CN109713282B - Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery - Google Patents
Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery Download PDFInfo
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Abstract
A lithium-sulfur battery positive electrode material, a preparation method thereof and a lithium-sulfur battery, wherein the positive electrode material comprises activated carbon, carbon black, transition metal or transition metal compound and sublimed sulfur; the transition metal compound is metal carbide, metal boride, metal nitride, metal phosphide, metal oxide or metal sulfide. The activated carbon is used as a main body for carrying sulfur, the carbon black can carry sulfur and enhance the conductivity of the cathode material, and the transition metal or the transition metal compound can play a role in fixing lithium polysulfide generated in an electrochemical reaction, inhibit the shuttle effect of polysulfide ions and improve the cycle performance of the lithium-sulfur battery. The lithium-sulfur battery cathode material disclosed by the invention has the advantages of simplicity, easiness in obtaining, easiness in large-scale preparation and the like, and can be used for obtaining a lithium-sulfur battery with long cycle, high specific capacity and high specific energy.
Description
Technical Field
The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to a lithium-sulfur battery positive electrode material, a preparation method thereof and a lithium-sulfur battery.
Background
A lithium sulfur battery includes a positive electrode containing electroactive sulfur, a negative electrode containing lithium, an electrolyte, and a separator. The theoretical specific energy of the lithium-sulfur battery is as high as 2600 Wh/kg, and the actual specific energy is higher than that of the current commercial lithium ion battery. The obvious advantage of the specific energy makes the lithium-sulfur battery have wide potential application in special power supplies, electric automobiles, high-altitude aircrafts and the like.
The positive electrode material of the lithium-sulfur battery is a key technology of the lithium-sulfur battery. Generally, sulfur needs to be compounded with porous carbon to improve conductivity, so that better energy can be exerted. The activated carbon is used as one of carbon materials, coke or natural organic plants such as charcoal or coconut shells and the like are used as raw materials, the particles of the activated carbon are large, are in a micron level, have a high specific surface area, and also have the advantages of low price, high density and mature production process, so the activated carbon can be used as a sulfur carrier material and applied to lithium-sulfur batteries. However, the conductivity of the activated carbon material is poor, and the conductivity of sulfur is very low, so that the specific capacity and the cycle performance of the lithium-sulfur battery anode using the activated carbon as a sulfur carrier are not ideal. Especially at high sulfur loading and large rate, the performance of lithium sulfur batteries is worse. Therefore, how to use activated carbon as a main body for carrying sulfur and improve the capacity of the lithium-sulfur battery has important practical application value.
Disclosure of Invention
The invention provides a lithium-sulfur battery positive electrode material, a preparation method thereof and a lithium-sulfur battery, and aims to solve the problems of poor battery cyclicity and unsatisfactory capacity exertion caused by poor conductivity of a compound of activated carbon and sulfur and the problem of dissolution of polysulfide ions.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the positive electrode material of the lithium-sulfur battery comprises active carbon, carbon black, transition metal and sulfur, wherein the mass ratio of the active carbon to the carbon black to the transition metal to the sulfur is (10-30): 1-10: 1-10: 60-80.
The preparation method of the lithium-sulfur battery cathode material comprises the following steps: mixing activated carbon, carbon black and transition metal, grinding until the mixture can be completely sieved, mixing with sulfur, grinding to enable the mixture to be completely sieved, adding carbon disulfide to submerge the solid surface, standing at room temperature until the carbon disulfide is completely volatilized, removing sulfur precipitated from the surface, and 60-100% of sulfuroC blast drying for 6-24 h, grinding and sieving, 150-350oC, placing the mixture in a closed container, heating for 1-24 hours, grinding and sieving to obtain a lithium-sulfur battery positive electrode material; the mesh number of the used sieve is 50-300 meshes; the grinding is manual grinding or mechanical ball milling.
A lithium sulfur battery containing the above prepared lithium sulfur battery positive electrode material is a laminated battery comprising a positive electrode plate, a negative electrode plate, a diaphragm and electrolyte; specifically, the method comprises the following steps: the preparation method of the positive plate comprises the following steps: dispersing a positive electrode material, a conductive agent and a binder in deionized water according to a mass ratio of 80-99: 0-10: 1-10 to form slurry, wherein the solid content of the slurry is 20-50%, and mixingCoating the slurry on a carbon-coated aluminum foil, and then coating the slurry on the carbon-coated aluminum foil by 60-100 percentoC, heating for 3-48 h and drying, wherein the surface density of the slurry on the carbon-coated aluminum foil is 1-20 mg/cm2(ii) a The negative plate contains lithium metal or lithium alloy; the diaphragm is (1) polyolefin microporous diaphragm base material, (2) polyolefin microporous diaphragm base material with polymer coated on the surface, (3) polyolefin microporous diaphragm base material with ceramic coated on the surface or (4) polyolefin microporous diaphragm base material with polymer and ceramic coated on the surface; the electrolyte is ether electrolyte.
The lithium-sulfur battery containing the lithium-sulfur battery positive electrode material is a laminated battery containing a positive plate, a negative plate, a diaphragm and electrolyte; specifically, the method comprises the following steps: the preparation method of the positive plate comprises the following steps: dispersing a positive electrode material, a conductive agent and a binder in deionized water according to a mass ratio of 80-99: 0-10: 1-10 to form slurry, wherein the solid content of the slurry is 20-50%, coating the slurry on a carbon-coated aluminum foil, and then coating the slurry on the carbon-coated aluminum foil by 60-100%oC, heating for 3-48 h and drying, wherein the surface density of the slurry on the carbon-coated aluminum foil is 1-20 mg/cm2(ii) a The negative plate contains lithium metal or lithium alloy; the diaphragm is (1) polyolefin microporous diaphragm base material, (2) polyolefin microporous diaphragm base material with polymer coated on the surface, (3) polyolefin microporous diaphragm base material with ceramic coated on the surface or (4) polyolefin microporous diaphragm base material with polymer and ceramic coated on the surface; the electrolyte is ether electrolyte.
The positive electrode material of the lithium-sulfur battery comprises active carbon, carbon black, a transition metal compound and sulfur, wherein the mass ratio of the active carbon to the carbon black to the transition metal compound to the sulfur is 10-30: 1-10: 1-10: 60-80.
The preparation method of the lithium-sulfur battery cathode material comprises the following steps: mixing activated carbon, carbon black and a transition metal compound, grinding until the mixture can be completely sieved, mixing with sulfur, grinding to enable the mixture to be completely sieved, adding carbon disulfide to submerge the solid surface, standing at room temperature until the carbon disulfide is completely volatilized, removing sulfur precipitated from the surface, and 60-100% of sulfuroC blastDrying for 6-24 h, grinding and sieving for 150-350 hoC, placing the mixture in a closed container, heating for 1-24 hours, grinding and sieving to obtain a lithium-sulfur battery positive electrode material; the mesh number of the used sieve is 50-300 meshes; the grinding is manual grinding or mechanical ball milling.
A lithium sulfur battery containing the above prepared lithium sulfur battery positive electrode material is a laminated battery comprising a positive electrode plate, a negative electrode plate, a diaphragm and electrolyte; specifically, the method comprises the following steps: the preparation method of the positive plate comprises the following steps: dispersing a positive electrode material, a conductive agent and a binder in deionized water according to a mass ratio of 80-99: 0-10: 1-10 to form slurry, wherein the solid content of the slurry is 20-50%, coating the slurry on a carbon-coated aluminum foil, and then coating the slurry on the carbon-coated aluminum foil by 60-100%oC, heating for 3-48 h and drying, wherein the surface density of the slurry on the carbon-coated aluminum foil is 1-20 mg/cm2(ii) a The negative plate contains lithium metal or lithium alloy; the diaphragm is (1) polyolefin microporous diaphragm base material, (2) polyolefin microporous diaphragm base material with polymer coated on the surface, (3) polyolefin microporous diaphragm base material with ceramic coated on the surface or (4) polyolefin microporous diaphragm base material with polymer and ceramic coated on the surface; the electrolyte is ether electrolyte.
The lithium-sulfur battery containing the lithium-sulfur battery positive electrode material is a laminated battery containing a positive plate, a negative plate, a diaphragm and electrolyte; specifically, the method comprises the following steps: the preparation method of the positive plate comprises the following steps: dispersing a positive electrode material, a conductive agent and a binder in deionized water according to a mass ratio of 80-99: 0-10: 1-10 to form slurry, wherein the solid content of the slurry is 20-50%, the slurry is coated on a carbon-coated aluminum foil, and then 60-100% of the slurry is coated on the carbon-coated aluminum foiloC, heating for 3-48 h and drying, wherein the surface density of the slurry on the carbon-coated aluminum foil is 1-20 mg/cm2(ii) a The negative plate contains lithium metal or lithium alloy; the diaphragm is (1) polyolefin microporous diaphragm base material, (2) polyolefin microporous diaphragm base material with polymer coated on the surface, (3) polyolefin microporous diaphragm base material with ceramic coated on the surface or (4) polyolefin microporous diaphragm base material with polymer and ceramic coated on the surface; the electrolyte is ether electrolyte.
The invention relates toThe beneficial effects of the prior art are: the invention develops the active carbon (C) with high specific surface area>1000 m2(g) adding a certain amount of carbon black material with high specific surface area as a main body for carrying sulfur (>600 m2And/g) and adding a certain amount of transition metal or transition metal sulfide, the capacity exertion and the cycling stability of the lithium-sulfur battery can be effectively improved. Because of the high specific surface area of the carbon black, the carbon black not only plays a role of enhancing the conductivity in a composite system, but also is used as a sulfur carrier, so that the higher specific gravity of the sulfur carrier can be ensured, and the defect of poor conductivity of a carbon-sulfur composite which only takes the activated carbon as the carrier is overcome. The metal or metal compound can play a role in fixing lithium polysulfide serving as an electrochemical intermediate product, presents stronger chemical adsorption than a simple carbon material, inhibits the shuttle effect of polysulfide ions, and effectively improves the capacity exertion and the cycling stability of the lithium-sulfur battery.
Detailed Description
The technical solutions of the present invention are further described below with reference to the following examples, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention. The reagents, materials and instruments used in the following description are all conventional reagents, conventional materials and conventional instruments, which are commercially available, and the reagents may be synthesized by a conventional synthesis method, if not specifically described.
Carbon black is another carbon material, and there are some significant differences from activated carbon. First, the raw materials are different, the raw material of the activated carbon is coke or natural organic plant, and the raw material of the carbon black is petroleum products such as heavy oil coal tar. Secondly, the structures are different, the active carbon particles are larger and micron-sized, and the specific surface area is higher; the carbon black has fine particles, is in a nano-scale chain structure, and the specific surface area can be regulated and controlled. Thirdly, the conductivity of the carbon black is different from that of the activated carbon. The carbon black has excellent conductivity, and can be used for improving the conductivity of the lithium-sulfur battery positive electrode material and improving the specific capacity and the cycle performance. In addition, the carbon black material can have a high specific surface area, so that the conductivity of the positive electrode material can be improved, and the carbon black material can be used as a sulfur carrier to increase the sulfur carrying amount of the positive electrode.
The first embodiment is as follows: the embodiment describes a lithium-sulfur battery positive electrode material, which comprises activated carbon, carbon black, a transition metal and sulfur, wherein the mass ratio of the activated carbon to the carbon black to the transition metal to the sulfur is 10-30: 1-10: 1-10: 60-80.
The second embodiment is as follows: in the lithium-sulfur battery cathode material of the first embodiment, the specific surface area of the activated carbon is 1000-4000 m2(ii)/g; the specific surface area of the carbon black is 600-3000 m2(ii)/g; the transition metal is Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Pt, lanthanide or actinide metal; the sulfur is sublimed sulfur.
The third concrete implementation mode: a method for preparing a positive electrode material for a lithium-sulfur battery according to one or two embodiments, the method comprising: mixing activated carbon, carbon black and transition metal, grinding until the mixture can be completely sieved, mixing with sulfur, grinding to enable the mixture to be completely sieved, adding carbon disulfide to submerge the solid surface, standing at room temperature until the carbon disulfide is completely volatilized, removing sulfur precipitated from the surface, and 60-100% of sulfuroC blast drying for 6-24 h, grinding and sieving, 150-350oC, placing the mixture in a closed container, heating for 1-24 hours, grinding and sieving to obtain a lithium-sulfur battery positive electrode material; the mesh number of the used sieve is 50-300 meshes; the grinding is manual grinding or mechanical ball milling.
The fourth concrete implementation mode: a lithium-sulfur battery containing the positive electrode material of the lithium-sulfur battery prepared in the third embodiment, wherein the lithium-sulfur battery is a laminated battery comprising a positive electrode sheet, a negative electrode sheet, a diaphragm and an electrolyte; specifically, the method comprises the following steps: the preparation method of the positive plate comprises the following steps: dispersing a positive electrode material, a conductive agent and a binder in deionized water according to a mass ratio of 80-99: 0-10: 1-10 to form slurry, wherein the solid content of the slurry is 20-50%, coating the slurry on a carbon-coated aluminum foil, and then coating the slurry on the carbon-coated aluminum foil by 60-100%oC, heating for 3-48 h and drying, wherein the slurry is coated with carbon-coated aluminumThe areal density of the foil is 1-20 mg/cm2(ii) a The negative plate contains lithium metal or lithium alloy; the diaphragm is (1) polyolefin microporous diaphragm base material, (2) polyolefin microporous diaphragm base material with polymer coated on the surface, (3) polyolefin microporous diaphragm base material with ceramic coated on the surface or (4) polyolefin microporous diaphragm base material with polymer and ceramic coated on the surface; the electrolyte is ether electrolyte.
The fifth concrete implementation mode: a lithium-sulfur battery comprising the positive electrode material of the lithium-sulfur battery according to the first or second embodiment, wherein the lithium-sulfur battery is a laminated battery comprising a positive electrode sheet, a negative electrode sheet, a separator and an electrolyte; specifically, the method comprises the following steps: the preparation method of the positive plate comprises the following steps: dispersing a positive electrode material, a conductive agent and a binder in deionized water according to a mass ratio of 80-99: 0-10: 1-10 to form slurry, wherein the solid content of the slurry is 20-50%, coating the slurry on a carbon-coated aluminum foil, and then coating the slurry on the carbon-coated aluminum foil by 60-100%oC, heating for 3-48 h and drying, wherein the surface density of the slurry on the carbon-coated aluminum foil is 1-20 mg/cm2(ii) a The negative plate contains lithium metal or lithium alloy; the diaphragm is (1) polyolefin microporous diaphragm base material, (2) polyolefin microporous diaphragm base material with polymer coated on the surface, (3) polyolefin microporous diaphragm base material with ceramic coated on the surface or (4) polyolefin microporous diaphragm base material with polymer and ceramic coated on the surface; the electrolyte is ether electrolyte.
The sixth specific implementation mode: the embodiment describes a lithium-sulfur battery positive electrode material, which comprises activated carbon, carbon black, a transition metal compound and sulfur, wherein the mass ratio of the activated carbon to the carbon black to the transition metal compound to the sulfur is 10-30: 1-10: 1-10: 60-80.
The seventh embodiment: in the positive electrode material for the lithium-sulfur battery according to the sixth embodiment, the specific surface area of the activated carbon is 1000 to 4000 m2(ii)/g; the specific surface area of the carbon black is 600-3000 m2(ii)/g; the transition metal compound is one or more of transition metal carbide, transition metal boride, transition metal nitride, transition metal phosphide, transition metal oxide and transition metal sulfide; the above-mentionedThe sulfur of (a) is sublimed sulfur.
The specific implementation mode is eight: in the positive electrode material of the lithium-sulfur battery according to the seventh embodiment, the transition metal carbide is TiC or Ti2C，Nb4C3，Ti3C2，V3C2，Cr3C2，Mo2TiC2，Mo2Ti2C3，V2C，Nb2C，V8C7，MoC，WC，ZrC，Mo2C，VC，Fe3One or more of C; the transition metal boride is one or more of Ni-B, Co-B, Fe-B, Ru-B, Pd-B, Ti-B, Cr-B and Zr-B; the transition metal nitride is WN, VN, TiN, W2N，LaN，Mo2One or more of N; the transition metal phosphide is Zn3P2，Cu3P2，Fe3P2，Co2P，FeP，Ni12P5，Ni2P，Ni5P4，CoP，Cu3P，Mo3P，MoP，MoP2One or more of WP; the transition metal oxide is MnO2，Fe2O3，Ti4O7，La2O3，TiO2，MoO3，ZrO2One or more of NiO; the transition metal sulfide is Co9S8，Co3S4，CoS2，FeS2，TiS2，MnS，CuS，ZnS，SnS2，NiS2，ZrS2，VS2，MoS2One or more of (a).
The specific implementation method nine: a method for preparing a positive electrode material for a lithium-sulfur battery according to any one of embodiments six to eight, the method comprising: mixing activated carbon, carbon black and transition metal compound, grinding until the mixture can be completely sieved, mixing with sulfur, grinding to make the mixture can be completely sieved, adding carbon disulfide to submerge solid surface, standing at room temperature until the carbon disulfide is completely volatilized, and removing the substances precipitated from the surface60 to 100 parts of sulfuroC blast drying for 6-24 h, grinding and sieving, 150-350oC, placing the mixture in a closed container, heating for 1-24 hours, grinding and sieving to obtain a lithium-sulfur battery positive electrode material; the mesh number of the used sieve is 50-300 meshes; the grinding is manual grinding or mechanical ball milling.
The detailed implementation mode is ten: a lithium-sulfur battery comprising the positive electrode material of the lithium-sulfur battery prepared according to the ninth embodiment, wherein the lithium-sulfur battery is a laminated battery comprising a positive electrode sheet, a negative electrode sheet, a diaphragm and an electrolyte; specifically, the method comprises the following steps: the preparation method of the positive plate comprises the following steps: dispersing a positive electrode material, a conductive agent and a binder in deionized water according to a mass ratio of 80-99: 0-10: 1-10 to form slurry, wherein the solid content of the slurry is 20-50%, coating the slurry on a carbon-coated aluminum foil, and then coating the slurry on the carbon-coated aluminum foil by 60-100%oC, heating for 3-48 h and drying, wherein the surface density of the slurry on the carbon-coated aluminum foil is 1-20 mg/cm2(ii) a The negative plate contains lithium metal or lithium alloy; the diaphragm is (1) polyolefin microporous diaphragm base material, (2) polyolefin microporous diaphragm base material with polymer coated on the surface, (3) polyolefin microporous diaphragm base material with ceramic coated on the surface or (4) polyolefin microporous diaphragm base material with polymer and ceramic coated on the surface; the electrolyte is ether electrolyte.
The concrete implementation mode eleven: a lithium-sulfur battery comprising the positive electrode material of the lithium-sulfur battery according to any one of the sixth to eighth embodiments, wherein the lithium-sulfur battery is a laminated battery comprising a positive electrode sheet, a negative electrode sheet, a separator and an electrolyte; specifically, the method comprises the following steps: the preparation method of the positive plate comprises the following steps: dispersing a positive electrode material, a conductive agent and a binder in deionized water according to a mass ratio of 80-99: 0-10: 1-10 to form slurry, wherein the solid content of the slurry is 20-50%, the slurry is coated on a carbon-coated aluminum foil, and then 60-100% of the slurry is coated on the carbon-coated aluminum foiloC, heating for 3-48 h and drying, wherein the surface density of the slurry on the carbon-coated aluminum foil is 1-20 mg/cm2(ii) a The negative plate contains lithium metal or lithium alloy; the diaphragm is (1) polyolefin microporous diaphragm base material, (2) polyolefin microporous diaphragm base material with polymer coated on the surface, (3) polyolefin microporous diaphragm base material with ceramic coated on the surface or (4) surface coatingA polyolefin microporous separator substrate having a polymer and a ceramic; the electrolyte is ether electrolyte.
Example 1
Activated carbon (commercially available, specific surface area 1000 m)2Per g), carbon black (commercially available, specific surface area 600 m)2/g) and VS2Mixing and grinding the materials (purchased) according to a mass ratio of 2:1:1, sieving the materials by a 80-mesh sieve, mixing the materials with sublimed sulfur, grinding, adding carbon disulfide to submerge the surfaces of the materials to be filtered, standing the materials until the carbon disulfide is completely volatilized, removing sulfur separated from the surfaces, drying, grinding, placing the materials in a closed container at 200 ℃ for heating for 6 hours, grinding, and sieving the materials by a 150-mesh sieve to obtain a positive electrode material C1, wherein the mass ratio of each component is as follows: activated carbon: carbon black: VS2: the sulfur content was 20:10:10: 60.
Comparative examples 1 to 1
Comparative example 1-1 differs from example 1 in that no VS was added2The method comprises the following steps of mixing active carbon and carbon black in a ratio of 3:1 to obtain a cathode material C1-1, wherein the mass ratio of the components is as follows: activated carbon: carbon black: the sulfur content was 30:10: 60.
Comparative examples 1 to 2
Comparative examples 1-2 differ from example 1 in that activated carbon and VS were added without the addition of a carbon black component2Mixing the components in a ratio of 3:1 to finally obtain a positive electrode material C1-2, wherein the mass ratio of the components is as follows: activated carbon: VS2: the sulfur content was 30:10: 60.
Comparative examples 1 to 3
Comparative examples 1-3 differ from example 1 in that no carbon black and no VS were added2And (3) finally obtaining a positive electrode material C1-3, wherein the mass ratio of the components is as follows: activated carbon: the sulfur was 40: 60.
Example 2
Activated carbon (commercially available, specific surface area 2100 m2Per g), carbon black (commercially available, specific surface area 1700 m)2Mixing/g) and Co (commercially available) at a mass ratio of 2:1:1, grinding, sieving with 200 mesh sieve, mixing with sublimed sulfur, grinding, adding carbon disulfide to submerge the solid surface, standing until the carbon disulfide is completely volatilized, removing sulfur precipitated on the surface, drying, grinding, heating in a closed container at 155 deg.C for 12 h, grinding, sieving with 300 deg.CAnd (3) sieving the mixture to obtain a positive electrode material C2, wherein the mass ratio of each component is as follows: activated carbon: carbon black: co: the sulfur content was 10:5:5: 80.
Comparative example 2-1
Comparative example 2-1 differs from example 2 in that, without adding carbon black and Co components, a positive electrode material C2-1 was obtained, the mass ratios of the components being: activated carbon: the sulfur is 20: 80.
Example 3
Activated carbon (commercially available, specific surface area 1400 m)2Per g), carbon black (commercially available, specific surface area 1400 m)2Per g) and Fe3C (commercially available) is mixed according to the mass ratio of 30:2:3, ground, sieved by a 100-mesh sieve, mixed with sublimed sulfur, ground, added with carbon disulfide to submerge the solid surface, kept stand until the carbon disulfide is completely volatilized, sulfur separated from the surface is removed, dried, ground, placed in a closed container at 200 ℃ for heating for 24 hours, ground and sieved by a 200-mesh sieve to obtain the anode material, wherein the mass ratio of each component is as follows: activated carbon: carbon black: fe3C: sulfur was 30:2:3: 65.
Comparative example 3-1
Comparative example 3-1 differs from example 3 in that, without adding carbon black and a metal oxide component, a positive electrode material C3-1 was obtained, the mass ratios of the components being: activated carbon: the sulfur was 35: 65.
Example 4
Activated carbon (commercially available, specific surface area 1400 m)2Per g), carbon black (commercially available, specific surface area 1700 m)2Mixing the raw materials and WP (commercially available) in a mass ratio of 4:1:1, grinding, sieving by a 100-mesh sieve, mixing with sublimed sulfur, grinding, adding carbon disulfide to submerge the solid surface, standing until the carbon disulfide is completely volatilized, removing sulfur separated from the surface, drying, grinding, placing in a closed container at 350 ℃, heating for 48 hours, grinding, and sieving by a 100-mesh sieve to obtain the cathode material, wherein the mass ratio of each component is as follows: activated carbon: carbon black: WP: the sulfur content was 20:5:5: 70.
Comparative example 4-1
Comparative example 4-1 differs from example 4 in that carbon black and WP components were not added to obtain a positive electrode material C4-1, the mass ratios of the components being: activated carbon: the sulfur is 30: 70.
Example 5
Activated carbon (commercially available, specific surface area 2100 m2Per g), carbon black (commercially available, specific surface area 1700 m)2/g）、ZrB2(commercially available), TiN (commercially available), MnO2Mixing the raw materials in a mass ratio of 10:10:3:3:4 (commercially available), grinding, sieving with a 50-mesh sieve, mixing with sublimed sulfur, grinding, adding carbon disulfide to submerge the solid surface, standing until the carbon disulfide is completely volatilized, removing sulfur precipitated on the surface, drying, grinding, placing in a closed container at 300 ℃ for heating for 6 hours, grinding, and sieving with a 150-mesh sieve to obtain a positive electrode material C5, wherein the mass ratio of each component is as follows: activated carbon: carbon black: ZrB2：TiN：MnO2: sulfur is 10:10:3:3: 4: 70.
comparative example 5-1
Comparative example 5-1 differs from example 5 in that the positive electrode material C5-1 was obtained without adding carbon black and the metal compound component, the mass ratios of the components being: activated carbon: the sulfur is 30: 70.
Preparing a positive plate: mixing the positive electrode material, a binder (SBR/CMC = 1: 1) and a conductive agent (Super P) according to a mass ratio of 80:10:10, preparing slurry by using deionized water as a solvent, coating the slurry on a carbon-coated aluminum foil, and drying to obtain a sulfur-carrying amount of 2mg/cm2The positive electrode sheet of (1).
Lithium sulfur battery assembly and testing: the positive plate, the negative electrode (metal lithium foil) and the electrolyte (0.5M LiTFSI) are dissolved in a mixed solvent of DOL/DME with the volume ratio of 1:1, and the additive is 0.1M LiNO3) The laminated battery was assembled with a mass ratio of the electrolyte to sulfur of 3.5, and charge and discharge tests (0.2C/0.2C) were performed with a battery test apparatus to compare the initial gram capacity and cycle performance (the number of cycles for which the capacity was reduced to 60% of the initial capacity) of each positive electrode material. The data obtained are shown in table 1. As can be seen from the battery performance of the cathode materials obtained in the examples and comparative examples in table 1, the cathode material and the synthesis method thereof disclosed by the invention can obtain higher gram capacity and better cycle performance. The carbon black and the metal sulfide in the anode material effectively improve the defect of poor conductivity of the active carbon, are beneficial to the exertion of gram volume and obtain better cycle performance。
Claims (11)
1. A positive electrode material for a lithium-sulfur battery, characterized in that: the positive electrode material comprises active carbon, carbon black, transition metal and sulfur, wherein the mass ratio of the active carbon to the carbon black to the transition metal to the sulfur is 10-30: 1-10: 1-10: 60-80 parts; the specific surface area of the activated carbon is 1000-4000 m2(ii)/g; the specific surface area of the carbon black is 600-3000 m2/g。
2. The positive electrode material for a lithium-sulfur battery according to claim 1, wherein: the transition metal is Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Pt, lanthanide or actinide metal; the sulfur is sublimed sulfur.
3. A method for preparing a positive electrode material for a lithium-sulfur battery according to claim 1 or 2, characterized in that: the preparation method comprises the following steps: mixing activated carbon, carbon black and transition metal, grinding until the mixture can be completely sieved, mixing with sulfur, grinding to enable the mixture to be completely sieved, adding carbon disulfide to submerge the solid surface, standing at room temperature until the carbon disulfide is completely volatilized, removing sulfur precipitated on the surface, drying by air blasting, grinding and sieving, wherein the drying speed is 150-350oAnd C, placing the mixture in a closed container, heating for 1-24 hours, grinding and sieving to obtain the lithium-sulfur battery positive electrode material.
4. A lithium sulfur battery comprising the positive electrode material for a lithium sulfur battery prepared according to claim 3, characterized in that: the lithium-sulfur battery is a laminated battery comprising a positive plate, a negative plate, a diaphragm and electrolyte; specifically, the method comprises the following steps: the preparation method of the positive plate comprises the following steps: dispersing a positive electrode material, a conductive agent and a binder in deionized water according to a mass ratio of 80-99: 0-10: 1-10 to form slurry, coating the slurry on the carbon-coated aluminum foil, and then heating and drying; the negative plate contains lithium metal or lithium alloy; the diaphragm is (1) polyolefin microporous diaphragm base material, (2) polyolefin microporous diaphragm base material with polymer coated on the surface, (3) polyolefin microporous diaphragm base material with ceramic coated on the surface or (4) polyolefin microporous diaphragm base material with polymer and ceramic coated on the surface; the electrolyte is ether electrolyte.
5. A lithium sulfur battery comprising the positive electrode material for lithium sulfur batteries according to claim 1 or 2, characterized in that: the lithium-sulfur battery is a laminated battery comprising a positive plate, a negative plate, a diaphragm and electrolyte; specifically, the method comprises the following steps: the preparation method of the positive plate comprises the following steps: dispersing a positive electrode material, a conductive agent and a binder in deionized water according to a mass ratio of 80-99: 0-10: 1-10 to form slurry, coating the slurry on the carbon-coated aluminum foil, and then heating and drying; the negative plate contains lithium metal or lithium alloy; the diaphragm is (1) polyolefin microporous diaphragm base material, (2) polyolefin microporous diaphragm base material with polymer coated on the surface, (3) polyolefin microporous diaphragm base material with ceramic coated on the surface or (4) polyolefin microporous diaphragm base material with polymer and ceramic coated on the surface; the electrolyte is ether electrolyte.
6. A positive electrode material for a lithium-sulfur battery, characterized in that: the positive electrode material comprises active carbon, carbon black, a transition metal compound and sulfur, wherein the mass ratio of the active carbon to the carbon black to the transition metal compound to the sulfur is 10-30: 1-10: 1-10: 60-80 parts; the specific surface area of the activated carbon is 1000-4000 m2(ii)/g; the specific surface area of the carbon black is 600-3000 m2/g。
7. The positive electrode material for a lithium-sulfur battery according to claim 6, wherein: the transition metal compound is one or more of transition metal carbide, transition metal boride, transition metal nitride, transition metal phosphide, transition metal oxide and transition metal sulfide; the sulfur is sublimed sulfur.
8. The positive electrode material for a lithium-sulfur battery according to claim 7, wherein: the transition metal carbide is TiC and Ti2C，Nb4C3，Ti3C2，V3C2，Cr3C2，Mo2TiC2，Mo2Ti2C3，V2C，Nb2C，V8C7，MoC，WC，ZrC，Mo2C，VC，Fe3One or more of C; the transition metal boride is one or more of Ni-B, Co-B, Fe-B, Ru-B, Pd-B, Ti-B, Cr-B and Zr-B; the transition metal nitride is WN, VN, TiN, W2N，LaN，Mo2One or more of N; the transition metal phosphide is Zn3P2，Cu3P2，Fe3P2，Co2P，FeP，Ni12P5，Ni2P，Ni5P4，CoP，Cu3P，Mo3P，MoP，MoP2One or more of WP; the transition metal oxide is MnO2，Fe2O3，Ti4O7，La2O3，TiO2，MoO3，ZrO2One or more of NiO; the transition metal sulfide is Co9S8，Co3S4，CoS2，FeS2，TiS2，MnS，CuS，ZnS，SnS2，NiS2，ZrS2，VS2，MoS2One or more of (a).
9. A method for preparing the positive electrode material of the lithium-sulfur battery according to any one of claims 6 to 8, wherein: the preparation method comprises the following steps: mixing activated carbon, carbon black and transition metal compound, grinding until the mixture can be completely sieved, mixing with sulfur, grinding to make the mixture can be completely sieved, adding carbon disulfide to submerge the solid surface, standing at room temperature until the carbon disulfide is completely volatilized, removing sulfur precipitated from the surface, and air-blast dryingGrinding and sieving, 150-350oAnd C, placing the mixture in a closed container, heating for 1-24 hours, grinding and sieving to obtain the lithium-sulfur battery positive electrode material.
10. A lithium sulfur battery comprising the positive electrode material for a lithium sulfur battery prepared according to claim 9, characterized in that: the lithium-sulfur battery is a laminated battery comprising a positive plate, a negative plate, a diaphragm and electrolyte; specifically, the method comprises the following steps: the preparation method of the positive plate comprises the following steps: dispersing a positive electrode material, a conductive agent and a binder in deionized water according to a mass ratio of 80-99: 0-10: 1-10 to form slurry, coating the slurry on a carbon-coated aluminum foil, and then heating and drying; the negative plate contains lithium metal or lithium alloy; the diaphragm is (1) polyolefin microporous diaphragm base material, (2) polyolefin microporous diaphragm base material with polymer coated on the surface, (3) polyolefin microporous diaphragm base material with ceramic coated on the surface or (4) polyolefin microporous diaphragm base material with polymer and ceramic coated on the surface; the electrolyte is ether electrolyte.
11. A lithium sulfur battery comprising the positive electrode material for lithium sulfur battery according to any one of claims 6 to 8, characterized in that: the lithium-sulfur battery is a laminated battery comprising a positive plate, a negative plate, a diaphragm and electrolyte; specifically, the method comprises the following steps: the preparation method of the positive plate comprises the following steps: dispersing a positive electrode material, a conductive agent and a binder in deionized water according to a mass ratio of 80-99: 0-10: 1-10 to form slurry, coating the slurry on a carbon-coated aluminum foil, and then heating and drying; the negative plate contains lithium metal or lithium alloy; the diaphragm is (1) polyolefin microporous diaphragm base material, (2) polyolefin microporous diaphragm base material with polymer coated on the surface, (3) polyolefin microporous diaphragm base material with ceramic coated on the surface or (4) polyolefin microporous diaphragm base material with polymer and ceramic coated on the surface; the electrolyte is ether electrolyte.
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