CN113270583A - Vulcanized polymer composite material, positive pole piece comprising vulcanized polymer composite material, and preparation method and application of positive pole piece - Google Patents
Vulcanized polymer composite material, positive pole piece comprising vulcanized polymer composite material, and preparation method and application of positive pole piece Download PDFInfo
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- CN113270583A CN113270583A CN202110546471.2A CN202110546471A CN113270583A CN 113270583 A CN113270583 A CN 113270583A CN 202110546471 A CN202110546471 A CN 202110546471A CN 113270583 A CN113270583 A CN 113270583A
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000011812 mixed powder Substances 0.000 claims abstract description 36
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 34
- 239000011593 sulfur Substances 0.000 claims abstract description 34
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- 229940005550 sodium alginate Drugs 0.000 claims description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 3
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
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- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical class [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 229910000423 chromium oxide Inorganic materials 0.000 description 4
- 238000013461 design Methods 0.000 description 4
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- 239000011149 active material Substances 0.000 description 3
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- 238000006243 chemical reaction Methods 0.000 description 3
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- -1 carboxylate ions Chemical class 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- LCBKDULHZJKFJQ-UHFFFAOYSA-N lithium chromium(3+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[Cr+3] LCBKDULHZJKFJQ-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a vulcanized polymer composite material, a positive pole piece comprising the vulcanized polymer composite material, and a preparation method and application of the positive pole piece, wherein the preparation method comprises the following steps: (1) mixing a sulfur raw material and a conductive polymer to obtain mixed powder; (2) firing and heat-treating the obtained mixed powder to obtain the vulcanized polymer composite material; according to the preparation method, the obtained mixed powder is ensured to have fluffy characteristic by a powder dry mixing mode, the material agglomeration generated in the sintering process can be reduced, the specific surface area of the material is reduced, the sulfur carrying capacity of the prepared positive pole piece can be further improved, support is provided for the realization of the high-energy-density lithium-sulfur battery, and the preparation method has important research value.
Description
Technical Field
The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to a vulcanized polymer composite material, a positive pole piece containing the vulcanized polymer composite material, and a preparation method and application of the vulcanized polymer composite material.
Background
The lithium-sulfur battery has the advantages of high theoretical energy density, abundant and easily available raw materials and low price, can be widely applied to the fields of aerospace, new energy automobiles and the like, and is one of the main development directions of next-generation high-specific-energy batteries; the lithium-sulfur battery is a novel lithium battery which is recognized at present and can reach the energy density of more than 400 Wh/kg. However, there are still many obstacles to its commercialization process, such as polysulfide shuttling effect, negative lithium dendrite problem, etc. From the viewpoint of improving the energy density of the lithium-sulfur battery, the core problem is the improvement of the surface capacity of the positive electrode, and the surface capacity of the positive electrode is mainly related to the specific capacity of the positive electrode material and the surface density of the positive electrode. So to say, the positive electrode material with high specific capacity is prepared into the positive plate of the high-capacity lithium-sulfur battery, and the utilization rate of the active substances is ensured, so that the design and the manufacture of the high-specific-energy lithium-sulfur battery are finished by 75 percent. One key factor in the preparation of the high-load lithium-sulfur battery positive plate is that the physical properties of the positive material, such as the particle size and the specific surface area, all affect the tabletting process.
Currently, the positive electrode materials of lithium-sulfur batteries are mainly classified into three major categories, including sulfur-carbon composites, sulfur-polymer composites, and metal sulfides. The sulfur-carbon composite material is mainly prepared by loading elemental sulfur on a carbon carrier with rich pores, and the material generates polysulfide through the reaction of the elemental sulfur, so that shuttle effect is easy to occur, the capacity of a battery is reduced, and the cycle life is influenced. The metal sulfide loads various metal sulfides on the carbon carrier, and the materials have the same problems as sulfur-carbon composite materials: shuttle effects tend to occur. Compared with the prior art, the sulfur polymer composite material anchors sulfur on the polymer, so the problem of sulfur loss does not exist, and the problem of battery capacity attenuation caused by the loss of positive active substances is solved fundamentally.
At present, sulfur polymer composite materials are prepared mainly by mixing elemental sulfur and polymer powder and then firing. CN109256554A discloses a vulcanized polymer composite material, a preparation method and application thereof. The preparation method of the vulcanized polymer composite material comprises the following steps: the sublimed sulfur and the conductive polymer are uniformly mixed, placed in a tubular furnace and subjected to a co-heating reaction under an inert atmosphere to obtain the vulcanized polymer composite material. In the material, small molecular sulfur is firmly bound among conductive polymer molecules under the actions of physical constraint and chemical bonding, so that the shuttle effect caused by the dissolution of polysulfide is effectively controlled, and the excellent conductivity of the polymer also effectively modifies the electronic conductivity of the small sulfur molecules. The material has good compatibility with a carbonate-based electrolyte, and can obtain excellent electrochemical performance, and the vulcanized polypyrrole lithium-sulfur battery cathode material prepared by the invention shows excellent reversibility and cycling stability. CN112194182A discloses a preparation method for the problems of slow electrode reaction kinetics, low first coulombic efficiency and specific capacity of the conventional chromium oxide positive electrode, and the like, which comprises the following steps: preparing chromium oxide; preparing vulcanized polyacrylonitrile; preparing lithiation vulcanized polyacrylonitrile; and mixing the prepared lithiation vulcanized polyacrylonitrile and the chromium oxide, and performing ball milling at 200rpm for 1 hour to obtain the chromium oxide anode containing lithiation vulcanized polyacrylonitrile. The prepared chromium oxide lithium ion battery anode material containing lithium sulfide polyacrylonitrile has uniform particles, and has the advantages of remarkably improving the first coulombic efficiency, reversible specific capacity and conductivity; the lithium-containing vulcanized polyacrylonitrile can be used for modifying other electrode materials, and the organic carbon skeleton has higher conductivity, lithium supplement capacity and electrochemical reaction voltage platform, and can be popularized to other electrode material systems. CN110416487A discloses a lithiated polyacrylonitrile sulfide used as a positive electrode active material of a lithium sulfur secondary battery, and a positive electrode sheet and a lithium sulfur secondary battery including the active material. The lithiated polyacrylonitrile sulfide is prepared by lithiating polyacrylonitrile sulfide. According to the invention, the polyacrylonitrile sulfide is lithiated, so that hydrophilic carboxylate ions are generated from the polyacrylonitrile sulfide active material, and when the polyacrylonitrile sulfide active material is compounded with the conductive adhesive, hydrogen bonds with strong acting force are formed in the system, and the sulfur loading capacity and unit area capacity of the anode are improved.
However, the vulcanized polymer material prepared by the above patent has a large specific surface area, which affects the preparation of the subsequent high-load sulfur positive electrode plate, and when the reaction between the sulfur raw material and the conductive polymer is insufficient, elemental sulfur still remains in the product, which affects the cycle life of the battery.
Therefore, the development of a preparation method which is simple and can obtain a vulcanized polymer composite material with a small specific surface area is a technical problem which is urgently needed to be solved in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a vulcanized polymer composite material, a positive pole piece comprising the vulcanized polymer composite material, a preparation method and application of the positive pole piece; the preparation method of the vulcanized polymer composite material comprises the steps of mixing a sulfur raw material and a conductive polymer to obtain mixed powder, and then firing and thermally treating the obtained mixed powder to obtain the vulcanized polymer composite material; the preparation method is simple, the prepared vulcanized polymer composite material has a small specific surface area, and is beneficial to the preparation of a subsequent high-load sulfur positive pole piece, so that the cycle life of the lithium-sulfur battery is prolonged, and the preparation method has important research significance.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a process for the preparation of a vulcanized polymer composite, said process comprising the steps of:
(1) mixing a sulfur raw material and a conductive polymer to obtain mixed powder;
(2) and (2) firing and heat treating the mixed powder obtained in the step (1) to obtain the vulcanized polymer composite material.
According to the preparation method of the vulcanized polymer composite material, firstly, the sulfur raw material and the conductive polymer are mixed to obtain mixed powder, then the mixed powder is fired, and finally the fired product is subjected to heat treatment, so that the residue of elemental sulfur in the fired product can be removed in the heat treatment process, the cycle stability of the finally obtained vulcanized polymer composite material is improved, and the cycle performance of the lithium-sulfur battery is further improved; the preparation method is simple, convenient and feasible, can realize large-scale production of the vulcanized polymer composite material, and has important research value.
Preferably, the mixing time in step (1) is 0.5-2 h, such as 0.7h, 0.9h, 1.1h, 1.3h, 1.5h, 1.7h or 1.9h, and the specific values therebetween are not exhaustive, and the invention is not limited to the specific values included in the range for brevity and conciseness.
Preferably, the mixing in step (1) is performed under stirring conditions, and more preferably under stirring conditions at a rotation speed of 5 to 25rpm (e.g., 7rpm, 9rpm, 11rpm, 13rpm, 15rpm, 17rpm, 19rpm, 21rpm, 23rpm, 25rpm, 27rpm, 29rpm, or the like).
Preferably, the mixing in the step (1) is performed by any one of a ball mill, a high-speed stirrer or a V-type blender.
In the preparation method provided by the invention, the sulfur raw material and the conductive polymer are subjected to dry powder mixing by any one of a ball mill, a high-speed stirrer or a V-shaped mixer, so that the obtained mixed powder has fluffy characteristic, the material agglomeration generated in the subsequent sintering process is reduced, and the specific surface area of the finally obtained vulcanized polymer composite material is favorably reduced.
Preferably, the mass ratio of the conductive polymer and the sulfur raw material in the step (1) is 1 (2-5), such as 1:2.3, 1:2.6, 1:2.9, 1:3.3, 1:3.6, 1:3.9, 1:4.3, 1:4.6 or 1: 4.9.
Preferably, the sulfur feedstock of step (1) comprises sublimed sulfur.
Preferably, the conductive polymer of step (1) comprises polyacrylonitrile and/or polyaniline.
Preferably, the firing in step (2) is performed under the protection of inert gas.
Preferably, the inert gas comprises nitrogen or argon.
Preferably, the flow rate of the inert gas is 0.05 to 1L/min, such as 0.1L/min, 0.2L/min, 0.3L/min, 0.4L/min, 0.5L/min, 0.6L/min, 0.7L/min, 0.8L/min or 0.9L/min, and the specific values therebetween are limited to space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the ranges.
Preferably, the firing in step (2) is performed under a condition of increasing temperature.
Preferably, the temperature raising speed is 3-10 ℃/min, such as 3.5 ℃/min, 4 ℃/min, 4.5 ℃/min, 5 ℃/min, 5.5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min or 9 ℃/min, and the specific values therebetween are limited by space and for the sake of brevity, and the specific values included in the range are not exhaustive.
Preferably, the firing temperature in step (2) is 250-450 ℃, for example, 270 ℃, 290 ℃, 310 ℃, 330 ℃, 350 ℃, 370 ℃, 390 ℃, 410 ℃ or 430 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the firing time in step (2) is 3 to 10 hours, such as 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 7 hours, 8 hours or 9 hours, and specific values therebetween, which are limited by space and for brevity, the invention is not exhaustive.
Preferably, the firing in step (2) is performed by filling the mixed powder into a crucible, and then placing the crucible filled with the mixed powder in a furnace.
In the invention, the mixed powder is filled into the crucible without compacting, thereby ensuring the fluffiness of the mixed powder.
Preferably, the crucible comprises a graphite crucible, a ceramic crucible or a quartz crucible.
Preferably, the furnace comprises a tube furnace or a muffle furnace.
Preferably, the temperature of the heat treatment in the step (2) is 450-600 ℃, such as 460 ℃, 480 ℃, 500 ℃, 520 ℃, 540 ℃, 560 ℃ or 580 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
As a preferred technical scheme, the temperature of the heat treatment provided by the invention is 450-600 ℃, and the elemental sulfur in the product can be removed more favorably in the temperature range, on one hand, if the temperature is too high, the vulcanized polymer composite material can be degraded; on the other hand, if the temperature is too low, the effect of removing excess elemental sulfur cannot be obtained.
Preferably, the heat treatment time is 1 to 5 hours, such as 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours or 4.5 hours, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) mixing the conductive polymer and the sulfur raw material in a mass ratio of 1 (2-5) for 0.5-2 h by any one of a ball mill, a high-speed stirrer or a V-shaped mixer under the condition that the rotating speed is 5-25 rpm to obtain mixed powder;
(2) filling the mixed powder obtained in the step (1) into a graphite crucible, a ceramic crucible or a quartz crucible, then placing the crucible filled with the mixed powder into a tubular furnace or a muffle furnace, firing for 3-10 h at the temperature rise speed of 3-10 ℃/min under the condition of inert gas protection at 250-450 ℃, and carrying out heat treatment for 1-5 h at the temperature of 450-600 ℃ to obtain the vulcanized polymer composite material.
In a second aspect, the present invention provides a vulcanized polymer composite prepared by the preparation method as described in the first aspect.
In a third aspect, the invention provides a positive electrode plate, and the raw materials for preparing the positive electrode plate comprise a conductive agent, a dispersing agent, a binder and the vulcanized polymer composite material as described in the second aspect.
Preferably, the conductive agent comprises any one of carbon black, graphite, carbon nanotubes or carbon fibers or a combination of at least two thereof.
Preferably, the dispersant comprises any one of deionized water, N-methyl pyrrolidone or alcohol complex solvent.
Preferably, the alcohol complex solvent includes a mixture of deionized water and alcohol.
Preferably, the alcohol comprises any one of ethanol, isopropanol, or n-butanol, or a combination of at least two thereof.
Preferably, the binder comprises any one or a combination of at least two of polyvinylidene fluoride, sodium carboxymethylcellulose, polyacrylic acid, polyacrylonitrile or sodium alginate.
Preferably, the single-sided surface density of the positive pole piece is not less than 8mg/cm2E.g. 8.5mg/cm2、9mg/cm2、9.5mg/cm2、10mg/cm2、10.5mg/cm2、11mg/cm2Or 11.5mg/cm2And the specific values between the foregoing, are not intended to be exhaustive or to limit the invention to the precise values encompassed within the scope, for reasons of brevity and clarity.
In a fourth aspect, the present invention provides a method for preparing the positive electrode plate according to the third aspect, wherein the method for preparing the positive electrode plate comprises the following steps:
(1) mixing a conductive agent and a dispersing agent to obtain a conductive agent dispersion liquid;
(2) mixing the conductive dispersion liquid obtained in the step (1) with a binder to obtain conductive slurry;
(3) mixing the conductive paste obtained in the step (2) with the vulcanized polymer composite material as described in the second aspect, and performing defoaming treatment to obtain positive electrode paste;
(4) and (4) coating the positive electrode slurry obtained in the step (3) on a current collector to obtain the positive electrode piece.
According to the preparation method of the positive pole piece, the conductive agent and the dispersing agent are mixed to obtain the conductive dispersion liquid, so that the conductive agent is wetted in advance, and the conductive agent agglomeration condition brought by adding the binder is favorably slowed down; then mixing the conductive dispersion liquid with a binder to obtain conductive slurry; and then mixing the anode slurry and the vulcanized polymer composite material for multiple times to obtain anode slurry, and finally coating the anode slurry on the surface of a current collector to obtain the anode piece.
Preferably, the mixing in step (1), step (2) and step (3) is carried out under stirring.
Preferably, the mixing of step (1), step (2) and step (3) is carried out under dispersive conditions.
Preferably, the mixing in step (1) is performed under dispersion conditions at a rotation speed of 1000 to 2000rpm (e.g., 1100rpm, 1200rpm, 1300rpm, 1400rpm, 1500rpm, 1600rpm, 1700rpm, 1800rpm, 1900rpm, etc.).
Preferably, the mixing in step (1) is performed under stirring conditions at a rotation speed of 10 to 20rpm (e.g., 11rpm, 12rpm, 13rpm, 14rpm, 15rpm, 16rpm, 17rpm, 18rpm, 19rpm, etc.).
Preferably, the mixing time in step (1) is 30-120 min, such as 40min, 50min, 60min, 70min, 80min, 90min, 100min or 110 min.
Preferably, the mixing in step (2) is performed under dispersion conditions at a rotation speed of 500 to 2000rpm (e.g., 700rpm, 900rpm, 1100rpm, 1300rpm, 1500rpm, 1700rpm, 1900rpm, etc.).
Preferably, the mixing in step (2) is performed under stirring conditions at a rotation speed of 10 to 50rpm (e.g., 15rpm, 20rpm, 25rpm, 30rpm, 35rpm, 40rpm, 45rpm, etc.).
Preferably, the mixing time in step (2) is 30-120 min, such as 40min, 50min, 60min, 70min, 80min, 90min, 100min or 110min, and the specific points between the above points are limited by space and for the sake of brevity, the invention is not exhaustive of the specific points included in the range.
Preferably, the mixing in step (3) is performed under stirring conditions at a rotation speed of 10 to 70rpm (e.g., 20rpm, 30rpm, 40rpm, 50rpm, 60rpm, etc.).
Preferably, the mixing in step (3) is performed under dispersion conditions at a rotation speed of 500 to 2500rpm (e.g., 700rpm, 900rpm, 1100rpm, 1300rpm, 1500rpm, 1900rpm, 2100rpm, 2300rpm, 2500rpm, 2700rpm, 2900rpm, etc.);
preferably, the mixing time in step (3) is 0.5-10 h, such as 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h or 9h, and the specific points between the above points are limited by space and for brevity, the invention is not exhaustive of the specific points included in the range.
Preferably, the viscosity of the positive electrode slurry in the step (3) is 1000 to 5000mpas, such as 1500mpas, 2000mpas, 2500mpas, 3000mpas, 3500mpas, 4000mpas or 4500mpas, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the defoaming treatment in the step (3) further comprises a sieving treatment.
Preferably, the step (4) further comprises a baking step after the coating is finished.
Preferably, the baking temperature is 60-120 ℃, for example, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃ or 115 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the screen for the screening treatment is a 100-200 mesh screen (for example, 110 mesh, 120 mesh, 130 mesh, 140 mesh, 150 mesh, 160 mesh, 170 mesh, 180 mesh or 190 mesh screen).
As a preferred technical scheme, the preparation method of the positive pole piece comprises the following steps:
(1) mixing a conductive agent and a dispersing agent for 30-120 min under the dispersion condition with the rotating speed of 1000-2000 rpm and the stirring condition with the rotating speed of 10-20 rpm to obtain a conductive agent dispersion liquid;
(2) mixing the conductive dispersion liquid obtained in the step (1) and a binder for 30-120 min under the dispersion condition with the rotating speed of 500-2000 rpm and the stirring condition with the rotating speed of 10-50 rpm to obtain conductive slurry;
(3) completely mixing the conductive paste obtained in the step (2) and the vulcanized polymer composite material in the second aspect under the dispersion condition of the rotating speed of 500-2500 rpm and the stirring condition of the rotating speed of 10-70 rpm, mixing for 0.5-10 h, defoaming, and sieving with a 100-200 mesh sieve to obtain the positive paste with the viscosity of 2500 mpas;
(4) enabling the positive electrode slurry obtained in the step (3) to have a single-side surface density of not less than 8mg/cm2Coating the mixture on a current collector, and baking at 160-120 ℃ to obtain the positive pole piece.
In a fifth aspect, the invention provides a lithium-sulfur battery comprising the positive electrode sheet according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method of the vulcanized polymer composite material provided by the invention comprises the steps of mixing a sulfur raw material and a conductive polymer to obtain mixed powder; then, firing and heat treating the obtained mixed powder to obtain the vulcanized polymer composite material; the heat treatment step can effectively remove elemental sulfur in the fired product, so that the circulating stability of the vulcanized polymer composite material is improved; the preparation method ensures that the material has fluffy characteristic by a dry powder mixing mode, can reduce material agglomeration generated in a sintering process, reduces the specific surface area of the material, further can improve the sulfur carrying capacity of the prepared positive pole piece, provides technical support for the realization of the high-energy-density lithium-sulfur battery, and has important research value.
(2) Specifically, the specific surface area of the vulcanized polymer composite material prepared by the preparation method provided by the invention is 6.3-6.7 m2(ii)/g; the sulfur content is 44-46%; preparing the lithium-sulfur battery into a lithium-sulfur battery, wherein the energy density of the lithium-sulfur battery is 321-350 Wh/kg; the reversible discharge specific capacity of the button cell is 720-750 mAh/g, and the number of cycles is 650-1100.
Drawings
FIG. 1 is a scanning electron micrograph of a vulcanized polymer composite provided in example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A preparation method of a vulcanized polymer composite material specifically comprises the following steps:
(1) sublimed sulfur and polyacrylonitrile (with the molecular weight of 15 ten thousand and the molecular weight distribution index of 2.9) in a mass ratio of 3:1 are mixed for 1 hour by a ball mill under the condition that the rotating speed is 15rpm, so as to obtain mixed powder;
(2) and (2) filling the mixed powder obtained in the step (1) into a graphite crucible, placing the graphite crucible in a tubular furnace, heating to 300 ℃ for firing for 7h at a heating rate of 5 ℃/min under the protection condition that the nitrogen flow rate is 0.5L/min, and carrying out heat treatment for 3h at 550 ℃ to obtain the vulcanized polymer composite material.
Example 2
A preparation method of a vulcanized polymer composite material specifically comprises the following steps:
(1) sublimed sulfur and polyacrylonitrile (molecular weight is 15 ten thousand, molecular weight distribution index is 2.9) with the mass ratio of 2:1 are mixed for 2 hours by a high-speed mixer under the condition that the rotating speed is 5rpm, and mixed powder is obtained;
(2) and (2) filling the mixed powder obtained in the step (1) into a ceramic crucible, placing the ceramic crucible in a muffle furnace under the protection condition that the nitrogen flow rate is 0.05L/min, heating to 250 ℃ according to the heating rate of 3 ℃/min, firing for 10h, and carrying out heat treatment for 5h at 450 ℃ to obtain the vulcanized polymer composite material.
Example 3
A preparation method of a vulcanized polymer composite material specifically comprises the following steps:
(1) mixing sublimed sulfur and polyaniline (molecular weight 15 ten thousand and molecular weight distribution index 2.9) in a mass ratio of 5:1 for 0.5h by a V-shaped mixer under the condition of a rotating speed of 25rpm to obtain mixed powder;
(2) and (2) filling the mixed powder obtained in the step (1) into a quartz crucible, placing the quartz crucible into a muffle furnace, heating to 450 ℃ for firing for 3h at a heating speed of 10 ℃/min under the protection condition that the nitrogen flow rate is 1L/min, and carrying out heat treatment for 3h at 600 ℃ to obtain the vulcanized polymer composite material.
Example 4
A method for preparing a vulcanized polymer composite, which is different from example 1 in that the temperature of the heat treatment in step (2) is 450 ℃, and other raw materials, conditions and steps are the same as those of example 1.
Example 5
A method for preparing a vulcanized polymer composite, which is different from example 1 in that the temperature of the heat treatment in step (2) is 600 ℃, and other raw materials, conditions and steps are the same as those of example 1.
Example 6
A method for preparing a vulcanized polymer composite, which is different from example 1 in that the temperature of the heat treatment in step (2) is 400 ℃, and other raw materials, conditions and steps are the same as those of example 1.
Comparative example 1
A preparation method of a vulcanized polymer composite material specifically comprises the following steps:
(1) sublimed sulfur and polyacrylonitrile (molecular weight is 15 ten thousand, molecular weight distribution index is 2.9) with the mass ratio of 3:1 are mixed for 1 hour by a ball mill under the condition that the rotating speed is 15rpm, and mixed powder is obtained;
(2) and (2) filling the mixed powder obtained in the step (1) into a graphite crucible, placing the graphite crucible into a tubular furnace, and heating to 300 ℃ for firing for 7 hours at a heating rate of 5 ℃/min under the protection condition that the nitrogen flow rate is 0.5L/min to obtain the vulcanized polymer composite material.
Comparative example 2
A preparation method of a vulcanized polymer composite material specifically comprises the following steps:
(1) dispersing sublimed sulfur and polyacrylonitrile (molecular weight is 15 ten thousand, molecular weight distribution index is 2.9) with the mass ratio of 3:1 in water, mixing for 1h by a ball mill under the condition that the rotating speed is 15rpm to obtain mixed slurry, and baking at 60 ℃ to remove moisture to obtain mixed powder;
(2) and (2) filling the mixed powder obtained in the step (1) into a graphite crucible, placing the graphite crucible into a tubular furnace, and heating to 300 ℃ for firing for 7 hours at a heating rate of 5 ℃/min under the protection condition that the nitrogen flow rate is 0.5L/min to obtain the vulcanized polymer composite material.
Application examples 1 to 6
A positive pole piece is prepared from the following raw materials of carbon black, sodium carboxymethylcellulose and a vulcanized polymer composite material (respectively in examples 1-6) in a mass ratio of 12:8:80, wherein a solvent is deionized water;
the preparation method of the positive pole piece obtained by the application example comprises the following steps:
(1) mixing carbon black and deionized water for 80min under the dispersion condition with the rotating speed of 1500rpm and the stirring condition with the rotating speed of 15rpm to obtain a conductive agent dispersion liquid;
(2) mixing the conductive dispersion liquid obtained in the step (1) with sodium carboxymethylcellulose for 80min under the dispersion condition with the rotating speed of 1000rpm and the stirring condition with the rotating speed of 25rpm to obtain conductive slurry;
(3) completely mixing the conductive paste obtained in the step (2) and a vulcanized polymer composite material (respectively, examples 1 to 7) under the dispersion condition of the rotation speed of 1000rpm and the stirring condition of the rotation speed of 25rpm, adjusting the dispersion condition of the rotation speed of 1500rpm and the stirring condition of the rotation speed of 45rpm for 5 hours, defoaming, and sieving by using a 100-200-mesh sieve to obtain positive electrode paste with the viscosity of 2500 mpas;
(4) the positive electrode slurry obtained in the step (3) is subjected to single-side surface density of 9mg/cm2Coating the mixture on an aluminum foil, and baking at 100 ℃ to obtain the positive pole piece.
Application examples 7 to 12
A lithium-sulfur battery comprises positive pole pieces obtained by applying examples 1-6 respectively;
the preparation process comprises the following steps: and (3) respectively rolling and die-cutting the positive pole piece obtained in the application examples 1-6, and laminating and injecting the negative pole piece (metal lithium) to obtain the lithium-sulfur battery.
Application examples 13 to 18
A button cell, the positive pole is the positive pole piece obtained from application examples 1-6 respectively;
the preparation process comprises the following steps: and (3) assembling the positive pole piece obtained by the method of application examples 1-6 in a button cell positive shell according to the order of the positive pole piece, the diaphragm and the metal lithium, adding the electrolyte, covering the negative pole shell, and sealing the opening.
Comparative application examples 1 to 2
A positive electrode sheet was distinguished from application example 1 only in that the vulcanized polymer composite materials obtained in comparative examples 1 and 2 were used instead of the vulcanized polymer composite material obtained in example 1, respectively, and the other materials, amounts and preparation methods were the same as in application example 1.
Comparative application examples 3 to 4
A lithium-sulfur battery is different from the lithium-sulfur battery in application example 7 only in that the positive pole piece obtained in application example 1 is replaced by the positive pole piece obtained in comparative application examples 1-2, so that the lithium-sulfur battery is obtained.
Comparative application examples 5 to 6
A button cell is only different from application example 13 in that the positive pole piece obtained in application example 1 is replaced by the positive pole piece obtained in comparative application examples 1-2 to obtain the button cell.
And (3) performance testing:
(1) surface morphology: a thin layer of sample powder is laid on a sample table, and observation and recording are carried out by using a scanning electron microscope at a 30000-fold.
The vulcanized polymer composite material obtained in example 1 is tested according to the test method (1), a scanning electron microscope spectrogram of the vulcanized polymer composite material obtained in example 1 is shown in fig. 1, and it can be seen from fig. 1 that the particle size of the vulcanized polymer composite material obtained by the preparation method provided in the example is 100-200 nm.
(2) Specific surface area: the test was carried out using a Gemini 2390 specific surface area Analyzer.
(3) Sulfur content: the sulfur content of the material was tested using a sulfur carbon analyzer.
The vulcanized polymer composites obtained in examples 1 to 6 and comparative examples 1 to 2 were tested according to the test method (2) described above, and the test results are shown in Table 1:
TABLE 1
As can be seen from the data in Table 1, the vulcanized polymer composite material prepared by the preparation method provided by the invention has a small specific surface area, specifically 6.3-6.7 m2(ii)/g; the sulfur content is 44-46%;
specifically, comparing example 1 with comparative example 1, it can be seen that the vulcanized polymer composite obtained by the preparation method provided by the present invention has a small specific surface area and a small sulfur content, and the vulcanized polymer composite obtained by comparative example 1 without heat treatment has a high sulfur content; comparing example 1 with comparative example 2, it can be seen that the vulcanized polymer composite obtained by wet mixing is not only high in sulfur content but also large in specific surface area.
Further comparison of examples 1 and 4 to 6 revealed that the sulfur content of the vulcanized polymer composite (example 5) obtained by the heat treatment of step (2) at too low a temperature was increased.
(4) Reversible specific discharge capacity: after being formed, each lithium-sulfur battery is subjected to constant current discharge at the temperature of 25 ℃ at 0.1C (specifically based on the design capacity of each battery), and the cut-off voltage is 1V; the reading capacity is C1, the voltage of a discharging platform is V, the weight of a battery is called as M, and the energy density of the battery is C1 multiplied by V/M;
the lithium-sulfur batteries obtained according to the test method (4) in the application examples 7 to 12 and the comparative application examples 3 to 4 were tested, and the test results are shown in table 2:
TABLE 2
As can be seen from Table 2, the energy density of the lithium-sulfur battery prepared from the vulcanized polymer composite materials obtained in examples 1 to 6 is 321 to 350 Wh/kg;
comparing application example 7 with comparative application examples 3-4, it can be found that the energy density of the lithium-sulfur battery obtained by comparing application examples 3-4 is greatly reduced, and it is proved that the vulcanized polymer composite material provided by the invention is beneficial to improving the energy density of the lithium-sulfur battery.
Further comparison of application examples 7 and 10 to 12 revealed that the energy density of the lithium-sulfur battery obtained in application example 12 was also reduced, because the sulfur content of the vulcanized polymer composite material obtained in seawater 6 was high.
(5) Specific discharge capacity: after the button cell is stood for 24 hours, the button cell is subjected to constant current discharge at the temperature of 25 ℃ at the temperature of 0.1C (specifically, the design capacity of each cell is taken as the standard), and the test voltage range is 1.0V-3.0V. The charge and discharge capacity was read as C, and the weight of the positive electrode active material was recorded as M. The mass specific energy of the battery is C/M;
(6) the number of circulating circles is as follows: and (3) taking the button cell manufactured in the step (5), and carrying out constant current charging and discharging at the temperature of 25 ℃ by 0.1C (specifically, taking the design capacity of each cell as the standard), wherein the test voltage range is 1.0V-3.0V. The first discharge capacity C1 and the capacity Cx of each subsequent turn were recorded, and the number of turns of Cx/C1-80% was taken as the number of cycles to be recorded.
The button cell obtained according to the test methods (5) and (6) in the application examples 13-18 and the comparative application examples 5-6 is tested, and the test results are shown in table 3:
TABLE 3
As can be seen from the data in table 3: the button cell prepared from the vulcanized polymer composite material prepared by the preparation method provided by the invention has the reversible discharge specific capacity of 720-750 mAh/g and the number of cycles of 650-1100.
Comparing application example 13 with comparative application examples 5-6, it can be found that the button cell obtained by comparing application examples 5-6 has lower reversible discharge specific capacity and cycle number, and the vulcanized polymer composite material provided by the invention is proved to be beneficial to improving the discharge specific capacity and cycle performance of the button cell.
Further comparison of application examples 13 and 16-18 shows that the button cell obtained in application example 18 has a poor cycle count.
The applicant states that the present invention is illustrated by the above examples to a vulcanized polymer composite material, a positive electrode plate comprising the same, and a preparation method and application thereof, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. A method of preparing a vulcanized polymer composite, comprising the steps of:
(1) mixing a sulfur raw material and a conductive polymer to obtain mixed powder;
(2) and (2) firing and heat treating the mixed powder obtained in the step (1) to obtain the vulcanized polymer composite material.
2. The preparation method according to claim 1, wherein the mixing time in the step (1) is 0.5-2 h;
preferably, the mixing in the step (1) is carried out under the condition of stirring, and further preferably under the condition of stirring at the rotating speed of 5-25 rpm;
preferably, the mixing in the step (1) is carried out by any one of a ball mill, a high-speed stirrer or a V-type blender;
preferably, the mass ratio of the conductive polymer to the sulfur raw material in the step (1) is 1 (2-5);
preferably, the sulfur feedstock of step (1) comprises sublimed sulfur;
preferably, the conductive polymer of step (1) comprises polyacrylonitrile and/or polyaniline.
3. The method according to claim 1 or 2, wherein the firing in step (2) is performed under an inert gas atmosphere, preferably at a flow rate of 0.05 to 1L/min;
preferably, the inert gas comprises nitrogen or argon;
preferably, the firing in the step (2) is performed under a temperature rising condition, and more preferably under a temperature rising condition with a temperature rising speed of 3-10 ℃/min;
preferably, the firing temperature in the step (2) is 250-450 ℃;
preferably, the firing time in the step (2) is 3-10 h;
preferably, the firing of step (2) is performed by filling the mixed powder into a crucible, and then placing the crucible filled with the mixed powder into a furnace;
preferably, the crucible comprises a graphite crucible, a ceramic crucible or a quartz crucible;
preferably, the furnace comprises a tube furnace or a muffle furnace;
preferably, the temperature of the heat treatment in the step (2) is 450-600 ℃;
preferably, the time of the heat treatment is 1-5 h.
4. The production method according to any one of claims 1 to 3, characterized by comprising the steps of:
(1) mixing the conductive polymer and the sulfur raw material in a mass ratio of 1 (2-5) for 0.5-2 h by any one of a ball mill, a high-speed stirrer or a V-shaped mixer under the condition that the rotating speed is 5-25 rpm to obtain mixed powder;
(2) filling the mixed powder obtained in the step (1) into a graphite crucible, a ceramic crucible or a quartz crucible, then placing the crucible filled with the mixed powder into a tubular furnace or a muffle furnace, firing for 3-10 h at the temperature rise speed of 3-10 ℃/min under the condition of inert gas protection at 250-450 ℃, and carrying out heat treatment for 1-5 h at the temperature of 450-600 ℃ to obtain the vulcanized polymer composite material.
5. A vulcanized polymer composite produced by the production method according to any one of claims 1 to 4.
6. A positive electrode plate, characterized in that the preparation raw materials of the positive electrode plate comprise a conductive agent, a dispersing agent, a binder and the vulcanized polymer composite material as claimed in claim 5.
7. The positive electrode sheet according to claim 6, wherein the conductive agent comprises any one or a combination of at least two of carbon black, graphite, carbon nanotubes, or carbon fibers;
preferably, the dispersant comprises any one of deionized water, N-methyl pyrrolidone or alcohol complex solvent;
preferably, the alcohol complex solvent comprises a mixture of deionized water and alcohol;
preferably, the alcohol comprises any one of ethanol, isopropanol or n-butanol or a combination of at least two thereof;
preferably, the binder comprises any one or a combination of at least two of polyvinylidene fluoride, sodium carboxymethylcellulose, polyacrylic acid, polyacrylonitrile or sodium alginate;
preferably, the single-sided surface density of the positive pole piece is not less than 8mg/cm2。
8. The preparation method of the positive electrode plate according to claim 6 or 7, characterized by comprising the following steps:
(1) mixing a conductive agent and a dispersing agent to obtain a conductive agent dispersion liquid;
(2) mixing the conductive dispersion liquid obtained in the step (1) with a binder to obtain conductive slurry;
(3) mixing the conductive paste obtained in the step (2) with the vulcanized polymer composite material as described in claim 5, and performing defoaming treatment to obtain a positive electrode paste;
(4) and (4) coating the positive electrode slurry obtained in the step (3) on a current collector to obtain the positive electrode piece.
9. The method according to claim 8, wherein the mixing in step (1), step (2) and step (3) is carried out under stirring;
preferably, the mixing of step (1), step (2) and step (3) is carried out under dispersive conditions;
preferably, the mixing in the step (1) is carried out under the dispersion condition with the rotating speed of 1000-2000 rpm;
preferably, the mixing in the step (1) is carried out under the stirring condition with the rotating speed of 10-20 rpm;
preferably, the mixing time in the step (1) is 30-120 min;
preferably, the mixing in the step (2) is carried out under the dispersion condition that the rotating speed is 500-2000 rpm;
preferably, the mixing in the step (2) is carried out under the stirring condition with the rotating speed of 10-50 rpm;
preferably, the mixing time in the step (2) is 30-120 min;
preferably, the mixing in the step (3) is carried out under the stirring condition with the rotating speed of 10-70 rpm;
preferably, the mixing in the step (3) is carried out under the dispersion condition that the rotating speed is 500-2500 rpm;
preferably, the mixing time in the step (3) is 0.5-10 h;
preferably, the viscosity of the positive electrode slurry in the step (3) is 1000-5000 mpas;
preferably, the step (3) further comprises a sieving treatment step after the defoaming treatment;
preferably, the screen for sieving treatment is a 100-200 mesh screen;
preferably, the step (4) further comprises a step of baking after the coating is finished;
preferably, the baking temperature is 60-120 ℃.
10. A lithium-sulfur battery, characterized in that it comprises a positive electrode sheet according to claim 6 or 7.
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| CN104241612A (en) * | 2013-06-14 | 2014-12-24 | 中国科学院大连化学物理研究所 | Sulphidepolymer coated sulfur / carbon composite material and preparation method thereof |
| CN105789561A (en) * | 2014-12-16 | 2016-07-20 | 中国科学院大连化学物理研究所 | Vulcanized-polymer-coated sulfur/carbon composite material and preparation method thereof |
| CN106920937A (en) * | 2017-03-30 | 2017-07-04 | 青岛亨迈新能源有限公司 | A kind of preparation method of electrode composite material |
| CN107275580A (en) * | 2017-07-10 | 2017-10-20 | 华南理工大学 | A kind of long circulation life height ratio capacity lithium sulfur battery anode material and lithium-sulphur cell positive electrode and its preparation |
| CN108666540A (en) * | 2018-04-02 | 2018-10-16 | 中南大学 | A kind of carbon coating curing nickel material and preparation method thereof and as anode material of lithium-ion battery application |
| CN109256554A (en) * | 2018-09-28 | 2019-01-22 | 河南科技学院 | A kind of sulfide polymer composite material and preparation method and application |
| CN110148739A (en) * | 2019-06-17 | 2019-08-20 | 中南大学 | A kind of carbon@allyl sulfides itrile group polymer composite anode active material, anode and its preparation and the application in lithium-sulfur cell |
| CN112194182A (en) * | 2020-10-09 | 2021-01-08 | 哈尔滨工业大学 | Preparation method of chromium oxide lithium ion battery anode material containing lithiated vulcanized polyacrylonitrile |
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| CN113903920A (en) * | 2021-10-08 | 2022-01-07 | 惠州亿纬锂能股份有限公司 | Preparation method of lithium-sulfur battery slurry, slurry prepared by preparation method and pole piece |
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