CN113571708A - Heterojunction ZnSe/CoSe based on positive and negative electrode protection of lithium-sulfur full cell2Preparation method of universal carrier - Google Patents
Heterojunction ZnSe/CoSe based on positive and negative electrode protection of lithium-sulfur full cell2Preparation method of universal carrier Download PDFInfo
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- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 title claims abstract description 56
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 47
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 25
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 37
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
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- 238000003756 stirring Methods 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
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- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 6
- 239000004280 Sodium formate Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
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- 238000005406 washing Methods 0.000 claims description 6
- 238000009792 diffusion process Methods 0.000 claims description 4
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
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- 125000005842 heteroatom Chemical group 0.000 description 4
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- 238000012512 characterization method Methods 0.000 description 3
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
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- 230000004913 activation Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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 heterojunction ZnSe/CoSe based on positive and negative electrode protection of a lithium-sulfur full battery2The preparation method of the universal carrier comprises the steps of synthesis of a ZIF-8 polyhedron, synthesis of a ZIF-8/ZIF-67 polyhedron, preparation of heterojunction ZnSe/CoSe2 and preparation of a positive electrode and a negative electrode of a lithium-sulfur full cell, so that the prepared universal electrode of the lithium-sulfur full cell can effectively inhibit the shuttle effect of the positive electrode, and meanwhile, the uniform deposition of lithium metal on the negative electrode is assisted, and the comprehensive improvement of the performance of the lithium-sulfur full cell is realized; the method has important significance for widening the application range of the carrier material and improving the utilization rate of the active material of the lithium-sulfur full battery, and brings new revelation for the optimization design of the anode and cathode carriers of the lithium-sulfur full battery.
Description
Technical Field
The invention relates to a heterojunction material, in particular to heterojunction ZnSe/CoSe2The preparation method of the material can be used as a general carrier for the positive electrode and the negative electrode of the lithium-sulfur full cell, and the positive electrode and the negative electrode of the lithium-sulfur full cell are effectively protected.
Background
The development of high energy density and low cost battery energy storage systems is an important goal of energy development strategies of all countries in the world. The theoretical energy density of the lithium-sulfur battery is as high as 2600Wh/kg, and the actual energy density can reach 500-1000 Wh/kg, which is 3-5 times of that of the traditional lithium ion battery. And the sulfur is abundant in the surface layer of the earth and low in price, and the lithium-sulfur battery is considered as a battery system which is closest to practical application after the lithium-ion battery. However, the problems of shuttling of lithium polysulfides, volumetric expansion and contraction during charging and discharging, low sulfur conductivity, and uncontrolled lithium dendrite growth have restricted commercial application of lithium sulfur batteries.
In recent years, scholars at home and abroad mainly carry out structural design on the lithium-sulfur battery anode carrier material from the aspects of physical limitation, chemical adsorption and dynamic catalysis, and effectively solve the problems of anode shuttle effect, volume change, insufficient power of electrochemical reaction and the like. These studies have been directed primarily to single-sided modification of the positive electrode, which typically employs a lithium plate directly. In commercial applications, lithium sheets as negative electrodes cause the following problems: (1) the negative electrode has no host characteristic, so that the deposited lithium metal is easy to vertically grow to form lithium dendrite, and serious safety problems are caused; (2) the lithium negative electrode is usually excessive by 1500-; (3) lithium polysulfide causes corrosion reaction to negative lithium and growth of lithium dendrite, so that a negative SEI film is repeatedly formed and damaged, more electrolyte and lithium metal are consumed, and the cycling stability and the coulombic efficiency of the battery are affected. It follows that negative electrode protection is also of great importance for commercial application of lithium sulphur batteries. The commercial application of the lithium-sulfur battery is promoted, and the bidirectional protection of the positive electrode and the negative electrode of the lithium-sulfur full battery must be realized at the same time.
The 'two-in-one' type carrier is an effective strategy for realizing the bidirectional protection of the lithium-sulfur full battery, namely, the carrier is designed to be used as a host material of a positive electrode and a negative electrode of the lithium-sulfur battery at the same time, so that the shuttle effect of the positive electrode can be inhibited, the uniform nucleation growth of metal lithium can be induced, and the formation of local lithium dendrites is avoided. The protection strategy has important significance for improving the utilization rate of the active material of the lithium-sulfur battery, improving the energy density of the battery and simplifying the preparation process. The two-in-one type carrier reported in the literature at present is mainly based on a three-dimensional conductive framework modified by amphiphilic lithium, a sulfur-philic heteroatom, a functional group and a metal compound. For example, nitrogen-doped porous carbon sphere structures reported by professor honggli Zhu of northeast university, cobalt and nitrogen-co-doped hollow carbon skeleton reported by subject group of qianyitai of china science and technology university, nano-cobalt embedded nitrogen-doped porous carbon nanosheet structures designed by subject group of professor wuding of wuding money of zhongshan university, bimetal nickelized cobalt particle-modified three-dimensional porous carbon fiber skeleton proposed by zhangho of north river industry university, carbon nanotube sponges containing carboxyl functional group nano-gully structures constructed by subject group of chongho Yu of germany agriculture university, porous nickel skeleton based on double-layer photonic crystals reported by professor hough of shanghai traffic university, carbon nanofiber skeleton modified by nitriding/nitriding titanium reported by professor Yu of china science and technology university, and the like.
Although the above "two-in-one" type vector has a certain control effect on the positive shuttle effect and the negative lithium dendrite growth of the lithium sulfur battery, it should be noted that: (1) the content of amphiphilic lithium, thiophilic heteroatom and functional group on the surface of the carrier is lower (less than or equal to 5 percent), and considering that under the condition of high sulfur load in practical application, the concentration of positive lithium polysulfide is higher, the viscosity is higher, and the problems of dissolution and delayed diffusion of a large amount of lithium polysulfide are difficult to relieve by a small amount of thiophilic active sites. In addition, fewer lithium-philic heteroatoms, functional groups are also not efficient enough to induce uniform deposition of metallic lithium on large specific surface area three-dimensional frameworks. (2) Compared with heteroatom doping and functional group modification, the polar metal compound has stronger parent sulfur and lithium characteristics, but the content of the polar metal compound can influence the sulfur carrying amount of the anode, and a 'two-in-one' type carrier which is low in content and high in adsorption-catalysis-conversion efficiency on an active material is lacked in the current research. (3) The above-mentioned "two-in-one" type lithium sulfur full cell shows a certain cycle stability, but in some studies, the use of inactive materials such as current collector, binder, conductive agent and excess electrolyte seriously reduces the actual energy density of the cell, so that the actual application value of the carrier material needs to be evaluated. Therefore, in summary, the following two key problems need to be solved to realize bidirectional protection of the "two-in-one" type carrier on the positive and negative electrodes of the lithium-sulfur battery: (1) how to efficiently regulate and control the oxidation-reduction reaction of the lithium polysulfide on the positive electrode under the environment with high sulfur surface loading and poor electrolyte. (2) How to regulate and control the uniform deposition of the metal lithium on the surface of the negative current collector in a large area and avoid the formation of local lithium dendrites.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a heterojunction ZnSe/CoSe based on positive and negative electrode protection of a lithium-sulfur full battery2The invention provides a preparation method of a universal carrier, which aims at the key problem of the existing 'two-in-one' carrier, and provides a heterojunction ZnSe/CoSe with a core-shell morphology by taking ZIF-67 and ZIF-8 as precursors2According to the carrier optimization scheme, the carrier can be used as a universal anode and cathode electrode of the lithium-sulfur battery, and bidirectional protection of the anode and the cathode of the lithium-sulfur full battery is realized.
In order to achieve the purpose, the invention adopts the technical scheme that: heterojunction ZnSe/CoSe based on positive and negative electrode protection of lithium-sulfur full cell2The preparation method of the universal carrier comprises the following specific steps:
s1, synthesis of ZIF-8 polyhedron: 2.5mmol of Zn (NO)3)2•6H2Dissolving O in 25mL of methanol and 25mL of ethanol to form a solution A; dissolving 10 mmol of 2-methylimidazole, 0.125g of sodium formate and 0.4105g of 1-methylimidazole in 25mL of methanol and 25mL of ethanol respectively to form a solution B; stirring the solution A and the solution B for 30 minutes respectively, then mixing the two solutions, stirring vigorously for 60 seconds, standing the obtained solution for 12 hours, finally centrifuging to collect white precipitate, washing with ethanol for 3 times, and fully drying in a vacuum oven at 60 ℃ for later use;
s2, synthesis of ZIF-8/ZIF-67 polyhedron: first, 8 mmol of 2-methylimidazole, 0.1 g of sodium formate and 0.3284 g of 1-methylimidazole were dissolved in a mixture of 20 mL of methanol and 20 mL of ethanol to form a solution C; then, 150 mg of ZIF-8 was ultrasonically dispersed in a mixed solution of 50ml of methanol and 50ml of ethanol, and 2mmol of Co (NO) was added3)2•6H2O, forming a Co ion outer package by taking ZIF-8 as an inner coreThe pink mixed solution was denoted as solution D; respectively stirring the solution C and the solution D for 30 minutes, then pouring the solution C into the solution D, violently stirring for 60 seconds, centrifuging, collecting precipitates, washing with ethanol for 3 times, and fully drying in a vacuum oven at 60 ℃ to obtain a ZIF-8/ZIF-67 polyhedron with a core-shell structure, wherein the ZIF-8 is used as an inner core and the ZIF-67 is wrapped outside the ZIF-67 polyhedron;
s3, heterojunction ZnSe/CoSe2The preparation method comprises the steps of placing ZIF-8/ZIF-67 and selenium powder at two ends of a porcelain boat according to the mass ratio of 1:2, and placing the selenium powder at one side close to an air inlet; the boat was placed in an argon stream (50 mL. min.)-1) Heating the tube furnace from room temperature to 500 ℃ at the heating rate of 2 ℃/min, preserving the heat for 2 hours, cooling the tube furnace to the room temperature, and collecting black ZnSe/CoSe2Powder;
s4, preparing a lithium-sulfur full-cell positive electrode: carrying sulfur by a melt diffusion method to prepare ZnSe/CoSe2Mixing with sulfur powder at a weight ratio of 3:7, heating to 155 deg.C under argon atmosphere, and maintaining for 12 hr to obtain S-ZnSe/CoSe2The prepared S-ZnSe/CoSe2The material is uniformly coated on the surface of aluminum foil or carbon paper to prepare the heterojunction ZnSe/CoSe2A lithium-sulfur full cell positive electrode as a carrier;
s6, preparing a lithium-sulfur full-cell cathode: the lithium in the glove box was heated to 450 ℃ in a tin furnace and coated with ZnSe/CoSe2Carbon paper penetration of (2); making lithium adsorb to load ZnSe/CoSe2The aluminum foil or the carbon paper is made into a heterojunction ZnSe/CoSe2Is a cathode of a lithium-sulfur full cell taking the lithium as a carrier.
The principle of the invention is as follows: the transition metal selenide adopted by the invention has the following advantages: (1) the method has the advantages of enhanced intrinsic conductivity and unique semiconductor characteristics, and rich phase boundaries can reduce activation potential barriers and enhance the transport kinetics of ions and electrons. (2) Simple element doping can cause lattice distortion and atom arrangement defects, thereby improving edge active sites and electrocatalytic activity. (3) The medium electronegativity difference between transition metal selenides and polysulfides favors the potential formation of Li-Se and M-S (M = Co, Mo, Zn, Ni) bonds, with strong adsorption capacity for positive electrode polysulfides. (4) The narrow energy gap triggered better conductivity isThe method is favorable for electron migration, the insertion gap size of the weaker metal selenium ion bond and the larger lithium ion bond is favorable for promoting the uniform deposition of the metal lithium of the cathode, and the transition metal selenide provides possibility for constructing a two-in-one type anode-cathode bidirectional protection carrier; heterojunction ZnSe/CoSe2The carrier improves the electrochemical performance of the two-in-one electrode and realizes the bidirectional protection of the lithium-sulfur full battery; first, among the numerous transition metal selenides, ZnSe, CoSe2Has good catalytic activity, excellent conductivity and higher stability, and meanwhile, the specific two-side lattice size of the heterostructure is not matched and can be in ZnSe and CoSe2Lattice stress and mismatching are generated in the two-phase interface region, defect formation (such as oxygen vacancy and cation vacancy) and carrier redistribution (local enrichment or deletion) are induced, the electronic structure and the charge distribution state of a heterogeneous interface are changed, and the electrochemical reaction of the lithium-sulfur anode and the lithium-sulfur cathode is promoted. In addition, the core-shell structure ZnSe/CoSe2The three-dimensional conductive framework can improve the sulfur content and the surface loading capacity of the anode, reduce the local current density of the cathode and induce the uniform deposition of the metal lithium. Thus, the "two-in-one" type heterojunction ZnSe, CoSe2The self-supporting carrier realizes bidirectional protection of the lithium-sulfur full battery.
The invention has the beneficial effects that: (1) ZnSe/CoSe2The positive and negative electrode general electrodes cooperatively improve the performance of the lithium-sulfur full battery: in the past, research is usually dedicated to solve the problem of the sulfur positive electrode side or the lithium negative electrode side of the lithium-sulfur battery, and bidirectional protection of the positive electrode and the negative electrode is rarely considered at the same time. However, the promotion of commercial application of the lithium sulfur battery must simultaneously achieve bidirectional protection of the positive and negative electrodes of the lithium sulfur battery. The application provides a 'two-in-one' type universal electrode design strategy, namely, a multifunctional ZnSe/CoSe with the characteristics of amphiphilic lithium and hydrophilic sulfur is constructed2The self-supporting structure is used as a common electrode for the positive electrode and the negative electrode of the lithium-sulfur battery, and meanwhile, the bidirectional protection of the positive electrode and the negative electrode of the lithium-sulfur full battery is realized; the method has important significance for widening the application range of the carrier material and improving the utilization rate of the active material of the lithium-sulfur full battery.
(2) Heterostructure ZnSe/CoSe2Uniformly depositing the boosting lithium metal: conventional affinity three-dimensional conductive skeleton design, metal oxideThe compounds are often used as lithium-philic materials to facilitate the controlled deposition of metallic lithium on a carbon skeleton, but the metal oxide reacts with lithium to form the ionic insulator Li2O covers the surface of the current collector, is not beneficial to lithium ion transportation and stable concentration gradient, and influences the electrochemical reaction activity of the surface of the negative electrode. The application proposes for the first time the use of heterojunctions ZnSe/CoSe2The modified lithium ion conductive material reacts with molten lithium in situ to improve the hydrophilicity, conductivity and ion conductivity of a negative current collector, further balance the transport of ions and electrons on the surface of the current collector, and accelerate the uniform deposition of the power-assisted metal lithium by the evolution of a modified heterostructure, thereby bringing new inspiration for the design of a three-dimensional conductive framework of a high-efficiency metal lithium negative electrode.
Drawings
FIG. 1 is ZnSe/CoSe2Transmission electron microscopy images of (a).
FIG. 2 is a ZnSe/CoSe2TEM-EDS images of and corresponding XRD diffraction patterns.
FIG. 3 is S-ZnSe/CoSe2And | | Li lithium sulfur half-cell in-situ raman characterization diagram.
FIG. 4 shows the respective ratios of Li-ZnSe/CoSe2、CoSe2And ZnSe and pure Li sheets are taken as carriers to assemble a comparison graph of the cycle performance of the lithium half cell.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be understood that the described embodiments are not to be construed as limiting the present invention.
The embodiment is based on heterojunction ZnSe/CoSe of positive and negative electrode protection of a lithium-sulfur full battery2The preparation method of the universal carrier comprises the following specific steps:
s1, synthesis of ZIF-8 polyhedron: 2.5mmol of Zn (NO)3)2•6H2Dissolving O in 25mL of methanol and 25mL of ethanol to form a solution A; dissolving 10 mmol of 2-methylimidazole, 0.125g of sodium formate and 0.4105g of 1-methylimidazole in 25mL of methanol and 25mL of ethanol respectively to form a solution B; stirring solution A and B for 30 min, mixing the two solutions, stirring vigorously for 60 s, standing the obtained solution for 12 hr, centrifuging to collect white precipitate, washing with ethanol for 3 times, and drying in vacuum oven at 60 deg.CStandby;
s2, synthesis of ZIF-8/ZIF-67 polyhedron: first, 8 mmol of 2-methylimidazole, 0.1 g of sodium formate and 0.3284 g of 1-methylimidazole were dissolved in a mixture of 20 mL of methanol and 20 mL of ethanol to form a solution C; then, 150 mg of ZIF-8 was ultrasonically dispersed in a mixed solution of 50ml of methanol and 50ml of ethanol, and 2mmol of Co (NO) was added3)2•6H2O, forming a pink mixed solution which takes ZIF-8 as an inner core and is wrapped outside Co ions and marking as a solution D; respectively stirring the solution C and the solution D for 30 minutes, then pouring the solution C into the solution D, violently stirring for 60 seconds, centrifuging, collecting precipitates, washing with ethanol for 3 times, and fully drying in a vacuum oven at 60 ℃ to obtain a core-shell structure ZIF-8/ZIF-67 polyhedron with ZIF-8 as an inner core and ZIF-67 as an outer wrapping layer;
s3, heterojunction ZnSe/CoSe2The preparation method comprises the steps of placing ZIF-8/ZIF-67 and selenium powder at two ends of a porcelain boat according to the mass ratio of 1:2, and placing the selenium powder at one side close to an air inlet; the boat was placed in an argon stream (50 mL. min.)-1) Heating the tube furnace from room temperature to 500 ℃ at the heating rate of 2 ℃/min, preserving the heat for 2 hours, cooling the tube furnace to the room temperature, and collecting black ZnSe/CoSe2Powder;
s4, preparing a lithium-sulfur full-cell positive electrode: carrying sulfur by a melt diffusion method to prepare ZnSe/CoSe2Mixing with sulfur powder at a weight ratio of 3:7, heating to 155 deg.C under argon atmosphere, and maintaining for 12 hr to obtain S-ZnSe/CoSe2The prepared S-ZnSe/CoSe2The material is uniformly coated on the surface of aluminum foil or carbon paper to prepare the heterojunction ZnSe/CoSe2A lithium-sulfur full cell positive electrode as a carrier;
s5, preparing a lithium-sulfur full-cell cathode: the lithium in the glove box was heated to 450 ℃ in a tin furnace and coated with ZnSe/CoSe2Carbon paper penetration of (2); making lithium adsorb to load ZnSe/CoSe2The aluminum foil or the carbon paper is made into a heterojunction ZnSe/CoSe2And the lithium-sulfur full-cell cathode is used as a carrier.
ZnSe/CoSe prepared in this example2FIG. 1 shows a transmission electron microscope image of: (a) is a ZIF-8/ZIF-67 scanning electron microscope picture; (b, c) is ZnSe/CoSe2Scanning an electron microscope picture;(d-f) is ZnSe/CoSe2The picture of a transmission electron microscope can obviously observe the ZnSe (200) crystal face and CoSe2(120) Crystal face, description of ZnSe/CoSe2Is a heterojunction structure.
ZnSe/CoSe prepared in this example2The TEM-EDS image and the corresponding XRD diffraction pattern are shown in figure 2, and the heterojunction ZnSe/CoSe2 prepared by the method is a standard core-shell structure as is obvious from figure 2.
FIG. 3 shows S-ZnSe/CoSe obtained in this example2And l in-situ Raman characterization of the Li lithium-sulfur half-cell. In fig. 3: (a) in-situ Raman testing of the in-situ pool structure; and (b, c) performing discharge in-situ Raman characterization. It is clear from FIG. 3 that the heterojunction ZnSe/CoSe is present during the discharge2The carrier has stronger adsorption property to soluble lithium polysulfide and can effectively pass through heterojunction ZnSe/CoSe2The chemisorption of the carrier inhibits the dissolution of lithium polysulfide into the electrolyte.
FIG. 4 shows the respective ratios of Li-ZnSe/CoSe2、CoSe2Comparison graph of cycle performance of lithium half cell assembled by taking ZnSe and pure Li sheets as carriers, and the heterojunction ZnSe/CoSe can be found in FIG. 42The cycle performance of the lithium half cell taking the carrier as the carrier is obviously superior to that of other three types of cells, and the heterojunction ZnSe/CoSe2The ohmic resistance and the electrochemical polarization of the lithium half battery are obviously lower, and the rate performance of the lithium-sulfur full battery in the charging and discharging process is favorably exerted.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (1)
1. Heterojunction ZnSe/CoSe based on positive and negative electrode protection of lithium-sulfur full cell2The preparation method of the universal carrier is characterized by comprising the following steps: the method comprises the following specific steps:
s1, synthesis of ZIF-8 polyhedron: 2.5mmol of Zn (NO)3)2•6H2Dissolving O in 25mL of methanol and 25mL of ethanol to form a solution A; dissolving 10 mmol of 2-methylimidazole, 0.125g of sodium formate and 0.4105g of 1-methylimidazole in 25mL of methanol and 25mL of ethanol respectively to form a solution B; stirring the solution A and the solution B for 30 minutes respectively, then mixing the two solutions, stirring vigorously for 60 seconds, standing the obtained solution for 12 hours, finally centrifuging to collect white precipitate, washing with ethanol for 3 times, and fully drying in a vacuum oven at 60 ℃ for later use;
s2, synthesis of ZIF-8/ZIF-67 polyhedron: first, 8 mmol of 2-methylimidazole, 0.1 g of sodium formate and 0.3284 g of 1-methylimidazole were dissolved in a mixture of 20 mL of methanol and 20 mL of ethanol to form a solution C; then, 150 mg of ZIF-8 was ultrasonically dispersed in a mixed solution of 50ml of methanol and 50ml of ethanol, and 2mmol of Co (NO) was added3)2•6H2O, forming a pink mixed solution which takes ZIF-8 as an inner core and is wrapped outside Co ions and marking as a solution D; respectively stirring the solution C and the solution D for 30 minutes, then pouring the solution C into the solution D, violently stirring for 60 seconds, centrifuging, collecting precipitates, washing with ethanol for 3 times, and fully drying in a vacuum oven at 60 ℃ to obtain a core-shell structure ZIF-8/ZIF-67 polyhedron with ZIF-8 as an inner core and ZIF-67 as an outer wrapping layer;
s3, heterojunction ZnSe/CoSe2The preparation method comprises the steps of placing ZIF-8/ZIF-67 and selenium powder at two ends of a porcelain boat according to the mass ratio of 1:2, and placing the selenium powder at one side close to an air inlet; the boat was placed in an argon stream (50 mL. min.)-1) Heating the tube furnace from room temperature to 500 ℃ at the heating rate of 2 ℃/min, preserving the heat for 2 hours, cooling the tube furnace to the room temperature, and collecting black ZnSe/CoSe2Powder;
s4, preparing a lithium-sulfur full-cell positive electrode: carrying sulfur by a melt diffusion method to prepare ZnSe/CoSe2Mixing with sulfur powder at a weight ratio of 3:7, heating to 155 deg.C under argon atmosphere, and maintaining for 12 hr to obtain S-ZnSe/CoSe2The prepared S-ZnSe/CoSe2The material is uniformly coated on the surface of aluminum foil or carbon paper to prepare the heterojunction ZnSe/CoSe2A lithium-sulfur full cell positive electrode as a carrier;
s5, preparing a lithium-sulfur full-cell cathode: melting lithium in a glove box by using a tin melting furnaceHeating to 450 deg.C and coating with ZnSe/CoSe2Carbon paper penetration of (2); making lithium adsorb to load ZnSe/CoSe2The aluminum foil or the carbon paper is made into a heterojunction ZnSe/CoSe2And the lithium-sulfur full-cell cathode is used as a carrier.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110998933A (en) * | 2017-06-05 | 2020-04-10 | 新加坡科技研究局 | Core-shell complexes |
| CN111292965A (en) * | 2020-02-25 | 2020-06-16 | 东南大学 | Lithium ion hybrid capacitor cathode material with core-shell structure, preparation and application |
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| CN110998933A (en) * | 2017-06-05 | 2020-04-10 | 新加坡科技研究局 | Core-shell complexes |
| CN111292965A (en) * | 2020-02-25 | 2020-06-16 | 东南大学 | Lithium ion hybrid capacitor cathode material with core-shell structure, preparation and application |
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| Title |
|---|
| SHEN ZH 等: "CoSe2/MoS2 Heterostructures to Couple Polysulfide Adsorption and Catalysis in Lithium-Sulfur Batteries", 《CHINESE JOURNAL OF CHEMISTRY》, vol. 39, pages 1138 - 1144 * |
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|---|---|---|---|---|
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