CN115676821A - Preparation method of lithium-sulfur battery positive electrode material, positive electrode material and application - Google Patents
Preparation method of lithium-sulfur battery positive electrode material, positive electrode material and application Download PDFInfo
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- CN115676821A CN115676821A CN202211263469.5A CN202211263469A CN115676821A CN 115676821 A CN115676821 A CN 115676821A CN 202211263469 A CN202211263469 A CN 202211263469A CN 115676821 A CN115676821 A CN 115676821A
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 53
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000002149 hierarchical pore Substances 0.000 claims abstract description 29
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 26
- 239000011593 sulfur Substances 0.000 claims abstract description 26
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- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000003546 flue gas Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 3
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 3
- 235000019252 potassium sulphite Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
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- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 235000020234 walnut Nutrition 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 241000219492 Quercus Species 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 7
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- DIRFUJHNVNOBMY-UHFFFAOYSA-N fenobucarb Chemical compound CCC(C)C1=CC=CC=C1OC(=O)NC DIRFUJHNVNOBMY-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/336—Preparation characterised by gaseous activating agents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
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- General Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of electrode material preparation, and discloses a preparation method of a lithium-sulfur battery positive electrode material, the positive electrode material and application thereof, wherein the preparation method comprises the following steps: performing delignification, precompression and activated pore-forming treatment on wood to obtain a self-supporting carbon framework material with a hierarchical pore structure of micropores and nanopores; and carrying out sulfur loading on the self-supporting carbon framework material with the hierarchical pore structure of the micropores and the nanopores by using a solid phase method or a liquid phase method to obtain the lithium-sulfur battery cathode material. The method utilizes methods of delignification, precompression and activation pore-forming to adjust the density and the pore structure of the wood-derived porous carbon skeleton. The nano-pores are introduced on the wall of the micron-sized pipeline through activating pore-forming, so that the dissolution and shuttling of lithium polysulfide are inhibited, and the cycling stability of the battery is improved; the pre-compression treatment effectively controls the density of the carbon skeleton, improves the strength, improves the conductivity of the three-dimensional current collector under the condition of keeping the pore structure, and is more favorable for the conduction of electrons.
Description
Technical Field
The invention belongs to the technical field of electrode material preparation, and particularly relates to a preparation method of a lithium-sulfur battery positive electrode material, the positive electrode material and application.
Background
At present, a lithium ion battery is one of the most widely applied energy storage systems, but the traditional anode material cannot meet the requirements of the current equipment on high capacity and high energy density of the battery. The theoretical capacity of sulfur reaches 1675mAh g -1 The theoretical energy density of the battery assembled with the lithium metal can reach 2600Wh kg -1 . However, the performance of the lithium-sulfur battery is seriously influenced by the insulating property of sulfur, volume expansion during discharge and shuttle effect of lithium polysulfide generated during charge and discharge.
In order to solve the above problems, it is common to use porous carbon materials as a support material for sulfur, including graphene, carbon nanotubes, mesoporous carbon, biomass pyrolytic carbon, and the like. The carbon material has good conductivity, can provide a conductive network and improve the electrochemical reaction activity of sulfur; on the other hand, abundant pore structure can cushion the volume expansion in the discharge process, keeps the structural stability of electrode. The existing porous carbon is mostly powder material, the lithium sulfur battery electrode is manufactured by mixing sulfur, the porous carbon, conductive carbon and a binder, the slurry is prepared and then coated on a current collector in a blade mode, an effective conductive network is difficult to form due to the insulating property of sulfur, and the binder can generate invalid sites and reduce the performance of the lithium sulfur battery.
The wood has the advantages of low price and reproducibility, has a regular pore structure and good mechanical strength, can keep a complete three-dimensional conductive network through carbonization treatment, and is an ideal sulfur carrier material. However, direct carbonization results in poor mechanical strength of the prepared porous carbon skeleton, even direct pulverization, and the density and pore structure of the carbon skeleton are limited by the properties of raw materials and are difficult to adjust.
Through the above analysis, the problems and defects of the prior art are as follows:
(1) The existing lithium-sulfur battery preparation method utilizes mixed sulfur, porous carbon and conductive carbon, an effective conductive network is difficult to form, a binder and the like are required to be additionally added, and the performance of the obtained lithium-sulfur battery is poor;
(2) The mechanical strength of the porous carbon skeleton obtained by direct carbonization of wood is poor, even the porous carbon skeleton is directly pulverized, and the density and the pore structure of the carbon skeleton are limited by the properties of raw materials and are difficult to adjust.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a lithium-sulfur battery positive electrode material.
The invention is realized in such a way that the preparation method of the lithium-sulfur battery cathode material comprises the following steps:
carrying out delignification, precompression, high-temperature carbonization and activated pore-forming treatment on natural wood to obtain a self-supporting porous carbon skeleton material with a hierarchical pore structure of micropores and nanopores;
and carrying out sulfur loading on the self-supporting porous carbon skeleton material with the hierarchical pore structure of the micropores and the nanopores by using a solid phase method or a liquid phase method to obtain the lithium-sulfur battery cathode material.
Further, the preparation method of the lithium-sulfur battery cathode material comprises the following steps:
cutting natural wood to obtain wood slices; the obtained wood slice is immersed in chemical washing liquor for removing lignin and hemicellulose, the removal of the lignin and the hemicellulose can obtain richer pore structures, and simultaneously, the density and the hardness of the natural wood are reduced, so that the aim of softening the wood is fulfilled;
step two, repeatedly soaking and cleaning the impregnated wood slices by using clean water to remove alkaline components in the cleaning solution, and then drying or freeze-drying the wood slices;
performing pre-compression treatment on the dried wood slices by using a press machine, further improving the density and compressive strength of the material, simultaneously realizing accurate regulation and control on the density and the pore structure, and performing high-temperature annealing treatment on the pre-compressed wood slices to obtain the self-supporting porous carbon skeleton material;
step four, activating the obtained self-supporting porous carbon skeleton material, and etching at high temperature by using gas to obtain a richer nano-pore structure so as to obtain a porous carbon material with a hierarchical pore structure of micro-pores and nano-pores;
and fifthly, carrying out sulfur loading on the obtained porous carbon material with the hierarchical pore structure by using a solid-phase method or a liquid-phase method to obtain the lithium-sulfur battery cathode material.
Further, the natural wood is any one of fir, birch, balsa wood, basswood, beech, pine, poplar, oak, willow, elm, maple, chinese ash, walnut, teak and ebony;
the thickness of the wood sheet is 0.5-80mm.
Further, the chemical washing liquid for removing lignin and hemicellulose consists of one or more of sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, ammonium carbonate, sodium sulfite, potassium sulfite and ammonium sulfite;
the concentration of the chemical washing liquid for removing lignin and hemicellulose is 0.5-10mol/L;
the dipping time is 1-24h, and the dipping temperature is 20-100 ℃.
Further, in the second step, the drying temperature is 40-80 ℃, and the drying time is 6-48h; the pre-compression pressure in the third step is 1-200MPa, and the pressure maintaining time is 0.1-12h; the thickness of the pre-compressed wood sheets is 3% -80% of that of the wood sheets before compression;
the high-temperature annealing treatment comprises the following steps: carrying out high-temperature carbonization treatment in an inert atmosphere;
the inert atmosphere is nitrogen or argon; the high-temperature carbonization temperature is 500-1500 ℃, and the carbonization time is 1-12h.
Further, the step of activating the obtained self-supporting biomass porous carbon to obtain the porous carbon material with the hierarchical pore structure comprises:
placing the obtained self-supporting biomass porous carbon in an activating atmosphere for heating treatment to obtain a porous carbon material with a hierarchical pore structure of micropores and nanopores;
the activating atmosphere consists of one or more of water vapor, flue gas, carbon dioxide and air; the activating and heating temperature is 600-1000 ℃, and the activating and heating time is 1-12h.
Further, the step of carrying out sulfur loading on the obtained porous carbon material with the hierarchical pore structure by using a solid-phase method or a liquid-phase method comprises the following steps:
the solid-phase method for loading sulfur on the obtained porous carbon material with the hierarchical pore structure comprises the following steps: uniformly spraying sulfur powder on the surface of a porous carbon material with a hierarchical pore structure, and heating at the temperature of 140-170 ℃ for 0.5-12h to melt the sulfur powder to obtain the lithium-sulfur battery positive electrode material
The method for carrying out sulfur loading on the obtained porous carbon material with the hierarchical pore structure by using the liquid phase method comprises the following steps: and dripping a carbon disulfide solution of sulfur on the surface of a porous carbon material with a hierarchical pore structure, volatilizing the solvent, and heating at 140-170 ℃ for 0.5-12h to obtain the lithium-sulfur battery cathode material.
Another object of the present invention is to provide a positive electrode material for a lithium-sulfur battery, which is prepared using the method for preparing a positive electrode material for a lithium-sulfur battery.
Another object of the present invention is to provide a lithium sulfur battery, which is assembled from the lithium sulfur battery positive electrode material and a metallic lithium negative electrode.
Further, the lithium-sulfur battery is a button battery or a square battery.
By combining the technical scheme and the technical problem to be solved, the technical scheme to be protected by the invention has the advantages and positive effects that:
the method utilizes the methods of delignification, precompression, high-temperature carbonization and activated pore-forming to adjust the density and the pore structure of the wood-derived porous carbon skeleton. Nano holes can be introduced into the wall of the micron-sized pipeline through activating pore-forming, so that the dissolution and shuttling of lithium polysulfide are inhibited, and the cycling stability of the battery is improved. The pre-compression treatment can effectively control the density of the carbon skeleton, improve the strength, improve the conductivity of the three-dimensional current collector under the condition of keeping the pore structure and is more favorable for the conduction of electrons.
The self-supporting porous carbon material has the characteristic of hierarchical pore structure, can be used for preparing a lithium-sulfur battery, can effectively inhibit the dissolution and diffusion of lithium polysulfide, and greatly improves the cycle stability and rate capability of the battery. The pre-compression treatment can improve the density and compressive strength of the porous carbon skeleton, and avoid the crushing and pulverization in the battery assembling process. In addition, the self-supporting carbon skeleton forms a three-dimensional conductive network, so that effective transmission of electrons and ions in a battery system can be guaranteed, the use of traditional conductive additives, binders and collectors can be avoided, and the cost can be greatly saved.
The technical scheme of the invention fills the technical blank in the industry at home and abroad: the invention provides a preparation method of a density-controllable self-supporting porous carbon skeleton for the first time, and the preparation method is applied to the field of lithium-sulfur batteries. The density and pore structure of the biomass charcoal material reported at present are limited by the original material and are difficult to effectively regulate. The preparation process of delignification, pre-compression, high-temperature carbonization and activation treatment provided by the invention can realize accurate regulation and control of the density and the pore structure of the prepared carbon skeleton material, and fills up the technical blank in the related field. The design of the hierarchical porous structure self-supporting porous carbon can effectively improve the cycling stability and the rate capability of the lithium-sulfur battery.
Drawings
Fig. 1 is a flow chart of a method for preparing a positive electrode material for a lithium-sulfur battery according to an embodiment of the present invention;
FIG. 2 is a cross-sectional scanning electron micrograph of a self-supporting porous carbon skeleton provided by an embodiment of the present invention;
FIG. 3 is a graph of cycle performance of a composite positive electrode material for a lithium sulfur battery provided in an embodiment of the present invention;
fig. 4 is a rate performance graph of the composite positive electrode material for a lithium sulfur battery provided by the embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
This section is an explanatory embodiment expanding on the claims so as to fully understand how the present invention is embodied by those skilled in the art.
As shown in fig. 1, a method for preparing a positive electrode material of a lithium-sulfur battery according to an embodiment of the present invention includes:
s101, cutting natural wood to obtain wood slices; dipping the obtained wood sheet in a chemical washing solution for removing lignin and hemicellulose;
s102, repeatedly soaking and cleaning the impregnated wood slices by using clean water, and drying or freeze-drying the wood slices;
s103, pre-compressing the dried wood slices by using a press, and performing high-temperature annealing treatment on the pre-compressed wood slices to obtain self-supporting biomass porous carbon;
s104, performing activation treatment on the obtained self-supporting biomass porous carbon to obtain a porous carbon material with a hierarchical pore structure;
and S105, carrying out sulfur loading on the obtained porous carbon material with the hierarchical pore structure by using a solid phase method or a liquid phase method to obtain the lithium-sulfur battery cathode material.
The natural wood provided by the embodiment of the invention can be selected from the woods such as cedar, birch, balsa wood, basswood, beech, pine, poplar, oak, willow, elm, maple, chinese ash, walnut, teak, ebony and the like.
The thickness range of the natural wood slice provided by the embodiment of the invention is 0.5-80mm.
The washing liquid for removing lignin and hemicellulose provided by the embodiment of the invention is composed of one or more of sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, ammonium carbonate, sodium sulfite, potassium sulfite and ammonium sulfite.
The concentration range of the prepared washing liquid provided by the embodiment of the invention is 0.5-10mol/L.
The wood chips are soaked in the washing liquor, the soaking time is 1-24h, and the temperature is controlled to be 20-100 ℃.
The wood chips or the bamboo chips after elution provided by the embodiment of the invention are repeatedly soaked and washed by clean water, the residual eluent is washed, and then the water is removed by drying or freeze drying, wherein the drying temperature is 40-80 ℃, and the drying time is 6-48h.
The processed wood chips provided by the embodiment of the invention are pre-compressed by a press, the pressure range is 1-200MPa, and the pressure maintaining time is 0.1-12h. The pre-compression treatment of the wood chips can effectively control the density of the carbon skeleton, improve the strength, improve the conductivity of the three-dimensional current collector under the condition of keeping the pore structure and be more beneficial to the conduction of electrons.
The thickness of the compressed wood chips provided by the embodiment of the invention is 3% -80% of the thickness before compression.
The compressed wood chips provided by the embodiment of the invention are carbonized at high temperature under inert atmosphere, wherein the carbonization temperature is 500-1500 ℃, the carbonization time is 1-12h, and the inert atmosphere refers to nitrogen or argon.
The activation treatment provided by the embodiment of the invention is to place the porous carbon skeleton obtained after carbonization in an activation atmosphere for heating treatment, wherein the activation atmosphere consists of one or more of water vapor, flue gas, carbon dioxide and air, the activation heating temperature is 600-1000 ℃, and the activation heating time is 1-12h. According to the embodiment of the invention, the nano-pores can be introduced on the wall of the micron-sized pipeline through activated pore-forming, so that the dissolution and shuttling of lithium polysulfide are inhibited, and the cycling stability of the battery is improved.
The specific surface area of the self-supporting carbon skeleton material prepared by the embodiment of the invention ranges from 100 m to 3000m 2 A density in the range of 0.02-1.80g/cm 3 And a hierarchical pore structure having both micropores and nanopores. The inventionThe self-supporting carbon skeleton provided by the embodiment is a three-dimensional conductive network, so that the use of traditional conductive additives, binders and collectors can be avoided, and the cost can be greatly saved.
The sulfur loading on the porous carbon provided by the embodiment of the invention is carried out by uniformly spraying sulfur powder on the surface of a porous carbon skeleton by using a solid phase method, then carrying out heating treatment to melt the sulfur, and fully contacting with the carbon skeleton, wherein the heating temperature is 140-170 ℃, and the heating time is 0.5-12h. The liquid phase method is characterized in that the carbon disulfide solution of sulfur is dripped on the surface of the porous carbon skeleton, after the solvent is volatilized, the heating treatment is carried out, the heating temperature is 140-170 ℃, and the heating time is 0.5-12h.
The mass proportion of sulfur in the composite anode material provided by the embodiment of the invention is 30-90%.
The self-supporting lithium-sulfur battery composite positive electrode material and the metal lithium negative electrode assembled battery provided by the embodiment of the invention do not need to additionally add a conductive additive, a binder and a current collector, and are suitable for button batteries and square batteries.
In order to prove the creativity and the technical value of the technical scheme of the invention, the part is the application example of the technical scheme of the claims on specific products or related technologies.
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1:
cutting Bassa into 0.8mm thick wood chips, soaking the wood chips in eluent (2.5 mol/LNaOH +0.5 mol/LNa) 2 SO 3 Aqueous solution), heating at 80 deg.C for 12 hr, repeatedly washing the wood chips with distilled water, removing adsorbed alkali solution, and freeze drying to remove water. Pre-compressing the treated wood chips by using a press, wherein the pressure is 16MPa, and the pressure maintaining time is 2h. And then carrying out high-temperature carbonization treatment, wherein the carbonization temperature is 1000 ℃ and the carbonization time is 2h under the argon atmosphere, finally carrying out activation treatment, and heating the carbonized material at 750 ℃ for 1h in the carbon dioxide atmosphere to carry out activation pore-forming, thus obtaining the self-supporting carbon skeleton material. CS to which S is added dropwise 2 Heating the solution at 155 ℃ for 1h to obtain the composite cathode material.
Example 2:
cutting linden wood into wood chips with thickness of 0.8mm, and soaking the wood chips in eluent (2.5 mol/LKOH +0.5 mol/LNa) 2 SO 3 Aqueous solution), heating at 100 deg.C for 6h, repeatedly washing the wood chips with distilled water, and freeze-drying to remove water. Pre-compressing the treated wood chips by using a press, wherein the pressure is 30MPa, and the pressure maintaining time is 2h. And then carrying out high-temperature carbonization treatment, wherein the carbonization temperature is 1000 ℃ and the carbonization time is 2h under the argon atmosphere, finally carrying out activation treatment, heating the carbonized material in a steam atmosphere for 1h at the temperature of 600 ℃ to carry out activation pore-forming, and obtaining the self-supporting carbon skeleton material. CS into which S is added dropwise 2 Heating the solution at 155 ℃ for 1h to obtain the composite cathode material.
Example 3:
cutting oak into 2mm thick pieces, immersing the pieces in eluent (2 mol/LNaOH +1 mol/LNa) 2 SO 3 Aqueous solution), heating to 80 ℃ for 6h, then repeatedly washing the wood chips by using distilled water, and drying at 80 ℃ for 12h under normal pressure to remove water. And pre-compressing the treated wood chips by using a press, wherein the pressure is 25MPa, and the pressure maintaining time is 1h. And then carrying out high-temperature carbonization treatment, wherein the carbonization temperature is 1000 ℃ and the carbonization time is 2h under the nitrogen atmosphere, finally carrying out activation treatment, and heating the carbonized material in the carbon dioxide atmosphere for 2h at 700 ℃ to carry out activation pore-forming, thus obtaining the self-supporting carbon skeleton material. And (3) uniformly scattering sulfur powder on the surface of the carbon skeleton, and heating at 160 ℃ for 2h to obtain the composite cathode material.
The embodiment of the invention achieves some positive effects in the process of research and development or use, and has great advantages compared with the prior art, and the following contents are described by combining data, diagrams and the like in the test process.
The lithium-sulfur battery assembled based on the self-supporting porous carbon skeleton material provided by the invention shows 1120mAh g at the charge-discharge rate of 0.1C -1 The specific capacity and the better cycling stability are shown in figure 3, and the specific capacity of the device can still be kept at 674mAh g after 100 times of charge-discharge cycles -1 . The higher capacity and good cycling stability are mainly attributed to the construction of a hierarchical pore structure, and the introduction of a large number of nano-pores plays a positive role in improving the stability of the battery. At a magnification ofIn terms of performance, as shown in fig. 4, as the current density increases, the discharge specific capacity of the assembled lithium-sulfur battery reaches 1132,853,706,633,499mAh g at the multiplying power of 0.1C,0.2C,0.5C,1C and 2C respectively -1 Then the current density returns to 0.1C, and the specific capacity can also return to 829mAh g -1 The results show that the lithium-sulfur battery based on the self-supporting porous carbon skeleton material provided by the invention has excellent rate performance, and is mainly due to the fact that the construction of a three-dimensional conductive network is favorable for rapid conduction of electrons, and the structure of micropores is also favorable for diffusion of electrolyte, so that good rate performance is realized. In addition, the design of the self-supporting carbon skeleton can form a high-efficiency conductive path to replace conductive additives, current collectors and adhesives in the traditional electrode preparation method, so that the production process is simplified, and the preparation cost of the battery is effectively reduced.
The above description is only for the purpose of illustrating the present invention and the appended claims are not to be construed as limiting the scope of the invention, which is intended to cover all modifications, equivalents and improvements that are within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a lithium-sulfur battery positive electrode material is characterized by comprising the following steps:
performing delignification, precompression and activated pore-forming treatment on wood to obtain a self-supporting carbon framework material with a hierarchical pore structure of micropores and nanopores;
and carrying out sulfur loading on the self-supporting carbon framework material with the hierarchical pore structure of the micropores and the nanopores by using a solid phase method or a liquid phase method to obtain the lithium-sulfur battery cathode material.
2. The method for preparing the positive electrode material for the lithium-sulfur battery according to claim 1, comprising the steps of:
cutting natural wood to obtain wood slices; dipping the obtained wood sheet in a chemical washing solution for removing lignin and hemicellulose;
step two, repeatedly soaking and cleaning the impregnated wood slices by using clean water, and then drying or freeze-drying the wood slices;
performing pre-compression treatment on the dried wood slices by using a press, and performing high-temperature annealing treatment on the pre-compressed wood slices to obtain self-supporting biomass porous carbon;
activating the obtained self-supporting biomass porous carbon to obtain a porous carbon material with a hierarchical pore structure;
and fifthly, carrying out sulfur loading on the obtained porous carbon material with the hierarchical pore structure by using a solid phase method or a liquid phase method to obtain the lithium-sulfur battery cathode material.
3. The method for preparing a positive electrode material for a lithium-sulfur battery according to claim 2, wherein the natural wood is any one of fir, birch, balsa wood, basswood, beech, pine, poplar, oak, willow, elm, maple, ash, walnut, teak, ebony;
the thickness of the wood sheet is 0.5-80mm.
4. The method for preparing the positive electrode material for the lithium-sulfur battery according to claim 2, wherein the chemical washing solution for removing lignin and hemicellulose comprises one or more of sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, ammonium carbonate, sodium sulfite, potassium sulfite and ammonium sulfite;
the concentration of the chemical washing liquid for removing lignin and hemicellulose is 0.5-10mol/L;
the dipping time is 1-24h, and the dipping temperature is 20-100 ℃.
5. The method for preparing the positive electrode material of the lithium-sulfur battery according to claim 2, wherein the drying temperature in the second step is 40 to 80 ℃ and the drying time is 6 to 48 hours; the pre-compression pressure in the third step is 1-200MPa, and the pressure maintaining time is 0.1-12h; the thickness of the pre-compressed wood sheets is 3% -80% of that of the wood sheets before compression;
the high-temperature annealing treatment comprises the following steps: carrying out high-temperature carbonization treatment in an inert atmosphere;
the inert atmosphere is nitrogen or argon; the high-temperature carbonization temperature is 500-1500 ℃, and the carbonization time is 1-12h.
6. The method for preparing the positive electrode material of the lithium-sulfur battery as claimed in claim 2, wherein the step of subjecting the obtained self-supporting biomass porous carbon to activation treatment to obtain the porous carbon material with the hierarchical pore structure comprises the following steps:
placing the obtained self-supporting biomass porous carbon in an activating atmosphere for heating treatment to obtain a porous carbon material with a hierarchical pore structure of micropores and nanopores;
the activating atmosphere consists of one or more of water vapor, flue gas, carbon dioxide and air; the activating and heating temperature is 600-1000 ℃, and the activating and heating time is 1-12h.
7. The method for preparing the positive electrode material for the lithium-sulfur battery according to claim 2, wherein the step of loading sulfur on the obtained porous carbon material having the hierarchical pore structure by using a solid-phase method or a liquid-phase method comprises:
the solid-phase method for loading sulfur on the obtained porous carbon material with the hierarchical pore structure comprises the following steps: uniformly spraying sulfur powder on the surface of a porous carbon material with a hierarchical pore structure, and heating at the temperature of 140-170 ℃ for 0.5-12h to melt the sulfur powder to obtain the lithium-sulfur battery positive electrode material
The method for carrying out sulfur loading on the obtained porous carbon material with the hierarchical pore structure by using the liquid phase method comprises the following steps: and dripping a carbon disulfide solution of sulfur on the surface of a porous carbon material with a hierarchical pore structure, volatilizing the solvent, and heating at 140-170 ℃ for 0.5-12h to obtain the lithium-sulfur battery cathode material.
8. A lithium-sulfur battery positive electrode material prepared by the method for preparing a lithium-sulfur battery positive electrode material according to any one of claims 1 to 7.
9. A lithium-sulfur battery, wherein the lithium-sulfur battery is obtained by assembling the positive electrode material of the lithium-sulfur battery according to claim 8 and a lithium metal negative electrode.
10. The lithium-sulfur battery of claim 9, wherein the lithium-sulfur battery is a button cell battery or a prismatic battery.
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| PCT/CN2022/127600 WO2024077665A1 (en) | 2022-10-14 | 2022-10-26 | Preparation method for lithium-sulfur battery positive electrode material, and positive electrode material and use thereof |
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