CN116936777B - Positive and negative electrode materials of lithium-sulfur battery, and preparation method and application thereof - Google Patents
Positive and negative electrode materials of lithium-sulfur battery, and preparation method and application thereof Download PDFInfo
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- CN116936777B CN116936777B CN202311191962.5A CN202311191962A CN116936777B CN 116936777 B CN116936777 B CN 116936777B CN 202311191962 A CN202311191962 A CN 202311191962A CN 116936777 B CN116936777 B CN 116936777B
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000007774 positive electrode material Substances 0.000 title description 7
- 239000007773 negative electrode material Substances 0.000 title description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 133
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000011787 zinc oxide Substances 0.000 claims abstract description 79
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 38
- 239000013078 crystal Substances 0.000 claims abstract description 36
- 239000002057 nanoflower Substances 0.000 claims abstract description 34
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 87
- 239000002243 precursor Substances 0.000 claims description 83
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 75
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 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 31
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 30
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 30
- 239000004202 carbamide Substances 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000010335 hydrothermal treatment Methods 0.000 claims description 15
- 239000012300 argon atmosphere Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 239000012459 cleaning agent Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 239000010405 anode material Substances 0.000 abstract description 21
- 239000010406 cathode material Substances 0.000 abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052744 lithium Inorganic materials 0.000 abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 abstract description 12
- 239000011593 sulfur Substances 0.000 abstract description 12
- 229920001021 polysulfide Polymers 0.000 abstract description 7
- 239000005077 polysulfide Substances 0.000 abstract description 7
- 150000008117 polysulfides Polymers 0.000 abstract description 7
- 230000001351 cycling effect Effects 0.000 abstract description 5
- 210000001787 dendrite Anatomy 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000008602 contraction Effects 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 238000006479 redox reaction Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 19
- 210000004027 cell Anatomy 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000037361 pathway Effects 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011853 conductive carbon based material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 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
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing 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
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- 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
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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
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of an ultrathin nanoflower-shaped cerium-doped zinc oxide coated carbon nanofiber and a nickel crystal lithium sulfur battery anode and cathode material embedded in the surface of cerium-doped zinc oxide, belonging to the technical field of preparation of lithium sulfur battery full-cell materials. The ultrathin nanoflower flake Ce-ZnO prepared by the method can load more sulfur/lithium, and effectively improve the wettability of electrolyte and the volume expansion and contraction problems of anode and cathode materials. In addition, ce doping can increase the conductivity of ZnO, with Ni crystals providing coupled electrons to accelerate the redox reaction of polysulfides. Through coordination of respective advantages, the composite can mutually promote the adsorption-diffusion-conversion process of polysulfide, has synergistic enhancement effect on inhibiting shuttling of lithium polysulfide and growth of lithium dendrite, and further improves the specific capacity and the cycling stability of the battery.
Description
Technical Field
The invention belongs to the technical field of preparation of lithium-sulfur battery full-battery materials, and particularly relates to a positive electrode material and a negative electrode material of a lithium-sulfur battery, and a preparation method and application thereof.
Background
Today, with the increasing demand for modern mobile electronic devices, electric vehicles, and intermittent renewable energy sources, the search for sustainable energy storage systems is more active. The lithium ion battery is successfully applied to the fields of portable electronic equipment, automobile industry and the like due to the excellent energy density and long-period cycle life, but the energy density of the lithium ion battery reaches the theoretical limit, and the continuous requirement of an electric automobile is difficult to meet. Therefore, lithium sulfur batteries are one of the alternative energy storage systems. It has high theoretical specific energy density (2600 Wh/kg), low cost, environment friendly and sulfur element to Li + The storage has extremely high theoretical specific capacity (1675 mAh/g), and has more potential than commercial lithium ion batteries (120-200 mAh/g). However, the development of lithium sulfur batteries has been limited by various problems such as the insulating properties of sulfur, the large volume changes of sulfur/lithium during cycling, the "shuttle effect" of lithium polysulfide (LiPS), and the growth of lithium dendrites.
In order to solve the above problems, various strategies have been studied to improve the electrochemical performance of lithium sulfur batteries. In terms of materials, one strategy is to store sulfur in highly conductive carbon-based materials, such as mesoporous carbon, carbon nanotubes, and graphene, as hosts for sulfur, to increase conductivity and accommodate the volume change of the overall positive electrode. However, because of weak chemical interaction between the nonpolar carbon material and the polar LiPS, the shuttle of the LiPS cannot be effectively inhibited. Another strategy is to use polar materials such as heteroatom doped carbon, transition metal compounds and polymers, etc., which have a high affinity for the LiPS, which can confine the soluble LiPS in the positive electrode region, and thus can significantly improve the cycling performance of lithium sulfur batteries.
Publication No. CN111204822A, discloses a preparation method of a NiO-ZnO lithium sulfur battery positive electrode material with a flower-shaped structure, which comprises the following steps: weighing zinc nitrate hexahydrate, nickel nitrate hexahydrate, urea and ammonium fluoride, dissolving in water, stirring and transferring to a hydrothermal reaction kettle; step (2): putting the solid product obtained by centrifugal separation in the step 1 into a vacuum drying oven for drying, putting the precursor into a porcelain boat, and carrying out annealing treatment to obtain NiO-ZnO; however, niO-ZnO is poor in conductivity, and soluble long-chain LiPS and insoluble Li during charge and discharge 2 S 2 /Li 2 The conversion process between S is slow, which can lead to the LiPS to be dissolved into the electrolyte under the drive of a concentration gradient, thereby reducing the utilization rate and the circularity of sulfur; in addition, the material can not solve the potential safety hazard caused by the growth of lithium dendrites, and seriously hinders the commercialization development of lithium-sulfur batteries.
Disclosure of Invention
The invention aims to provide a positive and negative electrode material of a lithium-sulfur battery, a preparation method and application thereof, which can solve the problems of low conductivity, negative electrode lithium dendrite growth and the like of the traditional material. The preparation method provided by the invention is simple and environment-friendly, and can be used as the anode and the cathode of the lithium sulfur battery without a conductive agent, an adhesive and a current collector. The provided anode and cathode materials of the lithium sulfur battery obviously improve the electrochemical performance and the cycle stability of the lithium sulfur battery.
In order to achieve the aim of the invention, the anode and cathode materials of the lithium sulfur battery provided by the invention consist of ultrathin nanoflower flake cerium-doped zinc oxide coated carbon nanofibers and nickel crystals embedded on the surface of the cerium-doped zinc oxide.
In the anode and cathode materials of the lithium sulfur battery provided by the invention, the length of the ultrathin nanoflower flaky cerium-doped zinc oxide is 500-1000 nm, the thickness of the ultrathin nanoflower flaky cerium-doped zinc oxide is 20-30 nm, and the equivalent diameter of the nickel crystal is 5-10 nm.
The invention provides a preparation method of anode and cathode materials of a lithium-sulfur battery, which comprises the following steps:
(1) Mixing cerium nitrate hexahydrate, zinc nitrate hexahydrate, nickel nitrate hexahydrate, ammonium fluoride, urea and acetic acid, and dissolving in water/ethanol to obtain a precursor solution;
(2) Putting the carbon nanofiber into the precursor solution obtained in the step (1) for hydrothermal treatment, taking out the treated carbon nanofiber, cleaning the carbon nanofiber by a cleaning agent, and drying the carbon nanofiber to obtain a precursor;
(3) Calcining the precursor obtained in the step (2) in argon atmosphere at 200-800 ℃ to obtain the anode and cathode materials of the lithium-sulfur battery.
In the step (1), the molar concentration of the zinc nitrate hexahydrate in the precursor solution is 0.01-0.1 mol/L, and the molar ratio of the cerium nitrate hexahydrate to the zinc nitrate hexahydrate is 1-5: 100, the mole ratio of acetic acid to zinc nitrate hexahydrate is 1-10: 1, the mole ratio of the nickel nitrate hexahydrate to the zinc nitrate hexahydrate is 1-5: 10, the molar ratio of the ammonium fluoride to the nickel nitrate hexahydrate is 1-6: 1, the mole ratio of urea to nickel nitrate hexahydrate is 1-10: 1.
preferably, in the step (1), the molar concentration of the zinc nitrate hexahydrate in the precursor solution is 0.03-0.08 mol/L, and the molar ratio of the cerium nitrate hexahydrate to the zinc nitrate hexahydrate is 1-3: 100, the mole ratio of acetic acid to zinc nitrate hexahydrate is 1-5: 1, the mole ratio of the nickel nitrate hexahydrate to the zinc nitrate hexahydrate is 3-5: 10, the molar ratio of the ammonium fluoride to the nickel nitrate hexahydrate is 1-3: 1, the mole ratio of urea to nickel nitrate hexahydrate is 1-6: 1.
preferably, in the step (2), the hydrothermal treatment temperature is 100-180 ℃ and the time is 4-8 hours; the cleaning agent is one of water and ethanol; the drying temperature is 60-80 ℃ and the drying time is 4-8 h.
Preferably, in the step (3), the precursor calcination is performed at 300-600 ℃ for 2-5 hours at a controlled heating rate of 2-4 ℃/min.
The anode and cathode materials of the lithium sulfur battery are applied to the anode and the cathode of the lithium sulfur battery.
The beneficial effects of the invention are as follows:
1. the invention is to calcine the precursor by argon to obtainThe method comprises the steps of constructing ultrathin nanoflower flake cerium-doped zinc oxide coated carbon nanofibers and nickel crystal lithium sulfur battery anode and cathode materials embedded in the surface of cerium-doped zinc oxide. In this conductive framework structure, ce doping can improve the conductivity of ZnO, ni crystals provide coupled electrons to accelerate redox reactions of polysulfide, while Ce-ZnO with three-dimensional structure provides smooth Li + Diffusion pathways. Through respective advantages, ni and Ce-ZnO can mutually promote the adsorption-diffusion-conversion process of polysulfide, and have synergistic enhancement effect on inhibiting the shuttling of lithium polysulfide and the growth of lithium dendrite.
2. The ultrathin nanoflower flake Ce-ZnO prepared by the method has larger specific surface area, can load more sulfur and lithium, and effectively solves the problems of volume expansion and contraction of anode and cathode materials; at the same time, it can improve the wettability of the electrolyte, li + Providing multiple pathways for diffusion/flow; in addition, the ultrathin nanoflower flake Ce-ZnO provides a buffer space for the dispersion of Ni crystals, prevents the Ni crystals from caking, is favorable for the full exposure of active sites, and further improves the utilization rate of Ni.
3. The ultrathin nanoflower flake cerium-doped zinc oxide coated carbon nanofiber and the nickel crystal material embedded in the surface of the cerium-doped zinc oxide are applied to the anode and the cathode of a lithium sulfur battery, and serve as host materials of sulfur and lithium, so that the structural stability of the anode and the cathode of the lithium sulfur battery can be improved.
4. In the precursor preparation process of the invention, acetic acid is adopted as a stabilizer, so that unstable reaction, such as decomposition, oxidation or reduction reaction, of metal ions can be prevented. The invention adopts ammonium fluoride and urea to carry out fluorination treatment on the surface of the material so as to improve the surface property of the material and improve the mechanical property and chemical stability of the material.
5. In conclusion, the Ce-ZnO/Ni@CNFs material prepared by the method provided by the invention is outstanding in application to the anode and the cathode of a lithium-sulfur battery. The initial specific capacity of the full battery reaches 1220.5-1224.8 mAh/g at 0.2C, and the specific capacity of 88.8-92.1% is maintained in 150 cycle tests. Even after 100 times of cyclic tests under the condition of 1C, the specific capacity of up to 908.6-941.8 mAh/g is still maintained, and the capacity retention rate is up to 86% or more.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of Ce-ZnO/Ni@CNFs material prepared in example 1;
FIG. 2 is an SEM magnification of the Ce-ZnO/Ni@CNFs material prepared in example 1;
FIG. 3 is an X-ray diffraction (XRD) pattern of the materials prepared in example 1, comparative example 2 and comparative example 3;
FIG. 4 Raman diagram of Ce-ZnO/Ni@CNFs material prepared in example 1;
fig. 5 is the cycle performance at 0.2C of the full cell prepared in example 1;
fig. 6 is a charge and discharge curve at 0.2C of the full cell prepared in example 1;
FIG. 7 is the long-term cycling stability at 1C of the full cell prepared in example 1;
Detailed Description
The invention will be further described with reference to the accompanying drawings and examples
Example 1
Cerium nitrate hexahydrate, zinc nitrate hexahydrate, nickel nitrate hexahydrate, ammonium fluoride, urea and acetic acid were dissolved in ethanol to obtain 100mL of precursor solution. Wherein the molar concentration of the zinc nitrate hexahydrate in the precursor solution is 0.065mol/L, and the molar ratio of the cerium nitrate hexahydrate to the zinc nitrate hexahydrate is 1:50, the molar ratio of acetic acid to zinc nitrate hexahydrate is 3:1, the mole ratio of nickel nitrate hexahydrate to zinc nitrate hexahydrate is 3:10, the molar ratio of ammonium fluoride to nickel nitrate hexahydrate is 2:1, the molar ratio of urea to nickel nitrate hexahydrate is 4:1.
will be 4X 4cm 2 Placing the carbon nano-fibers in a reaction kettle of the precursor solution, carrying out hydrothermal treatment for 5 hours in a baking oven at 120 ℃, taking out a sample from the reaction kettle, washing with ethanol, and drying for 4 hours in a drying oven at 60 ℃ to obtain the precursor.
And (3) heating the precursor to 400 ℃ at a heating rate of 2 ℃/min in an argon atmosphere, and preserving heat for 3 hours to calcine the precursor to obtain ultrathin nanoflower flake cerium-doped zinc oxide coated carbon nanofibers and nickel crystal lithium sulfur battery anode and cathode materials embedded on the surface of the cerium-doped zinc oxide, wherein the materials can be expressed as Ce-ZnO/Ni@CNFs. The ultra-thin nanoflower flake cerium-doped zinc oxide in the material is measured by an electron microscope, the length is 500-600 nm, and the thickness is 20-24 nm; the equivalent diameter of the nickel crystal is 5-7 nm.
Example 2
Cerium nitrate hexahydrate, zinc nitrate hexahydrate, nickel nitrate hexahydrate, ammonium fluoride, urea and acetic acid were dissolved in ethanol to obtain 100mL of precursor solution. Wherein the molar concentration of the zinc nitrate hexahydrate in the precursor solution is 0.01mol/L, and the molar ratio of the cerium nitrate hexahydrate to the zinc nitrate hexahydrate is 1:100, the molar ratio of acetic acid to zinc nitrate hexahydrate is 1:1, the molar ratio of nickel nitrate hexahydrate to zinc nitrate hexahydrate is 1:5, the molar ratio of the ammonium fluoride to the nickel nitrate hexahydrate is 4:1, the molar ratio of urea to nickel nitrate hexahydrate is 1:1.
will be 4X 4cm 2 Placing the carbon nano-fibers in a reaction kettle of the precursor solution, carrying out hydrothermal treatment for 4 hours in a baking oven at the temperature of 100 ℃, taking out a sample from the reaction kettle, washing with ethanol, and drying in a drying oven at the temperature of 80 ℃ for 6 hours to obtain the precursor.
And (3) heating the precursor to 270 ℃ at a heating rate of 3 ℃/min in an argon atmosphere, and preserving heat for 2 hours to calcine the precursor to obtain ultrathin nanoflower flake cerium-doped zinc oxide coated carbon nanofibers and nickel crystal lithium sulfur battery anode and cathode materials Ce-ZnO/Ni@CNFs embedded in the surface of the cerium-doped zinc oxide. The ultra-thin nanoflower flake cerium-doped zinc oxide in the material has the length of 700-800 nm and the thickness of 25-30 nm measured by an electron microscope; the equivalent diameter of the nickel crystal is 7-10 nm.
Example 3
Cerium nitrate hexahydrate, zinc nitrate hexahydrate, nickel nitrate hexahydrate, ammonium fluoride, urea and acetic acid were dissolved in ethanol to obtain 100mL of precursor solution. Wherein the molar concentration of the zinc nitrate hexahydrate in the precursor solution is 0.1mol/L, and the molar ratio of the cerium nitrate hexahydrate to the zinc nitrate hexahydrate is 3:100, the molar ratio of acetic acid to zinc nitrate hexahydrate is 5:1, the molar ratio of nickel nitrate hexahydrate to zinc nitrate hexahydrate is 2:5, the molar ratio of the ammonium fluoride to the nickel nitrate hexahydrate is 5:1, the molar ratio of urea to nickel nitrate hexahydrate is 6:1.
will be 4X 4cm 2 Placing the carbon nano-fibers in a reaction kettle of the precursor solution, carrying out hydrothermal treatment for 6 hours in a baking oven at 180 ℃, taking out a sample from the reaction kettle, washing with ethanol, and drying for 5 hours in a drying oven at 70 ℃ to obtain the precursor.
And (3) heating the precursor to 200 ℃ at a heating rate of 4 ℃/min under argon atmosphere, and preserving heat for 5 hours to calcine the precursor to obtain ultrathin nanoflower flake cerium-doped zinc oxide coated carbon nanofibers and nickel crystal lithium sulfur battery anode and cathode materials Ce-ZnO/Ni@CNFs embedded in the surface of the cerium-doped zinc oxide. The ultra-thin nanoflower flake cerium-doped zinc oxide in the material is measured by an electron microscope, the length is 500-1000 nm, and the thickness is 23-27 nm; the equivalent diameter of the nickel crystal is 5-8 nm.
Example 4
Cerium nitrate hexahydrate, zinc nitrate hexahydrate, nickel nitrate hexahydrate, ammonium fluoride, urea and acetic acid were dissolved in ethanol to obtain 100mL of precursor solution. Wherein the molar concentration of the zinc nitrate hexahydrate in the precursor solution is 0.03mol/L, and the molar ratio of the cerium nitrate hexahydrate to the zinc nitrate hexahydrate is 1:20, the molar ratio of acetic acid to zinc nitrate hexahydrate is 7:1, the molar ratio of nickel nitrate hexahydrate to zinc nitrate hexahydrate is 1:10, the molar ratio of ammonium fluoride to nickel nitrate hexahydrate is 6:1, the molar ratio of urea to nickel nitrate hexahydrate is 2:1.
will be 4X 4cm 2 Placing the carbon nano-fibers in a reaction kettle of the precursor solution, carrying out hydrothermal treatment for 4 hours in a baking oven at 150 ℃, taking out a sample from the reaction kettle, washing with water, and drying for 8 hours in a drying oven at 65 ℃ to obtain the precursor.
And (3) heating the precursor to 300 ℃ at a heating rate of 3 ℃/min in an argon atmosphere, and preserving heat for 4 hours to calcine the precursor to obtain ultrathin nanoflower flake cerium-doped zinc oxide coated carbon nanofibers and nickel crystal lithium sulfur battery anode and cathode materials Ce-ZnO/Ni@CNFs embedded on the surface of the cerium-doped zinc oxide. The ultra-thin nanoflower flake cerium-doped zinc oxide in the material is measured by an electron microscope, the length is 600-700 nm, and the thickness is 21-25 nm; the equivalent diameter of the nickel crystal is 6-10 nm.
Example 5
Cerium nitrate hexahydrate, zinc nitrate hexahydrate, nickel nitrate hexahydrate, ammonium fluoride, urea and acetic acid were dissolved in water to obtain 100mL of precursor solution. Wherein the molar concentration of the zinc nitrate hexahydrate in the precursor solution is 0.075mol/L, and the molar ratio of the cerium nitrate hexahydrate to the zinc nitrate hexahydrate is 1:25, the molar ratio of acetic acid to zinc nitrate hexahydrate is 9:1, the molar ratio of nickel nitrate hexahydrate to zinc nitrate hexahydrate is 1:2, the molar ratio of the ammonium fluoride to the nickel nitrate hexahydrate is 3:1, the molar ratio of urea to nickel nitrate hexahydrate is 7:1.
will be 4X 4cm 2 Placing the carbon nano-fibers in a reaction kettle of the precursor solution, carrying out hydrothermal treatment for 5 hours in a baking oven at 130 ℃, taking out a sample from the reaction kettle, washing with ethanol, and drying for 4 hours in a drying oven at 78 ℃ to obtain the precursor.
And (3) heating the precursor to 500 ℃ at a heating rate of 4 ℃/min under argon atmosphere, and preserving heat for 3.5h to calcine the precursor to obtain ultrathin nanoflower sheet-shaped cerium-doped zinc oxide coated carbon nanofibers and nickel crystal lithium sulfur battery anode and cathode materials Ce-ZnO/Ni@CNFs embedded on the surfaces of the cerium-doped zinc oxide. The ultra-thin nanoflower flake cerium-doped zinc oxide in the material is measured by an electron microscope, the length is 550-750 nm, and the thickness is 20-28 nm; the equivalent diameter of the nickel crystal is 7-9 nm.
Example 6
Cerium nitrate hexahydrate, zinc nitrate hexahydrate, nickel nitrate hexahydrate, ammonium fluoride, urea and acetic acid were dissolved in ethanol to obtain 100mL of precursor solution. Wherein the molar concentration of the zinc nitrate hexahydrate in the precursor solution is 0.05mol/L, and the molar ratio of the cerium nitrate hexahydrate to the zinc nitrate hexahydrate is 1:100, the molar ratio of acetic acid to zinc nitrate hexahydrate is 10:1, the molar ratio of nickel nitrate hexahydrate to zinc nitrate hexahydrate is 1:5, the molar ratio of the ammonium fluoride to the nickel nitrate hexahydrate is 1:1, the molar ratio of urea to nickel nitrate hexahydrate is 9:1.
will be 4X 4cm 2 Placing the carbon nano-fibers in a reaction kettle of the precursor solution, performing hydrothermal treatment for 8 hours in a baking oven at 170 ℃, taking out a sample from the reaction kettle, washing with water, and drying for 7 hours in a drying oven at 80 ℃ to obtain the precursor.
And (3) heating the precursor to 600 ℃ at a heating rate of 2 ℃/min under argon atmosphere, and preserving heat for 4.5 hours to calcine the precursor to obtain ultrathin nanoflower sheet-shaped cerium-doped zinc oxide coated carbon nanofibers and nickel crystal lithium sulfur battery anode and cathode materials Ce-ZnO/Ni@CNFs embedded on the surfaces of the cerium-doped zinc oxide. The ultra-thin nanoflower flake cerium-doped zinc oxide in the material is measured by an electron microscope, the length is 800-1000 nm, and the thickness is 20-30 nm; the equivalent diameter of the nickel crystal is 6-9 nm.
Example 7
Cerium nitrate hexahydrate, zinc nitrate hexahydrate, nickel nitrate hexahydrate, ammonium fluoride, urea and acetic acid were dissolved in ethanol to obtain 100mL of precursor solution. Wherein the molar concentration of the zinc nitrate hexahydrate in the precursor solution is 0.06mol/L, and the molar ratio of the cerium nitrate hexahydrate to the zinc nitrate hexahydrate is 1:20, the molar ratio of acetic acid to zinc nitrate hexahydrate is 2:1, the molar ratio of nickel nitrate hexahydrate to zinc nitrate hexahydrate is 1:2, the molar ratio of the ammonium fluoride to the nickel nitrate hexahydrate is 2:1, the molar ratio of urea to nickel nitrate hexahydrate is 10:1.
will be 4X 4cm 2 Placing the carbon nanofibers in a reaction kettle of the precursor solution, performing hydrothermal treatment for 6 hours in a baking oven at 110 ℃, taking out a sample from the reaction kettle, cleaning with ethanol, and drying for 5 hours in a drying oven at 63 ℃ to obtain the precursor.
And (3) heating the precursor to 450 ℃ at a heating rate of 3 ℃/min under argon atmosphere, and preserving heat for 2.5h to calcine the precursor to obtain ultrathin nanoflower sheet-shaped cerium-doped zinc oxide coated carbon nanofibers and nickel crystal lithium sulfur battery anode and cathode materials Ce-ZnO/Ni@CNFs embedded on the surfaces of the cerium-doped zinc oxide. The ultra-thin nanoflower flake cerium-doped zinc oxide in the material has the length of 750-900 nm and the thickness of 24-30 nm measured by an electron microscope; the equivalent diameter of the nickel crystal is 8-10 nm.
Example 8
Dissolving cerium nitrate hexahydrate, zinc nitrate hexahydrate, nickel nitrate hexahydrate, ammonium fluoride, urea and acetic acid in water to obtain 100mL of precursor solution, wherein the molar concentration of the zinc nitrate hexahydrate in the precursor solution is 0.09mol/L, and the molar ratio of the cerium nitrate hexahydrate to the zinc nitrate hexahydrate is 3:100, the molar ratio of acetic acid to zinc nitrate hexahydrate is 6:1, the molar ratio of nickel nitrate hexahydrate to zinc nitrate hexahydrate is 2:5, the molar ratio of the ammonium fluoride to the nickel nitrate hexahydrate is 3:1, the molar ratio of urea to nickel nitrate hexahydrate is 3:1.
will be 4X 4cm 2 Placing the carbon nano-fibers in a reaction kettle of the precursor solution, carrying out hydrothermal treatment for 7 hours in a baking oven at 150 ℃, taking out a sample from the reaction kettle, washing with ethanol, and drying for 6 hours in a drying oven at 67 ℃ to obtain the precursor.
And (3) heating the precursor to 750 ℃ at a heating rate of 3 ℃/min under argon atmosphere, and preserving heat for 4.5 hours to calcine the precursor to obtain ultrathin nanoflower sheet-shaped cerium-doped zinc oxide coated carbon nanofibers and nickel crystal lithium sulfur battery anode and cathode materials Ce-ZnO/Ni@CNFs embedded on the surfaces of the cerium-doped zinc oxide. The ultra-thin nanoflower flake cerium-doped zinc oxide in the material is measured by an electron microscope, the length is 500-900 nm, and the thickness is 27-30 nm; the equivalent diameter of the nickel crystal is 5-9 nm.
Example 9
Cerium nitrate hexahydrate, zinc nitrate hexahydrate, nickel nitrate hexahydrate, ammonium fluoride, urea and acetic acid were dissolved in ethanol to obtain 100mL of precursor solution. Wherein the molar concentration of the zinc nitrate hexahydrate in the precursor solution is 0.08mol/L, and the molar ratio of the cerium nitrate hexahydrate to the zinc nitrate hexahydrate is 1:50, the molar ratio of acetic acid to zinc nitrate hexahydrate is 8:1, the mole ratio of nickel nitrate hexahydrate to zinc nitrate hexahydrate is 3:10, the molar ratio of ammonium fluoride to nickel nitrate hexahydrate is 5:1, the molar ratio of urea to nickel nitrate hexahydrate is 5:1.
will be 4X 4cm 2 Placing the carbon nanofibers in a reaction kettle of the precursor solution, performing hydrothermal treatment in an oven at 140 ℃ for 8 hours, taking out a sample from the reaction kettle, cleaning with ethanol, and drying in a drying oven at 75 ℃ for 7 hours to obtain the precursor.
And (3) heating the precursor to 800 ℃ at a heating rate of 2 ℃/min in an argon atmosphere, and preserving heat for 5 hours to calcine the precursor to obtain ultrathin nanoflower flake cerium-doped zinc oxide coated carbon nanofibers and nickel crystal lithium sulfur battery anode and cathode materials Ce-ZnO/Ni@CNFs embedded in the surface of the cerium-doped zinc oxide. The ultra-thin nanoflower flake cerium-doped zinc oxide in the material has the length of 900-1000 nm and the thickness of 22-25 nm measured by an electron microscope; the equivalent diameter of the nickel crystal is 5-8 nm.
Example 10
Cerium nitrate hexahydrate, zinc nitrate hexahydrate, nickel nitrate hexahydrate, ammonium fluoride, urea and acetic acid were dissolved in water to obtain 100mL of precursor solution. Wherein the molar concentration of the zinc nitrate hexahydrate in the precursor solution is 0.035mol/L, and the molar ratio of the cerium nitrate hexahydrate to the zinc nitrate hexahydrate is 1:25, the molar ratio of acetic acid to zinc nitrate hexahydrate is 4:1, the molar ratio of nickel nitrate hexahydrate to zinc nitrate hexahydrate is 1:10, the molar ratio of ammonium fluoride to nickel nitrate hexahydrate is 6:1, the molar ratio of urea to nickel nitrate hexahydrate is 8:1.
will be 4X 4cm 2 Placing the carbon nanofibers in a reaction kettle of the precursor solution, performing hydrothermal treatment for 7 hours in a 160 ℃ oven, taking out a sample from the reaction kettle, cleaning with ethanol, and drying for 8 hours in a drying box at 73 ℃ to obtain the precursor.
And (3) heating the precursor to 650 ℃ at a heating rate of 4 ℃/min in an argon atmosphere, and preserving heat for 3 hours to calcine the precursor to obtain ultrathin nanoflower flake cerium-doped zinc oxide coated carbon nanofibers and nickel crystal lithium sulfur battery anode and cathode materials Ce-ZnO/Ni@CNFs embedded in the surface of the cerium-doped zinc oxide. The ultra-thin nanoflower flake cerium-doped zinc oxide in the material is measured by an electron microscope, the length is 500-950 nm, and the thickness is 21-28 nm; the equivalent diameter of the nickel crystal is 7-9 nm.
Example 11
Cerium nitrate hexahydrate, zinc nitrate hexahydrate, nickel nitrate hexahydrate, ammonium fluoride, urea and acetic acid were dissolved in ethanol to obtain 100mL of precursor solution. Wherein the molar concentration of the zinc nitrate hexahydrate in the precursor solution is 0.025mol/L, and the molar ratio of the cerium nitrate hexahydrate to the zinc nitrate hexahydrate is 3:100, the molar ratio of acetic acid to zinc nitrate hexahydrate is 7:1, the mole ratio of nickel nitrate hexahydrate to zinc nitrate hexahydrate is 3:10, the molar ratio of ammonium fluoride to nickel nitrate hexahydrate is 4:1, the molar ratio of urea to nickel nitrate hexahydrate is 5:1.
will be 4X 4cm 2 Placing the carbon nano-fibers in a reaction kettle of the precursor solution, carrying out hydrothermal treatment for 5 hours in a baking oven at 120 ℃, taking out a sample from the reaction kettle, washing with water, and drying for 4 hours in a drying oven at 80 ℃ to obtain the precursor.
And (3) heating the precursor to 700 ℃ at a heating rate of 2 ℃/min under argon atmosphere, and preserving heat for 5 hours to calcine the precursor to obtain ultrathin nanoflower flake cerium-doped zinc oxide coated carbon nanofibers and nickel crystal lithium sulfur battery anode and cathode materials Ce-ZnO/Ni@CNFs embedded in the surface of the cerium-doped zinc oxide. The ultra-thin nanoflower flake cerium-doped zinc oxide in the material has the length of 700-1000 nm and the thickness of 23-30 nm measured by an electron microscope; the equivalent diameter of the nickel crystal is 5-10 nm.
Comparative example 1
This comparative example was not supplemented with cerium nitrate hexahydrate and nickel nitrate hexahydrate, and the procedure of example 1 was otherwise identical.
Comparative example 2
This comparative example was not supplemented with cerium nitrate hexahydrate and zinc nitrate hexahydrate, and the procedure of example 1 was otherwise identical.
Comparative example 3
The comparative example was not added cerium nitrate hexahydrate, and the procedure of example 1 was otherwise identical.
The positive and negative electrode materials of the lithium-sulfur batteries obtained in examples 1 to 11 and comparative examples 1 to 3 were respectively immersed in a sulfur-containing carbon disulfide solution, and after the carbon disulfide was volatilized, the sulfur was carried by heating to 155 ℃ and the sulfur carrying amount was controlled at 70wt%, to obtain a sulfur-carrying positive electrode.
The positive and negative electrode materials of the lithium-sulfur batteries obtained in examples 1 to 11 and comparative examples 1 to 3 were respectively subjected to lithium loading of 0.1g by a known electrochemical deposition method, and the lithium-loaded negative electrode was obtained.
Putting the sulfur-carrying positive electrode and the lithium-carrying negative electrode into a glove box filled with high-purity argonFull cell assembled by rows, polypropylene porous membrane (Celgard 2300) as separator, electrolyte of 1.0mol/L LiTFSI and 0.2mol/LLiN0 3 Mixed solution with 1, 3-dioxolane and 1, 2-dimethoxyethane (w/w, 1/1). On the CT-4008-5A6V system, the potential range was fixed (1.7-2.8 Vvs. Li + Cycling tests were performed on the cells at different current densities of/Li). The test current density was 0.2C/1C, where 1C equals 1672mA/g and the test voltage range was 1.7-2.8V.
By scanning electron microscope characterization of example 1, it can be found (see fig. 1 and 2) that Ce-ZnO is in the form of regular ultrathin nanoflower flakes, a portion of the ultrathin nanoflower flakes of cerium-doped zinc oxide is labeled in fig. 2, and a portion of the nickel crystals is circled. The carbon nano fiber has the length of 500-600 nm and the thickness of 20-24 nm and is uniformly coated on the surface of the carbon nano fiber, and the structure is uniformly distributed and has the characteristics of relative flatness and continuity. In addition, ni crystals are embedded in the surfaces of the nano-sheets, and the equivalent diameter is 5-7 nm as measured by an electron microscope, so that no obvious caking phenomenon exists. This can be attributed to the fact that Ce-ZnO with a large specific surface area provides a buffer space for the dispersion of Ni crystals, which is advantageous for the sufficient exposure of active sites, thereby further improving the utilization rate of Ni and the performance of the material.
The crystallographic structure and chemical composition of the materials prepared by XRD characterization of exploring example 1, comparative example 2 and comparative example 3 are shown in fig. 3. All major diffraction peaks in comparative example 1 are very consistent with the ZnO hexagonal phase (PDF # 89-0511) with a space group of P63/mc. Similarly, comparative example 2 shows Ni cubic phase (PDF # 87-0712) with space group Fm-3 m. Both example 1 and comparative example 3 exhibited an intermediate state in which ZnO and Ni phases coexist, without any impurity phase. It is to be noted that the doping of Ce did not change the crystalline form of ZnO in example 1 compared with comparative example 3, and no observation of Ce or CeO was made 2 The corresponding diffraction peak proves that the synthesized material is successfully doped with Ce. On the other hand, the XRD pattern of the prepared material is notThere were diffraction peaks observed belonging to carbon, but the presence of carbon nanofibers could be verified in Raman spectra (fig. 4).
The electrochemical cycle performance of the full cell prepared in example 1 was tested at 0.2C, and the specific test results are shown in fig. 5 and 6. The full cell prepared in example 1 has a specific capacity of 1224.8mAh/g after initial discharge, and a specific capacity of 92.1% is maintained after 150 charge and discharge cycles. Meanwhile, the full cell prepared in example 1 was subjected to a long-period charge and discharge test at 1C, and the result is shown in fig. 7. The initial discharge specific capacity of the full battery prepared in the example 1 at 1C is 1055.9mAh/g, and after 100 times of cyclic tests, the high specific capacity of 941.8mAh/g is still maintained, and the coulombic efficiency is as high as more than 98%.
The same test was conducted on the materials of examples 2 to 11, and the results were similar to those of example 1 (Table 1), in that the difference in specific discharge capacity of the samples of each example at a current density of 0.2C was not more than 5mAh/g, and the difference in capacity retention was not more than 4%; the difference of specific discharge capacities of the samples of the examples at the current density of 1C is not more than 5mAh/g, and the difference of capacity retention rates is not more than 3%.
Example 1 has a higher specific discharge capacity at 0.2C than the comparative example sample, the specific capacity difference from the comparative example exceeds 130mAh/g, and the capacity retention difference after 150 cycles is greater than 7%. The specific discharge capacity difference between example 1 and the comparative example was more than 187mAh/g under 1C condition, and the capacity retention difference was more than 8% after 150 cycles (table 1). These results indicate that the co-doping of Ce, the synergy between ZnO and Ni, significantly affects the electrochemical performance of its lithium-sulfur battery, providing a beneficial idea for the preparation of various electrode materials with excellent electrochemical performance.
The invention has been described in further detail in the foregoing description of the embodiments, but such description is not to be construed as limiting the invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. The material for the positive electrode and the negative electrode of the lithium sulfur battery is characterized by comprising ultrathin nanoflower-shaped cerium-doped zinc oxide coated carbon nanofibers and nickel crystals embedded on the surfaces of the cerium-doped zinc oxide; the length of the ultrathin nanoflower sheet-shaped cerium-doped zinc oxide is 500-1000 nm, the thickness of the ultrathin nanoflower sheet-shaped cerium-doped zinc oxide is 20-30 nm, and the equivalent diameter of the nickel crystal is 5-10 nm; the preparation method of the material comprises the following steps:
(1) Mixing cerium nitrate hexahydrate, zinc nitrate hexahydrate, nickel nitrate hexahydrate, ammonium fluoride, urea and acetic acid, and dissolving in water/ethanol to obtain a precursor solution;
(2) Putting the carbon nanofiber into the precursor solution obtained in the step (1) for hydrothermal treatment, taking out the treated carbon nanofiber, cleaning the carbon nanofiber by a cleaning agent, and drying the carbon nanofiber to obtain a precursor;
(3) Calcining the precursor obtained in the step (2) at 200-800 ℃ in argon atmosphere to obtain the material;
in the step (1), the molar concentration of the zinc nitrate hexahydrate in the precursor solution is 0.01-0.1 mol/L, and the molar ratio of the cerium nitrate hexahydrate to the zinc nitrate hexahydrate is 1-5: 100, the mole ratio of acetic acid to zinc nitrate hexahydrate is 1-10: 1, the mole ratio of the nickel nitrate hexahydrate to the zinc nitrate hexahydrate is 1-5: 10, the molar ratio of the ammonium fluoride to the nickel nitrate hexahydrate is 1-6: 1, the mole ratio of urea to nickel nitrate hexahydrate is 1-10: 1, a step of;
in the step (2), the hydrothermal treatment temperature is 100-180 ℃ and the time is 4-8 h; the cleaning agent is one of water and ethanol; the drying temperature is 60-80 ℃ and the drying time is 4-8 h;
in the step (3), the precursor calcination is performed at 300-600 ℃ for 2-5 h at a controlled heating rate of 2-4 ℃/min.
2. The method for preparing the material for the positive electrode and the negative electrode of the lithium sulfur battery according to claim 1, wherein the molar concentration of the zinc nitrate hexahydrate in the precursor solution is 0.03-0.08 mol/L, and the molar ratio of the cerium nitrate hexahydrate to the zinc nitrate hexahydrate is 1-3: 100, the mole ratio of acetic acid to zinc nitrate hexahydrate is 1-5: 1, the mole ratio of the nickel nitrate hexahydrate to the zinc nitrate hexahydrate is 3-5: 10, the molar ratio of the ammonium fluoride to the nickel nitrate hexahydrate is 1-3: 1, the mole ratio of urea to nickel nitrate hexahydrate is 1-6: 1.
3. the material for positive and negative electrodes of lithium-sulfur batteries according to claim 1 is applied to the positive and negative electrodes of lithium-sulfur batteries.
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| CN105552282A (en) * | 2015-11-13 | 2016-05-04 | 北京理工大学 | Lithium-sulfur battery based on functional carbon fiber cloth as positive electrode barrier layer |
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| CN111204822A (en) * | 2020-01-08 | 2020-05-29 | 九江学院 | Preparation method of NiO-ZnO/S lithium-sulfur battery positive electrode material with flower-like structure |
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| CN115832617A (en) * | 2022-11-30 | 2023-03-21 | 惠州锂威新能源科技有限公司 | Intercalation composite film, preparation method thereof and lithium-sulfur battery |
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| CN105552282A (en) * | 2015-11-13 | 2016-05-04 | 北京理工大学 | Lithium-sulfur battery based on functional carbon fiber cloth as positive electrode barrier layer |
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