
-
2022
- 2022-08-22 CN CN202211007269.3A patent/CN115224286A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120115048A1 (en) * | 2010-11-04 | 2012-05-10 | Samsung Electronics Co., Ltd. | Positive electrode for lithium air battery, method of preparing the positive electrode, and lithium air battery including the positive electrode |
| CN111659436A (en) * | 2020-05-19 | 2020-09-15 | 中国科学院山西煤炭化学研究所 | Electronegative heteroatom-transition metal co-doped carbon-based non-noble metal electrocatalyst and preparation method thereof |
| CN113957474A (en) * | 2020-07-03 | 2022-01-21 | 中国科学院大连化学物理研究所 | Water electrolysis material with heterojunction structure and preparation method and application thereof |
| KR20220090596A (en) * | 2020-12-21 | 2022-06-30 | 동국대학교 산학협력단 | Air electrode for Lithium Air Battery and Method of manufacturing the same |
| CN113078328A (en) * | 2021-03-17 | 2021-07-06 | 浙江大学 | Co-FPOH microsphere material for water system zinc-air battery and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| BO WEN等: "Advances and Challenges on Cathode Catalysts for Lithium-Oxygen Batteries", 《JOURNAL OF ELECTROCHEMISTRY》, 24 June 2022 (2022-06-24) * |
| YANG YANG等: "An Interfacial Electron Transfer on Tetrahedral NiS2/NiSe2 Heterocages with Dual-Phase Synergy for Efficiently Triggering the Oxygen Evolution Reaction", 《SMALL》, 6 December 2019 (2019-12-06) * |
| 徐梦婷等: "非水系锂空气电池催化剂", 《化学进展》, 22 December 2020 (2020-12-22) * |
| 曾晓苑著: "《碳基复合材料的制备及其在能源存储中的应用》", 31 March 2021, 冶金工业出版社, pages: 32 * |
| 曾晓苑著: "《锂空气电池高性能催化剂的制备与应用》", 30 April 2019, 冶金工业出版社, pages: 27 * |
| 沈培康著: "《电化学氧还原的理论基础和应用技术》", 31 December 2018, 广西科学技术出版社, pages: 116 - 118 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116864714A (en) * | 2023-08-16 | 2023-10-10 | 山东大学 | Bimetal selenide/carbon composite conductive powder material, and preparation method and application thereof |
| CN117486264A (en) * | 2023-12-29 | 2024-02-02 | 洛阳理工学院 | Carbon nano-sheet loaded cobalt-based heterojunction material and preparation method and application thereof |
| CN117486264B (en) * | 2023-12-29 | 2024-04-02 | 洛阳理工学院 | Carbon nano-sheet loaded cobalt-based heterojunction material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109378449B (en) | NiCo for positive electrode material of lithium-sulfur battery2S4Preparation method of coated porous carbon skeleton | |
| CN113410440B (en) | Cobalt diselenide @ porous nitrogen-doped carbon nanocomposite, potassium ion battery and preparation method of cobalt diselenide @ porous nitrogen-doped carbon nanocomposite | |
| CN115224286A (en) | Hollow cubic cage-shaped nickel disulfide/nickel diselenide lithium oxygen battery anode catalyst and preparation method thereof | |
| CN102237519A (en) | Fluorine-free preparation method for three-dimensional porous silica powder anode material of lithium ion battery | |
| CN111193014B (en) | Cobaltosic oxide-nitrogen doped carbon/carbon nanocage composite material with eggshell-yolk structure and preparation method and application thereof | |
| CN107768645B (en) | Porous nitrogen-doped carbon nanosheet composite negative electrode material and preparation method thereof | |
| WO2022021643A1 (en) | Novel lithium-ion battery negative electrode material and preparation method therefor | |
| CN108428870B (en) | Large-scale preparation method and application of two-dimensional carbon sheet aerogel material compounded by metal and metal derivatives thereof | |
| CN112875764B (en) | Preparation method of high-entropy oxide of lithium ion battery negative electrode material | |
| CN106450185B (en) | MoS2Nanoneedle/carbon nanotube composite negative pole material preparation method | |
| CN112499631A (en) | Fe3C/C composite material and application thereof | |
| CN112054174A (en) | Potassium ion battery negative electrode material and preparation method and application thereof | |
| CN111276694A (en) | Preparation method of polyimide derived carbon/molybdenum disulfide negative electrode material and application of polyimide derived carbon/molybdenum disulfide negative electrode material in potassium ion battery | |
| CN113636607A (en) | Preparation method of high-entropy oxide of lithium ion battery negative electrode material | |
| CN112960688A (en) | ZnIn2S4Sodium ion battery negative electrode material and preparation method thereof | |
| CN109167026B (en) | Silicon-cobalt composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN113506862B (en) | Nano carbon fiber composite material for lithium-sulfur battery anode and preparation method and application thereof | |
| CN114864939A (en) | Lithium-sulfur battery anode catalytic material and preparation method and application thereof | |
| CN109742341B (en) | Method for preparing Fe-doped two-dimensional porous NiO electrode material with high lithium storage performance under assistance of glucose | |
| CN113410460A (en) | Three-dimensional ordered macroporous carbon-coated nickel selenide nanocrystalline material, preparation and application | |
| CN108666569B (en) | Preparation method of spongy carbon material | |
| CN113113607A (en) | Liquid metal/oxide lithium-sulfur battery positive electrode material | |
| Zhang et al. | Simple Preparation of Co3O4 with a Controlled Shape and Excellent Lithium Storage Performance | |
| CN114551802B (en) | Preparation method and application of carbon nano rod composite material | |
| CN114262955B (en) | Size-controllable Ni-NiO heterojunction nanoparticle doped carbon fiber, preparation method and application thereof in lithium-sulfur battery diaphragm |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |