CN114583167A - Preparation method of metal/metal oxide lithium-sulfur battery positive electrode framework structure - Google Patents
Preparation method of metal/metal oxide lithium-sulfur battery positive electrode framework structure Download PDFInfo
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 25
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 25
- 239000002184 metal Substances 0.000 title claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002135 nanosheet Substances 0.000 claims abstract description 38
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011258 core-shell material Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 239000004744 fabric Substances 0.000 claims abstract description 14
- 238000000137 annealing Methods 0.000 claims description 12
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 2
- 239000011159 matrix material Substances 0.000 claims 2
- 229910021536 Zeolite Inorganic materials 0.000 claims 1
- 239000010457 zeolite Substances 0.000 claims 1
- -1 zeolite imidazole ester Chemical class 0.000 claims 1
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 14
- 229910052717 sulfur Inorganic materials 0.000 description 13
- 239000011593 sulfur Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 8
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- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 1
- 229910021281 Co3O4In Inorganic materials 0.000 description 1
- 229910003003 Li-S Inorganic materials 0.000 description 1
- 229910001216 Li2S Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 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
- 230000014759 maintenance of location Effects 0.000 description 1
- QXYJCZRRLLQGCR-UHFFFAOYSA-N molybdenum(IV) oxide Inorganic materials O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 1
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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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- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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 provides a preparation method of a metal/metal oxide lithium-sulfur battery positive electrode framework structure, which grows a porous core-shell structure and Oxygen Vacancy (OVs) combined CC @ Co/CoO on Carbon Cloth (CC)1‑xThe nanosheet array is used as a positive electrode framework structure, and the electrochemical performance of the lithium-sulfur battery is improved by utilizing the synergistic effect between the two-dimensional (2D) core-shell heterostructure and the OVs.
Description
Technical Field
The invention relates to a preparation method of a lithium-sulfur battery positive electrode framework structure, and particularly relates to CC @ Co/CoO with a two-dimensional porous core-shell structure and oxygen vacancy combination1-xAnd (3) preparing the positive electrode framework structure of the nanosheet array lithium-sulfur battery.
Background
Lithium-sulfur batteries have theoretical specific capacity (1675mAh g)-1) The system has the advantages of high efficiency, low cost, good environmental compatibility and the like, is considered to be a next generation energy storage system with great development prospect and is widely concerned by global research institutions. However, practical application of lithium-sulfur batteries is seriously hindered by problems such as poor conductivity of sulfur, shuttle effect of polysulfide (LiPS), and poor reaction kinetics thereof.
Carbon materials are considered ideal sulfur storage materials due to their high electrical conductivity, low mass density and large specific surface area. However, the non-polarity of carbon makes the interaction with polar LipS weak and does not effectively inhibit the shuttling effect. Due to the characteristics of high electrochemical stability, strong affinity with LiPS, low cost, rich resource reserves and the like, various polar metal oxides such as TiO are used at present2、Co3O4、MoO2MgO and the like have become research hotspots and are considered to be Li-S battery materials with wide application prospects. However, due to the low conductivity of metal oxides, their electrocatalytic activity tends to be unsatisfactory, severely limiting their catalytic activity for the conversion of LiPS.
Oxygen Vacancies (OVs) are taken as surface defects, and the introduction of OVs on the surface of the metal oxide can generate a large amount of local electrons and unsaturated cations on the surface of the oxide, which is helpful for effectively improving the conductivity of the metal oxide, enhancing the interaction between the metal oxide and the LiPS and promoting charge transfer, and the experimental results of the predecessor prove that the strategy can obviously improve the redox kinetics of sulfur. However, this approach has limited enhancement of the intrinsic conductivity of the metal oxide.
The formation of heterostructures by recombination with other polar conductive materials is another effective strategy to improve the electrochemical performance of metal oxides. The heterostructure can not only improve the conductivity of the metal oxide, but also combine the advantages of different materials to play a synergistic role, and remarkably promote the reaction kinetics of sulfur. Various heterostructure materials such as TiO have been reported2-TiN、VO2-VN、MoC-MoOxAnd CoO-Co8S9Has better electrochemistry as the positive electrode framework structure of the lithium-sulfur batteryHowever, the conductivity is still not ideal and the active sites are limited, so the performance of the material is far from meeting the requirement of commercialization.
Therefore, promoting the application of metal oxides in lithium-sulfur batteries through reasonable structural design and component design is a problem to be solved urgently at present.
Disclosure of Invention
In order to solve the technical problem, the invention provides a CC @ Co/CoO with a two-dimensional porous core-shell structure and oxygen vacancy combination1-xA preparation method of a nanosheet array lithium-sulfur battery positive electrode framework structure. Oxygen vacancies as a surface defect in CoO1-xOVs are introduced into the surface, so that a large number of local electrons and unsaturated cations can be generated on the surface of the oxide, which is helpful for effectively improving CoO1-xElectrical conductivity and enhanced CoO1-xThe interaction with the LiPS promotes charge transfer, and the experimental result of the predecessor proves that the strategy can obviously improve the redox kinetics of the sulfur.
The invention firstly provides a synergistic effect, combines a two-dimensional core-shell heterostructure and OVs to enhance the catalytic activity of metal oxide to the maximum extent, and converts a ZIF-L array vertically grown on Carbon Cloth (CC) into a two-dimensional core-shell Co/CoO with a large number of oxygen vacancies by two-step simple heat treatment1-xNanosheet array (CC @ Co/CoO)1-x). CoO with abundant OVs1-xThe porous shell and the LiPS have strong chemical interaction, can promote the fracture of S-S in the LiPS, and simultaneously has strong capacity of adsorbing the LiPS. In addition, the Co core at the bottom of the nanosheet is combined with the carbon cloth to form a complete and continuous conductive framework network, so that the carbon cloth and CoO can be realized1-xThe surface is fast in electron transfer, and reaction kinetics of sulfur are enhanced. Due to these synergistic effects, Co/CoO1-xThe nanosheet can simultaneously realize strong LipS adsorption, LipS rapid conversion and Li2Rapid nucleation of S. Thus, CC @ Co/CoO is used1-xPositive electrode skeleton structure, even if sulfur load is as high as 5.1mg cm-2Lithium sulfur batteries also have excellent electrochemical performance.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a lithium-sulfur battery positive electrode framework structure with a two-dimensional porous core-shell structure and an oxygen vacancy combined nanosheet array comprises the following specific steps:
step 1: preparation of CC @ ZIF-L precursor. Growing the ZIF-L nanosheets on carbon cloth to obtain CC @ ZIF-L;
step 2: CC @ Co3O4And (4) preparing. Annealing CC @ ZIF-L for 2h at the heating rate of 2 ℃/min of 350 ℃ in the air atmosphere to obtain CC @ Co3O4I.e. Co3O4CC coated by nano sheets;
and step 3: CC @ Co/CoO1-xThe preparation of (1): h2Mixing CC @ Co with Ar in the volume ratio of 1:93O4Annealing at the temperature rise rate of 2 ℃/min and the temperature of 240 ℃ and 260 ℃ for 2 h. Annealing at 250 ℃ for 2h is preferred, and CC @ Co/CoO with porous core-shell structure and oxygen vacancy combination cannot be obtained at other temperatures1-x。
Wherein CC @ Co/CoO1-xIs a nano-sheet, Co cores at the bottom of the nano-sheet are intensively distributed on the surface of the CC, CoO1-xDistributed outside the Co core, CC @ Co/CoO1-xLithium polysulfide is adsorbed as a skeleton.
In particular, the CC @ Co/CoO1-xThe nano-sheet array has a two-dimensional porous core-shell structure and oxygen vacancies, and the performance of the nano-sheet array as a positive electrode framework structure of the lithium-sulfur battery is directly limited by the components of the heterogeneous core-shell structure, the nano-pores and the content of the oxygen vacancies. The adjustment of heterogeneous components, nano holes and oxygen vacancy content of the core-shell structure can be realized by adjusting and changing the annealing temperature, and the reaction condition is H2Mixing CC @ Co with Ar in the volume ratio of 1:93O4Annealing at 200-350 ℃ for 2h at a heating rate of 2 ℃/min.
Specifically, 2.60g of 2-methylimidazole and 1.17g of Co (NO)3)2·6H2O is respectively dispersed in 80mL deionized water, and then the two precursor solutions are uniformly mixed under magnetic stirring; and putting the clean carbon cloth CC sheet into the mixed solution, storing for 4h at room temperature, taking out, washing with deionized water, and drying at 80 ℃ to obtain the CC @ ZIF-L precursor with the ZIF-L nanosheets growing on the carbon cloth.
In particular toAnnealing the CC @ ZIF-L precursor for 2h at the heating rate of 2 ℃/min and the temperature of 350 ℃ in the air atmosphere to obtain Co3O4CC @ Co of nanosheet-coated CC3O4。
Specifically, the CC @ Co obtained in the step 2) is used3O4At H2Annealing at 230-260 ℃ for 2h under the temperature rise rate of 2 ℃/min in the mixed atmosphere with the volume ratio of/Ar of 1:9 to obtain CC @ Co/CoO1-x。
The invention has the beneficial effects that:
a method for preparing the positive skeleton structure of metal/metal oxide lithium-sulfur battery is provided, which utilizes the synergistic effect between two-dimensional (2D) core-shell heterostructure and OVs, namely, by growing porous core-shell structure on Carbon Cloth (CC) and combining with oxygen vacancy CC @ Co/CoO1-xThe nanosheet array is used as a positive electrode framework structure, so that the electrochemical performance of the lithium-sulfur battery is improved. The unique 2D porous structure of the material enables CoO1-xThe nano-sheet has a high active site, has strong chemical interaction with the LiPS, and is favorable for promoting the breakage of S-S bonds in the LiPS. In addition, the Co core on the carbon cloth and the carbon cloth form a continuous integrated conductive framework, so that rapid charge transfer can be realized, and further the immobilized LiPS conversion can be accelerated. Due to CoO1-xSynergistic interaction between the thiophilic shell and the Co conductive core, CC @ Co/CoO1-xAs the positive electrode framework of the lithium-sulfur battery, the lithium-sulfur battery has excellent rate performance and long cycle stability, and the capacity fading rate per week is only 0.023% after the lithium-sulfur battery is cycled for 400 weeks.
In particular, the CC @ Co/CoO1-xThe bottom Co core is tightly combined with the carbon cloth, so that the electron transmission is accelerated, and the CoO is remarkably promoted1-xAnd S conversion on the surface of the shell layer enhances the dynamic performance of the lithium-sulfur battery. CoO1-xThe shell layer contains rich oxygen vacancies with the content of 47.8 percent, and the oxidation-reduction kinetics of sulfur is obviously improved. Metal/metal oxide CC @ Co/CoO1-xThe positive electrode framework structure of the lithium-sulfur battery is 3.35A g-1(2C) The reversible capacity is 527mAh g after the circulation for 400 weeks under the heavy current density-1The coulombic efficiency is as high as 99.8%, the capacity decline of each week is only 0.023%, and the long-cycle performance is excellent.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a flow chart of the material preparation of the present invention;
FIG. 2 is a CC @ Co/CoO representation of an embodiment of the present invention1-xSEM picture of (1);
FIG. 3 is a CC @ Co/CoO representation of an embodiment of the present invention1-xA) STEM and b) EDS line scan, c) HRTEM image corresponding to the lower left square area in a) image;
FIG. 4 is a CC @ Co/CoO representation of an embodiment of the present invention1-xA) an XRD pattern and b) a SAED diffraction pattern;
FIG. 5 is a CC @ Co/CoO representation of an embodiment of the present invention1-xAt 3.35A g-1Cyclic characteristics at current density;
FIG. 6 is a CC @ Co/CoO representation of an embodiment of the present invention1-xAt 167.5mA g-1-3.35A g-1(0.1-2C) rate characteristics at current density;
FIG. 7 is a schematic representation of CC @ Co/CoO according to an embodiment of the present invention1-xCycling profile at different sulfur loading per unit area.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following embodiments are further described in detail. It should be understood that the specific embodiments described herein are merely illustrative of the invention and that the invention is not limited in this regard.
[ examples ]
CC @ Co/CoO with two-dimensional porous core-shell structure and oxygen vacancy combined1-xThe positive electrode framework structure of the nanosheet array lithium-sulfur battery is characterized by being CC @ Co/CoO as shown in figure 2a1-xHas a uniform nanosheet array structure, and is formed by connecting a plurality of irregular nanosheets in a seamless manner, wherein the irregular nanosheets are derived from H2Reduction of Co3O4Co atoms obtained by the nano particles are polymerized, and the structure is favorable for accelerating charge transfer and enhancing the structural stability. As shown in FIG. 2b, the Co/CoO1-xThe nano-sheet is of a porous structure, and the nano-pores are derived from Co3O4Conversion of particles into huge bodies in the process of CoVolume shrinkage (about 49%). As shown in FIG. 3a, STEM and line scan results indicate Co/CoO1-xIn the nano-sheet, Co is mainly distributed in the core of the nano-sheet; as shown in FIG. 3b, HRTEM results confirmed that Co/CoO1-xThe nano-sheets have a core-shell structure, and the lattice spacing of 0.204nm corresponds to the (002) plane (JCPDS No.05-0727) of crystalline Co; at a thin outer shell with a thickness of about 2.5nm, 2 completely different lattice spacings were found: 0.240 and 0.211nm, corresponding to the (111) face of CoO and the (200) face of CoO, respectively (JCPDS No. 48-1719). As shown in FIG. 4, the CC @ Co/CoO1-xThe crystallinity is good, and the characteristic peaks of metal Co and CoO are obvious; in addition, it can be in CoO1-xMany lattice defects caused by oxygen vacancies, Co/CoO, were found in the shell1-xHas diffraction rings belonging to hcp Co and CoO, respectively. The CC @ Co/CoO1-xThe unique 2D porous structure of the nanosheet array enables CoO1-xThe nano-sheet has a high active site, has strong chemical interaction with the LiPS, and is favorable for promoting the breakage of S-S bonds in the LiPS. In addition, Co at the bottom of the nanosheets and the carbon cloth form a continuous integrated conductive framework, so that rapid charge transfer can be realized, and further the immobilized LiPS conversion can be accelerated. Due to thiophilic CoO1-xSynergism between the shell and the Co conductive core, CC @ Co/CoO1-xThe lithium-sulfur battery cathode skeleton structure has excellent rate performance and long cycle stability.
CC @ Co/CoO with two-dimensional porous core-shell structure and oxygen vacancy combined1-xThe preparation method of the nanosheet array lithium sulfur battery positive electrode framework structure comprises the following steps of:
1) 2.60g of 2-methylimidazole, 1.17g of Co (NO)3)2·6H2O is respectively dispersed in 80mL deionized water, and then the two precursor solutions are uniformly mixed under magnetic stirring; putting a clean Carbon Cloth (CC) sheet into the mixed solution, storing for 4h at room temperature, taking out, washing with deionized water, and drying at 80 ℃ to obtain a CC @ ZIF-L precursor;
2) annealing CC @ ZIF-L for 2h at the heating rate of 2 ℃/min of 350 ℃ in the air atmosphere to obtain CC @ Co3O4Nanosheets;
3) mixing CC @ Co3O4In H2Annealing at 250 ℃ for 2h at the heating rate of 2 ℃/min under the mixed atmosphere of which the volume ratio of/Ar is 1:9 to obtain CC @ Co/CoO1-xA nanosheet array.
The CC @ Co/CoO obtained by the step 3) is added1-xThe lithium-sulfur battery is assembled, and the specific assembling process is as follows:
1) preparing a blank electrolyte: first 1.0M LiTFSI, 2 wt.% LiNO3Adding the mixture into a mixed solution with a volume ratio of DOL/DME of 1:1, and uniformly stirring and mixing the mixture on a magnetic stirrer to obtain a blank electrolyte.
2) Preparing a sulfur-based electrolyte: mixing sulfur powder and Li in a mass ratio of 5:12And adding the S powder into the blank electrolyte, and placing the blank electrolyte on a magnetic stirrer to be stirred and mixed uniformly to obtain the sulfur-based electrolyte.
3) Assembling the battery: mixing CC @ Co/CoO1-xDrying in a vacuum drying oven to remove water, cutting into circular electrode plate with diameter of 12mm, and drying in a vacuum drying oven2O/O2<The cell was assembled in a 0.1ppm Ar filled glove box and CC @ Co/CoO was added sequentially1-xAnd adding the pole piece, the sulfur-based electrolyte, the Celgard 2400 diaphragm, the blank electrolyte and the lithium metal current collector into the CR2032 type button battery, and packaging.
The lithium-sulfur battery, deposited Li2S completely covers Co/CoO1-xNanopores on nanosheets, Li2The S is uniformly deposited, so that ions/electrons can be rapidly transmitted in the circulating process, and the S plays an important role in excellent electrochemical performance. The excellent cycling stability is due to CC @ Co/CoO1-xThe positive electrode framework structure can simultaneously realize excellent structural stability and Li2Controlled deposition of S.
The lithium-sulfur battery, as shown in FIG. 2, is a metal/metal oxide CC @ Co/CoO1-xIs an array structure formed by uniform self-supporting nano-sheets.
The lithium-sulfur battery, as shown in FIG. 3, is Co/CoO1-xThe nano-sheet has a core-shell structure, and Co is mainly distributed in Co/CoO1-xThe core of the nanosheet.
The lithium-sulfur battery, as shown in FIG. 4, is a metal/metal oxide CC @ Co/CoO1-xGood crystallinity, derivatives thereofThe peak contains the (002) plane of Co, the (111) plane of CoO and the (200) plane of CoO. A number of lattice defects caused by oxygen vacancies, Co/CoO, were found in the CoO shell1-xHas diffraction rings belonging to hcp Co and CoO, respectively.
The lithium sulfur battery, as shown in FIG. 5, is at 3.35A g-1Has a reversible capacity of 527mAh g after circulating for 400 weeks at a high current density-1The coulombic efficiency is as high as 99.8%, the capacity decline of each week is only 0.023%, and the long-cycle performance is excellent.
The lithium sulfur battery, as shown in FIG. 6, was operated at 167.5mA g-1(0.1C)、502.5mAg-1(0.3C)、837.5mA g-1(0.5C)、1.675A g-1(1C) And 3.35A g-1(2C) At current density of 1167mAh g respectively-1、1136mAh g-1、1047mAh g-1、897mAh g-1And 701mAh g-1(ii) a When the current density is recovered to 167.5mA g-1After (0.1C) the capacity was 1204mAh g-1It was demonstrated that the reversible capacity retention rate was excellent.
The lithium sulfur battery, as shown in FIG. 7, increased the sulfur loading per unit area from 2.03 to 5.10mg cm-2At 837.5mA g-1The current density still has excellent cycle stability.
Claims (9)
1. A preparation method of a metal/metal oxide lithium-sulfur battery positive electrode framework structure is characterized by comprising the following steps:
step (1), preparing a zeolite imidazole ester (ZIF-L) framework structure CC @ ZIF-L precursor;
step (2), annealing the CC @ ZIF-L precursor in the air atmosphere to prepare CC @ Co3O4；
Step (3), mixing CC @ Co3O4The nano sheet is arranged in H2Annealing in mixed atmosphere with volume ratio of/Ar of 1:9 to prepare CC @ Co/CoO1-x。
2. The method of claim 1, wherein the metal/metal oxide positive electrode comprises a metal oxide/carbon matrix, wherein the metal oxide/carbon matrix is formed by mixing CC @ Co3O4The nanosheet is placed in H2Annealing at 230-260 ℃ for 2h in a mixed atmosphere with the volume ratio of/Ar being 1: 9.
3. The method of claim 2, wherein the Co/CoO is selected from the group consisting of Co, Ni, Co1-xIs in a core-shell structure.
4. The method of claim 3, wherein the Co/CoO is selected from the group consisting of Co, Ni, Co1-xIs a nano-sheet array.
5. The method of claim 4, wherein the Co/CoO is selected from the group consisting of Co, Ni, Co1-xHas a porous structure.
6. The method of claim 4, wherein the Co/CoO is selected from the group consisting of Co, Ni, Co1-xRich in oxygen vacancies.
7. The method for preparing the positive electrode framework structure of the metal/metal oxide lithium-sulfur battery according to claim 5, wherein the step (1): 2.60g 2-methylimidazole, 1.17g Co (NO)3)2·6H2O is respectively dispersed in 80mL deionized water, and then the two precursor solutions are uniformly mixed under magnetic stirring; putting the clean carbon cloth piece into the mixed solution, storing at room temperature for 4h, taking out, washing with deionized water, and drying at 80 ℃; preparation of CC @ ZIF-L precursor.
8. The method for preparing the metal/metal oxide lithium sulfur battery positive electrode framework structure according to claim 6, wherein in the step (2), CC @ ZIF-L is annealed for 2h at a heating rate of 2 ℃/min and 350 ℃ in an air atmosphere to obtain CC @ Co3O4。
9. The method for preparing the positive electrode framework structure of the metal/metal oxide lithium-sulfur battery according to claim 7, wherein the step (3), H2Mixing CC @ Co with Ar in the volume ratio of 1:93O4Annealing at 250 deg.C for 2h at a heating rate of 2 deg.C/min.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106970116A (en) * | 2017-03-20 | 2017-07-21 | 中国石油大学(华东) | A kind of polyhedral cobaltosic oxide three-dimensional porous Graphene gel composite material film sensitive to acetone |
| CN107768652A (en) * | 2017-10-25 | 2018-03-06 | 北京理工大学 | A kind of lithium sulfur battery anode material based on middle micro-diplopore metal oxide or spinelle and preparation method thereof |
| CN107819117A (en) * | 2017-09-27 | 2018-03-20 | 北京理工大学 | The flexible compound sulphur positive electrode and preparation method of a kind of oxide modifying |
| CN108336308A (en) * | 2017-01-20 | 2018-07-27 | 华为技术有限公司 | A kind of lithium-sulphur cell positive electrode protection materials and its application |
| CN108923030A (en) * | 2018-06-29 | 2018-11-30 | 大连理工大学 | A kind of cobalt nitride/porous carbon sheet/carbon cloth self-supporting lithium sulfur battery anode material preparation method |
| CN109802093A (en) * | 2019-01-21 | 2019-05-24 | 深圳大学 | Modified non-carbon anode of lithium-air battery and preparation method thereof and lithium-air battery |
-
2020
- 2020-12-01 CN CN202011387790.5A patent/CN114583167A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108336308A (en) * | 2017-01-20 | 2018-07-27 | 华为技术有限公司 | A kind of lithium-sulphur cell positive electrode protection materials and its application |
| CN106970116A (en) * | 2017-03-20 | 2017-07-21 | 中国石油大学(华东) | A kind of polyhedral cobaltosic oxide three-dimensional porous Graphene gel composite material film sensitive to acetone |
| CN107819117A (en) * | 2017-09-27 | 2018-03-20 | 北京理工大学 | The flexible compound sulphur positive electrode and preparation method of a kind of oxide modifying |
| CN107768652A (en) * | 2017-10-25 | 2018-03-06 | 北京理工大学 | A kind of lithium sulfur battery anode material based on middle micro-diplopore metal oxide or spinelle and preparation method thereof |
| CN108923030A (en) * | 2018-06-29 | 2018-11-30 | 大连理工大学 | A kind of cobalt nitride/porous carbon sheet/carbon cloth self-supporting lithium sulfur battery anode material preparation method |
| CN109802093A (en) * | 2019-01-21 | 2019-05-24 | 深圳大学 | Modified non-carbon anode of lithium-air battery and preparation method thereof and lithium-air battery |
Non-Patent Citations (2)
| Title |
|---|
| JUN CAO等: ""A Co/CoO hybrid rooted on carbon cloth as an efficient electrocatalyst for the hydrogen evolution reaction in alkaline solution"", 《SUSTAINABLE ENERGY FUELS》, vol. 4, pages 1924 - 1932 * |
| YANGUO LIU等: ""Porous Co3O4@CoO composite nanosheets as improved anodes for lithium-ion batteries"", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 834, pages 1 - 8 * |
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