CN109616643B - Sulfur-containing cathode material and preparation method and application thereof - Google Patents
Sulfur-containing cathode material and preparation method and application thereof Download PDFInfo
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 239000011593 sulfur Substances 0.000 title claims abstract description 130
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 130
- 239000010406 cathode material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000835 fiber Substances 0.000 claims abstract description 155
- 239000006256 anode slurry Substances 0.000 claims abstract description 54
- 238000007731 hot pressing Methods 0.000 claims abstract description 24
- 239000013543 active substance Substances 0.000 claims abstract description 19
- 239000010405 anode material Substances 0.000 claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 49
- 239000002041 carbon nanotube Substances 0.000 claims description 49
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 49
- 239000007788 liquid Substances 0.000 claims description 45
- 229920003235 aromatic polyamide Polymers 0.000 claims description 38
- 229920006231 aramid fiber Polymers 0.000 claims description 28
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 16
- 239000011268 mixed slurry Substances 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 13
- 239000002033 PVDF binder Substances 0.000 claims description 9
- 239000006229 carbon black Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000002048 multi walled nanotube Substances 0.000 claims description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000006257 cathode slurry Substances 0.000 claims description 6
- 239000008394 flocculating agent Substances 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 238000001035 drying Methods 0.000 description 14
- 238000010008 shearing Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 238000000498 ball milling Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000002270 dispersing agent Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000003828 vacuum filtration Methods 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 238000010009 beating Methods 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 6
- 229920002401 polyacrylamide Polymers 0.000 description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 4
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910002096 lithium permanganate Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/66—Selection of materials
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- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
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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
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Abstract
The invention provides a sulfur-containing cathode material and a preparation method and application thereof, belonging to the technical field of batteries. The invention provides a sulfur-containing anode material, which is obtained by using sulfur-containing anode slurry as an active substance and organic fiber microporous paper as a carrier, and placing the sulfur-containing anode slurry between two layers of the organic fiber microporous paper for hot pressing. According to the invention, the sulfur-containing anode slurry is coated by the organic fiber microporous paper, on one hand, the organic fiber microporous paper can collect current as a current collector, and on the other hand, the organic fiber microporous paper can block the outflow of active substances in the sulfur-containing anode slurry, so that the loss of the active substances is effectively reduced, and the rate capability and specific capacity of the battery are improved.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a sulfur-containing cathode material and a preparation method and application thereof.
Background
The increasing environmental and energy crisis in the world today has accelerated the general attention of people to environmentally friendly equipment. Since the 90 s of the 20 th century, the introduction of lithium ion batteries was first introduced by sony corporation, and lithium ion batteries have rapidly developed due to their own advantages. The research and development work on the anode material of the lithium ion battery also goes throughLiCoO2、LiMnO4、LiFePO4And ternary materials and the like, which meet the requirements of electric equipment on batteries to a certain extent, but the development space of the lithium ion battery is still in urgent need of expansion for the market demand of high-speed development. At present, the battery performance with high specific capacity, high energy density, low price and long cycle life becomes the trend of the development of the lithium battery later, and is also the target which is continuously reached by researchers.
Sulfur has a high theoretical specific capacity (1675mAh g)-1) And the material has the advantages of rich resources, low price, environmental friendliness, easiness in large-scale application and the like, and can quickly become the most potential anode material of a novel energy storage system. Sulfur electrochemically paired with lithium negative electrode based on 16Li + S8＝8Li2The lithium-sulfur battery with the electrochemical reaction of S has ultrahigh theoretical energy density (2600Wh kg)-1) The energy density of the commercial lithium ion battery is about 10 times of the energy density actually achieved at present, and the successful application of the commercial lithium ion battery is predicted to show great value in the fields of electric automobile power batteries, smart power grids, clean energy large-scale energy storage batteries and the like, so that the commercial lithium ion battery attracts people's wide attention and becomes the research focus of a new generation of high-energy-density battery in recent years.
However, the energy density of lithium-sulfur batteries that can be achieved in practice is far lower than the theoretical energy density and the cycle life is poor, which seriously hampers the progress of lithium-sulfur battery industrialization. The reason is mainly that in a lithium-sulfur battery system, lithium polysulfide which is a charge-discharge intermediate product is easily dissolved in electrolyte and shuttled to a negative electrode to react with the negative electrode to cause a shuttle effect, so that irreversible loss of active substances and deterioration of the negative electrode are caused, the cycle life of the battery is seriously influenced, and finally, the performance of a battery device is reduced and loses efficacy.
Disclosure of Invention
The invention aims to provide a sulfur-containing cathode material, a preparation method and application thereof, which improve the rate capability and specific capacity of a battery, and the preparation method is simple to operate and suitable for industrial production.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a sulfur-containing anode material, which is obtained by using sulfur-containing anode slurry as an active substance and organic fiber microporous paper as a carrier, and placing the sulfur-containing anode slurry between two layers of the organic fiber microporous paper for hot pressing.
Preferably, the raw materials for preparing the sulfur-containing cathode slurry comprise sulfur, multi-walled carbon nanotubes, superconducting carbon black and polyvinylidene fluoride.
Preferably, the raw materials for preparing the organic fiber microporous paper comprise para-aramid pulp fiber, para-aramid chopped fiber and carbon nano tubes.
Preferably, the preparation method of the organic fiber microporous paper comprises the following steps:
dispersing para-aramid pulp fibers in an organic solvent to obtain a first fiber dispersion liquid;
dispersing the para-aramid chopped fibers in water to obtain a second fiber dispersion liquid;
mixing the first fiber dispersion liquid and the second fiber dispersion liquid to obtain aramid fiber slurry;
dispersing carbon nanotubes in water to obtain a carbon nanotube dispersion liquid;
mixing the aramid fiber slurry with the carbon nanotube dispersion liquid to obtain carbon nanotube/aramid fiber mixed slurry;
and mixing the carbon nano tube/aramid fiber mixed slurry with a flocculating agent and then filtering to obtain the organic fiber microporous paper.
Preferably, the mass ratio of the para-aramid pulp fibers to the para-aramid chopped fibers is 1 (1-3).
Preferably, the mass ratio of the total mass of the para-aramid pulp fibers and the para-aramid chopped fibers to the carbon nanotubes is 1 (0.5-1).
Preferably, the thickness of the organic fiber microporous paper is 200-300 μm; the aperture of the organic fiber microporous paper is 2-110 nm.
Preferably, the hot pressing pressure is 8-10 MPa; the hot pressing temperature is 160-200 ℃.
The invention provides a preparation method of the sulfur-containing cathode material in the scheme, which comprises the following steps:
(1) covering organic fiber microporous paper on the upper surface and the lower surface of the sulfur-containing anode slurry to obtain sulfur-containing anode slurry covering the organic fiber microporous paper;
(2) and carrying out hot pressing on the sulfur-containing anode slurry covering the organic fiber microporous paper to obtain the sulfur-containing anode material.
The invention provides application of the sulfur-containing anode slurry in the technical scheme or the sulfur-containing anode slurry prepared by the preparation method in the technical scheme in a lithium-sulfur battery.
The invention provides a sulfur-containing anode material, which is obtained by using sulfur-containing anode slurry as an active substance and organic fiber microporous paper as a carrier, and placing the sulfur-containing anode slurry between two layers of the organic fiber microporous paper for hot pressing. According to the invention, the sulfur-containing anode slurry is coated by the organic fiber microporous paper, on one hand, the organic fiber microporous paper can collect current as a current collector, and on the other hand, the organic fiber microporous paper can block the outflow of active substances in the sulfur-containing anode slurry, so that the loss of the active substances is effectively reduced, and the rate capability and specific capacity of the battery are improved. The experimental result of the embodiment shows that the lithium-sulfur battery prepared by the sulfur-containing cathode material provided by the invention is subjected to constant-current charge-discharge test at a rate of 0.1-2C, and the specific capacity reaches 900-1500 mAh/g, so that the problem of active substance loss in the existing lithium-sulfur battery system is solved, and the performance of a battery device is improved.
Drawings
Fig. 1 is a schematic cross-sectional structural view of a sulfur-containing cathode material prepared in example 1 of the present invention, wherein 1 is a support; 2 is an active substance.
Fig. 2 is a graph of rate cycling performance of the lithium sulfur battery prepared in example 4.
Detailed Description
The invention provides a sulfur-containing anode material, which is obtained by using sulfur-containing anode slurry as an active substance and organic fiber microporous paper as a carrier, and placing the sulfur-containing anode slurry between two layers of the organic fiber microporous paper for hot pressing.
The invention has no special requirement on the sulfur-containing anode slurry, and the conventional sulfur-containing anode slurry in the field can be adopted. In the present invention, the raw materials for preparing the sulfur-containing cathode slurry preferably include sulfur, multi-walled carbon nanotubes, superconducting carbon black, and polyvinylidene fluoride. In the invention, the mass ratio of the sulfur to the multi-walled carbon nanotube to the superconducting carbon black to the polyvinylidene fluoride is preferably (5-9): (1-3): (1-3): (0.5-2), more preferably (6-8): (1-2): (1-2): (0.5 to 1), and most preferably 7:1:1: 1. In the invention, sulfur is used as an active substance and has higher theoretical specific capacity; polyvinylidene fluoride is used as a binder, and can tightly combine sulfur, the multi-walled carbon nanotube and the superconducting carbon black together; by controlling the amount of each component within the above range, high specific capacity and high energy density of the sulfur positive electrode slurry can be ensured.
In the present invention, the method for preparing the sulfur-containing cathode slurry preferably includes the steps of: and mixing sulfur, the multi-walled carbon nanotube, the superconducting carbon black and polyvinylidene fluoride to obtain the sulfur-containing anode slurry. In the present invention, the mixing is preferably performed by ball milling, and the specific process of ball milling preferably includes: adding sulfur, multi-walled carbon nanotubes, superconducting carbon black and polyvinylidene fluoride into a planetary ball mill, then dropwise adding N-methyl pyrrolidone, and carrying out ball milling under the normal temperature condition to obtain the sulfur-containing anode slurry. The mass ratio of the sulfur to the N-methylpyrrolidone is preferably 1: 13-18, and more preferably 1: 15-16. The ball milling rotating speed is preferably 100-130 r/min, more preferably 110-120 r/min, and most preferably 115 r/min. The ball milling time is not specially limited, and raw materials are preferably uniformly dispersed; in the invention, the ball milling time is preferably 6-10 h, more preferably 8-9 h, and most preferably 8.5 h.
In the invention, the raw materials for preparing the organic fiber microporous paper preferably comprise para-aramid pulp fiber, para-aramid chopped fiber and carbon nano tubes. In the invention, the para-aramid pulp fiber and the para-aramid chopped fiber can provide a loose and porous structure and are beneficial to subsequent hot-pressing crosslinking packaging; the carbon nano tube can construct a three-dimensional conductive network to improve the conductivity of sulfur on one hand, and also has a certain adsorption function to adsorb polysulfide and reduce the loss of active substances on the other hand.
In the present invention, the method for preparing the organic fiber microporous paper preferably comprises the following steps:
dispersing para-aramid pulp fibers in an organic solvent to obtain a first fiber dispersion liquid;
dispersing the para-aramid chopped fibers in water to obtain a second fiber dispersion liquid;
mixing the first fiber dispersion liquid and the second fiber dispersion liquid to obtain aramid fiber slurry;
dispersing carbon nanotubes in water to obtain a carbon nanotube dispersion liquid;
mixing the aramid fiber slurry with the carbon nanotube dispersion liquid to obtain carbon nanotube/aramid fiber mixed slurry;
and mixing the carbon nano tube/aramid fiber mixed slurry with a flocculating agent and then filtering to obtain the organic fiber microporous paper.
The method comprises the step of dispersing para-aramid pulp fibers in an organic solvent to obtain a first fiber dispersion liquid. In the present invention, the specific process for preparing the first fiber dispersion preferably includes: adding para-aramid pulp fiber and a first dispersing agent into an organic solvent, and uniformly dispersing to obtain a first fiber dispersion liquid. In the present invention, the first dispersant is preferably an acrylate or polyethylene oxide, more preferably polyethylene oxide; the mass ratio of the para-aramid pulp fiber to the first dispersing agent is preferably 1: 0.01-0.07, and more preferably 1: 0.067. The organic solvent is preferably methanol or ethanol, and more preferably ethanol solution with the mass fraction of 99.9%; the mass ratio of the para-aramid pulp fiber to the organic solvent is preferably 1: 50-150, and more preferably 1: 100. The invention has no special requirement on the dispersion mode, and the dispersion mode which is conventional in the field can be adopted. In the present invention, the dispersion method is preferably stirring, and the stirring speed and the stirring time are not particularly limited in the present invention, and it is preferable that the stirring and dispersion are uniform.
The method comprises the step of dispersing the para-aramid chopped fibers in water to obtain a second fiber dispersion liquid. In the present invention, the specific process for preparing the second fiber dispersion preferably includes: and adding the para-aramid chopped fibers and a second dispersing agent into water, and uniformly dispersing to obtain a second fiber dispersion liquid. In the present invention, the second dispersant is preferably polyvinylpyrrolidone or sodium dodecylbenzenesulfonate, more preferably sodium dodecylbenzenesulfonate; the mass ratio of the para-aramid chopped fibers to the second dispersing agent is preferably 1: 0.01-0.07, and more preferably 1: 0.017. The water is preferably deionized water. The mass ratio of the para-aramid chopped fibers to water is preferably 1: 200-300, and more preferably 1: 250. The dispersion mode is not particularly required, and the conventional dispersion mode in the field can be adopted, the dispersion mode is preferably stirring, the stirring speed and the stirring time are not particularly limited, and the stirring and the uniform dispersion are preferably adopted.
After the first fiber dispersion liquid and the second fiber dispersion liquid are obtained, the first fiber dispersion liquid and the second fiber dispersion liquid are mixed to obtain the aramid fiber slurry. In the invention, the mass ratio of the para-aramid pulp fibers to the para-aramid chopped fibers is preferably 1 (1-3), and more preferably 1: 2.
In the invention, the mixing of the first fiber dispersion liquid and the second fiber dispersion liquid is preferably realized by beating treatment in a beating device, the beating device is preferably a cylindrical beating machine, the beating pressure is preferably 1-2 MPa, more preferably 1.5MPa, and the beating shearing force is preferably 100-300N, more preferably 200N.
The invention disperses the carbon nano tube in water to obtain the carbon nano tube dispersion liquid. In the present invention, the specific process of preparing the carbon nanotube dispersion preferably includes: wetting the carbon nano tube and the third dispersing agent by using an ethanol solution with the mass fraction of 99.9%, then adding water, and uniformly dispersing to obtain a carbon nano tube dispersion liquid.
In the invention, the length of the carbon nano tube is preferably 3-10 μm, more preferably 5-10 μm, and most preferably 8-10 μm; the diameter of the carbon nano tube is preferably 30-150 nm, more preferably 50-130 nm, and most preferably 60-120 nm. In the present invention, the third dispersing agent is preferably N, N-dimethylformamide or sodium lauryl sulfate, more preferably sodium lauryl sulfate, and the water is preferably deionized water. In the present invention, the mass ratio of the carbon nanotubes to the third dispersant is preferably 1:0.03 to 0.08, and more preferably 1: 0.067. The mass ratio of the carbon nano tube to the ethanol solution is preferably 1: 10-20, and more preferably 1: 15; the mass ratio of the carbon nanotubes to water is preferably 1: 200-400, and more preferably 1: 250-350. In the invention, the dispersing mode is preferably ultrasonic dispersing and shear dispersing which are sequentially carried out, the ultrasonic dispersing time is preferably 30-60 min, more preferably 30-45 min, the shear dispersing is preferably high-speed shearing, and the shear time is preferably 30-60 min, more preferably 30-45 min; the rotation speed of the shearing is preferably 2000-3000 r/min, more preferably 2200-3000 r/min, and most preferably 2500-2800 r/min.
After the aramid fiber slurry and the carbon nano tube dispersion liquid are obtained, the aramid fiber slurry and the carbon nano tube dispersion liquid are mixed to obtain the carbon nano tube/aramid fiber mixed slurry. The aramid fiber pulp and the carbon nanotube dispersion liquid are preferably mixed in a high-speed shearing machine, and the mass ratio of the total mass of the para-aramid pulp fibers and the para-aramid chopped fibers to the carbon nanotubes is 1 (0.5-1), and more preferably 1: 1. The rotating speed of the high-speed shearing machine is preferably 1500-2500 r/min, more preferably 1800-2200 r/min, and the high-speed shearing time is preferably 30-60 min, more preferably 30-45 min.
After the carbon nano tube/aramid fiber mixed slurry is obtained, the carbon nano tube/aramid fiber mixed slurry is mixed with a flocculating agent and then filtered, and the organic fiber microporous paper is obtained. The mass ratio of the carbon nanotube/aramid fiber mixed slurry to the flocculating agent is preferably 1: 0.01-0.03, and more preferably 1: 0.015-0.025. The flocculating agent is preferably anionic polyacrylamide or cationic polyacrylamide, more preferably anionic polyacrylamide. The invention has no special requirements on the mixing mode, and the conventional mixing mode in the field can be adopted. In the invention, the filtration preferably adopts a vacuum filtration mode, the vacuum filtration equipment preferably adopts a vacuum filtration box, and the pressure of the vacuum filtration is preferably 2-3 MPa, and more preferably 2 MPa. In the invention, after the filtration is finished, the solid matter obtained by the filtration is preferably dried, the drying is preferably carried out under a vacuum condition, and the vacuum degree is preferably 0.05-0.1 MPa, more preferably 0.06-0.09 MPa, and most preferably 0.07-0.08 MPa; the drying temperature is preferably 60-80 ℃, more preferably 60-75 ℃, and most preferably 65-70 ℃; the drying time is preferably 30-180 min, more preferably 60-150 min, and most preferably 100-120 min.
In the invention, the thickness of the organic fiber microporous paper is preferably 200-300 μm, and more preferably 250-300 μm; the pore diameter of the organic fiber microporous paper is preferably 2-110 nm, more preferably 2-100 nm, and most preferably 2-95 nm. In the invention, the organic fiber microporous paper has a three-dimensional network porous structure, and sulfur can be uniformly sublimated into the pore structure of the organic fiber microporous paper at high temperature.
The invention provides a preparation method of the sulfur-containing cathode material in the scheme, which comprises the following steps:
(1) covering organic fiber microporous paper on the upper surface and the lower surface of the sulfur-containing anode slurry to obtain sulfur-containing anode slurry covering the organic fiber microporous paper;
(2) and carrying out hot pressing on the sulfur-containing anode slurry covering the organic fiber microporous paper to obtain the sulfur-containing anode material.
According to the invention, the upper surface and the lower surface of the sulfur-containing anode slurry are covered with the organic fiber microporous paper, so as to obtain the sulfur-containing anode slurry covering the organic fiber microporous paper. Preferably, the sulfur-containing anode slurry is coated on one side of the organic fiber microporous paper and dried to obtain the sulfur-containing anode slurry with the lower surface covered with the organic fiber microporous paper. In the invention, the coating thickness is preferably 80-120 μm, more preferably 90-110 μm, the drying is preferably carried out under vacuum condition, the vacuum degree of the drying is preferably-0.08-0.1 MPa, and the drying temperature is preferably 50-70 ℃, more preferably 60 ℃.
After the sulfur-containing anode slurry with the lower surface covered by the organic fiber microporous paper is obtained, the sulfur-containing anode slurry with the lower surface covered by the organic fiber microporous paper is preferably arranged with the sulfur-containing anode slurry part upwards, and another piece of organic fiber microporous paper is placed on the surface of the sulfur-containing anode slurry to obtain the sulfur-containing anode slurry covered by the organic fiber microporous paper. In the present invention, the thickness of the lower surface-coated organic fiber microporous paper and the thickness of the upper surface-coated organic fiber microporous paper are preferably the same.
After the sulfur-containing anode slurry covering the organic fiber microporous paper is obtained, the sulfur-containing anode slurry covering the organic fiber microporous paper is subjected to hot pressing to obtain the sulfur-containing anode material. In the invention, the hot pressing preferably means that the periphery of the sulfur-containing cathode slurry covering the organic fiber microporous paper is sealed by a coating material, and the sulfur-containing cathode material is obtained by removing the coating material after hot pressing. In the present invention, the covering material preferably includes a polyimide film or a polyphenylene sulfide plastic film, more preferably a polyimide film; the thickness of the coating material is preferably 20 to 30 μm, and more preferably 23 to 28 μm. In the invention, the sulfur-containing anode slurry for covering the organic fiber microporous paper is sealed by the coating material, so that the evaporation loss of sulfur in the hot pressing process can be avoided, and the sulfur can be uniformly evaporated into the organic fiber microporous paper.
In the invention, the hot pressing is preferably carried out by a flat vulcanizing machine, and in the invention, the hot pressing temperature is preferably 160-200 ℃, and more preferably 180 ℃; the hot pressing time is preferably 2-5 min, more preferably 5min, and the hot pressing pressure is preferably 8-10 MPa, more preferably 10 MPa. The invention limits the hot pressing condition in the range, which can ensure that the organic fiber microporous paper and the sulfur-containing anode slurry are tightly combined together and can also ensure that the active substances are uniformly distributed in the sulfur-containing anode material.
In the invention, the thickness of the sulfur-containing cathode material is preferably 80-120 μm, and more preferably 90-110 μm; the thickness of the active substance in the sulfur-containing cathode material is preferably 15-30 μm, more preferably 20-28 μm, and most preferably 23-35 μm; the thickness of the carrier in the sulfur-containing cathode material is preferably 50-105 μm, more preferably 60-90 μm, and most preferably 70-80 μm.
The invention provides an application of the sulfur-containing cathode material in the technical scheme or the sulfur-containing cathode material prepared by the preparation method in the technical scheme in a lithium-sulfur battery, and preferably the sulfur-containing cathode material is cut into positive plates with the diameter of 14mm by a slicer to obtain the sulfur-containing positive plates, and then the lithium-sulfur battery is assembled in a dry Glove Box (MBRAUN LABSTAR Glove Box) filled with argon according to the sequence of a positive plate shell, the sulfur-containing positive plate, a diaphragm, a lithium plate negative electrode, a gasket, a negative plate shell and electrolyte dropwise. The separator is preferably Celgrad 2300, and the solute of the electrolyte is preferably 1mol lithium bistrifluoromethylsulfonate (LiTFSI) containing 1% LiNO3(ii) a The solvent of the electrolyte is preferably ethylene glycol dimethyl ether (DME) and 1, 3-Dioxolane (DOL), and the volume ratio of the ethylene glycol dimethyl ether (DME) to the 1, 3-Dioxolane (DOL) is preferably 1: 1. in the invention, the sulfur-containing cathode material is used as a cathode plate in the lithium-sulfur battery, and the rate capability and specific capacity of the lithium-sulfur battery can be improved. The experimental result of the embodiment shows that the lithium-sulfur battery prepared by the sulfur-containing cathode material provided by the invention is subjected to constant-current charge-discharge test at a rate of 0.1-2C, and the specific capacity reaches 900-1500 mAh/g, so that the problem of active substance loss in the existing lithium-sulfur battery system is solved, and the performance of a battery device is improved.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing sulfur-containing anode slurry:
and (3) putting 0.7g of sulfur, 0.1g of multi-walled carbon nanotube, 0.1g of super carbon black and 0.1g of polyvinylidene fluoride into a planetary ball mill, dropwise adding 20-30 mLN-methyl pyrrolidone solution, and carrying out ball milling at normal temperature for 8 hours at the ball milling speed of 120r/min to obtain the uniformly dispersed sulfur-containing anode slurry.
Preparing organic fiber microporous paper:
dissolving 1.5g of para-aramid pulp fiber and 0.1g of polyethylene oxide (PEO) in 200mL of ethanol solution with the mass fraction of 99.9%, and uniformly stirring and dispersing to obtain a first fiber dispersion liquid; dissolving 3g of para-aramid chopped fiber and 0.05g of sodium dodecyl sulfate in 100mL of water, and uniformly stirring and dispersing to obtain a second fiber dispersion liquid;
mixing the first fiber dispersion liquid and the second fiber dispersion liquid to obtain aramid fiber slurry;
wetting 3g of carbon nano tube and 0.2g of Sodium Dodecyl Sulfate (SDS) by using an ethanol solution with the mass fraction of 99.9%, then adding 500mL of deionized water, carrying out ultrasonic treatment for 30min at the ultrasonic power of 100%, and carrying out high-speed shearing for 30min at the speed of 2000r/min to obtain a carbon nano tube dispersion liquid;
placing the aramid fiber slurry and the carbon nano tube dispersion liquid in a high-speed shearing machine, and shearing for 30min at the speed of 3000r/min by the high-speed shearing machine to obtain carbon nano tube/aramid fiber mixed slurry;
adding 0.05g of anionic polyacrylamide into the carbon nano tube/aramid fiber mixed slurry, and performing vacuum filtration in a hollow suction filtration box under the pressure of 2 MPa;
drying the solid substance obtained by filtering under the vacuum condition to obtain the organic fiber microporous paper, wherein the vacuum degree is 0.09 Mpa; the drying temperature is 60 ℃; the drying time is 60min, and the thickness of the obtained organic fiber microporous paper is 300 mu m.
Preparing a sulfur-containing cathode material:
uniformly coating the sulfur-containing anode slurry on the surface of the organic fiber microporous paper, wherein the coating thickness is 100 micrometers, drying the organic fiber microporous paper in a vacuum drying oven at the temperature of 60 ℃, placing the organic fiber microporous paper coated with the sulfur-containing anode slurry at the bottom, the sulfur-containing anode slurry is upward, placing another piece of organic fiber microporous paper on the top layer, sealing the periphery of the other piece of organic fiber microporous paper by using a polyimide film, and then pressing the other piece of organic fiber microporous paper by using a clamp;
heating a flat vulcanizing machine to 180 ℃, then putting the sulfur anode slurry covered with the organic fiber microporous paper and tightly clamped by the clamp into a lower die, closing the die and carrying out hot pressing for 5min at the pressure of 10MPa, and removing the polyimide film to obtain the sulfur anode material.
A schematic cross-sectional structure diagram of the sulfur-containing cathode material prepared in this example is shown in fig. 1, where 1 is a carrier; 2 is an active substance. As can be seen from FIG. 1, the sulfur-containing cathode material prepared by the method is a structure similar to a sandwich, wherein the sulfur-containing cathode slurry is positioned between two layers of organic fiber microporous paper.
Example 2
Preparing sulfur-containing anode slurry:
and (3) putting 0.8g of sulfur, 0.2g of multi-walled carbon nanotube, 0.1g of super carbon black and 0.1g of polyvinylidene fluoride into a planetary ball mill, dropwise adding 20-30 mLN-methyl pyrrolidone solution, and carrying out ball milling at normal temperature for 8 hours at the ball milling speed of 120r/min to obtain the uniformly dispersed sulfur-containing anode slurry.
Preparing organic fiber microporous paper:
dissolving 3g of para-aramid pulp fiber and 0.05g of polyethylene oxide (PEO) in 200mL of ethanol solution with the mass fraction of 99.9%, and uniformly stirring and dispersing to obtain a first fiber dispersion liquid; dissolving 3g of para-aramid chopped fiber and 0.05g of sodium dodecyl sulfate in 100mL of water, and uniformly stirring and dispersing to obtain a second fiber dispersion liquid;
mixing the first fiber dispersion liquid and the second fiber dispersion liquid to obtain aramid fiber slurry;
wetting 3g of carbon nanotube and 0.2g of Sodium Dodecyl Sulfate (SDS) by using an ethanol solution with the mass fraction of 99.9%, then adding 500mL of deionized water, carrying out ultrasonic treatment for 30min at the ultrasonic power of 100%, and obtaining a carbon nanotube dispersion liquid at the speed of 2000 r/min;
placing the aramid fiber slurry and the carbon nano tube dispersion liquid in a high-speed shearing machine, and shearing for 30min at the speed of 3000r/min by the high-speed shearing machine to obtain carbon nano tube/aramid fiber mixed slurry;
adding 0.1g of anionic polyacrylamide into the carbon nano tube/aramid fiber mixed slurry, and performing vacuum filtration in a hollow filtration tank, wherein the pressure of the vacuum filtration is 2 MPa;
drying the solid substance obtained by filtering under the vacuum condition to obtain the organic fiber microporous paper, wherein the vacuum degree is 0.08 Mpa; the drying temperature is 80 ℃; the drying time is 60min, and the thickness of the obtained organic fiber microporous paper is 300 mu m.
Preparing a sulfur-containing cathode material:
uniformly coating the sulfur-containing anode slurry on the surface of the organic fiber microporous paper, wherein the coating thickness is 100 micrometers, drying the organic fiber microporous paper in a vacuum drying oven at the temperature of 60 ℃, placing the organic fiber microporous paper coated with the sulfur-containing anode slurry at the bottom, the sulfur-containing anode slurry is upward, placing another piece of organic fiber microporous paper on the top layer, sealing the periphery of the other piece of organic fiber microporous paper by using a polyimide film, and then pressing the other piece of organic fiber microporous paper by using a clamp;
heating a flat vulcanizing machine to 180 ℃, then putting the sulfur anode slurry covered with the organic fiber microporous paper and tightly clamped by the clamp into a lower die, closing the die and carrying out hot pressing for 5min at the pressure of 10MPa, and removing the polyimide film to obtain the sulfur anode material.
The sectional structure of the sulfur-containing cathode material prepared in this example was similar to that of example 1.
Example 3
And (3) carrying out performance detection on the organic fiber microporous paper:
testing the porosity, the specific surface area and the pore diameter of the obtained organic fiber microporous paper by using a specific surface area analyzer;
testing the surface resistance of the obtained organic fiber microporous paper by using a four-probe resistance meter;
the tensile strength of the obtained organic fiber microporous paper was measured by a method of hanging a weight under a unit sectional area, and the test results are shown in table 1.
TABLE 1 results of Performance test of the organic fiber microporous paper obtained in examples 1 to 2
Example 4
Preparing a sulfur-containing positive plate:
the sulfur-containing positive electrode material prepared in example 1 was sliced with a slicer to obtain a positive electrode sheet having a diameter of 14mm, and a sulfur-containing positive electrode sheet was prepared.
Preparation of lithium-sulfur battery:
in a dry glove box filled with argon, assembling a lithium-sulfur battery according to the sequence of a positive electrode shell, a sulfur-containing positive electrode plate, a diaphragm, a lithium plate, a gasket, a negative electrode shell and dropwise adding electrolyte; the diaphragm is preferably Celgrad 2300, and the solute of the electrolyte is 1mol of lithium bistrifluoromethylsulfonate imide (LiTFSI) containing 1 percent LiNO3The solvent of the electrolyte is ethylene glycol dimethyl ether (DME) and 1, 3-Dioxolane (DOL), and the volume ratio of the ethylene glycol dimethyl ether (DME) to the 1, 3-Dioxolane (DOL) is 1: 1.
the assembled lithium-sulfur battery is placed for 24 hours, a new battery tester is adopted to perform constant-current charge and discharge tests on the lithium-sulfur battery at different multiplying powers (0.1-2C) at room temperature, the voltage interval is 1.6-2.8V, and the obtained test results are shown in figure 2.
As can be seen from FIG. 2, the lithium-sulfur battery prepared by the sulfur-containing cathode material provided by the invention is subjected to constant current charge and discharge test at a rate of 0.1-2C, and the specific capacity reaches 900-1500 mAh/g, which shows that the problem of active substance loss in the existing lithium-sulfur battery system is solved, the performance of a battery device is improved, and the preparation method is simple and easy to operate and is suitable for large-scale production.
Example 5
The sulfur-containing positive electrode material prepared in example 2 was used to prepare a sulfur-containing positive electrode sheet and a lithium sulfur battery in the same manner as in example 3, and the performance of the lithium sulfur battery was tested, with the test results being similar to those of example 3.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A sulfur-containing anode material is obtained by taking sulfur-containing anode slurry as an active substance and organic fiber microporous paper as a carrier, and placing the sulfur-containing anode slurry between two layers of the organic fiber microporous paper for hot pressing;
the preparation raw materials of the organic fiber microporous paper comprise para-aramid pulp fiber, para-aramid chopped fiber and carbon nano tubes;
the preparation method of the organic fiber microporous paper comprises the following steps:
dispersing para-aramid pulp fibers in an organic solvent to obtain a first fiber dispersion liquid;
dispersing the para-aramid chopped fibers in water to obtain a second fiber dispersion liquid;
mixing the first fiber dispersion liquid and the second fiber dispersion liquid to obtain aramid fiber slurry;
dispersing carbon nanotubes in water to obtain a carbon nanotube dispersion liquid;
mixing the aramid fiber slurry with the carbon nanotube dispersion liquid to obtain carbon nanotube/aramid fiber mixed slurry;
and mixing the carbon nano tube/aramid fiber mixed slurry with a flocculating agent and then filtering to obtain the organic fiber microporous paper.
2. The sulfur-containing cathode material according to claim 1, wherein the raw material for preparing the sulfur-containing cathode slurry comprises sulfur, multi-walled carbon nanotubes, superconducting carbon black, and polyvinylidene fluoride.
3. The sulfur-containing cathode material according to claim 1, wherein the mass ratio of the para-aramid pulp fibers to the para-aramid chopped fibers is 1 (1-3).
4. The sulfur-containing cathode material according to claim 3, wherein the mass ratio of the total mass of the para-aramid pulp fibers and the para-aramid chopped fibers to the carbon nanotubes is 1 (0.5-1).
5. The sulfur-containing positive electrode material according to any one of claims 1 and 3 to 4, wherein the organic fiber microporous paper has a thickness of 200 to 300 μm; the aperture of the organic fiber microporous paper is 2-110 nm.
6. The sulfur-containing cathode material according to claim 1, wherein the hot pressing pressure is 8 to 10 MPa; the hot pressing temperature is 160-200 ℃.
7. The method for producing a sulfur-containing positive electrode material as claimed in any one of claims 1 to 6, comprising the steps of:
(1) covering organic fiber microporous paper on the upper surface and the lower surface of the sulfur-containing anode slurry to obtain sulfur-containing anode slurry covering the organic fiber microporous paper;
(2) and carrying out hot pressing on the sulfur-containing anode slurry covering the organic fiber microporous paper to obtain the sulfur-containing anode material.
8. The sulfur-containing cathode material according to any one of claims 1 to 6 or the sulfur-containing cathode material prepared by the preparation method according to claim 7 is applied to a lithium-sulfur battery.
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| CN108744297B (en) * | 2018-07-06 | 2020-02-07 | 江西克莱威纳米碳材料有限公司 | Far infrared paper, preparation method thereof and aramid far infrared physiotherapy electric heating device |
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| CN101591868A (en) * | 2009-06-23 | 2009-12-02 | 东华大学 | Preparation of Carbon Fiber Paper for Gas Diffusion Layer of Proton Exchange Membrane Fuel Cell |
| US8916310B2 (en) * | 2010-08-27 | 2014-12-23 | Toho Tenax Co., Ltd. | Conductive sheet and production method for same |
| CN104916813A (en) * | 2015-05-08 | 2015-09-16 | 南昌大学 | Making method of lithium-sulfur battery positive electrode piece |
| WO2017120391A1 (en) * | 2016-01-08 | 2017-07-13 | The Texas A&M University System | Large energy density batteries and methods of manufacture |
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