CN111969244A - Composite electrolyte membrane, solid-state battery, and method for producing same - Google Patents
Composite electrolyte membrane, solid-state battery, and method for producing same Download PDFInfo
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- CN111969244A CN111969244A CN202011030458.3A CN202011030458A CN111969244A CN 111969244 A CN111969244 A CN 111969244A CN 202011030458 A CN202011030458 A CN 202011030458A CN 111969244 A CN111969244 A CN 111969244A
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
Abstract
The invention discloses a composite electrolyte membrane, a solid-state battery and a preparation method thereof. Wherein the composite electrolyte membrane includes: a flow state electrolyte layer and a self-supporting state electrolyte layer. The mobile electrolyte layer comprises a first polymer, a solvent and a lithium salt; the self-supporting electrolyte layer includes a second polymer and a lithium salt. The flowing electrolyte layer in the composite electrolyte membrane has excellent fluidity and adhesive property, and can permeate into the pole pieces, so that the problems of insufficient contact, large contact resistance and the like between the pole pieces and the electrolyte membrane, between the active materials and the electrolyte material and between the active materials and the active material are effectively solved, and the electrical property of the solid-state battery is remarkably improved.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a composite electrolyte membrane, a solid-state battery and a preparation method thereof.
Background
Solid-state batteries refer to lithium ion batteries that employ a solid-state electrolyte. The solid electrolyte is used as the core of the solid battery and has the advantages of incombustibility, no corrosion, no volatilization, no liquid leakage, wide electrochemical window and the like, so that the solid battery has the characteristics of high safety, long service life and high energy density.
For the problems of large interface resistance, low charging voltage and the like of the existing solid-state battery, the solution proposed by the prior art is to add lithium salt, solid electrolyte material and other components in the positive and negative electrode plates to improve the interface ionic conductivity of the solid-state battery. However, these additives have large particle sizes and high densities, which seriously decrease the energy density of the battery. In addition, the added substance is also in a solid state, and the key problem of insufficient solid-solid interface cannot be solved fundamentally. Thus, the existing solid electrolyte and solid battery still remain to be improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, an object of the present invention is to propose a composite electrolyte membrane, a solid-state battery, and a method for producing the same. The flowing electrolyte layer in the composite electrolyte membrane has excellent fluidity and adhesive property, and can permeate into the pole pieces, so that the problems of insufficient contact, large contact resistance and the like between the pole pieces and the electrolyte membrane, between the active materials and the electrolyte material and between the active materials and the active material are effectively solved, and the electrical property of the solid-state battery is remarkably improved.
In one aspect of the invention, a composite electrolyte membrane is presented. According to an embodiment of the present invention, the composite electrolyte membrane includes: a mobile state electrolyte layer comprising a first polymer, a solvent and a lithium salt; a self-supporting state electrolyte layer comprising a second polymer and a lithium salt.
In the composite electrolyte membrane according to the above embodiment of the present invention, the fluid electrolyte layer is viscous, has excellent fluidity, and has high ionic conductivity and functions of an adhesive and a wetting agent. The flowing electrolyte layer can permeate into the pole piece after contacting with the pole piece, thereby effectively solving the problems of insufficient contact, large contact resistance and the like between the pole piece and the electrolyte membrane, between the active material and the electrolyte material and between the active material and the active material. On the other hand, the self-supporting electrolyte layer can provide sufficient mechanical strength for the composite electrolyte membrane to inhibit the growth of lithium dendrites. Therefore, the composite electrolyte membrane has the advantages of wide electrochemical window, high mechanical strength, low interface impedance and the like, and the electrical property of the solid-state battery can be remarkably improved by applying the composite electrolyte membrane to the solid-state battery.
In addition, the composite electrolyte membrane according to the above embodiment of the invention may also have the following additional technical features:
in some embodiments of the invention, the flowable electrolyte layer is in a gel state, a molten state, or a pre-cured state.
In some embodiments of the invention, the electrolyte layer in a self-supporting state comprises a support.
In some embodiments of the invention, the support is a nonwoven fabric, a polymer-based film, or a battery separator.
In some embodiments of the invention, the first polymer is a high oxidative decomposition potential polymer and the second polymer is a low reductive decomposition potential polymer.
In some embodiments of the invention, the first polymer is a low reductive decomposition potential polymer and the second polymer is a high oxidative decomposition potential polymer.
In some embodiments of the present invention, the high oxidative decomposition potential polymer is selected from at least one of polyacrylonitrile, polycarbonate, polythioether, polyphenylene sulfide, polytetrafluoroethylene, polyvinylidene fluoride, and the low reductive decomposition potential polymer is selected from at least one of polyethylene oxide, polyethylene glycol, polytetrahydrofuran, polytetrafluoroethylene, polyvinylidene fluoride.
In some embodiments of the present invention, the mass ratio of the first polymer to the lithium salt is (50-100): 1-50.
In some embodiments of the present invention, the mass ratio of the second polymer to the lithium salt is (50-100): 1-50.
In some embodiments of the invention, the mobile state electrolyte layer further comprises a first inorganic material, the self-supporting state electrolyte layer further comprises a second inorganic material; the first inorganic material and the second inorganic material are each independently selected from at least one of an oxide electrolyte, a halide electrolyte, a sulfide electrolyte, and inorganic nanoparticles.
In some embodiments of the invention, the oxide electrolyte is selected from at least one of LATP, LLZO, LLTO, LLZTO.
In some embodiments of the invention, the halide electrolyte is selected from Li3ErCl6、Li3YBr6、Li3YCl6、Li3InCl6、Li1.6Mg1.2Cl4、Li2.5Y0.5Zr0.5Cl6At least one of;
in some embodiments of the invention, the sulfide electrolyte is selected from Li2S-P2S5、Li6PS5Cl、Li6PS5Br、LGPS、Ag8GeS6At least one of (a).
In some embodiments of the present invention, the inorganic nanoparticles are selected from at least one of silica, alumina.
In some embodiments of the present invention, the first inorganic material is present in the flowing electrolyte layer in an amount of 1 wt% to 50 wt%.
In some embodiments of the invention, the second inorganic material is present in the self-supporting electrolyte layer in an amount of 1 wt% to 50 wt%.
In some embodiments of the invention, the mobile state electrolyte layer further comprises a first additive, the self-supporting state electrolyte layer further comprises a second additive; the first additive and the second additive are each independently selected from at least one of a flame retardant, a film former, and an oxygen radical scavenger.
In some embodiments of the present invention, the first additive is present in the mobile state electrolyte layer in an amount of 1 wt% to 10 wt%.
In some embodiments of the invention, the second additive is present in the electrolyte layer in the free-standing state in an amount of 1 wt% to 10 wt%.
In another aspect of the present invention, a solid-state battery is presented. According to an embodiment of the present invention, the solid-state battery includes: a positive electrode, a negative electrode, and the composite electrolyte membrane of the above example. Thus, the solid-state battery has all the features and advantages described above for the composite electrolyte membrane, and thus, detailed description thereof is omitted, and as a whole, the solid-state battery has excellent electrical properties.
In still another aspect of the present invention, the present invention provides a method of manufacturing the solid-state battery of the above embodiment. According to an embodiment of the invention, the method comprises: providing a positive plate and a negative plate; forming a flowing state electrolyte layer on the surface of the positive plate or the negative plate, arranging a self-supporting state electrolyte layer on the surface of the flowing state electrolyte layer, arranging the positive plate or the negative plate on the surface of the self-supporting state electrolyte layer, and packaging to obtain the solid-state battery; or forming a flowing state electrolyte layer on the surface of the self-supporting state electrolyte layer, respectively arranging a positive plate or a negative plate on the surface of the self-supporting state electrolyte layer and the surface of the flowing state electrolyte layer, and packaging to obtain the solid-state battery. Therefore, the method can simply and efficiently prepare the solid-state battery by using the composite electrolyte membrane of the embodiment, and is easy for commercial batch production of the solid-state battery.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In one aspect of the invention, a composite electrolyte membrane is presented. According to an embodiment of the present invention, the composite electrolyte membrane includes: a flow state electrolyte layer and a self-supporting state electrolyte layer. Wherein the mobile electrolyte layer comprises a first polymer, a solvent and a lithium salt; the self-supporting electrolyte layer includes a second polymer and a lithium salt.
The composite electrolyte membrane according to the embodiment of the invention is further described in detail below.
According to some embodiments of the present invention, the flowable electrolyte layer may be in a gel state, a molten state, or a pre-cured state.
It should be noted that, in the composite electrolyte membrane of the present invention, the self-supporting electrolyte layer may be prepared by tape casting using a material suitable for forming the self-supporting electrolyte layer, so as to obtain a membrane layer having a certain mechanical strength. In addition, according to some embodiments of the present invention, the self-supporting electrolyte layer may include a support. That is, the mechanical strength of the film layer can be further improved by providing a support in the film layer.
The support may be a film having continuous pores and having a certain mechanical strength, for example, according to some embodiments of the present invention, the support may be a film having continuous pores, such as a non-woven fabric, a polymer-based film, a battery separator, and the like. By using the above materials as the support of the self-supporting electrolyte layer, the electrical properties of the composite electrolyte membrane are not excessively affected, and the mechanical properties of the self-supporting electrolyte layer can be further improved.
According to some embodiments of the invention, the first polymer is a high oxidative decomposition potential polymer and the second polymer is a low reductive decomposition potential polymer; alternatively, the first polymer is a low reductive decomposition potential polymer and the second polymer is a high oxidative decomposition potential polymer. The inventors have found that it is possible to further contribute to widening the electrochemical window of the composite electrolyte membrane by employing polymers of different properties for the flow state electrolyte layer and the self-supporting state electrolyte layer forming the composite electrolyte membrane, respectively. It is understood that, in the composite electrolyte membrane of the present invention, the membrane layer formed of the high oxidative decomposition potential polymer may be either a flow state electrolyte layer or a self-supporting state electrolyte layer; the film layer formed by the low reduction decomposition potential polymer can be a flow state electrolyte layer or a self-supporting state electrolyte layer. Preferably, the second polymer employs a low reductive decomposition potential polymer, that is, the polymer in the self-supporting state electrolyte layer employs a low reductive decomposition potential polymer, and in the solid-state battery, the self-supporting state electrolyte layer is in contact with the battery negative electrode. Therefore, the compatibility of the composite electrolyte membrane and the negative electrode can be further improved, the electrochemical window can be further widened, and the electrical property of the solid-state battery can be improved.
According to some embodiments of the present invention, the high oxidative decomposition potential polymer is at least one selected from polyacrylonitrile, polycarbonate, polythioether, polyphenylene sulfide, polytetrafluoroethylene and polyvinylidene fluoride, and the low reductive decomposition potential polymer is at least one selected from polyethylene oxide, polyethylene glycol, polytetrahydrofuran, polytetrafluoroethylene and polyvinylidene fluoride. Therefore, the composite electrolyte membrane can better improve the electrical performance of the solid-state battery.
According to some embodiments of the present invention, the mass ratio of the first polymer to the lithium salt may be (50-100): 1-50. Specifically, the mass fraction of the first polymer may be 50, 60, 70, 80, 90, 100, etc., and the weight fraction of the lithium salt may be 1, 2, 5, 8, 10, 20, 30, 40, 50, etc. The inventors have found that by controlling the ratio of the first polymer to the lithium salt within the above range, the stability of the contact surface between the composite electrolyte membrane and the electrode can be further improved, and the impedance can be reduced. If the amount of the first polymer is too high, the interface on the negative electrode side is unstable and the impedance continues to increase; if the amount of the first polymer used is too low, the positive electrode side becomes unstable, and the charging voltage is difficult to increase.
According to some embodiments of the present invention, the mass ratio of the second polymer to the lithium salt may be (50-100): 1-50. Specifically, the mass fraction of the second polymer may be 50, 60, 70, 80, 90, 100, etc., and the weight fraction of the lithium salt may be 1, 2, 5, 8, 10, 20, 30, 40, 50, etc. The inventors have found that by controlling the ratio of the second polymer to the lithium salt within the above range, the stability of the contact surface with the electrode can be improved while ensuring sufficient conductivity of the composite electrolyte membrane. If the amount of the second polymer is too high, the conductivity is insufficient; if the amount of the second polymer used is too low, the interface on the negative electrode side becomes unstable and the impedance continues to increase.
According to some embodiments of the present invention, the mobile state electrolyte layer further comprises a first inorganic material, and the self-supporting state electrolyte layer further comprises a second inorganic material; the first inorganic material and the second inorganic material are each independently selected from at least one of an oxide electrolyte, a halide electrolyte, a sulfide electrolyte, and inorganic nanoparticles. Thereby, the conductivity and electrochemical stability of the composite electrolyte can be further improved.
According to some embodiments of the present invention, the oxide electrolyte may be selected from at least one of LATP, LLZO, LLTO, and LLZTO. The halide electrolyte may be selected from Li3ErCl6、Li3YBr6、Li3YCl6、Li3InCl6、Li1.6Mg1.2Cl4、Li2.5Y0.5Zr0.5Cl6At least one of (a). The sulfide electrolyte may be selected from Li2S-P2S5、Li6PS5Cl、Li6PS5Br、LGPS、Ag8GeS6At least one of (a).
According to some embodiments of the present invention, the content of the first inorganic material in the flowing dynamic electrolyte layer may be 1 wt% to 50 wt%, for example, 1 wt%, 2 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, etc. The inventors found that if the content of the first inorganic material is too low, the conductivity is low; if the content of the first inorganic material is too high, the obtained film has poor toughness and is not resistant to cell expansion.
According to some embodiments of the present invention, the content of the above-mentioned second inorganic material in the self-supporting electrolyte layer may be 1 wt% to 50 wt%, for example, 1 wt%, 2 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, etc. The inventors found that if the content of the second inorganic material is too low, the conductivity is low; if the content of the second inorganic material is too high, the toughness of the resulting film is poor and the battery expansion is not resisted.
According to some embodiments of the invention, the mobile state electrolyte layer further comprises a first additive, and the self-supporting state electrolyte layer further comprises a second additive; the first additive and the second additive are each independently selected from at least one of a flame retardant, a film former, and an oxygen radical scavenger. Therefore, the interface stability of the solid electrolyte and the positive and negative electrode plates can be further improved.
According to some embodiments of the present invention, the content of the above-mentioned first additive in the flow dynamic electrolyte layer may be 1 wt% to 10 wt%, for example, 1 wt%, 2 wt%, 5 wt%, 8 wt%, 10 wt%, etc. The inventors found that if the content of the first additive is excessively low, the battery cycle performance is poor; if the content of the first additive is too high, the conductivity of the electrolyte membrane is affected.
According to some embodiments of the present invention, the content of the above-mentioned second additive in the self-supporting electrolyte layer may be 1 wt% to 10 wt%, for example, 1 wt%, 2 wt%, 5 wt%, 8 wt%, 10 wt%, etc. The inventors found that if the content of the second additive is excessively low, the battery cycle performance is poor; if the content of the second additive is too high, the conductivity of the electrolyte membrane is affected.
In another aspect of the present invention, a solid-state battery is presented. According to an embodiment of the present invention, the solid-state battery includes: a positive electrode, a negative electrode, and the composite electrolyte membrane of the above example. Thus, the solid-state battery has all the features and advantages described above for the composite electrolyte membrane, and thus, detailed description thereof is omitted, and as a whole, the solid-state battery has excellent electrical properties.
According to some embodiments of the present invention, in the composite electrolyte membrane of the present invention, the specific kinds of lithium salts and solvents are not particularly limited, and lithium salts and solvents commonly used in the art may be used.
In still another aspect of the present invention, the present invention provides a method of manufacturing the solid-state battery of the above embodiment. According to an embodiment of the invention, the method comprises:
providing a positive plate and a negative plate;
forming a flowing state electrolyte layer on the surface of the positive plate or the negative plate, arranging a self-supporting state electrolyte layer on the surface of the flowing state electrolyte layer, arranging the positive plate or the negative plate on the surface of the self-supporting state electrolyte layer, and packaging to obtain the solid-state battery;
or forming a flowing state electrolyte layer on the surface of the self-supporting state electrolyte layer, respectively arranging a positive plate or a negative plate on the surface of the self-supporting state electrolyte layer and the surface of the flowing state electrolyte layer, and packaging to obtain the solid-state battery.
Therefore, the method can simply and efficiently prepare the solid-state battery by using the composite electrolyte membrane of the embodiment, and is easy for commercial batch production of the solid-state battery.
In addition, it should be noted that all the features and advantages described above for the composite electrolyte membrane and the solid-state battery are also applicable to the method for manufacturing the solid-state battery, and are not described in detail herein.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
(1) Preparing positive and negative pole pieces:
adding 3% of PVDF (polyvinylidene fluoride) binder into a stirrer, adding a proper amount of NMP (N-methyl pyrrolidone) as an organic solvent, stirring, sequentially adding 2% of SP (conductive agent) and 88% of ternary cathode material, stirring for 4 hours to prepare cathode slurry, preparing a cathode plate by extrusion coating, drying at 120 ℃, and rolling to obtain the cathode plate; the negative pole piece adopts metal lithium foil.
(2) Preparing a self-supporting electrolyte layer:
adding 20% of LiTFSI into acetonitrile, fully stirring and dissolving, adding 15% of LLZTO, dispersing by using ultrasonic waves, slowly adding 65% of polyoxyethylene, and stirring at 1200r/min for 2h to obtain composite electrolyte slurry with the solid content of 15%; and then pouring a film on the non-woven fabric, and heating and drying at 60 ℃ for 24h to obtain the self-supporting electrolyte layer.
(3) Preparation of composite electrolyte slurry for forming a fluidized electrolyte layer
Adding 20% of LiTFSI into polycarbonate, fully stirring and dissolving, adding 15% of LATP, dispersing by using ultrasonic, slowly adding 65% of polyacrylonitrile, and stirring at 1200r/min for 2h to obtain the composite electrolyte slurry for forming the flowing electrolyte layer, wherein the solid content of the composite electrolyte slurry is 10%.
(4) Assembled solid-state battery
Placing the positive pole piece into a mold, coating the composite electrolyte slurry prepared in the step (3) on the surface of the positive pole piece, heating and drying at 60 ℃ in vacuum for 12 hours, sequentially arranging a self-supporting electrolyte layer and a negative pole piece on a formed electrolyte layer to obtain a solid-state battery precursor, carrying out vacuum packaging on the assembled solid-state battery precursor at 150-180 ℃, and carrying out hot cold pressing at 25-80 ℃ and 0.2-0.6 MPa for 3-10 min to obtain the solid-state battery.
Example 2
(1) Preparing positive and negative pole pieces:
adding 3% of PVDF (polyvinylidene fluoride) binder into a stirrer, adding a proper amount of NMP (N-methyl pyrrolidone) as an organic solvent, stirring, sequentially adding 2% of SP (conductive agent) and 88% of ternary cathode material, stirring for 4 hours to obtain cathode slurry, applying the cathode slurry on the surface of a current collector by extrusion coating, drying at 120 ℃, and rolling to obtain a cathode plate; adding 3% of PVDF (polyvinylidene fluoride) binder into a stirrer, adding a proper amount of NMP (N-methyl pyrrolidone) as an organic solvent, stirring, sequentially adding 2% of SP (conductive agent) and 88% of artificial graphite, stirring for 4 hours to obtain a negative electrode slurry, applying the negative electrode slurry on the surface of a current collector by extrusion coating, drying at 120 ℃, and rolling to obtain a negative electrode piece.
(2) Preparing a self-supporting electrolyte layer:
adding 20% of LiTFSI into acetonitrile, fully stirring and dissolving, adding 15% of LLZTO, dispersing by using ultrasonic waves, slowly adding 65% of polyoxyethylene, and stirring at 1200r/min for 2h to obtain composite electrolyte slurry with the solid content of 15%; and then pouring a film on the non-woven fabric, and heating and drying at 60 ℃ for 24h to obtain the self-supporting electrolyte layer.
(3) Preparation of composite electrolyte slurry for forming a fluidized electrolyte layer
Adding 20% of LiTFSI into polycarbonate, fully stirring and dissolving, adding 15% of LATP, dispersing by using ultrasonic, slowly adding 65% of polyacrylonitrile, and stirring at 1200r/min for 2h to obtain the composite electrolyte slurry for forming the flowing electrolyte layer, wherein the solid content of the composite electrolyte slurry is 10%.
(4) Assembled solid-state battery
Placing the positive pole piece into a mold, coating the composite electrolyte slurry prepared in the step (3) on the surface of the positive pole piece, heating and drying at 60 ℃ in vacuum for 12 hours, sequentially arranging a self-supporting electrolyte layer and a negative pole piece on a formed electrolyte layer to obtain a solid-state battery precursor, carrying out vacuum packaging on the assembled solid-state battery precursor at 150-180 ℃, and carrying out hot cold pressing at 25-80 ℃ and 0.2-0.6 MPa for 3-10 min to obtain the solid-state battery.
Example 3
(1) Preparing positive and negative pole pieces:
adding 3% of PVDF (polyvinylidene fluoride) binder into a stirrer, adding a proper amount of NMP (N-methyl pyrrolidone) as an organic solvent, stirring, sequentially adding 2% of SP (conductive agent) and 88% of ternary cathode material, stirring for 4 hours to obtain cathode slurry, applying the cathode slurry on the surface of a current collector by extrusion coating, drying at 120 ℃, and rolling to obtain a cathode plate; adding 3% of PVDF (polyvinylidene fluoride) binder into a stirrer, adding a proper amount of NMP (N-methyl pyrrolidone) as an organic solvent, stirring, sequentially adding 2% of SP (conductive agent) and 88% of artificial graphite, stirring for 4 hours to obtain a negative electrode slurry, applying the negative electrode slurry on the surface of a current collector by extrusion coating, drying at 120 ℃, and rolling to obtain a negative electrode piece.
(2) Preparing a self-supporting electrolyte layer:
adding 20% LiTFSI into DMF, fully stirring and dissolving, adding 10% LATP, dispersing by using ultrasonic, slowly adding 65% polyacrylonitrile, and stirring at 1200r/min for 2h to obtain composite electrolyte slurry with the solid content of 15%; and then pouring a film on the non-woven fabric, and heating and drying at 60 ℃ for 24h to obtain the self-supporting electrolyte layer.
(3) Preparation of composite electrolyte slurry for forming a fluidized electrolyte layer
Adding 20% of LiTFSI into ethyl acetate, fully stirring and dissolving, adding 15% of LLZO, dispersing by using ultrasonic waves, slowly adding 65% of polyethylene oxide, and stirring at 1200r/min for 2 hours to obtain the composite electrolyte slurry for forming the flowing electrolyte layer, wherein the solid content of the composite electrolyte slurry is 10%.
(4) Assembled solid-state battery
And (3) placing a negative pole piece into a mold, coating the composite electrolyte slurry prepared in the step (3) on the surface of the negative pole piece, heating and drying at 60 ℃ in vacuum for 12 hours, sequentially arranging a self-supporting electrolyte layer and a positive pole piece on a formed electrolyte layer to obtain a solid-state battery precursor, carrying out vacuum packaging on the assembled solid-state battery precursor at 150-180 ℃, and carrying out hot cold pressing at 25-80 ℃ and 0.2-0.6 MPa for 3-10 min to obtain the solid-state battery.
Example 4
(1) Preparing positive and negative pole pieces:
adding 3% of PVDF (polyvinylidene fluoride) binder into a stirrer, adding a proper amount of NMP (N-methyl pyrrolidone) as an organic solvent, stirring, sequentially adding 2% of SP (conductive agent) and 88% of ternary cathode material, stirring for 4 hours to prepare cathode slurry, preparing a cathode plate by extrusion coating, drying at 120 ℃, and rolling to obtain the cathode plate; the negative pole piece adopts metal lithium foil.
(2) Preparing a self-supporting electrolyte layer:
adding 20% LiTFSI into DMF, fully stirring and dissolving, adding 10% LATP, dispersing by using ultrasonic, slowly adding 65% polyacrylonitrile, and stirring at 1200r/min for 2h to obtain composite electrolyte slurry with the solid content of 15%; and then pouring a film on the non-woven fabric, and heating and drying at 60 ℃ for 24h to obtain the self-supporting electrolyte layer.
(3) Preparation of composite electrolyte slurry for forming a fluidized electrolyte layer
Adding 20% of LiTFSI into ethyl acetate, fully stirring and dissolving, adding 15% of LLZO, dispersing by using ultrasonic waves, slowly adding 65% of polyethylene oxide, and stirring at 1200r/min for 2 hours to obtain the composite electrolyte slurry for forming the flowing electrolyte layer, wherein the solid content of the composite electrolyte slurry is 10%.
(4) Assembled solid-state battery
And (3) placing a negative pole piece into a mold, coating the composite electrolyte slurry prepared in the step (3) on the surface of the negative pole piece, heating and drying at 60 ℃ in vacuum for 12 hours, sequentially arranging a self-supporting electrolyte layer and a positive pole piece on a formed electrolyte layer to obtain a solid-state battery precursor, carrying out vacuum packaging on the assembled solid-state battery precursor at 150-180 ℃, and carrying out hot cold pressing at 25-80 ℃ and 0.2-0.6 MPa for 3-10 min to obtain the solid-state battery.
Comparative example 1
(1) Preparing positive and negative pole pieces:
adding 3% of PVDF (polyvinylidene fluoride) binder into a stirrer, adding a proper amount of NMP (N-methyl pyrrolidone) as an organic solvent, stirring, sequentially adding 2% of SP (conductive agent) and 88% of ternary cathode material, stirring for 4 hours to prepare cathode slurry, preparing a cathode plate by extrusion coating, drying at 120 ℃, and rolling to obtain the cathode plate; the negative pole piece adopts metal lithium foil.
(2) Preparation of composite electrolyte slurry for forming a fluidized electrolyte layer
Adding 20% of LiTFSI into ethyl acetate, fully stirring and dissolving, adding 15% of LLZO, dispersing by using ultrasonic waves, slowly adding 65% of polyethylene oxide, and stirring at 1200r/min for 2 hours to obtain the composite electrolyte slurry for forming the flowing electrolyte layer, wherein the solid content of the composite electrolyte slurry is 10%.
(3) Assembled solid-state battery
And (3) placing a negative pole piece into a mold, coating the composite electrolyte slurry prepared in the step (2) on the surface of the negative pole piece, heating and drying at 60 ℃ in vacuum for 12 hours, arranging a positive pole piece on a formed electrolyte layer to obtain a solid-state battery precursor, carrying out vacuum packaging on the assembled solid-state battery precursor at 150-180 ℃, and carrying out hot cold pressing at 25-80 ℃ and 0.2-0.6 MPa for 3-10 minutes to obtain the solid-state battery.
Comparative example 2
(1) Preparing positive and negative pole pieces:
adding 3% of PVDF (polyvinylidene fluoride) binder into a stirrer, adding a proper amount of NMP (N-methyl pyrrolidone) as an organic solvent, stirring, sequentially adding 2% of SP (conductive agent) and 88% of ternary cathode material, stirring for 4 hours to prepare cathode slurry, preparing a cathode plate by extrusion coating, drying at 120 ℃, and rolling to obtain the cathode plate; the negative pole piece adopts metal lithium foil.
(2) Preparation of composite electrolyte slurry for forming a fluidized electrolyte layer
Adding 20% LiTFSI into ethyl methyl carbonate, fully stirring and dissolving, adding 15% LATP, dispersing by using ultrasonic waves, slowly adding 65% polyacrylonitrile, and stirring at 1200r/min for 2 hours to obtain composite electrolyte slurry for forming a flowing electrolyte layer, wherein the solid content of the composite electrolyte slurry is 10%.
(3) Assembled solid-state battery
And (3) placing the positive pole piece into a mold, coating the composite electrolyte slurry prepared in the step (2) on the surface of the positive pole piece, heating and drying at 60 ℃ in vacuum for 12 hours, arranging a negative pole piece on the formed electrolyte layer to obtain a solid-state battery precursor, carrying out vacuum packaging on the assembled solid-state battery precursor at 150-180 ℃, and carrying out hot cold pressing at 25-80 ℃ and 0.2-0.6 MPa for 3-10 minutes to obtain the solid-state battery.
Comparative example 3
(1) Preparing positive and negative pole pieces:
adding 3% of PVDF (polyvinylidene fluoride) binder into a stirrer, adding a proper amount of NMP (N-methyl pyrrolidone) as an organic solvent, stirring, sequentially adding 2% of SP (conductive agent) and 88% of ternary cathode material, stirring for 4 hours to prepare cathode slurry, preparing a cathode plate by extrusion coating, drying at 120 ℃, and rolling to obtain the cathode plate; the negative pole piece adopts metal lithium foil.
(2) Preparation of composite electrolyte slurry for forming a fluidized electrolyte layer
Adding 20% of lithium iron phosphate into ethyl methyl carbonate, fully stirring and dissolving, adding 15% of LZTO, dispersing by using ultrasonic, slowly adding 65% of polycarbonate, and stirring at 1200r/min for 2h to obtain the composite electrolyte slurry for forming the flowing electrolyte layer, wherein the solid content of the composite electrolyte slurry is 10%.
(3) Assembled solid-state battery
And (3) placing the positive pole piece into a mold, coating the composite electrolyte slurry prepared in the step (2) on the surface of the positive pole piece, heating and drying at 60 ℃ in vacuum for 12 hours, arranging a negative pole piece on the formed electrolyte layer to obtain a solid-state battery precursor, carrying out vacuum packaging on the assembled solid-state battery precursor at 150-180 ℃, and carrying out hot cold pressing at 25-80 ℃ and 0.2-0.6 MPa for 3-10 minutes to obtain the solid-state battery.
Comparative example 4
(1) Preparing positive and negative pole pieces:
adding 3% of PVDF (polyvinylidene fluoride) binder into a stirrer, adding a proper amount of NMP (N-methyl pyrrolidone) as an organic solvent, stirring, sequentially adding 2% of SP (conductive agent) and 88% of ternary cathode material, stirring for 4 hours to prepare cathode slurry, preparing a cathode plate by extrusion coating, drying at 120 ℃, and rolling to obtain the cathode plate; the negative pole piece adopts metal lithium foil.
(2) Preparing a self-supporting electrolyte layer:
adding 20% of LiTFSI into acetonitrile, fully stirring and dissolving, adding 15% of LLZTO, dispersing by using ultrasonic waves, slowly adding 65% of polyoxyethylene, and stirring at 1200r/min for 2h to obtain composite electrolyte slurry with the solid content of 15%; and then pouring a film on the non-woven fabric, and heating and drying at 60 ℃ for 24h to obtain the self-supporting electrolyte layer.
(3) Assembled solid-state battery
Placing the positive pole piece into a mold, sequentially arranging a self-supporting state electrolyte layer and a negative pole piece on the positive pole piece to obtain a solid-state battery precursor, carrying out vacuum packaging on the assembled solid-state battery precursor at 150-180 ℃, and then carrying out hot cold pressing at 25-80 ℃ and 0.2-0.6 MPa for 3-10 min to obtain the solid-state battery.
Comparative example 5
(1) Preparing positive and negative pole pieces:
adding 3% of PVDF (polyvinylidene fluoride) binder into a stirrer, adding a proper amount of NMP (N-methyl pyrrolidone) as an organic solvent, stirring, sequentially adding 2% of SP (conductive agent) and 88% of ternary cathode material, stirring for 4 hours to prepare cathode slurry, preparing a cathode plate by extrusion coating, drying at 120 ℃, and rolling to obtain the cathode plate; the negative pole piece adopts metal lithium foil.
(2) Preparation of composite electrolyte slurry for forming a fluidized electrolyte layer
Adding 20% of LiTFSI into polycarbonate, fully stirring and dissolving, adding 15% of LATP, dispersing by using ultrasonic, slowly adding 65% of polyacrylonitrile, and stirring at 1200r/min for 2h to obtain the composite electrolyte slurry for forming the flowing electrolyte layer, wherein the solid content of the composite electrolyte slurry is 10%.
(3) Assembled solid-state battery
And (3) placing the positive pole piece into a mold, coating the composite electrolyte slurry prepared in the step (2) on the surface of the positive pole piece, heating and drying at 60 ℃ in vacuum for 12 hours, arranging the positive pole piece on the formed electrolyte layer to obtain a solid-state battery precursor, carrying out vacuum packaging on the assembled solid-state battery precursor at 150-180 ℃, and carrying out hot cold pressing at 25-80 ℃ and 0.2-0.6 MPa for 3-10 min to obtain the solid-state battery.
Test example
The solid-state batteries prepared in examples 1 to 4 and comparative examples 1 to 5 were subjected to electrical property tests, and the results are shown in table 1.
TABLE 1 test results
The test results show that the solid-state batteries of the examples of the present invention have better overall performance than the solid-state batteries of the comparative examples.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A composite electrolyte membrane, comprising:
a mobile state electrolyte layer comprising a first polymer, a solvent and a lithium salt;
a self-supporting state electrolyte layer comprising a second polymer and a lithium salt.
2. The composite electrolyte membrane according to claim 1, wherein the flowable electrolyte layer is in a gel state, a molten state, or a pre-cured state.
3. The composite electrolyte membrane according to claim 1, wherein a support is included in the self-supporting electrolyte layer;
optionally, the support is a nonwoven fabric, a polymer-based film, or a battery separator.
4. The composite electrolyte membrane according to claim 1, wherein the first polymer is a high oxidative decomposition potential polymer, and the second polymer is a low reductive decomposition potential polymer;
alternatively, the first polymer is a low reductive decomposition potential polymer and the second polymer is a high oxidative decomposition potential polymer.
5. The composite electrolyte membrane according to claim 4, wherein the high oxidative decomposition potential polymer is selected from at least one of polyacrylonitrile, polycarbonate, polythioether, polyphenylene sulfide, polytetrafluoroethylene, and polyvinylidene fluoride, and the low reductive decomposition potential polymer is selected from at least one of polyethylene oxide, polyethylene glycol, polytetrahydrofuran, polytetrafluoroethylene, and polyvinylidene fluoride.
6. The composite electrolyte membrane according to claim 1, wherein the mass ratio of the first polymer to the lithium salt is (50-100): 1-50;
optionally, the mass ratio of the second polymer to the lithium salt is (50-100): 1-50.
7. The composite electrolyte membrane according to claim 1, wherein the flow state electrolyte layer further comprises a first inorganic material, and the self-supporting state electrolyte layer further comprises a second inorganic material; the first inorganic material and the second inorganic material are each independently selected from at least one of an oxide electrolyte, a halide electrolyte, a sulfide electrolyte, inorganic nanoparticles;
optionally, the oxide electrolyte is selected from at least one of LATP, LLZO, LLTO, LLZTO;
optionally, the halide electrolyte is selected from Li3ErCl6、Li3YBr6、Li3YCl6、Li3InCl6、Li1.6Mg1.2Cl4、Li2.5Y0.5Zr0.5Cl6At least one of;
optionally, the sulfide electrolyte is selected from Li2S-P2S5、Li6PS5Cl、Li6PS5Br、LGPS、Ag8GeS6At least one of;
optionally, the inorganic nanoparticles are selected from at least one of silica, alumina;
optionally, the content of the first inorganic material in the flowing dynamic electrolyte layer is 1 wt% to 50 wt%;
optionally, the content of the second inorganic material in the self-supporting electrolyte layer is 1 wt% to 50 wt%.
8. The composite electrolyte membrane according to claim 1, wherein the flow state electrolyte layer further comprises a first additive, and the self-supporting state electrolyte layer further comprises a second additive; the first additive and the second additive are each independently selected from at least one of a flame retardant, a film former, an oxygen radical scavenger;
optionally, the content of the first additive in the flowing state electrolyte layer is 1 wt% to 10 wt%;
optionally, the content of the second additive in the self-supporting electrolyte layer is 1 wt% to 10 wt%.
9. A solid-state battery, comprising: a positive electrode, a negative electrode, and the composite electrolyte membrane according to any one of claims 1 to 8.
10. A method of producing the solid-state battery according to claim 9, comprising:
providing a positive plate and a negative plate;
forming a flowing state electrolyte layer on the surface of the positive plate or the negative plate, arranging a self-supporting state electrolyte layer on the surface of the flowing state electrolyte layer, arranging the positive plate or the negative plate on the surface of the self-supporting state electrolyte layer, and packaging to obtain the solid-state battery;
or forming a flowing state electrolyte layer on the surface of the self-supporting state electrolyte layer, respectively arranging a positive plate or a negative plate on the surface of the self-supporting state electrolyte layer and the surface of the flowing state electrolyte layer, and packaging to obtain the solid-state battery.
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