CN112038591A - Magnesium-sulfur battery, transition metal sulfide/sulfur composite positive electrode material and composite method - Google Patents
Magnesium-sulfur battery, transition metal sulfide/sulfur composite positive electrode material and composite method Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 143
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 109
- 239000011593 sulfur Substances 0.000 title claims abstract description 109
- -1 transition metal sulfide Chemical class 0.000 title claims abstract description 109
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 101
- SMDQFHZIWNYSMR-UHFFFAOYSA-N sulfanylidenemagnesium Chemical compound S=[Mg] SMDQFHZIWNYSMR-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000011777 magnesium Substances 0.000 claims abstract description 72
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 40
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- 239000010406 cathode material Substances 0.000 claims abstract description 30
- 239000003792 electrolyte Substances 0.000 claims abstract description 30
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 27
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- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 5
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- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 5
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- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 3
- IWCVDCOJSPWGRW-UHFFFAOYSA-M magnesium;benzene;chloride Chemical compound [Mg+2].[Cl-].C1=CC=[C-]C=C1 IWCVDCOJSPWGRW-UHFFFAOYSA-M 0.000 claims description 3
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
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- 229910016002 MoS2a Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
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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
- H01M4/38—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
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
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- H—ELECTRICITY
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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
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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
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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
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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 magnesium-sulfur battery, a transition metal sulfide/sulfur composite positive electrode material and a composite method, wherein the magnesium-sulfur battery comprises a positive electrode containing the transition metal sulfide/sulfur composite positive electrode material, magnesium ion electrolyte and a magnesium metal negative electrode; wherein in the transition metal sulfide/sulfur composite cathode material, the transition metal sulfide is MxSyM is a cation, including: one or more of Mo, Ti, Cu, Co, V, Fe, Cr, Ni, Mn, Zn, Sc, Nb, Mo, Zr, W, Re and Ta; x is more than or equal to 1 and less than or equal to 9, y is more than or equal to 1 and less than or equal to 9, and the values of x and y satisfy the condition of keepingThe compound is electrically neutral; in the transition metal sulfide/sulfur composite anode material, the sulfur source comprises elemental sulfur, MgS and magnesium polysulfide MgSzOne or more of; wherein z is more than 1 and less than or equal to 4; in the transition metal sulfide/sulfur composite cathode material, the mass percent of sulfur is 5-95%.
Description
Technical Field
The invention relates to the technical field of novel batteries, in particular to a magnesium-sulfur battery, a transition metal sulfide/sulfur composite positive electrode material and a composite method.
Background
With the social demand for green energy, lithium ion batteries are becoming the mainstream power sources for mobile electronic devices and electric vehicles. Through the development of many years, the energy density of the lithium ion battery is gradually close to the theoretical limit of embedded chemistry, and the capacity and the energy density of the lithium ion battery are difficult to be greatly improved. The metal secondary battery can combine the metal cathode and the anode material, and the energy density of the battery can be further improved by virtue of the high capacity and low potential of the metal cathode. While in all metal cathodes, magnesium metal has a high capacity (in particular a volumetric capacity of 3833mA h/cm)3Comparison of 2046mA h/cm for lithium metal3) And low reduction potential (-2.4V vs. SHE). More importantly, the magnesium metal cathode can realize the deposition and dissolution of 100 percent of coulombic efficiency, does not generate dendrite and has high safety performance. However, magnesium ions have two units of positive charges and have strong interaction with the anode material, so that the diffusion is slow and the dynamic performance is poor. Therefore, the overpotential of many magnesium battery positive electrode materials is relatively large, and the intercalation degree of magnesium ions is low. Finding a positive electrode material with fast kinetics and high energy density has become a major challenge in the development of magnesium batteries.
The theoretical energy density of the magnesium-sulfur battery with sulfur as a positive electrode and magnesium metal as a negative electrode is 1700Wh/kg and 3200 Wh/L. Meanwhile, sulfur is used as a magnesium battery anode material to perform solid-liquid two-phase reaction, so that faster reaction kinetics can be obtained. Therefore, the magnesium-sulfur battery has better safety performance, lower price, higher energy density, and the like, compared to the conventional lithium ion battery. However, the development of magnesium-sulfur batteries is still in the primary stage, compared to conventional lithium ion batteries and lithium-sulfur batteries. The factors limiting the development of magnesium-sulfur batteries are mainly: sulfur and its final discharge products MgS and MgS2Is an insulator, has poor reaction activity, and causes poor reversibility of the battery; in addition, sulfur is present during charging and dischargingForm polysulfide ions, and the shuttling effect of the polysulfide ions can lead to the passivation of the magnesium cathode. To address the above issues, researchers often design S/C composites to improve the conductivity of the positive electrode while mitigating the shuttling effect. But the addition of the carbon material reduces the capacity of the composite anode, simultaneously improves the using amount of the electrolyte and reduces the overall energy density of the magnesium-sulfur battery. In addition, the carbon material has limited adsorption capacity to polysulfide ions and cannot inhibit the shuttle effect, so that the cycle performance of the magnesium-sulfur battery is difficult to greatly improve. The capacity retention rate of most S/C composite anode materials in 100 cycles is lower than 50%, the overall capacity of the anode is generally lower than 200mA h/g, and the capacity utilization rate of sulfur is lower (lower than 400mA h/g).
Disclosure of Invention
The invention aims to provide a magnesium-sulfur battery, a transition metal sulfide/sulfur composite positive electrode material and a composite method, which can improve the cycle stability of the magnesium-sulfur battery while maintaining high energy density of the magnesium-sulfur battery.
In order to achieve the above object, in a first aspect, an embodiment of the present invention provides a magnesium-sulfur battery, including a positive electrode including a transition metal sulfide/sulfur composite positive electrode material, a magnesium ion electrolyte, and a magnesium metal negative electrode;
wherein in the transition metal sulfide/sulfur composite cathode material, the transition metal sulfide is MxSyM is a cation, including: one or more of Mo, Ti, Cu, Co, V, Fe, Cr, Ni, Mn, Zn, Sc, Nb, Mo, Zr, W, Re and Ta; x is more than or equal to 1 and less than or equal to 9, y is more than or equal to 1 and less than or equal to 9, and the values of x and y meet the requirement of keeping the electric neutrality of the compound; in the transition metal sulfide/sulfur composite anode material, the sulfur source comprises elemental sulfur, MgS and magnesium polysulfide MgSzOne or more of; wherein z is more than 1 and less than or equal to 4;
in the transition metal sulfide/sulfur composite cathode material, the mass percent of sulfur is 5-95%.
Preferably, the transition metal sulfide/sulfur composite positive electrode material further includes a carbon material;
the carbon material specifically comprises one or more of graphene, Ketjen black, carbon nanotubes, acetylene black and Super-P carbon black;
the mass percentage of the carbon material in the transition metal sulfide/sulfur composite cathode material is 0-50%.
Preferably, the positive electrode further comprises a conductive additive and a binder;
the conductive additive specifically comprises one or more of graphene, Ketjen black, carbon nanotubes, acetylene black and Super-P carbon black;
the binder comprises one or a mixture of Polytetrafluoroethylene (PTFE), hydroxymethyl cellulose (CMC), sodium alginate, polyvinylidene fluoride (PVDF), polyacrylic acid (PAA) and Styrene Butadiene Rubber (SBR).
Preferably, the solute of the magnesium ion electrolyte comprises MgCl2、AlCl3、PhMgCl、Mg(TFSI)2、Mg(BH4)2、Mg(oTf)2One or more of (a); the solvent comprises one or more of tetrahydrofuran, dimethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether; the concentration of the magnesium ion electrolyte is 0.01-0.5 mol/L.
Preferably, the magnesium metal negative electrode comprises one or more of magnesium metal foil, magnesium powder, magnesium mesh and magnesium alloy.
In a second aspect, an embodiment of the present invention provides a transition metal sulfide/sulfur composite positive electrode material in the magnesium-sulfur battery according to the first aspect, where in the transition metal sulfide/sulfur composite positive electrode material, the transition metal sulfide is MxSyM is a cation, including: one or more of Mo, Ti, Cu, Co, V, Fe, Cr, Ni, Mn, Zn, Sc, Nb, Mo, Zr, W, Re and Ta; x is more than or equal to 1 and less than or equal to 9, y is more than or equal to 1 and less than or equal to 9, and the values of x and y meet the requirement of keeping the electric neutrality of the compound; in the transition metal sulfide/sulfur composite anode material, the sulfur source comprises elemental sulfur, MgS and magnesium polysulfide MgSzOne or more of; wherein z is more than 1 and less than or equal to 4;
in the transition metal sulfide/sulfur composite cathode material, the mass percent of sulfur is 5-95%.
Preferably, the transition metal sulfide/sulfur composite positive electrode material further includes a carbon material;
the carbon material specifically comprises one or more of graphene, Ketjen black, carbon nanotubes, acetylene black and Super-P carbon black;
the mass percentage of the carbon material in the transition metal sulfide/sulfur composite cathode material is 0-50%.
Preferably, the transition metal sulfide/sulfur composite cathode material further comprises a conductive additive and a binder;
the conductive additive specifically comprises one or more of graphene, Ketjen black, carbon nanotubes, acetylene black and Super-P carbon black;
the binder comprises one or a mixture of Polytetrafluoroethylene (PTFE), hydroxymethyl cellulose (CMC), sodium alginate, polyvinylidene fluoride (PVDF), polyacrylic acid (PAA) and Styrene Butadiene Rubber (SBR).
In a third aspect, an embodiment of the present invention provides a method for compounding a transition metal sulfide/sulfur composite cathode material according to the second aspect, where the method for compounding includes: weighing a proper amount of transition metal sulfide and a sulfur source, placing the transition metal sulfide and the sulfur source in a ball milling tank, and performing sealed ball milling for 1-48 hours to obtain the transition metal sulfide/sulfur composite cathode material.
In a fourth aspect, an embodiment of the present invention provides a method for compounding a transition metal sulfide/sulfur composite cathode material according to the second aspect, where the method for compounding includes: weighing a proper amount of transition metal sulfide and a sulfur source, placing the transition metal sulfide and the sulfur source in a ball milling tank, adding a proper amount of solvent, and performing sealed ball milling for 1-48 hours;
then dissolving a proper amount of thiosulfuric acid or sodium thiosulfate into the mixture, and dropwise adding 0.05-5 mol of H2SO4Stirring evenly at room temperature;
and (3) washing the reaction product with water, and drying in a vacuum oven to obtain the transition metal sulfide/sulfur composite cathode material.
The magnesium-sulfur battery provided by the invention adopts the composite material of the transition metal sulfide and the sulfur as the anode, and improves the utilization rate of the sulfur and reduces the use of carbon materials by utilizing the high conductivity and the high capacity of the transition metal sulfide. First the transition metal sulphide may be in phase with sulphurUnder the same voltage window, certain magnesium embedding capacity is contributed; the transition metal sulfide has rapid magnesium ion transmission performance, and can improve the reaction kinetics of the composite cathode material; the product of the transition metal sulfide embedded with magnesium can greatly improve the affinity to magnesium polysulfide, thereby inhibiting shuttle effect and increasing the cycle stability; the transition metal can also catalytically decompose the sulfur discharge products MgS and MgS2The reversibility of the magnesium-sulfur battery is improved; in addition, the transition metal sulfide has higher electronic conductivity and electrochemical activity, and the use of high specific surface carbon can be effectively reduced due to extremely low resistance, so that the porosity of the anode material is greatly reduced, the using amount of electrolyte is reduced, and the energy density of the magnesium-sulfur full battery is improved.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail with reference to the accompanying drawings and embodiments.
FIG. 1 shows Mo in example 1 of the present invention6S8the/S is a constant current charge-discharge diagram of the magnesium-sulfur battery with the anode;
FIG. 2 shows Mo in example 1 of the present invention6S8and/S is the cycle performance schematic diagram of the magnesium-sulfur battery of the positive electrode.
Detailed Description
The embodiment of the invention provides a magnesium-sulfur battery which comprises a positive electrode containing a transition metal sulfide/sulfur composite positive electrode material, magnesium ion electrolyte and a magnesium metal negative electrode.
Wherein, in the transition metal sulfide/sulfur composite anode material, the transition metal sulfide is MxSyM is a cation, including: one or more of Mo, Ti, Cu, Co, V, Fe, Cr, Ni, Mn, Zn, Sc, Nb, Mo, Zr, W, Re and Ta; x is more than or equal to 1 and less than or equal to 9, y is more than or equal to 1 and less than or equal to 9, and the values of x and y meet the requirement of keeping the electric neutrality of the compound; in the transition metal sulfide/sulfur composite anode material, the sulfur source comprises elemental sulfur, MgS and magnesium polysulfide MgSzOne or more of; wherein z is more than 1 and less than or equal to 4;
in the transition metal sulfide/sulfur composite anode material, the mass percent of sulfur is 5-95%.
In some examples, the transition metal sulfide/sulfur composite positive electrode material may further include a carbon material, i.e., a transition metal sulfide/sulfur/carbon composite positive electrode material; the carbon material specifically comprises one or more of graphene, Ketjen black, carbon nanotubes, acetylene black and Super-P carbon black; the mass percentage of the carbon material in the transition metal sulfide/sulfur composite anode material is 0-50%.
In addition, the positive electrode further comprises a conductive additive and a binder;
the conductive additive specifically comprises one or more of graphene, Ketjen black, carbon nanotubes, acetylene black and Super-P carbon black;
the binder comprises one or a mixture of Polytetrafluoroethylene (PTFE), hydroxymethyl cellulose (CMC), sodium alginate, polyvinylidene fluoride (PVDF), polyacrylic acid (PAA) and Styrene Butadiene Rubber (SBR).
Transition metal sulfide/sulfur, conductive additive and adhesive in a ratio of 1: (0.1-2): (0.1-0.5).
The positive electrode containing the transition metal sulfide/sulfur composite positive electrode material is formed by coating the transition metal sulfide/sulfur composite positive electrode material on a positive electrode current collector. The positive current collector can be specifically one of a stainless steel mesh, a molybdenum mesh, a titanium mesh, a nickel mesh and a tantalum sheet. And drying the coated anode in an oven at 50-120 ℃ for 2-24 hours to form the required anode.
In a magnesium-sulfur battery, the solute of the magnesium ion electrolyte comprises MgCl2、AlCl3、PhMgCl、Mg(TFSI)2、Mg(BH4)2、Mg(oTf)2One or more of (a); the solvent comprises one or more of tetrahydrofuran, dimethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether; the concentration of the magnesium ion electrolyte is 0.01-0.5 mol/L.
The magnesium metal negative electrode comprises one or more of magnesium metal foil, magnesium powder, magnesium mesh and magnesium alloy.
The transition metal sulfide/sulfur composite cathode material used in the magnesium-sulfur battery can be obtained by different composite methods, for example, can be prepared by a physical composite method or a chemical composite method.
The physical compounding method comprises the following steps: weighing a proper amount of transition metal sulfide and a sulfur source, adding a proper amount of carbon source, placing the mixture in a ball milling tank, and performing sealed ball milling for 1-48 hours to obtain the transition metal sulfide/sulfur composite cathode material.
To produce Mo6S8the/S composite material is taken as an example. Weighing 1g of Mo6S80.1-9g of settled sulfur, 0.1-1g of graphene and 0.1-1g of ketjen black are put into a ball milling tank and ball milled for 1-48 hours in a sealing way to obtain Mo6S8a/S composite material.
The chemical compounding method comprises the following steps: weighing a proper amount of transition metal sulfide and a sulfur source, adding a proper amount of carbon source, placing in a ball milling tank, adding a proper amount of solvent, and performing sealed ball milling for 1-48 hours; then dissolving a proper amount of thiosulfuric acid or sodium thiosulfate into the mixture, and dropwise adding 0.05-5 mol of H2SO4Stirring evenly at room temperature; and (3) washing the reaction product with water, and drying in a vacuum oven to obtain the transition metal sulfide/sulfur composite cathode material.
To produce Mo6S8the/S composite material is taken as an example. Weighing 1g of Mo6S80.1-1g of carbon nano tube and 0.1-1g of acetylene black are put into a ball milling tank, 20mL of water and 20mL of ethanol are added, and the ball milling is carried out for 1-48 hours in a sealing way; then 0.5-45g of thiosulfuric acid or sodium thiosulfate is dissolved therein, followed by slow dropwise addition of 0.05-5 mol of H2SO4Stirring at room temperature for 2 hours; washing the reaction product with water, and drying in a vacuum oven at 50-120 ℃ to obtain Mo6S8a/S composite material.
The working temperature of the magnesium-sulfur battery is 10-70 ℃.
The magnesium-sulfur battery adopts the transition metal sulfide/sulfur composite cathode material, utilizes the high capacity and high energy density of sulfur, utilizes the high conductivity of the transition metal sulfide, inhibits shuttle effect and the catalytic action of the transition metal sulfide, obtains high energy density and stable cycle performance at the same time, and promotes the commercial application of the magnesium-sulfur battery. The transition metal sulfide/sulfur composite material anode has simple preparation process and strong repeatability, and is easy for large-scale production. The transition metal sulfide/sulfur composite anode material can obtain the integral capacity of an anode of more than 200mA h/g, wherein sulfur can release the capacity of about 1000mAh/g, and the transition metal sulfide/sulfur composite anode material has better capacity retention rate.
The magnesium-sulfur battery of the invention utilizes the high conductivity and high capacity of the transition metal sulfide to improve the utilization rate of sulfur and reduce the use of carbon materials. Firstly, transition metal sulfide can contribute to certain magnesium insertion capacity under the same voltage window as sulfur; the transition metal sulfide has rapid magnesium ion transmission performance, and can improve the reaction kinetics of the composite cathode material; the product of the transition metal sulfide embedded with magnesium can greatly improve the affinity to magnesium polysulfide, thereby inhibiting shuttle effect and increasing the cycle stability; the transition metal can also catalytically decompose the sulfur discharge products MgS and MgS2The reversibility of the magnesium-sulfur battery is improved; in addition, the transition metal sulfide has higher electronic conductivity and electrochemical activity, and the use of high specific surface carbon can be effectively reduced due to extremely low resistance, so that the porosity of the anode material is greatly reduced, the using amount of electrolyte is reduced, and the energy density of the magnesium-sulfur full battery is improved.
The present invention is further illustrated by the following specific examples.
Example 1
The embodiment provides a Mo6S8And preparing the/S composite anode material and testing the performance of the material.
(1)Mo6S8The synthesis of (2): taking the molar ratio as 3: 2: 3 molybdenum disulfide, copper sulfide, and molybdenum powder, ball milling for 0.5h, then 106Pressing into granules, and placing into a sealed stainless steel tube; heating to 900 ℃ at the rate of 2 ℃ per minute in argon, keeping for 24 hours, and naturally cooling to obtain Cu2Mo6S8. The tube was then placed in 6 molar HCl and oxygen was bubbled through for 12 hours to remove the Cu. Washing the product with water and drying in a vacuum oven at 100 ℃ for 12 hours to obtain Mo6S8。
(2)Mo6S8Preparation of the/S composite material: weighing 1g of Mo6S80.1g of precipitated sulfur, 1g of graphene,1g of Keqin black is put in a ball milling tank and ball milled for 1 hour in a sealing way to obtain Mo6S8a/S composite material.
(3) And (3) adding the following components in percentage by weight of 7: 1: 1: 1, respectively weighing Mo6S8The positive pole piece is prepared from a/S composite material, Ketjen black, carbon nanotubes and polytetrafluoroethylene through uniformly grinding, rolling to form a film and drying. Wherein the content of active substance is 2mg/cm2。
(4) In a glove box filled with argon, the positive plate, magnesium foil, and 0.4 mol MgCl2-AlCl3Dissolving in dimethyl ether electrolyte to assemble the soft package battery. And performing cyclic voltammetry test on the battery, wherein the scanning voltage range is 0.2-2.5V vs. Mg/Mg2+. Then, the battery is subjected to a constant current charge and discharge test, and the current density is 20 mA/g. The test results are shown in Table 1.
FIG. 1 Mo in example 1 of the present invention6S8and/S is the constant current charge-discharge curve of the magnesium-sulfur battery of the anode. FIG. 2 shows Mo in example 1 of the present invention6S8and/S is the cycle performance schematic diagram of the magnesium-sulfur battery of the positive electrode. As can be seen from FIG. 1, the discharge capacity of the first coil is 220mAh/g, and the charge capacity is 235 mAh/g. Four platforms of the charging process are respectively corresponding to the magnesium ions embedded into Mo6S8And the process of magnesium-forming of sulphur. High capacity and high potential correspond to Mo6S8High energy density of the/S positive electrode material. As can be seen from FIG. 2, the capacity of the first ten cycles is maintained at 200mAh/g, and the coulombic efficiency approaches 100%, indicating that Mo6S8the/S positive electrode material has excellent cycle stability.
Example 2
The embodiment provides a Mo6S8And preparing the/S composite anode material and testing the performance of the material.
(1)Mo6S8The synthesis of (2): taking the molar ratio as 3: 2: 3 molybdenum disulfide, copper sulfide, and molybdenum powder, ball milling for 0.5h, then 106Pressing into granules, and placing into a sealed stainless steel tube; heating to 900 ℃ at the rate of 2 ℃ per minute in argon, keeping for 24 hours, and naturally cooling to obtain Cu2Mo6S8. Followed byThen, the reaction mixture was put into 6 mol of HCl and oxygen was introduced thereinto for 12 hours to remove Cu. Washing the product with water, and drying in a vacuum oven at 100 ℃ for 12h to obtain Mo6S8。
(2)Mo6S8Preparation of the/S composite material: weighing 1gMo6S80.1g of carbon nano tube and 0.1g of acetylene black are put into a ball milling tank, 20mL of water and 20mL of ethanol are added, and the ball milling is carried out for 1 hour in a sealing way; then 0.5g of sodium thiosulfate was dissolved therein, followed by slow dropwise addition of 0.5mol of H2SO4Stirring at room temperature for 2 hours; washing the reaction product with water, and drying in a vacuum oven at 60 ℃ to obtain Mo6S8a/S composite material.
(3) And (3) adding the following components in percentage by weight of 7: 1: 1: 1, respectively weighing Mo6S8The positive pole piece is prepared from a/S composite material, Ketjen black, Super-P carbon black and polyvinylidene fluoride through uniformly grinding, rolling to form a film and drying. Wherein the content of active substance is 2mg/cm2。
(4) In a glove box filled with argon, the positive plate, the magnesium foil, and 0.25 mol of PhMgCl-AlCl were placed3Dissolving in tetrahydrofuran electrolyte to assemble the soft package battery. And performing cyclic voltammetry test on the battery, wherein the scanning voltage range is 0.2-2.5V vs. Mg/Mg2+. Then, the battery is subjected to a constant current charge and discharge test, and the current density is 20 mA/g. The results of the capacity test are shown in Table 1.
Example 3
This example provides a TiS2And preparing the/S composite anode material and testing the performance of the material.
(1)TiS2Preparation of the/S composite material: weighing 1g of TiS21g of precipitated sulfur, 0.7g of graphene and 0.7g of Ketjen black are placed in a ball milling tank and ball milled for 24 hours in a sealing manner to obtain TiS2a/S composite material.
(2) And (3) adding the following components in percentage by weight of 7: 1: 1: 1 weight ratio of TiS2The positive pole piece is prepared by uniformly grinding a/S composite material, Super-P carbon black, a carbon nano tube and polyacrylic acid, rolling to form a film and drying. Wherein the content of active substance is 2mg/cm2.
(3) In a glove box filled with argon, the mixture isPole piece, magnesium foil, and 0.03 molar MgCl2-AlCl3-Mg(TFSI)2Dissolving in tetrahydrofuran electrolyte to assemble the soft package battery. And 0.2-2.5Vvs. Mg/Mg for the cell2+Electrochemical tests were performed within the range. The results of the capacity test are shown in Table 1.
Example 4
This example provides a TiS3And preparing the/S composite anode material and testing the performance of the material.
(1)TiS3Preparation of the/S composite material: weighing 2gTiS31g of precipitated sulfur, 1g of graphene and 1g of Ketjen black are placed in a ball milling tank and ball milled for 3 hours in a sealing manner to obtain TiS3a/S composite material.
(2) And (3) adding the following components in percentage by weight of 7: 2: 1 weight ratio of TiS3And grinding the/S composite material, Super-P carbon black and polyacrylic acid uniformly, rolling to form a film, and drying to obtain the positive pole piece. Wherein the content of active substance is 2mg/cm2。
(3) In a glove box filled with argon, the positive electrode plate, magnesium foil, and 0.25 mol MgCl2And 0.5mol of Mg (TFSI)2And dissolving the mixture in glycol dimethyl ether electrolyte to assemble the soft package battery. And for the battery, the voltage is 0.2-2.5V vs. Mg/Mg2+Electrochemical tests were performed within the range. The results of the capacity test are shown in Table 1.
Example 5
The embodiment provides a preparation method and a performance test of a CuS/S composite cathode material.
(1) Preparing a CuS/S composite material: weighing 1g of CuS, 9g of settled sulfur, 0.1g of graphene and 0.1g of Ketjen black, placing the CuS, 9g of settled sulfur, 0.1g of graphene and 0.1g of Ketjen black in a ball milling tank, and performing sealed ball milling for 6 hours to obtain the CuS/S composite material.
(2) And (3) adding the following components in percentage by weight of 7: 1: 1: 1, respectively weighing the CuS/S composite material, Ketjen black, the carbon nano tube and polytetrafluoroethylene, uniformly grinding, rolling to form a film, and drying to obtain the positive pole piece. Wherein the content of active substance is 2mg/cm2。
(3) In a glove box filled with argon, the positive electrode plate, the magnesium foil, and 0.03 mol of MgCl2-AlCl3-Mg(TFSI)2Dissolving in tetrahydrofuran electrolyte to assemble the soft package battery. And to itThe battery is subjected to cyclic voltammetry test, and the scanning voltage range is 0.2-2.5Vvs2+. Then, the battery is subjected to a constant current charge and discharge test, and the current density is 20 mA/g. The results of the capacity test are shown in Table 1.
Example 6
The embodiment provides a CoS2And preparing the/S composite anode material and testing the performance of the material.
(1)CoS2Preparation of the/S composite material: 3g of CoS are weighed21g of precipitated sulfur, 0.3g of graphene and 0.3g of Ketjen black are placed in a ball milling tank and ball milled for 10 hours in a sealing manner to obtain CoS2a/S composite material.
(2) And (3) adding the following components in percentage by weight of 7: 1: 1: 1 weight ratio of CoS2The positive pole piece is prepared from a/S composite material, Ketjen black, carbon nanotubes and Styrene Butadiene Rubber (SBR) through uniformly grinding, rolling into a film and drying. Wherein the content of active substance is 1mg/cm2。
(3) In a glove box filled with argon, the positive electrode plate, magnesium foil, and 0.4 mol of Mg (TFSI)2-AlCl3Dissolving in dimethyl ether electrolyte to assemble the soft package battery. And performing cyclic voltammetry test on the battery, wherein the scanning voltage range is 0.2-3Vvs2+. Then, the battery is subjected to a constant current charge and discharge test, and the current density is 20 mA/g. The results of the capacity test are shown in Table 1.
Example 7
The present embodiment provides a Co9S8And preparing the/S composite anode material and testing the performance of the material.
(1)Co9S8Preparation of the/S composite material: weighing 1g of Co9S83g of precipitated sulfur, 0.3g of graphene and 0.3g of Ketjen black are placed in a ball milling tank and ball milled for 12 hours in a sealing manner to obtain Co9S8a/S composite material.
(2) And (3) adding the following components in percentage by weight of 7: 2: 1 by weight ratio of Co9S8The composite material is prepared from a/S composite material, Keqin black and Styrene Butadiene Rubber (SBR) through uniformly grinding, rolling to form a film and drying to obtain the positive pole piece. Wherein the content of active substance is 3mg/cm2。
(3) In a glove box filled with argon, the positive plate and magnesium are put into the glove boxFoil, and 0.25 moles of Mg (TFSI)2-MgCl2And dissolving the electrolyte in diethylene glycol dimethyl ether to assemble the soft package battery. And performing cyclic voltammetry test on the battery, wherein the scanning voltage range is 0.5-2.5V vs. Mg/Mg2+. Then, the battery is subjected to a constant current charge and discharge test, and the current density is 20 mA/g. The results of the capacity test are shown in Table 1.
Example 8
This example provides a FeS2And preparing the/S composite anode material and testing the performance of the material.
(1)FeS2Preparation of the/S composite material: 19g of FeS are weighed out21g of precipitated sulfur, 1g of graphene and 1g of Ketjen black are placed in a ball milling tank and ball milled for 15 hours in a sealing manner to obtain FeS2a/S composite material.
(2) And (3) adding the following components in percentage by weight of 7: 1: 1, respectively weighing FeS according to the mass ratio2And grinding the/S composite material, namely Ketjen black and polytetrafluoroethylene uniformly to form a film, and drying to obtain the positive pole piece. Wherein the content of active substance is 4mg/cm2。
(3) In a glove box filled with argon, the positive electrode plate, magnesium foil, and 1 mol of Mg (TFSI)2-MgCl2Dissolving in dimethyl ether electrolyte to assemble the soft package battery. And performing cyclic voltammetry test on the battery, wherein the scanning voltage range is 0.2-2.5V vs. Mg/Mg2+. Then, the battery is subjected to a constant current charge and discharge test, and the current density is 10 mA/g. The results of the capacity test are shown in Table 1.
Example 9
This example provides a Fe0.5Co0.5S2And preparing the/S composite anode material and testing the performance of the material.
(1)Fe0.5Co0.5S2Preparation of the/S composite material: 14g of Fe were weighed0.5Co0.5S26g of precipitated sulfur, 1g of graphene and 2g of ketjen black are placed in a ball milling tank and ball milled for 18 hours in a sealing way to obtain Fe0.5Co0.5S2a/S composite material.
(2) And (3) adding the following components in percentage by weight of 7: 1: 1: 1 weight ratio of Fe0.5Co0.5S2(S) composite material, acetylene black, carbon nanotube, methylolAnd uniformly grinding the base cellulose (CMC), rolling the ground base cellulose (CMC) into a film, and drying the film to obtain the positive pole piece. Wherein the content of active substance is 0.5mg/cm2。
(3) In a glove box filled with argon, the positive plate, magnesium foil, and 0.4 mol MgCl2-Mg(TFSI)2Dissolving in triglyme electrolyte to assemble the soft package battery. And performing cyclic voltammetry test on the battery, wherein the scanning voltage range is 0.2-2.5V vs. Mg/Mg2+. Then, the battery is subjected to a constant current charge and discharge test, and the current density is 20 mA/g. The results of the capacity test are shown in Table 1.
Example 10
The present embodiment provides a VS2And preparing the/S composite anode material and testing the performance of the material.
(1)VS2Preparation of the/S composite material: weighing 9g VS21g of precipitated sulfur and 3g of Keqin black are placed in a ball milling tank and ball milled for 20 hours in a sealing way to obtain VS2a/S composite material.
(2) And (3) adding the following components in percentage by weight of 8: 1: 1 weighing VS respectively2And grinding the graphene and the polyvinylidene fluoride uniformly, rolling to form a film, and drying to obtain the positive pole piece. Wherein the content of active substance is 2mg/cm2。
(3) In a glove box filled with argon, the positive electrode plate, the magnesium foil, and 0.03 mol of MgCl2-AlCl3-Mg(TFSI)2And dissolving in tetrahydrofuran and dimethyl ether electrolyte to assemble the soft package battery. And for the battery, the voltage is 0.2-2.5V vs. Mg/Mg2 +Electrochemical tests were performed within the range. The results of the capacity test are shown in Table 1.
Example 11
The present embodiment provides a VS4And preparing the/S composite anode material and testing the performance of the material.
(1)VS4Preparation of the/S composite material: weighing 4g VS41g of settled sulfur and 1g of graphene are placed in a ball milling tank and ball milled for 25 hours in a sealing way to obtain VS4a/S composite material.
(2) And (3) adding the following components in percentage by weight of 8: 1: 1 weighing VS respectively4The preparation method comprises the steps of grinding graphene and polyvinylidene fluoride uniformly, rolling into a film, and dryingAnd drying to obtain the positive pole piece. Wherein the content of active substance is 2mg/cm2。
(3) In a glove box filled with argon, the positive plate, magnesium foil, and 0.4 mol MgCl2-AlCl3Dimethyl ether and glycol dimethyl ether electrolyte are assembled into the soft package battery. And for the battery, the voltage is 0.2-2.5V vs. Mg/Mg2+Electrochemical tests were performed within the range. The results of the capacity test are shown in Table 1.
Example 12
This example provides a NiS2And preparing the/S composite anode material and testing the performance of the material.
(1)NiS2Preparation of the/S composite material: weighing 3g of NiS22g of precipitated sulfur, 0.5g of graphene and 0.5g of carbon nano tube are placed in a ball milling tank and ball milled for 30 hours in a sealing way to obtain NiS2a/S composite material.
(2) And (3) adding the following components in percentage by weight of 8: 1: 1 by weight ratio of NiS2And grinding the/S composite material, acetylene black and sodium alginate uniformly, rolling to form a film, and drying to obtain the positive pole piece. Wherein the content of active substance is 4mg/cm2。
(3) In a glove box filled with argon, the positive plate, magnesium foil, and 0.4 mol MgCl2-AlCl3And (4) assembling the triethylene glycol dimethyl ether electrolyte into the soft package battery. And for the battery at 0.2-3Vvs. Mg/Mg2+Electrochemical tests were performed within the range. The results of the capacity test are shown in Table 1.
Example 13
The embodiment provides an NbS3And preparing the/S composite anode material and testing the performance of the material.
(1)NbS3Preparation of the/S composite material: weighing 2g NbS33g of precipitated sulfur, 1g of graphene and 0.5g of acetylene black are placed in a ball milling tank, and ball milling is carried out for 35 hours in a sealing manner to obtain NbS3a/S composite material.
(2) And (3) adding the following components in percentage by weight of 8: 1: weighing NbS respectively according to the mass ratio of 13And grinding the/S composite material, Super-P carbon black and carboxymethyl cellulose uniformly, rolling to form a film, and drying to obtain the positive pole piece. Wherein the content of active substance is 5mg/cm2。
(3) In a glove box filled with argonIn (1), a positive electrode sheet, a magnesium foil, and 0.4 mol of MgCl2-AlCl3And assembling the diethylene glycol dimethyl ether electrolyte into the soft package battery. And for the battery, the voltage is 0.5-3V vs. Mg/Mg2+Electrochemical tests were performed within the range. The results of the capacity test are shown in Table 1.
Example 14
The embodiment provides a MoS2And preparing the/S composite anode material and testing the performance of the material.
(1)MoS2Preparation of the/S composite material: weighing 1g of MoS24g of precipitated sulfur, 3g of Super-P carbon black and 3g of acetylene black are placed in a ball milling tank, and ball milling is carried out for 40 hours in a sealing manner to obtain MoS2a/S composite material.
(2) And (3) adding the following components in percentage by weight of 7: 1: 1: 1 MoS is weighed respectively2And grinding the Super-P carbon black, the Keqin black and the polyacrylic acid uniformly, rolling to form a film, and drying to obtain the positive pole piece. Wherein the content of active substance is 2mg/cm2。
(3) In a glove box filled with argon, the positive plate, magnesium foil, and 0.4 mol MgCl2-AlCl3And (4) assembling the ethylene glycol dimethyl ether electrolyte into the soft package battery. And for the battery at 0.2-3Vvs. Mg/Mg2+Electrochemical tests were performed within the range. The results of the capacity test are shown in Table 1.
Comparative example 1
This comparative example 1 provides Mo6S8And preparing the/C composite positive electrode material and testing the performance of the/C composite positive electrode material.
(1)Mo6S8The synthesis of (2): taking the molar ratio as 3: 2: 3 molybdenum disulfide, copper sulfide, and molybdenum powder, ball milling for 0.5h, then 106Pressing into granules, and placing into a sealed stainless steel tube; heating to 900 ℃ at the rate of 2 ℃ per minute in argon, keeping for 24 hours, and naturally cooling to obtain Cu2Mo6S8. The tube was then placed in 6 molar HCl and oxygen was bubbled through for 12 hours to remove the Cu. Washing the product with water and drying in a vacuum oven at 100 ℃ for 12 hours to obtain Mo6S8。
(2)Mo6S8Preparation of/C: weighing 1gMo6S80.1g of graphene and 0.1g of Ketjen black are placed in a ball milling tank and ball milled for 1 hour in a sealing manner to obtain Mo6S8And C, material.
(3) And (3) adding the following components in percentage by weight of 7: 1: 1: 1, respectively weighing Mo6S8And C, uniformly grinding Keqin black, carbon nano tubes and sodium alginate, rolling into a film, and drying to obtain the positive pole piece. Wherein the content of active substance is 2mg/cm2。
(4) In a glove box filled with argon, the positive plate, magnesium foil, and 0.4 mol MgCl2-AlCl3Dissolving in dimethyl ether electrolyte to assemble the soft package battery. And performing cyclic voltammetry test on the battery, wherein the scanning voltage range is 0.2-2.5V vs. Mg/Mg2+. Then, the battery is subjected to a constant current charge and discharge test, and the current density is 20 mA/g. The results of the capacity test are shown in Table 1.
Comparative example 2
The comparative example 2 provides preparation and performance test of an S/C composite positive electrode material.
(1) Preparing an S/C composite material: weighing 1g of precipitated sulfur, 0.5g of graphene and 0.5g of Ketjen black, placing the weighed materials in a ball milling tank, and performing sealed ball milling for 1 hour to obtain the S/C composite material.
(2) And (3) adding the following components in percentage by weight of 7: 1: 1: 1, respectively weighing the S/C composite material, ketjen black, the carbon nano tube and sodium alginate, uniformly grinding, rolling to form a film, and drying to obtain the positive pole piece. Wherein the content of active substance is 2mg/cm2。
(3) In a glove box filled with argon, the positive plate, magnesium foil, and 0.4 mol MgCl2-AlCl3Dissolving in dimethyl ether electrolyte to assemble the soft package battery. And performing cyclic voltammetry test on the battery, wherein the scanning voltage range is 0.2-2.5Vvs2+. Then, the battery is subjected to a constant current charge and discharge test, and the current density is 20 mA/g. The test results are shown in Table 1. Table 1 shows theoretical capacities and actual capacities of the composite positive electrode materials of examples and comparative examples. It can be seen that the utilization rate of theoretical capacity is different when sulfur and different transition metal sulfides form the composite positive electrode material.
TABLE 1
Shown in Table 2 below as Mo6S8In the/S composite cathode material, the theoretical capacity of the cathode material is continuously improved along with the increase of the sulfur content. It can be seen that the actual capacity of the entire positive electrode material is increasing, although the theoretical capacity utilization is decreasing.
| Ratio of sulfur (wt%) | Theoretical capacity (mA h/g) | Actual capacity (mA h/g) |
| 5 | 205 | 185 |
| 10 | 282 | 200 |
| 15 | 360 | 250 |
| 20 | 437 | 295 |
| 25 | 515 | 330 |
| 30 | 592 | 360 |
| 35 | 669 | 390 |
| 40 | 747 | 415 |
| 45 | 824 | 440 |
| 50 | 901 | 460 |
| 55 | 979 | 475 |
| 60 | 1056 | 490 |
| 65 | 1133 | 505 |
| 70 | 1211 | 515 |
| 75 | 1288 | 525 |
| 80 | 1365 | 530 |
| 85 | 1443 | 535 |
| 90 | 1520 | 540 |
| 95 | 1597 | 545 |
TABLE 2
The magnesium-sulfur battery adopts the transition metal sulfide/sulfur composite cathode material, utilizes the high capacity and high energy density of sulfur, utilizes the high conductivity of the transition metal sulfide, inhibits shuttle effect and the catalytic action of the transition metal sulfide, obtains high energy density and stable cycle performance at the same time, and promotes the commercial application of the magnesium-sulfur battery. The transition metal sulfide/sulfur composite material anode has simple preparation process and strong repeatability, and is easy for large-scale production. The transition metal sulfide/sulfur composite anode material can obtain the integral capacity of an anode of more than 200mA h/g, wherein sulfur can release the capacity of about 1000mAh/g, and the transition metal sulfide/sulfur composite anode material has better capacity retention rate.
The magnesium-sulfur battery of the invention utilizes the high conductivity and high capacity of the transition metal sulfide to improve the utilization rate of sulfur and reduce the use of carbon materials. Firstly, transition metal sulfide can contribute to certain magnesium insertion capacity under the same voltage window as sulfur; the transition metal sulfide has rapid magnesium ion transmission performance, and can improve the reaction kinetics of the composite cathode material; transitionThe product of the metal sulfide embedded with magnesium can greatly improve the affinity to magnesium polysulfide, thereby inhibiting shuttle effect and increasing the cycle stability; the transition metal can also catalytically decompose the sulfur discharge products MgS and MgS2The reversibility of the magnesium-sulfur battery is improved; in addition, the transition metal sulfide has higher electronic conductivity and electrochemical activity, and the use of high specific surface carbon can be effectively reduced due to extremely low resistance, so that the porosity of the anode material is greatly reduced, the using amount of electrolyte is reduced, and the energy density of the magnesium-sulfur full battery is improved.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. The magnesium-sulfur battery is characterized by comprising a positive electrode containing a transition metal sulfide/sulfur composite positive electrode material, a magnesium ion electrolyte and a magnesium metal negative electrode;
wherein in the transition metal sulfide/sulfur composite cathode material, the transition metal sulfide is MxSyM is a cation, including: one or more of Mo, Ti, Cu, Co, V, Fe, Cr, Ni, Mn, Zn, Sc, Nb, Mo, Zr, W, Re and Ta; x is more than or equal to 1 and less than or equal to 9, y is more than or equal to 1 and less than or equal to 9, and the values of x and y meet the requirement of keeping the electric neutrality of the compound; in the transition metal sulfide/sulfur composite anode material, the sulfur source comprises elemental sulfur, MgS and magnesium polysulfide MgSzOne or more of; wherein z is more than 1 and less than or equal to 4;
in the transition metal sulfide/sulfur composite cathode material, the mass percent of sulfur is 5-95%.
2. The magnesium sulfur battery according to claim 1, wherein the transition metal sulfide/sulfur composite positive electrode material further includes a carbon material;
the carbon material specifically comprises one or more of graphene, Ketjen black, carbon nanotubes, acetylene black and Super-P carbon black;
the mass percentage of the carbon material in the transition metal sulfide/sulfur composite cathode material is 0-50%.
3. The magnesium sulfur battery of claim 1 wherein the positive electrode further comprises a conductive additive and a binder;
the conductive additive specifically comprises one or more of graphene, Ketjen black, carbon nanotubes, acetylene black and Super-P carbon black;
the binder comprises one or more of Polytetrafluoroethylene (PTFE), hydroxymethyl cellulose (CMC), sodium alginate, polyvinylidene fluoride (PVDF), polyacrylic acid (PAA) and Styrene Butadiene Rubber (SBR).
4. The magnesium-sulfur battery of claim 1 wherein the solute of the magnesium-ion electrolyte comprises MgCl2、AlCl3、PhMgCl、Mg(TFSI)2、Mg(BH4)2、Mg(oTf)2One or more of (a); the solvent comprises one or more of tetrahydrofuran, dimethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether; the concentration of the magnesium ion electrolyte is 0.01-0.5 mol/L.
5. The magnesium-sulfur battery of claim 1, wherein the metallic magnesium negative electrode comprises one or more of a metallic magnesium foil, a magnesium powder, a magnesium mesh, a magnesium alloy.
6. The magnesium-sulfur battery transition metal sulfide/sulfur composite positive electrode material according to claim 1, wherein the transition metal sulfide is MxSyM is a cation, including: one or more of Mo, Ti, Cu, Co, V, Fe, Cr, Ni, Mn, Zn, Sc, Nb, Mo, Zr, W, Re and Ta; x is more than or equal to 1 and less than or equal to 9, y is more than or equal to 1 and less than or equal to 9, and x and y areThe value is selected to keep the electrical neutrality of the compound; in the transition metal sulfide/sulfur composite anode material, the sulfur source comprises elemental sulfur, MgS and magnesium polysulfide MgSzOne or more of; wherein z is more than 1 and less than or equal to 4;
in the transition metal sulfide/sulfur composite cathode material, the mass percent of sulfur is 5-95%.
7. The transition metal sulfide/sulfur composite positive electrode material according to claim 6, further comprising a carbon material;
the carbon material specifically comprises one or more of graphene, Ketjen black, carbon nanotubes, acetylene black and Super-P carbon black;
the mass percentage of the carbon material in the transition metal sulfide/sulfur composite cathode material is 0-50%.
8. A method for compounding the transition metal sulfide/sulfur composite positive electrode material according to claim 6, characterized by comprising: weighing a proper amount of transition metal sulfide and a sulfur source, placing the transition metal sulfide and the sulfur source in a ball milling tank, and performing sealed ball milling for 1-48 hours to obtain the transition metal sulfide/sulfur composite cathode material.
9. A method for compounding the transition metal sulfide/sulfur composite positive electrode material according to claim 6, characterized by comprising:
weighing a proper amount of transition metal sulfide and a sulfur source, placing the transition metal sulfide and the sulfur source in a ball milling tank, adding a proper amount of solvent, and performing sealed ball milling for 1-48 hours;
then dissolving a proper amount of thiosulfuric acid or sodium thiosulfate into the mixture, and dropwise adding 0.05-5 mol of H2SO4Stirring evenly at room temperature;
and (3) washing the reaction product with water, and drying in a vacuum oven to obtain the transition metal sulfide/sulfur composite cathode material.
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