CN114024019A - Preparation method and application of all-solid-state battery cell - Google Patents
Preparation method and application of all-solid-state battery cell Download PDFInfo
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- CN114024019A CN114024019A CN202111272957.8A CN202111272957A CN114024019A CN 114024019 A CN114024019 A CN 114024019A CN 202111272957 A CN202111272957 A CN 202111272957A CN 114024019 A CN114024019 A CN 114024019A
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- 239000002861 polymer material Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 59
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 18
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 9
- 229910000921 lithium phosphorous sulfides (LPS) Inorganic materials 0.000 claims description 9
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 claims description 8
- 229920002223 polystyrene Polymers 0.000 claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 229920001684 low density polyethylene Polymers 0.000 claims description 6
- 239000004702 low-density polyethylene Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229910003405 Li10GeP2S12 Inorganic materials 0.000 claims description 5
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 5
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 5
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 5
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 5
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 5
- 229910021382 natural graphite Inorganic materials 0.000 claims description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 5
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 229920006324 polyoxymethylene Polymers 0.000 claims description 4
- 229920002292 Nylon 6 Polymers 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 3
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- 238000005266 casting Methods 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- 229920001903 high density polyethylene Polymers 0.000 claims description 3
- 239000004700 high-density polyethylene Substances 0.000 claims description 3
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- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
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- 239000002245 particle Substances 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 27
- 230000014759 maintenance of location Effects 0.000 description 26
- 229910052782 aluminium Inorganic materials 0.000 description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 20
- 239000011889 copper foil Substances 0.000 description 20
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- 238000007796 conventional method Methods 0.000 description 13
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- 239000007774 positive electrode material Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
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- 239000007784 solid electrolyte Substances 0.000 description 10
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 9
- 239000013543 active substance Substances 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 239000007773 negative electrode material Substances 0.000 description 6
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- 238000004806 packaging method and process Methods 0.000 description 5
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- 230000009286 beneficial effect Effects 0.000 description 2
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- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
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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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/121—Organic material
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a preparation method and application of an all-solid-state battery cell, wherein the preparation method comprises the following steps: and placing the initial cell in a mold, pouring a molten polymer material on the outer side of the initial cell, and cooling to obtain the cell with the surface coated with the polymer material. The polymer in the molten state is cooled and solidified at room temperature, and after the material is cooled and shrunk, the battery core is encapsulated to form the battery with internal pressure, so that the contact capacity among particles is effectively enhanced, the particle expansion generated in circulation is inhibited, meanwhile, the polymer layer can be utilized, the side effect of air and moisture on the battery core is reduced, and the circulation life of the battery is prolonged.
Description
Technical Field
The invention belongs to the field of new energy batteries, and relates to a preparation method and application of an all-solid-state battery
Background
The traditional fuel oil automobile consumes a large amount of petroleum resources, so the development of new energy automobiles is a necessary way for the development of the automobile industry. The new energy automobile comprises three main components: the system comprises a motor, an electric controller and a battery, wherein the performance of the battery has important influence on the industrialization of the new energy automobile. In recent years, batteries have become an energy storage medium for new energy sources, and have become industrially important as a power source for portable electronic devices. Lithium ion batteries have high energy density and high power density, and are generally considered to be the most ideal portable power source. The traditional liquid lithium ion battery contains a large amount of combustible electrolyte and has potential safety hazard problems. In order to further improve the safety of lithium ion batteries, all-solid-state lithium batteries have been actively developed. The all-solid-state lithium battery can effectively solve the problem of battery safety, and meanwhile, the all-solid-state lithium battery brings a prospect for improving the energy density of the battery by using a metal lithium cathode. Whether conventional lithium ion batteries or new system batteries (such as lithium sulfur batteries and all solid state lithium batteries), there are problems with material particle expansion and insufficient material contact capacity during cycling. Many studies have been made by scientists on how to solve this problem.
CN209401779U discloses processingequipment of coiling formula electricity core, through setting up end plate and book needle, makes the leptoprosopy of electricity core extrude with the end plate when the hot pressing to improve the compactness of electricity core leptoprosopy, reduced the clearance between the negative and positive pole piece of electricity core leptoprosopy department, reduced the internal resistance of battery, improved the capacity of battery, simultaneously, can also reduce the cracked risk of pole piece. However, the structure of the battery core is complex, the assembly process is troublesome, and the battery core is not suitable for large-scale production.
CN209388893U discloses a high-reliability internal-string type cylindrical super capacitor, including electric core, utmost point post and peripheral packaging structure, the electric core periphery is poured and is had sealing resin. But the pouring sealing resin can only play a role in sealing, the compaction of the internal structure of the battery cell cannot play a role in beneficial effect, and the problems of expansion of material particles and insufficient material contact capability still exist in the circulating process.
CN109585783A discloses an infiltration method of lithium ion battery pole pieces, which comprises preparing negative electrode slurry containing microcapsules into negative electrode pieces, assembling the positive electrode pieces and the negative electrode pieces into a battery cell: pressurizing the battery cell to 0.5-3 Mpa at 70-80 ℃, preserving heat and pressure for 10-20 min, vacuumizing to-90-55 Kpa, and maintaining vacuum for 10-20 min: circulating the steps of pressurizing, heat preservation and pressure maintaining, vacuumizing and vacuum maintaining for more than one time until the microcapsules are broken; standing the battery cell for 20-40 min to finish pre-infiltration; and packaging the pre-soaked battery cell, and standing for 10-14 hours to finish high-temperature soaking. Pressurization is carried out outside the electric core to increase, the inside of the electric core is easily damaged due to overlarge pressure, a pressure instrument is used, the process is complex, the cost is high, the problem of continuous pressurization of expansion after poor follow-up battery circulation is solved, the defect of insufficient material contact capacity still occurs in follow-up operation, and therefore the method for permanently pressurizing the electric core still needs to be improved.
How to effectively alleviate the problem of cycle degradation of the battery caused by expansion or deterioration of the particles, thereby improving the cycle life of the battery, is an important research direction in the field.
Disclosure of Invention
The invention aims to provide a preparation method and application of an all-solid-state battery, wherein the all-solid-state lithium battery has pressure inside and can relieve the problem of cycle degradation of the battery caused by the problem of particle expansion.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the objectives of the present invention is to provide a method for preparing an all-solid-state battery cell, wherein the method comprises: and placing the initial cell in a mold, pouring a molten polymer material on the outer side of the initial cell, and cooling to obtain the all-solid-state cell with the surface coated with the polymer material.
The polymer material coated on the surface of the all-solid-state battery cell is cooled by the molten polymer material, and the molten polymer material generates a shrinkage force after being cooled, so that the battery cell with internal pressure is formed. The structure includes: positive pole, negative pole, solid electrolyte, the polymer layer of outside parcel.
As a preferred embodiment of the present invention, the molten polymer material comprises any one or a combination of at least two of high density polyethylene, low density polyethylene, polypropylene, general purpose polystyrene, impact-resistant polystyrene, acrylonitrile-butadiene-styrene copolymer, polycarbonate, polyoxymethylene, nylon 6, polyhexamethylene adipamide, polyvinyl chloride, thermoplastic polyurethane elastomer, polymethyl methacrylate, or polybutylene terephthalate, wherein typical but non-limiting examples of the combination are: a combination of high density polyethylene and low density polyethylene, a combination of polypropylene and general purpose grade polystyrene, a combination of impact grade polystyrene and acrylonitrile-butadiene-styrene copolymer, a combination of polycarbonate and polyoxymethylene, a combination of nylon 6 and polyhexamethylene adipamide, a combination of polyvinyl chloride and a thermoplastic polyurethane elastomer, a combination of polymethyl methacrylate and polyoxymethylene, or a combination of polybutylene terephthalate and low density polyethylene, and the like.
In a preferred embodiment of the present invention, the temperature of the molten polymer material is 125 to 280 ℃, and the temperature may be 125 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃ or 280 ℃, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable.
In a preferred embodiment of the present invention, the temperature at which the molten polymer material is cooled is 18 to 30 ℃, and the temperature may be 18 ℃, 19 ℃, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, or 30 ℃, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
In a preferred embodiment of the present invention, the thickness of the molten polymer material after cooling is 1 to 10mm, and the thickness may be 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm, or 10mm, but the present invention is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
In a preferred embodiment of the present invention, the casting is performed under a vacuum degree of-0.1 to-0.05 MPa, wherein the vacuum degree may be-0.1 MPa, -0.08MPa, -0.06MPa, or-0.05 MPa, but the present invention is not limited to the above values, and other values not listed in the above range are also applicable.
The second purpose of the invention is to provide an all-solid-state battery cell, which is prepared by the preparation method of the all-solid-state battery cell of the first purpose, and comprises a positive pole piece, a solid electrolyte and a negative pole piece.
Preferably, the material of the positive electrode plate comprises any one or a combination of at least two of a carbon-sulfur composite positive electrode, lithium cobaltate, lithium nickel cobalt manganese oxide or lithium iron phosphate, and the combination is typically but not limited to: a combination of lithium iron phosphate and lithium cobaltate, a combination of lithium cobaltate and lithium nickel cobalt manganese oxide, a combination of lithium nickel cobalt manganese oxide and lithium iron phosphate, and the like.
Preferably, the material of the negative electrode plate comprises any one or a combination of at least two of artificial graphite, natural graphite, silicon carbon or metallic lithium, wherein the combination is typically but not limited to: a combination of artificial graphite and natural graphite, a combination of natural graphite and silicon carbon, a combination of silicon carbon and metallic lithium, a combination of natural graphite and metallic lithium, or the like.
As a preferable embodiment of the present invention, the solid electrolyte includes a sulfide solid electrolyte.
Preferably, the sulfide solid state electrolyte comprises Li10GeP2S12、Li3PS4Or Li6PS5Any one or a combination of at least two of Cl, wherein typical but non-limiting examples of such combinations are: li10GeP2S12And Li3PS4Combination of (1), Li3PS4And Li6PS5Combinations of Cl or Li10GeP2S12And Li3PS4And Li6PS5Combinations of Cl, and the like.
The third object of the present invention is to provide an application of the all-solid-state battery cell according to the second object, wherein the all-solid-state battery cell is applied to the field of lithium ion batteries.
Compared with the prior art, the invention has the following beneficial effects:
the packaging structure of the all-solid-state battery prepared by the invention effectively enhances the contact capacity between particles and inhibits the expansion of the particles generated in circulation, and meanwhile, the polymer layer is utilized to reduce the side effects of air and moisture on the battery core, so that the circulation life of the battery is prolonged, and the commercialization of the lithium battery is possible. The lithium battery with the internally pressurized packaging structure has high capacity retention rate, and the capacity retention rate can reach more than 76% after the 0.1C charge-discharge cycle test is carried out at 25 ℃, so that the capacity retention rate is obviously improved compared with the lithium battery without the packaging structure.
Drawings
Fig. 1 is a structural view of an all solid-state lithium battery in examples 1 to 5 of the present invention.
Fig. 2 is a graph showing capacity retention rates for 80 cycles before the all solid-state lithium batteries in example 1 of the present invention and comparative example 1.
Fig. 3 is a graph showing capacity retention rates for the first 70 cycles of the all solid-state lithium batteries in example 2 of the present invention and comparative example 2.
Fig. 4 is a graph showing capacity retention rates for 90 cycles before the all solid-state lithium batteries in example 3 and comparative example 3 according to the present invention.
Fig. 5 is a graph showing capacity retention rates for the first 50 cycles of the all solid-state lithium batteries in example 4 of the present invention and comparative example 4.
Fig. 6 is a graph showing capacity retention ratios for the first 40 cycles of the all solid-state lithium batteries in example 5 of the present invention and comparative example 5.
In the figure: 1-positive electrode; 2-a solid electrolyte; 3-a negative electrode; 4-a battery case; 5-a layer of polymer material.
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
The embodiment provides a preparation method of an all-solid-state lithium battery, which comprises the following steps:
selecting aluminum foil as a positive electrode current collector and lithium cobaltate as a positive electrode active substance, and uniformly coating the aluminum foil on the positive electrode active substance to prepare a positive electrode 1, namely a sulfide Li6PS5Cl is coated as the solid electrolyte 2 on the surface of the positive electrode material containing lithium cobaltate. The copper foil was selected as a negative current collector, and graphite was selected as a negative active material, which was uniformly coated on the copper foil to prepare a negative electrode 3.
Cutting the positive electrode and the negative electrode into preset sizes according to a conventional method, stacking the materials, putting the materials into a battery case 4 of an injection mold, heating impact-resistant polystyrene to 240 ℃, enabling the impact-resistant polystyrene to be in a molten state, pouring the battery cell under the vacuum degree of-0.1 MPa, and naturally cooling at room temperature to obtain the polymer material layer 5 with the thickness of 10 mm. And placing the pole group into a battery shell for edge sealing, and obtaining the all-solid-state lithium battery. The structure of the all-solid-state lithium battery is shown in fig. 1.
Example 2
The embodiment provides a preparation method of an all-solid-state lithium battery, which comprises the following steps:
selecting aluminum foil as a positive electrode current collector and nickel cobalt lithium manganate as a positive electrode active substance, and uniformly coating the positive electrode current collector and the nickel cobalt lithium manganate on the aluminum foil to prepare a positive electrode 1, namely a sulfide Li6PS5Cl is coated on the surface of the nickel cobalt lithium manganate-containing positive electrode material as the solid electrolyte 2. The copper foil is selected as a negative current collector, silicon carbon is selected as a negative active material, and the copper foil is uniformly coated on the copper foil to prepare a negative electrode 3.
Cutting the positive electrode and the negative electrode into preset sizes according to a conventional method, stacking the materials, putting the materials into a battery shell 4 of an injection mold, heating the acrylonitrile-butadiene-styrene copolymer to 170 ℃ to enable the acrylonitrile-butadiene-styrene copolymer to be in a molten state, pouring the battery cell under the vacuum degree of-0.1 MPa, and naturally cooling at room temperature to obtain the thickness of the polymer material layer 5 of 1 mm. And placing the pole group into a battery shell for edge sealing, and obtaining the all-solid-state lithium battery. The structure of the all-solid-state lithium battery is shown in fig. 1.
Example 3
The embodiment provides a preparation method of an all-solid-state lithium battery, which comprises the following steps:
selecting aluminum foil as a positive current collector and lithium iron phosphate as a positive active material, and uniformly coating the aluminum foil on the positive active material to prepare the positive electrode 1, namely the sulfide Li10GeP2S12As a solid electrolyte 2, is coated on the surface of the lithium iron phosphate-containing positive electrode material. The copper foil was selected as a negative current collector, and graphite was selected as a negative active material, which was uniformly coated on the copper foil to prepare a negative electrode 3.
Cutting the anode and the cathode into preset sizes according to a conventional method, stacking and placing the anode and the cathode into a battery shell 4 of an injection mold, cutting the anode and the cathode into the preset sizes according to the conventional method, stacking and placing the anode and the cathode into the injection mold, heating polyhexamethylene adipamide to 280 ℃ to enable the polyhexamethylene adipamide to be in a molten state, casting the battery cell under the vacuum degree of-0.1 MPa, and naturally cooling at room temperature to obtain the thickness of the polymer material layer 5 of 2 mm. And placing the pole group into a battery shell for edge sealing, and obtaining the all-solid-state lithium battery. The structure of the all-solid-state lithium battery is shown in fig. 1.
Example 4
The embodiment provides a preparation method of an all-solid-state lithium battery, which comprises the following steps:
selecting aluminum foil as a positive electrode current collector and nickel cobalt lithium manganate as a positive electrode active substance, and uniformly coating the positive electrode current collector and the nickel cobalt lithium manganate on the aluminum foil to prepare a positive electrode 1, namely a sulfide Li3PS4As a solid electrolyte 2, is coated on the surface of the lithium nickel cobalt manganese oxide-containing positive electrode material. The lithium metal was rolled on the copper foil to form a negative electrode 3.
Cutting the anode and the cathode into preset sizes according to a conventional method, stacking and placing the anode and the cathode into a battery shell 4 of an injection mold, cutting the anode and the cathode into the preset sizes according to the conventional method, stacking and placing the anode and the cathode into the injection mold, heating polybutylene terephthalate to 230 ℃ to enable the polybutylene terephthalate to be in a molten state, pouring a battery cell under the vacuum degree of-0.1 MPa, and naturally cooling at room temperature to obtain a polymer material layer 5 with the thickness of 5 mm. And placing the pole group into a battery shell for edge sealing, and obtaining the all-solid-state lithium battery. The structure of the all-solid-state lithium battery is shown in fig. 1.
Example 5
The embodiment provides a preparation method of an all-solid-state lithium battery, which comprises the following steps:
selecting aluminum foil as a positive electrode current collector and carbon-sulfur compound as a positive electrode active substance, and uniformly coating the positive electrode current collector and the carbon-sulfur compound on the aluminum foil to prepare a positive electrode 1, namely a sulfide Li3PS4As a solid electrolyte 2, is coated on the surface of the positive electrode material containing the carbon-sulfur composite. The lithium metal was rolled on the copper foil to form a negative electrode 3.
Cutting the anode and the cathode into preset sizes according to a conventional method, stacking and placing the anode and the cathode into a battery shell 4 of an injection mold, cutting the anode and the cathode into the preset sizes according to the conventional method, stacking and placing the anode and the cathode into the injection mold, heating low-density polyethylene to 125 ℃ to enable the low-density polyethylene to be in a molten state, pouring a battery cell under the vacuum degree of-0.1 MPa, and naturally cooling at room temperature to obtain a polymer material layer 5 with the thickness of 7 mm. And placing the pole group into a battery shell for edge sealing, and obtaining the all-solid-state lithium battery. The structure of the all-solid-state lithium battery is shown in fig. 1.
Comparative example 1
The present comparative example provides a method of preparing an all-solid-state lithium battery:
selecting aluminum foil as a positive electrode current collector, lithium cobaltate as a positive electrode active substance, uniformly coating the aluminum foil with the lithium cobaltate to prepare a positive electrode, and preparing a sulfide Li6PS5Cl is coated as a solid electrolyte on the surface of the lithium cobaltate-containing positive electrode material. The copper foil is selected as a negative current collector, the graphite is selected as a negative active material, and the copper foil is uniformly coated on the copper foil to prepare the negative electrode.
And cutting the positive electrode and the negative electrode into preset sizes by a conventional method, laminating, placing into an aluminum plastic shell, and sealing edges under-0.1 Mpa to obtain the all-solid-state lithium battery. The capacity retention rate is 60.10 percent after 80 times of circulation. The capacity retention rates of example 1 and comparative example 1 at the first 80 cycles are shown in fig. 2.
Comparative example 2
The present comparative example provides a method of preparing an all-solid-state lithium battery:
selecting aluminum foil as a positive current collector and nickel cobalt lithium manganate as a positive electrodeUniformly coating the aluminum foil with the electrolyte solution, and preparing a sulfide solid electrolyte Li6PS5Cl is coated on the surface of the nickel cobalt lithium manganate-containing positive electrode material. Copper foil is selected as a negative current collector, silicon carbon is selected as a negative active material, and the copper foil is uniformly coated on the copper foil.
And cutting the positive electrode and the negative electrode into preset sizes by a conventional method, laminating, placing into an aluminum plastic shell, and sealing edges under-0.1 Mpa to obtain the all-solid-state lithium battery. The capacity retention rate is 62.26 percent after 70 times of circulation. The capacity retention of example 2 and comparative example 2 at the first 80 cycles is shown in fig. 3.
Comparative example 3
The present comparative example provides a method of preparing an all-solid-state lithium battery:
selecting aluminum foil as a positive current collector, lithium iron phosphate as a positive active material, uniformly coating the aluminum foil with the lithium iron phosphate, and sulfide solid electrolyte Li10GeP2S12Coated on the surface of the lithium iron phosphate-containing positive electrode material. Copper foil is selected as a negative current collector, graphite is selected as a negative active material, and the copper foil is uniformly coated on the copper foil.
And cutting the positive electrode and the negative electrode into preset sizes by a conventional method, laminating, placing into an aluminum plastic shell, and sealing edges under-0.1 Mpa to obtain the all-solid-state lithium battery. The capacity retention rate is 68.94 percent after 90 times of circulation. The capacity retention rates of the first 90 cycles of example 3 and comparative example 3 are shown in fig. 4.
Comparative example 4
The present comparative example provides a method of preparing an all-solid-state lithium battery:
selecting aluminum foil as a positive electrode current collector, nickel cobalt lithium manganate as a positive electrode active substance, uniformly coating the positive electrode current collector on the aluminum foil, and using sulfide solid electrolyte Li3PS4Is coated on the surface of the positive material containing the nickel cobalt lithium manganate. The lithium metal was rolled on the copper foil to form a negative electrode.
And cutting the positive electrode and the negative electrode into preset sizes by a conventional method, laminating, placing into an aluminum plastic shell, and sealing edges under-0.1 Mpa to obtain the all-solid-state lithium battery. The capacity retention rate is 59.9 percent after 50 times of circulation. The capacity retention rates of the first 50 cycles of example 4 and comparative example 4 are shown in fig. 5.
Comparative example 5
The present comparative example provides a method of preparing an all-solid-state lithium battery:
selecting aluminum foil as a positive electrode current collector, carbon-sulfur compound as a positive electrode active substance, uniformly coating the positive electrode current collector and the carbon-sulfur compound on the aluminum foil, and using sulfide solid electrolyte Li3PS4Coated on the surface of the carbon-sulfur composite anode material. The lithium metal was rolled on the copper foil to form a negative electrode.
And cutting the positive electrode and the negative electrode into preset sizes by a conventional method, laminating, placing into an aluminum plastic shell, and sealing edges under-0.1 Mpa to obtain the all-solid-state lithium battery. The capacity retention rate is 45.74 percent after 40 times of circulation. The capacity retention of the first 40 cycles of example 5 and comparative example 5 is shown in fig. 6.
The all-solid-state lithium batteries prepared in examples 1 to 5 and comparative examples 1 to 5 were subjected to a 0.1C charge-discharge cycle test at 25 ℃, and the number of cycles was recorded, and the capacity retention rate was calculated by dividing the discharge capacity of the last cycle of the number of cycles by the first discharge capacity.
Example 1 first discharge: 90.5mAh, discharge 80: 63.13 mAh; comparative example 1 first discharge: 89.3mAh, discharge 80: 53.67 mAh; the capacity retention rate of example 1 was 69.76% after 80 cycles.
Example 2 first discharge: 94.9mAh, discharge 70: 67.45 mAh; comparative example 2 first discharge: 95.7mAh, discharge 70: 59.58 mAh; example 2 capacity retention 71.07% for 70 cycles.
Example 3 first discharge: 87.1mAh, discharge 90: 66.32 mAh; comparative example 3 first discharge: 86.8mAh, discharge 90: 59.84 mAh; example 3 capacity retention 76.14% was cycled 90 times.
Example 4 first discharge 95.1mAh, 50 th discharge: 65.78 mAh; comparative example 4: first discharging: 94.3mAh, discharge 50: 56.49 mAh; example 4 capacity retention 69.17% after 50 cycles.
Example 5 first discharge: 125.8mAh, discharge 40: 72.27 mAh; comparative example 5: first discharging: 128.2mAh, discharge 40: 58.63 mAh; the capacity retention rate of 57.45% after 40 cycles of the example 5.
It can be observed from the drawings that the capacity retention of examples 1 to 5 is significantly higher than that of comparative examples 1 to 5. Indicating that the lithium battery having the internally pressurized package structure has a high capacity retention rate.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of an all-solid-state battery cell is characterized by comprising the following steps: and placing the initial cell in a mold, pouring a molten polymer material on the outer side of the initial cell, and cooling to obtain the all-solid-state cell with the surface coated with the polymer material.
2. The method of claim 1, wherein the molten polymer material comprises any one of high density polyethylene, low density polyethylene, polypropylene, general purpose polystyrene, impact-resistant polystyrene, acrylonitrile-butadiene-styrene copolymer, polycarbonate, polyoxymethylene, nylon 6, polyhexamethylene adipamide, polyvinyl chloride, thermoplastic polyurethane elastomer, polymethyl methacrylate, or polybutylene terephthalate, or a combination of at least two thereof.
3. The method of claim 1 or 2, wherein the temperature of the molten polymer material is 125 to 280 ℃.
4. The method according to any one of claims 1 to 3, wherein the temperature of the molten polymer material is cooled to 18 to 30 ℃.
5. The method according to any one of claims 1 to 4, wherein the molten polymer material has a thickness of 1 to 10mm after cooling.
6. The method according to any one of claims 1 to 5, wherein the vacuum degree of the casting is from-0.1 to-0.05 MPa.
7. An all-solid-state cell prepared by the method of any one of claims 1-6, comprising a positive electrode sheet, a solid-state electrolyte, and a negative electrode sheet.
8. The all-solid-state battery cell according to claim 7, wherein the material of the positive electrode sheet comprises any one of or a combination of at least two of a carbon-sulfur composite positive electrode, lithium cobaltate, lithium nickel cobalt manganese oxide or lithium iron phosphate;
preferably, the material of the negative electrode plate comprises any one or a combination of at least two of artificial graphite, natural graphite, silicon carbon or metallic lithium.
9. The all-solid state cell of claim 7 or 8, wherein the solid state electrolyte comprises a sulfide solid state electrolyte;
preferably, the sulfide solid state electrolyte comprises Li10GeP2S12、Li3PS4Or Li6PS5Any one or a combination of at least two of Cl.
10. Use of the all-solid-state cell according to any of claims 7 to 9, wherein the all-solid-state cell is used in the field of lithium ion batteries.
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