CN116470024A - Preparation method of metal oxide-based composite positive electrode material for lithium-sulfur battery - Google Patents
Preparation method of metal oxide-based composite positive electrode material for lithium-sulfur battery Download PDFInfo
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 19
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 17
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 145
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 85
- 239000010941 cobalt Substances 0.000 claims abstract description 85
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000000463 material Substances 0.000 claims abstract description 67
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 59
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 54
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 37
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 239000010405 anode material Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000003763 carbonization Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 11
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 239000010406 cathode material Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 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 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000003929 acidic solution Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 42
- 239000011593 sulfur Substances 0.000 abstract description 42
- 239000012876 carrier material Substances 0.000 abstract description 36
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract description 18
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract description 18
- 229920001021 polysulfide Polymers 0.000 abstract description 18
- 239000005077 polysulfide Substances 0.000 abstract description 18
- 150000008117 polysulfides Polymers 0.000 abstract description 18
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- WBVDQFAPFUMTFF-UHFFFAOYSA-N [C].[N].[Co] Chemical compound [C].[N].[Co] WBVDQFAPFUMTFF-UHFFFAOYSA-N 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 22
- 238000005245 sintering Methods 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 7
- 238000004146 energy storage Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910018091 Li 2 S Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- -1 low price Chemical compound 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000006177 thiolation reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a preparation method of a lithium-sulfur battery positive electrode material, in particular to preparation of a metal oxide-based composite positive electrode material for a lithium-sulfur battery. It comprises the following steps: 1. pretreating a carbon nano tube material; 2. preparing a metal organic framework/carbon nano tube precursor; 3. preparing a cobalt-based nitrogen-doped porous carbon skeleton material; 4. preparing a cobalt-based nitrogen-doped porous carbon carrier loaded with cerium oxide; 5. and (3) preparing the lithium-sulfur battery composite anode material. The metal oxide-based composite anode material prepared by combining the high-temperature carbonization method and the hydrothermal reaction method effectively solves the problems of poor conductivity of elemental sulfur materials, shuttle effect of polysulfide and volume expansion of electrodes in the lithium sulfur battery through the chemical adsorption action of the porous carbon conductive framework and the bipolar substance, and realizes excellent cycle stability by the combined compatibility of ceria, cobalt-nitrogen-carbon and a porous structure. Meanwhile, the prepared sulfur carrier material has rich raw materials, low cost and simple synthesis method, so that the sulfur carrier material is suitable for further commercialization of the lithium sulfur battery anode material.
Description
Technical Field
The invention relates to the technical field of lithium-sulfur battery positive electrode materials, in particular to a preparation method of a metal oxide-based composite positive electrode material for a lithium-sulfur battery.
Background
With the rapid development of society, electric automobiles, intelligent networks, and mobile electronic devices have become an integral part of human society. However, the energy density provided by some materials such as lithium cobalt oxide or lithium iron phosphate used in the current Lithium Ion Batteries (LiBs) as energy storage systems cannot meet the demands of people. Accordingly, there is an urgent need to find other advanced battery energy storage devices with high energy density. Lithium sulfur (Li-S) batteries have a higher theoretical energy density (2600 Wh kg) than conventional lithium ion batteries -1 ) The inherent advantages of elemental sulfur, such as low price, no pollution, rich reserves and the like of sulfur, attract attention and research of lithium sulfur batteries. However, lithium sulfur batteries have some troublesome problems in commercialization processes, such as sulfur (S) and its reduction products (Li 2 S 2 /Li 2 S) is poor in conductivity, limiting the utilization of active materials; the "shuttle effect" generated by dissolution of lithium polysulfide in the electrolyte during discharge causes problems of low coulomb efficiency and fast capacity decay of the battery, and the loss of active material occurring by the volume change of the sulfur positive electrode during charge and discharge causes poor cycling stability of the battery. In order to solve the above problems, a carrier material is generally introduced to be compounded with elemental sulfur, and the carrier material is the most common at present, which is formed by wrapping elemental sulfur in various carbon materials, and improving the electron conductivity and the porosity of the carbon materials to improve the problem of the sulfur positive electrode. However, physical adsorption using carbon as a carrier material can only adsorb polysulfide by Van der Waals force, and the phenomenon of polysulfide dissolution shuttling still occurs due to weak interaction, which is unfavorable for long-term stable cycle of the lithium-sulfur battery. Thus, the preparation of a positive electrode active material support material capable of effectively limiting polysulfide shuttling is a key point in the development of high energy density lithium sulfur batteries (1, W.W.Sun, S.K.Liu, Y.J.Li, D.Q.Wang, Q.P Guo, X.B.Hong, K.Xie, Z.Y.Ma, C.M.Zheng, S.Z.Xiong.Advanced Functional Materials,2022,32 (43): 2205471.2, Y.Yao, C.Y.Chang, R.G.Li, D.Guo, Z.X).Liu,X.Pu,J.Y.Zhai.Chemical Engineering Journal,2022,431:134033)。
Disclosure of Invention
The invention aims to provide a high-efficiency sulfur carrier material for a lithium sulfur battery in an energy storage system, and a preparation method and application thereof, wherein the carrier material can solve the technical problems of poor electrochemical performance of the lithium sulfur battery caused by dissolution shuttle of polysulfide, low conductivity of elemental sulfur and volume expansion.
In order to solve the technical problems, the invention provides the following technical solutions:
a metal oxide based composite positive electrode material for a lithium sulfur battery specifically comprises the following steps:
1. pretreatment of carbon nanotubes
Stirring and mixing carbon nano tubes with the mass ratio of 0.1-1:0.01-1 with an acidic solution at room temperature, centrifuging and washing to obtain a pretreated carbon nano tube material;
2. preparation of metal organic framework/carbon nano tube precursor
Preparing the carbon nano tube treated in the first step, a dispersing agent, cobalt nitrate hexahydrate, 2-methylimidazole and methanol into a solution according to the mass ratio of 0.01-0.1:0.1-1:1-3:1-5:0.01-1, stirring at room temperature, centrifuging after dissolving, and washing to obtain a metal organic framework/carbon nano tube precursor;
3. preparation of cobalt-based nitrogen-doped porous carbon skeleton material
Placing the metal organic framework/carbon nano tube precursor obtained in the second step into a tube furnace with protective gas for programming temperature rise, roasting and carbonizing treatment, and cooling to room temperature after heat preservation to obtain a cobalt-based nitrogen-doped porous carbon framework material;
4. preparation of cobalt-based nitrogen-doped porous carbon carrier loaded with cerium oxide
Preparing a solution from the cobalt-based nitrogen-doped porous carbon framework material obtained in the step three, cerium nitrate hexahydrate and deionized water according to the mass ratio of 0.1-1:0.01-1:0.01-0.1, stirring, adding a certain volume of alkaline solution, stirring, transferring to a reaction kettle, heating, cooling to room temperature, centrifuging and washing to obtain a cerium oxide-loaded cobalt-based nitrogen-doped porous carbon carrier;
5. preparation of lithium-sulfur battery composite anode material
Mixing the cobalt-based nitrogen doped porous carbon carrier loaded with cerium oxide obtained in the step four with elemental sulfur in a mass ratio of 1:2-5, grinding, transferring into a tube furnace, heating in a protective gas in a programmed manner, heating, preserving heat, and cooling to room temperature to obtain the lithium-sulfur battery composite anode material.
The acid solution in the first step is one or more of hydrochloric acid, sulfuric acid or nitric acid, and the concentration is 0.05-1mol/L. The carbon nano tube treated by the acid solution can grow on the surface of the carbon nano tube with a plurality of oxygen-containing functional groups, thereby increasing the polarity of the carbon nano tube and being beneficial to improving the adsorption effect on polysulfide.
Further, the dispersing agent in the second step is one or more of polyvinylpyrrolidone, polyethylene glycol or sodium polyacrylate. One or more of polyvinylpyrrolidone, polyethylene glycol or sodium polyacrylate as a dispersing agent in the solution can fully disperse the solute in the solution, which is beneficial to the full reaction of the material.
Further, the stirring time of the mixed solution in the second step is 12-48h.
Further, the temperature programming rate in the third step is 1-5 ℃/min, the roasting carbonization temperature is 600-900 ℃, and the heat preservation time is 2-6h.
Further, in the fourth step, the alkaline solution is one of sodium hydroxide or potassium hydroxide, and the added volume is 10% -40% of the mixed solution of the cobalt-based nitrogen doped porous carbon skeleton and cerium nitrate hexahydrate. .
Further, in the fourth step, the heating temperature is 150-180 ℃, and the heat preservation time is 12-24 hours.
Further, in the fifth step, the synthetic carrier material is mixed with elemental sulfur according to a mass ratio of 1:2-5.
Further, the temperature programming rate in the step five is 1-5 ℃/min, the heating temperature is 150-155 ℃, and the heat preservation time is 12-24h.
Further, the shielding gas in the third and fifth steps is one of nitrogen, argon and argon/hydrogen mixture.
Based on the technical proposal, the method has the following beneficial effects:
according to the invention, the metal organic framework grown in situ on the carbon nano tube is designed to be used as a precursor material for constructing the sulfur carrier, and the electron transmission channel formed by the interconnected carbon nano tubes can promote the migration efficiency of electrons and enhance the conductivity of elemental sulfur. The cobalt-based nitrogen doped porous carbon skeleton derived from carbonization treatment of the precursor material and cerium nitrate hexahydrate are subjected to hydrothermal reaction to form cerium dioxide-loaded cobalt-based nitrogen doped porous carbon serving as a sulfur carrier material, so that bipolar chemisorption is realized, polysulfide dissolved in electrolyte can be effectively adsorbed, the utilization rate of active substances is further improved, meanwhile, the nitrogen doped porous carbon skeleton can effectively contain sulfur molecules and relieve volume expansion in a thiolation process so as to prolong the cycle service life of a lithium sulfur battery, therefore, the lithium sulfur battery assembled by the composite positive electrode material prepared by combining the carrier material and sulfur has high initial discharge specific capacity of 1095.4mAh/g at 0.1 multiplying power, after different multiplying powers of 0.1 multiplying power, 0.5 multiplying power, 1 multiplying power and 2 multiplying power are circulated, 787.5mAh/g of discharge specific capacity still remains after the multiplying power is repeated at 0.1 multiplying power, the capacity retention rate is more than 72%, and the coulombic efficiency is kept at more than 98% after the multiplying power is circulated for 100 times at 0.5 multiplying power. In a word, the cobalt-based nitrogen-doped porous carbon loaded with cerium oxide prepared by combining a high-temperature carbonization method and a hydrothermal reaction method is used as a sulfur carrier material, has the advantages of a continuous electron transmission channel consisting of carbon nanotubes and nitrogen-doped porous carbon and bipolar adsorption sites consisting of cerium oxide and cobalt nitrogen carbon, effectively solves the problems of poor conductivity of elemental sulfur materials, shuttle effect of polysulfide and volume expansion of electrodes in the lithium sulfur battery of an energy storage system, and realizes long cycle life and high stability of the lithium sulfur battery by the combined compatibility of the cerium oxide, the cobalt-nitrogen-carbon and the porous structure. Meanwhile, the prepared carrier material has rich raw materials, low cost and simple synthesis method, so that the carrier material is suitable for further commercialization on lithium-sulfur batteries in energy storage systems.
Drawings
In order to more clearly illustrate the modified results of the embodiments of the present invention, the drawings used in the description of the comparative examples and the embodiments will be briefly described below.
FIG. 1 is an X-ray diffraction pattern of a metal-organic framework/carbon nanotube precursor material prepared in accordance with an example;
FIG. 2 is an X-ray diffraction pattern of a cobalt-based nitrogen-doped porous carbon material prepared in the examples;
FIG. 3 is an X-ray diffraction pattern of a cerium oxide loaded cobalt-based nitrogen-doped porous carbon support material prepared in the examples;
FIG. 4 is an electron microscope image of a metal organic framework/carbon nanotube precursor material prepared in the examples;
FIG. 5 is an electron microscope image of a cobalt-based nitrogen-doped porous carbon material prepared in the examples;
FIG. 6 is an electron micrograph of a cerium oxide loaded cobalt-based nitrogen-doped porous carbon skeleton sulfur support material prepared in the examples;
fig. 7 is a charge-discharge curve diagram of a lithium sulfur battery assembled by using cerium oxide-loaded cobalt-based nitrogen-doped porous carbon as a sulfur carrier material prepared in the example at different multiplying powers;
FIG. 8 is a graph of the rate capability of a lithium sulfur battery assembled with cerium oxide loaded cobalt-based nitrogen-doped porous carbon as a sulfur support material prepared in the examples;
FIG. 9 is a cyclic voltammogram of a lithium sulfur battery assembled with ceria-loaded cobalt-based nitrogen-doped porous carbon as the sulfur carrier material prepared in the example;
FIG. 10 is a graph of cycle performance at 0.5 rate of a lithium sulfur battery assembled with cerium oxide-loaded cobalt-based nitrogen-doped porous carbon as a sulfur carrier material prepared in the example, with coulombic efficiency and specific discharge capacity in that order from top to bottom;
FIG. 11 is a graph showing the charge and discharge curves of a lithium sulfur battery assembled with cerium oxide-loaded cobalt-based nitrogen-doped porous carbon as a sulfur carrier material prepared in comparative example 1 at different rates;
FIG. 12 is a graph of the rate performance of a lithium sulfur battery assembled with ceria-loaded cobalt-based nitrogen-doped porous carbon as a sulfur support material prepared in comparative example 1;
FIG. 13 is a graph showing the cycle performance of a lithium sulfur battery assembled with cerium oxide-loaded cobalt-based nitrogen-doped porous carbon prepared in comparative example 1 as a sulfur carrier material at a rate of 0.5, with the coulombic efficiency and specific discharge capacity in that order from top to bottom;
FIG. 14 is a graph showing the cycle performance of a lithium sulfur battery assembled with cerium oxide-loaded cobalt-based nitrogen-doped porous carbon prepared in comparative example 2 as a sulfur carrier material at 0.5 rate, with coulombic efficiency and specific discharge capacity in that order from top to bottom;
FIG. 15 is a graph showing the cycle performance of a lithium sulfur battery assembled with cerium oxide-loaded cobalt-based nitrogen-doped porous carbon prepared in comparative example 3 as a sulfur carrier material at 0.5 rate, with coulombic efficiency and specific discharge capacity in that order from top to bottom;
fig. 16 is a graph showing the cycle performance of a lithium sulfur battery assembled by using the ceria-supported cobalt-based nitrogen-doped porous carbon prepared in comparative example 4 as a sulfur carrier material at a rate of 0.5, in which the coulombic efficiency and specific discharge capacity are sequentially shown from top to bottom.
Detailed Description
The above-described matters of the present invention will be described in further detail by way of examples, but the subject matter of the present invention is not limited to the following examples, and all techniques realized based on the above-described matters of the present invention are within the scope of the present invention.
Experimental medicine
Experimental equipment
The following is a further description of the preparation process steps of the examples with reference to the figures and comparative examples, but the scope of the invention is not limited to the following examples.
Examples: the metal oxide based composite positive electrode material for lithium sulfur battery of this example is prepared according to the following steps:
1. pretreatment of carbon nanotube material
Adding 0.3g of carbon nano tube into 20mL of nitric acid solution with the concentration of 15mol/L, stirring and mixing at room temperature, centrifuging, washing and drying;
2. preparation of metal organic framework/carbon nano tube precursor
Dissolving 0.1g of treated carbon nano tube and 0.5g of polyvinylpyrrolidone in 80mL of methanol solution, stirring for 2h, adding 1.75g of cobalt nitrate hexahydrate into the solution, stirring for 6h, adding 1.98g of 2-methylimidazole, stirring for 18h, centrifuging and washing to obtain a metal organic framework/carbon nano tube precursor;
3. preparation of cobalt-based nitrogen-doped porous carbon skeleton material
Placing the metal organic framework/carbon nano tube precursor obtained in the second step into a tube furnace with protective gas, sintering for 4 hours at the temperature rising rate of 5 ℃/min to 800 ℃, and cooling to room temperature to obtain the cobalt-based nitrogen-doped porous carbon framework material;
4. preparation of cobalt-based nitrogen-doped porous carbon carrier loaded with cerium oxide
After dispersing 0.2g of the cobalt-based nitrogen-doped porous carbon skeleton material and 0.05g of cerium nitrate hexahydrate in 40mL of deionized water and stirring for 6 hours, 15mL of a sodium hydroxide solution having a concentration of 0.02mol/L was added to the above solution and stirred for 6 hours. Transferring the solution into a hydrothermal kettle, preserving heat at 180 ℃ for 16 hours, cooling to room temperature, centrifuging and washing to obtain the cobalt-based nitrogen doped porous carbon skeleton carrier loaded with cerium oxide;
5. preparation of composite cathode material
Mixing the cobalt-based nitrogen-doped porous carbon skeleton material carrier loaded with cerium oxide obtained in the step four with elemental sulfur according to the mass ratio of 1:3, grinding, transferring into a tube furnace, and sintering at 155 ℃ for 12 hours under the condition of nitrogen to obtain the lithium-sulfur battery composite anode material.
Comparative example 1: the metal oxide based composite positive electrode material for lithium sulfur battery of this example is prepared according to the following steps:
1. pretreatment of carbon nanotube material
Adding 0.3g of carbon nano tube into 20mL of nitric acid solution with the concentration of 15mol/L, stirring and mixing at room temperature, centrifuging, washing and drying;
2. preparation of metal organic framework/carbon nano tube precursor
Dissolving 0.1g of treated carbon nano tube and 0.5g of polyvinylpyrrolidone in 80mL of methanol solution, stirring for 2h, adding 1.75g of cobalt nitrate hexahydrate into the solution, stirring for 6h, adding 1.98g of 2-methylimidazole, stirring for 18h, centrifuging and washing to obtain a metal organic framework/carbon nano tube precursor;
3. preparation of cobalt-based nitrogen-doped porous carbon skeleton material
Placing the metal organic framework/carbon nano tube precursor obtained in the second step into a tube furnace with protective gas, sintering for 4 hours at the temperature rising rate of 5 ℃/min to 800 ℃, and cooling to room temperature to obtain the cobalt-based nitrogen-doped porous carbon framework material;
4. preparation of cobalt-based nitrogen-doped porous carbon carrier loaded with cerium oxide
After dispersing 0.2g of the cobalt-based nitrogen-doped porous carbon skeleton material and 0.01g of cerium nitrate hexahydrate in 40mL of deionized water and stirring for 6 hours, 15mL of a sodium hydroxide solution having a concentration of 0.02mol/L was added to the above solution and stirred for 6 hours. Transferring the solution into a hydrothermal kettle, preserving heat at 180 ℃ for 16 hours, cooling to room temperature, centrifuging and washing to obtain the cobalt-based nitrogen doped porous carbon skeleton carrier loaded with cerium oxide;
5. preparation of composite cathode material
Mixing the cobalt-based nitrogen-doped porous carbon skeleton material carrier loaded with cerium oxide obtained in the step four with elemental sulfur according to the mass ratio of 1:3, grinding, transferring into a tube furnace, and sintering at 155 ℃ for 12 hours under the condition of nitrogen to obtain the lithium-sulfur battery composite anode material.
Comparative example 2:
1. pretreatment of carbon nanotube material
Adding 0.3g of carbon nano tube into 20mL of nitric acid solution with the concentration of 15mol/L, stirring and mixing at room temperature, centrifuging, washing and drying;
2. preparation of metal organic framework/carbon nano tube precursor
Dissolving 0.1g of treated carbon nano tube and 0.5g of polyvinylpyrrolidone in 80mL of methanol solution, stirring for 2h, adding 1.75g of cobalt nitrate hexahydrate into the solution, stirring for 6h, adding 1.98g of 2-methylimidazole, stirring for 18h, centrifuging and washing to obtain a metal organic framework/carbon nano tube precursor;
3. preparation of cobalt-based nitrogen-doped porous carbon skeleton material
Placing the metal organic framework/carbon nano tube precursor obtained in the second step into a tube furnace with protective gas, sintering for 4 hours at the temperature rising rate of 5 ℃/min to 800 ℃, and cooling to room temperature to obtain the cobalt-based nitrogen-doped porous carbon framework material;
4. preparation of cobalt-based nitrogen-doped porous carbon carrier loaded with cerium oxide
After dispersing 0.2g of the cobalt-based nitrogen-doped porous carbon skeleton material and 0.025g of cerium nitrate hexahydrate in 40mL of deionized water and stirring for 6 hours, 15mL of a sodium hydroxide solution having a concentration of 0.02mol/L was added to the above solution, and stirring was carried out for 6 hours. Transferring the solution into a hydrothermal kettle, preserving heat at 180 ℃ for 16 hours, cooling to room temperature, centrifuging and washing to obtain the cobalt-based nitrogen doped porous carbon skeleton carrier loaded with cerium oxide;
5. preparation of composite cathode material
Mixing the cobalt-based nitrogen-doped porous carbon skeleton material carrier loaded with cerium oxide obtained in the step four with elemental sulfur according to the mass ratio of 1:3, grinding, transferring into a tube furnace, and sintering at 155 ℃ for 12 hours under the condition of nitrogen to obtain the lithium-sulfur battery composite anode material.
Comparative example 3:
1. pretreatment of carbon nanotube material
Adding 0.3g of carbon nano tube into 20mL of nitric acid solution with the concentration of 15mol/L, stirring and mixing at room temperature, centrifuging, washing and drying;
2. preparation of metal organic framework/carbon nano tube precursor
Dissolving 0.1g of treated carbon nano tube and 0.5g of polyvinylpyrrolidone in 80mL of methanol solution, stirring for 2h, adding 1.75g of cobalt nitrate hexahydrate into the solution, stirring for 6h, adding 1.98g of 2-methylimidazole, stirring for 18h, centrifuging and washing to obtain a metal organic framework/carbon nano tube precursor;
3. preparation of cobalt-based nitrogen-doped porous carbon skeleton material
Placing the metal organic framework/carbon nano tube precursor obtained in the second step into a tube furnace with protective gas, sintering for 4 hours at the temperature rising rate of 5 ℃/min to 800 ℃, and cooling to room temperature to obtain the cobalt-based nitrogen-doped porous carbon framework material;
4. preparation of cobalt-based nitrogen-doped porous carbon carrier loaded with cerium oxide
After dispersing 0.2g of the cobalt-based nitrogen-doped porous carbon skeleton material and 0.075g of cerium nitrate hexahydrate in 40mL of deionized water and stirring for 6 hours, 15mL of a sodium hydroxide solution having a concentration of 0.02mol/L was added to the above solution, and stirring was performed for 6 hours. Transferring the solution into a hydrothermal kettle, preserving heat for 16 hours at 180 ℃, centrifuging and washing to obtain a cobalt-based nitrogen-doped porous carbon skeleton carrier loaded with cerium dioxide;
5. preparation of composite cathode material
Mixing the cobalt-based nitrogen-doped porous carbon skeleton material carrier material loaded with cerium oxide obtained in the step four with elemental sulfur according to the mass ratio of 1:3, grinding, transferring into a tube furnace, and sintering at 155 ℃ for 12 hours under the condition of nitrogen to obtain the lithium-sulfur battery composite anode material.
Comparative example 4:
1. pretreatment of carbon nanotube material
Adding 0.3g of carbon nano tube into 20mL of nitric acid solution with the concentration of 15mol/L, stirring and mixing at room temperature, centrifuging, washing and drying;
2. preparation of metal organic framework/carbon nano tube precursor
Dissolving 0.1g of treated carbon nano tube and 0.5g of polyvinylpyrrolidone in 80mL of methanol solution, stirring for 2h, adding 1.75g of cobalt nitrate hexahydrate into the solution, stirring for 6h, adding 1.98g of 2-methylimidazole, stirring for 18h, centrifuging and washing to obtain a metal organic framework/carbon nano tube precursor;
3. preparation of cobalt-based nitrogen-doped porous carbon skeleton material
Placing the metal organic framework/carbon nano tube precursor obtained in the second step into a tube furnace with protective gas, sintering for 4 hours at the temperature rising rate of 5 ℃/min to 800 ℃, and cooling to room temperature to obtain the cobalt-based nitrogen-doped porous carbon framework material;
4. preparation of cobalt-based nitrogen-doped porous carbon carrier loaded with cerium oxide
After dispersing 0.2g of the cobalt-based nitrogen-doped porous carbon skeleton material and 0.1g of cerium nitrate hexahydrate in 40mL of deionized water and stirring for 6 hours, 15mL of a sodium hydroxide solution having a concentration of 0.02mol/L was added to the above solution and stirred for 6 hours. Transferring the solution into a hydrothermal kettle, preserving heat for 16 hours at 180 ℃, centrifuging and washing to obtain a cobalt-based nitrogen-doped porous carbon skeleton carrier loaded with cerium dioxide;
5. preparation of composite cathode material
Mixing the cobalt-based nitrogen-doped porous carbon skeleton material carrier material loaded with cerium oxide obtained in the step four with elemental sulfur according to the mass ratio of 1:3, grinding, transferring into a tube furnace, and sintering at 155 ℃ for 12 hours under the condition of nitrogen to obtain the lithium-sulfur battery composite anode material.
The four groups from comparative examples 1 to 4 differ from the examples only in the ceria loadings, and lithium sulfur batteries assembled by preparing synthetic ceria-loaded cobalt-based nitrogen-doped porous carbon as a sulfur support material from examples to comparative example 4 were tested as follows:
characterization of the Performance of the above comparative examples and examples
1) X-ray diffraction (XRD) testing. The phase structure of different samples is characterized by an X-ray diffraction measuring instrument with the model of X' Pert PRO, the test current and the test voltage are 40mA and 40mV respectively, and the scanning range is 10-90 degrees.
2) Scanning Electron Microscope (SEM) testing. The microcosmic morphology of different samples is characterized by a scanning electron microscope with the model of FEI sirion200, the accelerating voltage is 0.2-30kV, and the resolution is 20kV.
3) Cyclic Voltammetry (CV) test. And (3) carrying out cyclic voltammetry test on the composite anode material for the lithium-sulfur battery at a scanning rate of 0.05mV/s and a downloading rate of 1.5-3V by an electrochemical workstation with the model of CHI760E, and judging the potential of the occurrence of the redox reaction and the reduction reaction in the electrochemical reaction according to the positions of the oxidation peak and the reduction peak.
4) And (5) charge and discharge testing. The lithium sulfur battery assembled by the novel composite anode is tested by a blue battery tester with the model of CT2001A in different multiplying powers and cyclic charge and discharge within the voltage range of 1.5-3V, the electrochemical performance of the novel composite anode material is evaluated according to the multiplying power performance and the cyclic stability of the test,
FIG. 1 is an X-ray diffraction pattern of a metal-organic framework in situ grown material on carbon nanotubes prepared in accordance with an example. The crystalline structure of the metal-organic framework has strong diffraction peaks at a plurality of low angles, while the carbon nanotubes have no diffraction peaks due to their low content, which is consistent with previous research results (X.Gao, S.Li, Y.Du, B.Wang.APL Materials,2019,7 (9): 091115), which may demonstrate successful preparation of the metal-organic framework in situ grown material on the carbon nanotubes.
Fig. 2 is an X-ray diffraction pattern of the cobalt-based nitrogen-doped porous carbon material prepared in the example. The distinct diffraction peaks at 44.2 °, 51.3 ° and 75.7 ° correspond to the (111), (200) and (220) crystal planes of cubic cobalt (pdf#15-0806), respectively, indicating successful conversion of cobalt ions to metallic cobalt upon carbonization, and the diffraction peak at 26.1 ° corresponds to the (002) crystal plane of graphitic carbon, indicating successful conversion of organic ligands to graphitic carbon (C.H.Chen, S.H.Lin, Y.J.Wu, J.T.Su, C.C.Cheng, P.Y.Cheng, Y.C.Ting, S.Y.Lu.Chemical Engineering Journal,2022, 431:133924).
Fig. 3 is an X-ray diffraction pattern of the ceria-loaded cobalt-based nitrogen-doped porous carbon sulfur support material prepared in the example. Diffraction peaks at 28.5 °, 33.1 °, 47.5 ° and 56.4 ° of the material correspond to the (111), (200), (220) and (311) crystal planes of cubic phase ceria (PDF # 81-0792), indicating successful loading of ceria in a sulfur support material by hydrothermal reaction (W.J.Feng, J.Z.Chen, Y.P.Niu, W.Zhao, L.Zhang.Journal of Alloys and Compounds,2022,906: 164341).
Fig. 4 is an electron microscope image of the metal-organic framework prepared in the example in-situ growth material on carbon nanotubes. The metal-organic frameworks have typical rhombohedral shapes, the rhombohedral shapes being connected with carbon nanotubes, which form electron transport channels that promote electron transport efficiency while enhancing the conductivity of elemental sulfur (W.J.Feng, W.Zhao, Z.J.Shi, J.Z.Chen.Journal of Materials Science: materials in Electronics,2022,33 (22): 17483-17492.).
Fig. 5 is an electron microscope image of the cobalt-based nitrogen-doped porous carbon skeleton material prepared in the example. The cobalt-based nitrogen doped porous carbon particles are uniformly distributed, which indicates that the size of the cobalt-based nitrogen doped porous carbon after carbonization treatment is obviously reduced.
Fig. 6 is an electron microscopic scan of the cerium oxide-loaded cobalt-based nitrogen-doped porous carbon material prepared in the example. It can be clearly seen that the ceria formed after hydrothermal reaction is uniformly distributed on the surface of the cobalt-based nitrogen-doped porous carbon skeleton material, which is more advantageous for adsorption of polysulfides to reduce loss of active substances (X.C.Chen, L.B.Li, Y.H.Shan, D.Zhou, W.J.Cui, Y.M.Y, zhao.Journal of Energy Chemistry,2022, 70:502-510.).
Fig. 7 is initial charge and discharge curves at different rates for lithium sulfur batteries prepared in the examples with ceria-loaded cobalt-based nitrogen-doped porous carbon as the sulfur support material. The initial specific discharge capacities at 0.1 rate, 0.2 rate, 0.5 rate, 1 rate and 2 rate are 1095.4mAh/g, 860.4mAh/g, 668.3mAh/g, 560.1mAh/g and 456.1mAh/g respectively, and compared with the data of the comparative example, the lithium sulfur battery shows excellent specific discharge capacity due to the effective synergistic adsorption effect of ceria and cobalt nitrogen carbon bipolar substances in the carrier material on polysulfide.
Fig. 8 is a graph of the rate performance of a lithium sulfur battery assembled with ceria-loaded cobalt-based nitrogen-doped porous carbon as a sulfur support material prepared in the example. After the lithium sulfur battery is recycled from 0.1 multiplying power to different multiplying power, the specific discharge capacity of 787.5mAh/g is still remained when the multiplying power is recycled to 0.1 multiplying power, and the capacity retention rate is more than 72%, so that the lithium sulfur battery of the sulfur carrier material has excellent multiplying power performance, and the excellent multiplying power performance is attributed to the fact that cerium oxide and cobalt nitrogen carbon bipolar substances in the carrier material accelerate the oxidation-reduction reaction rate during charge and discharge.
FIG. 9 is a cyclic voltammogram of a lithium sulfur battery assembled from a composite positive electrode prepared by mixing cerium oxide-loaded cobalt-based nitrogen-doped porous carbon as a sulfur carrier material with elemental sulfur in a mass ratio of 1:3 at 0.05mV/s in the example. Two reduction peaks were observed at 2.28V and 2.01V, indicating that elemental sulfur was converted to long chain polysulfides followed by final conversion to solid phase lithium sulfide; the oxidation peak at 2.49V is initiated by the reversible reaction of solid phase lithium sulfide through lithium polysulfide and finally to elemental sulfur, with good reversibility through a tertiary cycle curve, which means that lithium sulfur batteries with cerium oxide-loaded cobalt-based nitrogen-doped porous carbon frameworks as sulfur support materials have excellent cycling stability (C.C.Hu, X.Y.Zhang, H.P.Li, Y.Zhao.Solid State Sciences,2022, 134:107025).
Fig. 10 is a cycle performance curve of a lithium sulfur battery assembled with ceria-supported cobalt-based nitrogen-doped porous carbon as a sulfur support material prepared in the example. The reversible discharge specific capacity of 557.2mAh/g is achieved after 100 cycles at 0.5 multiplying power, the capacity retention rate is 66.6% and the coulombic efficiency is above 98%, and the excellent cycle performance is attributed to the fact that the uniform distribution of cerium oxide on the surface of porous carbon in the carrier material promotes the transformation of polysulfide and the porous carbon structure slows down the volume expansion problem of elemental sulfur and discharge products.
Fig. 11 is initial charge and discharge curves at different rates of lithium sulfur batteries assembled with ceria-loaded cobalt-based nitrogen-doped porous carbon as a sulfur support material prepared in comparative example 1. Initial specific discharge capacities at 0.1 multiplying power, 0.2 multiplying power, 0.5 multiplying power, 1 multiplying power and 2 multiplying power are 997.7mAh/g, 528.8mAh/g, 355mAh/g, 263.4mAh/g and 190.6mAh/g respectively, the specific discharge capacities at different multiplying powers are lower, polarization between charge and discharge curves is serious, and the prepared sulfur carrier material is low in conductivity and can not effectively adsorb polysulfide.
Fig. 12 is a graph showing the rate performance of a lithium sulfur battery assembled with ceria-supported cobalt-based nitrogen-doped porous carbon as a sulfur support material prepared in comparative example 1. When the lithium sulfur battery is recycled from 0.1 multiplying power to different multiplying power, the lithium sulfur battery has a specific discharge capacity of 815.7mAh/g when the lithium sulfur battery is recycled to 0.1 multiplying power, and the capacity retention rate is more than 81%, so that the prepared sulfur carrier material has excellent multiplying power performance.
Fig. 13 is a cycle performance curve of a lithium sulfur battery fabricated with ceria-supported cobalt-based nitrogen-doped porous carbon as a sulfur carrier material prepared in comparative example 1. The capacity of the sulfur carrier material after 100 times of circulation at the rate of 0.5C is only 308.6mAh/g, which shows that the electrochemical performance of the sulfur carrier material prepared under the condition is poor.
Fig. 14 is a cycle performance curve of the lithium sulfur battery fabricated with the ceria-supported cobalt-based nitrogen-doped porous carbon as the sulfur carrier material prepared in comparative example 2. The reversible discharge specific capacity of 511.3mAh/g after 100 cycles at 0.5 multiplying power, the capacity retention rate is 63.5%.
Fig. 15 is a cycle performance curve of the lithium sulfur battery assembled with the ceria-supported cobalt-based nitrogen-doped porous carbon as the sulfur carrier material prepared in comparative example 3. The reversible discharge specific capacity of 825.1mAh/g after 100 cycles at 0.5 multiplying power, the capacity retention rate is 65.3%.
Fig. 16 is a cycle performance curve of the lithium sulfur battery assembled with the ceria-supported cobalt-based nitrogen-doped porous carbon as the sulfur carrier material prepared in comparative example 4. The reversible specific discharge capacity of 758.4mAh/g over 100 cycles at 0.5 rate had a capacity retention of 53.1% which is a decrease in cycling stability compared to example 1 of fig. 13, indicating that too much ceria loading may result in a decrease in conductivity of the carbon-based material and a decrease in the porous voids resulting in a decrease in the ability of the support material to adsorb polysulfides.
In summary, the composite anode material prepared by combining proper ceria content with the cobalt-based porous carbon skeleton can effectively promote the transformation and adsorption of polysulfide, solve the problems of poor conductivity, shuttle effect of polysulfide and volume expansion of the simple substance sulfur active material of the anode material of the lithium sulfur battery in an energy storage system, and provide an effective technical implementation scheme for realizing stable circulation and excellent multiplying power performance of the lithium sulfur battery. Therefore, the novel composite positive electrode material for the lithium-sulfur battery has good application prospect in energy storage systems of various electronic equipment based on the advantages.
Claims (9)
1. The preparation method of the metal oxide-based composite positive electrode material for the lithium sulfur battery is characterized by comprising the following steps of:
1. pretreatment of carbon nanotubes
Stirring and mixing carbon nano tubes with the mass ratio of 0.1-1:0.01-1 with an acidic solution at room temperature, centrifuging and washing to obtain a pretreated carbon nano tube material;
2. preparation of metal organic framework/carbon nano tube precursor
Preparing the carbon nano tube treated in the first step, a dispersing agent, cobalt nitrate hexahydrate, 2-methylimidazole and methanol into a solution according to the mass ratio of 0.01-0.1:0.1-1:1-3:1-5:0.01-1, stirring at room temperature, centrifuging after dissolving, and washing to obtain a metal organic framework/carbon nano tube precursor;
3. preparation of cobalt-based nitrogen-doped porous carbon skeleton material
Placing the metal organic framework/carbon nano tube precursor obtained in the second step into a tube furnace with protective gas for programming temperature rise, roasting and carbonizing treatment, and cooling to room temperature after heat preservation to obtain a cobalt-based nitrogen-doped porous carbon framework material;
4. preparation of cobalt-based nitrogen-doped porous carbon carrier loaded with cerium oxide
Preparing a solution from the cobalt-based nitrogen-doped porous carbon framework material obtained in the step three, cerium nitrate hexahydrate and deionized water according to the mass ratio of 0.1-1:0.01-1:0.01-0.1, stirring, adding a certain volume of alkaline solution, stirring, transferring to a reaction kettle, heating, cooling to room temperature, centrifuging and washing to obtain a cerium oxide-loaded cobalt-based nitrogen-doped porous carbon carrier;
5. preparation of lithium-sulfur battery composite anode material
Mixing the cobalt-based nitrogen doped porous carbon carrier loaded with cerium oxide obtained in the step four with elemental sulfur in a mass ratio of 1:2-5, grinding, transferring into a tube furnace, heating in a protective gas in a programmed manner, heating, preserving heat, and cooling to room temperature to obtain the lithium-sulfur battery composite anode material.
2. The method for preparing a metal oxide-based composite cathode material for a lithium-sulfur battery according to claim 1, wherein the acidic solution in the first step is one or more of hydrochloric acid, sulfuric acid and nitric acid, and the concentration is 0.05-1mol/L.
3. The method for preparing a metal oxide-based composite positive electrode material for a lithium-sulfur battery according to claim 1, wherein the dispersing agent in the second step is one or more of polyvinylpyrrolidone, polyethylene glycol or sodium polyacrylate.
4. The method for preparing a metal oxide-based composite positive electrode material for a lithium-sulfur battery according to claim 1, wherein the stirring time in the second step is 12-48 hours.
5. The method for preparing a metal oxide-based composite positive electrode material for a lithium-sulfur battery according to claim 1, wherein the temperature programming rate in the third step is 1-5 ℃/min, the roasting carbonization temperature is 600-900 ℃, and the heat preservation time is 2-6h.
6. The method for preparing a metal oxide-based composite positive electrode material for a lithium-sulfur battery according to claim 1, wherein the alkaline solution in the fourth step is one of sodium hydroxide or potassium hydroxide, the concentration is 0.01-1mol/L, and the added volume is 10% -40% of the mixed solution of cobalt-based nitrogen-doped porous carbon skeleton and cerium nitrate hexahydrate.
7. The method for preparing a metal oxide-based composite positive electrode material for a lithium-sulfur battery according to claim 1, wherein the heating temperature in the fourth step is 150-180 ℃, and the heat preservation time is 12-24 hours.
8. The method for preparing a metal oxide-based composite positive electrode material for a lithium-sulfur battery according to claim 1, wherein the temperature programming rate in the fifth step is 1-5 ℃/min, the heating temperature is 150-155 ℃, and the heat preservation time is 12-24h.
9. The method for preparing a metal oxide based composite cathode material for a lithium-sulfur battery according to claim 1, wherein the shielding gas in the tube furnace in the third and fifth steps is one of nitrogen, argon or argon/hydrogen mixture.
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