WO2022134496A1 - 一种复合固态电解质浆料、薄膜、制备方法及全固态电池 - Google Patents

一种复合固态电解质浆料、薄膜、制备方法及全固态电池 Download PDF

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WO2022134496A1
WO2022134496A1 PCT/CN2021/100173 CN2021100173W WO2022134496A1 WO 2022134496 A1 WO2022134496 A1 WO 2022134496A1 CN 2021100173 W CN2021100173 W CN 2021100173W WO 2022134496 A1 WO2022134496 A1 WO 2022134496A1
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solid electrolyte
composite solid
rubber
lithium
electrolyte slurry
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English (en)
French (fr)
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卞均操
卢周广
赵予生
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南方科技大学
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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
    • 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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/497—Ionic conductivity
    • 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
    • H01M2300/0068—Solid electrolytes inorganic
    • 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
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • 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
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • 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

Definitions

  • the invention relates to the technical field of all-solid-state batteries, in particular to a composite solid-state electrolyte slurry, a film, a preparation method and an all-solid-state battery.
  • the mainstream in the field of all-solid-state batteries adopts the method of dry powder mixing to prepare all-solid-state batteries.
  • this process is only suitable for basic research and cannot be mass-produced. Therefore, for commercialization, it is necessary to develop a new film-forming process that is compatible with traditional lithium-ion battery preparation processes.
  • the existing solid electrolytes react with many organic solvents, and it is difficult to disperse uniformly in the slurry, and it is difficult to obtain a slurry suitable for the preparation of solid electrolyte membranes.
  • the present invention provides a composite solid-state electrolyte slurry, a preparation method and an all-solid-state battery, and aims to solve the problem that the solid electrolyte in the prior art is difficult to be ball-milled, dispersed evenly in the slurry, and difficult to obtain a solid state suitable for preparing chemically stable solid electrolytes.
  • Technical problem of slurry for electrolyte membrane is difficult to be ball-milled, dispersed evenly in the slurry, and difficult to obtain a solid state suitable for preparing chemically stable solid electrolytes.
  • a method for preparing a composite solid electrolyte slurry comprising:
  • the polymer is added to the non-polar solvent and mixed to obtain a sol
  • the non-polar solvent is an organic solvent that does not react with the solid electrolyte powder.
  • the preparation method of the composite solid electrolyte slurry wherein, the polymer is selected from styrene-butadiene rubber, nitrile rubber, butyl rubber, hydrogenated nitrile rubber, natural rubber, isoprene rubber, cis-butadiene One or more of rubber, neoprene rubber, silicone rubber, fluorine rubber, polysulfide rubber, urethane rubber, chlorohydrin rubber, acrylate rubber, ethylene propylene rubber.
  • the preparation method of the composite solid electrolyte slurry wherein the non-polar solvent is an organic solvent with a polarity value less than 5; the organic solvent is selected from hexane, toluene, o-xylene, p-diol One or more of toluene, dichloromethane, and dibromomethane.
  • the non-polar solvent is an organic solvent with a polarity value less than 5; the organic solvent is selected from hexane, toluene, o-xylene, p-diol One or more of toluene, dichloromethane, and dibromomethane.
  • the lithium salt in the lithium salt solution is selected from lithium bis(trifluoromethylsulfonyl)imide, lithium bisfluorosulfonylimide, One or more of aluminum perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium trifluoromethanesulfonate, tetraethylammonium tetrafluoroborate, lithium bis-oxalate borate, and lithium difluorooxalate borate.
  • the preparation method of the composite solid electrolyte slurry wherein the solid electrolyte powder is obtained by pulverizing the solid electrolyte, and the solid electrolyte is selected from anti-perovskite (RAP), sulfide solid electrolyte, lithium One of lanthanum zirconium oxide, lithium titanium aluminum phosphate, lithium titanium aluminum phosphate halide.
  • RAP anti-perovskite
  • sulfide solid electrolyte lithium One of lanthanum zirconium oxide
  • lithium titanium aluminum phosphate lithium titanium aluminum phosphate halide.
  • the preparation method of the composite solid electrolyte slurry wherein, the anti-perovskite is selected from but not limited to one of Li 3-x M x OX, Li 2- y My OHX or Various, among them, 0 ⁇ x ⁇ 3, 0 ⁇ y ⁇ 2, M is selected from Na, K, Rb, Cs, Be, Ca, Mg, Al, Sr, Ba, Ga, In, Fe, Co, Ni, One or more of Y and La, and X is selected from one or more of F, Cl, Br, I, BF 4 , BH 4 , and NH 2 .
  • the preparation method of the composite solid electrolyte slurry, wherein the solid electrolyte is RAP, and the RAP powder is obtained after pulverizing the RAP which specifically includes:
  • the RAP containing the non-polar solvent obtained after grinding is dried to obtain RAP powder.
  • the preparation method of the composite solid electrolyte slurry, wherein the mixing RAP and the non-polar solvent, and grinding the RAP containing the non-polar solvent specifically includes:
  • the RAP, the grinding ball and the non-polar solvent are added to a ball mill jar, and ground under predetermined grinding conditions;
  • the predetermined grinding conditions include: grinding time, and the grinding time is 0.01-120 hours.
  • RAP powder which specifically includes:
  • the RAP containing the non-polar solvent obtained after grinding is dried under vacuum or heating conditions; the vacuum conditions are maintained at 0.01-10 5 Pa for 0.01-120 hours.
  • the heating condition is heating at 25-200° C. for 0.01-120 hours.
  • the preparation method of the composite solid electrolyte slurry wherein the polymer is added to a non-polar solvent and mixed to obtain a sol, wherein the mass of the polymer and the non-polar solvent is than 0.001-99.999%.
  • the preparation method of the composite solid electrolyte slurry wherein the solid electrolyte powder and the lithium salt solution are added to the sol, and mixed to obtain a composite solid electrolyte slurry, wherein the solid electrolyte powder and the solid electrolyte powder are mixed.
  • the mass percentage of the polymer in the sol is 0.1-99.9%.
  • a composite solid electrolyte slurry is prepared by using the above-mentioned preparation method.
  • a composite solid electrolyte film is prepared by using the composite solid electrolyte slurry described above.
  • an all-solid-state battery includes a positive electrode plate, wherein the above-mentioned solid electrolyte film is deposited on the positive electrode plate.
  • the invention provides a preparation method of composite solid electrolyte slurry.
  • the sol is formed by mixing a polymer with a non-polar solvent, solid electrolyte powder and lithium salt are added to the sol, and the composite solid electrolyte slurry is obtained after mixing;
  • the high shear force of the sol disperses the solid electrolyte powder and the lithium salt solution, so that the solid electrolyte powder and the lithium salt solution are uniformly dispersed in the sol.
  • the obtained composite solid electrolyte slurry has high stability.
  • Figure 1 shows the dispersion photos of RAP in different solvents, wherein TEGDE: ethylene glycol dimethyl ether, Ethanol: ethanol, NMP: methylpyrrolidone, DBM: dibromomethane, AN: acetonitrile, DMF: dimethylformamide;
  • TEGDE ethylene glycol dimethyl ether
  • Ethanol ethanol
  • NMP methylpyrrolidone
  • DBM dibromomethane
  • AN acetonitrile
  • DMF dimethylformamide
  • Figure 2 is the photo of RAP after ball milling, a does not add organic solvent, hardening occurs, b, c ball milling effect after adding solvent, b contains solvent after ball milling, c is dry after ball milling, there is no hardening phenomenon after ball milling, ball milling is uniform, white in the picture
  • the small ball is a grinding ball
  • FIG. 3 is a flowchart of a method for preparing a composite solid electrolyte slurry provided by an embodiment of the present invention
  • Fig. 4 is the preparation process flow chart of the RAP-based composite solid electrolyte provided by the embodiment of the present invention.
  • Fig. 6 is the XRD pattern of dry powder after mixing RAP 24h in different polar solvents provided in the embodiment of the present invention
  • FIG. 7 is a photo of the RAP/polymer composite solid electrolyte gel after in-situ curing provided by an embodiment of the present invention.
  • FIG. 8 is a temperature-variable lithium ion conductivity curve of Li 2 OHCl 0.5 Br 0.5 /nitrile rubber composite solid electrolytes with different mass fractions provided in an embodiment of the present invention
  • FIG. 11 is a voltage-capacity curve in a cyclic charge-discharge process of a button-type all-solid-state battery provided by an embodiment of the present invention.
  • FIG. 13 is a voltage-time curve in a cyclic charge-discharge process of a pouch type all-solid-state battery provided by an embodiment of the present invention.
  • lithium-ion batteries Due to the advantages of high energy density, high output power, no memory effect and low self-discharge, lithium-ion batteries have been widely used in the field of 3C, new energy vehicles and energy storage power stations.
  • electrolyte due to the use of electrolyte, commercial lithium-ion batteries have shortcomings such as easy leakage, flammability, and poor stability, which are prone to safety accidents and become a major technical obstacle restricting the development of new energy vehicles.
  • solid-state electrolytes are mainly divided into two categories: polymeric SSEs and inorganic SSEs.
  • the polymer electrolyte uses organic substances (such as polyethylene oxide PEO, PVDF-HFP, etc.).
  • Inorganic solid-state electrolytes include oxides (such as lithium lanthanum zirconium oxide Li 7 La 3 Zr 2 O 12 , LLZO, lithium titanium aluminum phosphate Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 ) and sulfides (Li 7 P 3 S 11 ) .
  • Polymer solid-state electrolytes are flexible, easy to process, and low-cost, but these electrolytes have low room-temperature Li-ion conductivity (on the order of 10-6 S cm -1 ), poor mechanical strength, and are not resistant to lithium dendrites, which can easily lead to battery short-circuits.
  • Inorganic SSE has high lithium ion conductivity (up to the order of 10 -2 S cm -1 ) and good safety, but oxide SSE is hard and brittle, and is not easy to process and shape, and sulfide is prone to produce H 2 S after contact with water Highly toxic gas, bringing security risks.
  • Composite solid electrolytes can be prepared by mixing polymer solid electrolytes with inorganic solid electrolytes, combining the advantages of the two and making up for their respective deficiencies. Studies have shown that replacing SiO2 or Al2O3 with inorganic solid electrolytes as fillers can improve the Li - ion conductivity of CPE by an order of magnitude. At present, the highest CPE lithium ion conductivity reported in the literature can reach the order of 10 -3 S cm -1 , which has broad commercial prospects.
  • RAP SSE has high lithium ion conductivity (up to 10 -3 S cm -1 ), wide electrochemical stability window, low preparation temperature, low cost, easy large-scale production, and has broad commercial prospects .
  • powder with uniform particles and small particle size cannot be prepared, mainly because a large amount of RAP adheres to the inner wall of the ball mill and the surface of the grinding ball after ball milling, as shown in a in Figure 2, which greatly reduces the effect of ball milling, and The powder loss is large. How to reduce the particle size of RAP is one of the technical difficulties in this field.
  • RAP reacts with most organic solvents (as shown in Figure 1), it is difficult to mechanically finely pulverize, and it is easy to harden and adhere in the ball mill under the action of mechanical force (as shown in a in Figure 2), and it is difficult to be crushed in the slurry Difficult to disperse evenly.
  • the present invention provides a solution that can solve the above-mentioned technical problems, the details of which will be described in the following embodiments.
  • an embodiment of the present invention provides a method for preparing a composite solid electrolyte slurry.
  • the method includes the following steps:
  • the polymer is a type of organic matter that dissolves in an organic solvent and has cohesive properties
  • the polymer can be natural rubber or synthetic rubber, including but not limited to styrene-butadiene rubber, nitrile-butadiene rubber, butadiene Base rubber, hydrogenated nitrile rubber, natural rubber, isoprene rubber, polybutadiene rubber, neoprene rubber, silicone rubber, fluorine rubber, polysulfide rubber, polyurethane rubber, chlorohydrin rubber, acrylate rubber, ethylene propylene rubber.
  • the polymer may be a single natural rubber or synthetic rubber, or may be a mixture of natural rubber and synthetic rubber. When it is a mixture, the mixing ratio of natural rubber and synthetic rubber is not limited.
  • the non-polar solvent can be all organic solvents with a polarity less than 5, including but not limited to hexane, toluene, o-xylene, p-xylene, dichloromethane, and dibromomethane.
  • the non-polar solvent can be a single organic solvent with a polarity less than 5, or a mixture of multiple organic solvents with a polarity less than 5, such as a single toluene, o-xylene, Hexane and the like may be a mixture of toluene and o-xylene, or a mixture of toluene, o-xylene, p-xylene, dichloromethane, and dibromomethane.
  • the specific mixing ratio and the type of mixing are not limited here.
  • dichloromethane can be selected as the solvent, styrene-butadiene rubber as the polymer, a certain amount of styrene-butadiene rubber and a certain amount of dichloromethane are added to a container with a stirring function, and under heating conditions Dissolve at a certain speed (the dissolving speed of styrene-butadiene rubber can be accelerated by heating), and prepare a sol.
  • the mass ratio of styrene-butadiene rubber to dichloromethane can be 0.001% to 1.0%, 1.0% to 10.0%, 10.0% to 20.0%, 20.0% to 40.0%, 40.0% to 60.0%, 60.0% to 80.0%, 80.0% to 90.0%, 90.0% to 99.999%.
  • the heating temperature may be 25°C to 50°C, 50°C to 80°C, 80°C to 120°C, 120°C to 140°C, 140°C to 160°C, 160°C to 180°C, 180°C to 200°C. It should be noted that the model of the agitator and the rotational speed of the agitator can be adjusted according to actual needs.
  • the non-polar solvent is an organic solvent that does not react with the solid electrolyte powder.
  • the solid electrolyte powder can be firstly added to the sol under stirring conditions to disperse the solid electrolyte powder to obtain a dispersion liquid containing the solid electrolyte powder. Then, a certain concentration of lithium salt solution is added into the dispersion liquid, and the composite solid electrolyte slurry is obtained by dispersion.
  • the solid electrolyte powder can also be selected to be added together with a certain concentration of lithium salt solution, and then dispersed to obtain a composite solid electrolyte slurry.
  • the shear force of the slurry on the particles during high-speed motion is proportional to the viscosity of the liquid. Since the polymer is dissolved in an organic solvent, a viscous sol is formed. The higher the mass fraction of polymer, the higher the viscosity of the sol and the greater the shear force during stirring.
  • the solid-state electrolyte powder and the lithium salt solution can be better dispersed in the sol.
  • a non-polar organic liquid is used as a solvent to perform RAP ball milling and to formulate a matrix of a rubber-based polymer electrolyte, so that the RAP ball milling does not stick to the wall and the material remains stable, and a slurry with uniform particle size and uniform dispersion can be prepared. material.
  • the use of rubber as the matrix of the polymer electrolyte has good chemical compatibility with both non-polar solvents and RAP.
  • in-situ polymerization of the polymer is carried out under the condition of lower than 100 °C, which further improves the cycle performance of lithium symmetric batteries of CPE materials.
  • An appropriate amount of LiPF 6 electrolyte is added to the CPE, and LiPF 6 is decomposed at 60-80 °C to release PF 5 gas.
  • PF 5 will act as an initiator to polymerize polymers with unsaturated chemical bonds in situ.
  • the molecular structural formula of styrene-butadiene rubber before in-situ polymerization as shown below:
  • the solid electrolyte powder is obtained by pulverizing the solid electrolyte.
  • the solid electrolyte includes but is not limited to RAP, sodium-rich anti-perovskite, potassium-rich anti-perovskite, sulfide solid electrolyte, lithium lanthanum zirconium oxide, lithium aluminum titanium phosphate, lithium aluminum titanium phosphate halide, the present invention is particularly applicable For solid electrolytes that readily react chemically with conventional organic solvents.
  • the pulverization can be carried out by using a mortar, a mechanical pulverizer, a universal pulverizer, a solid pulverizer, a pulverizer, or the like. It should be noted that, in order to make the obtained slurry have better electrochemical performance, the size of the electrolyte powder needs to be reduced to a certain particle size.
  • the solid electrolyte when it is an anti-perovskite, it includes but is not limited to one or more of Li 3-x M x OX and Li 2- y My OHX, wherein 0 ⁇ x ⁇ 3, 0 ⁇ y ⁇ 2, M is selected from one or more of Na, K, Rb, Cs, Be, Ca, Mg, Al, Sr, Ba, Ga, In, Fe, Co, Ni, Y, La species, X is selected from one or more of F, Cl, Br, I, BF 4 , BH 4 , and NH 2 .
  • Li 2 OHCl 0.5 Br 0.5 Li 1.5 Na 0.5 OHCl 0.3 Br 0.7
  • Li 2.75 La 0.05 Mg 0.05 OCl 0.95 (BF 4 ) 0.05 Li 2.75 La 0.05 Mg 0.05 OCl 0.95 (BF 4 ) 0.05 , and the like.
  • the solid electrolyte is lithium-rich perovskite
  • the specific steps of pulverizing RAP to prepare RAP powder may include:
  • the RAP prepared by the solid-phase reaction is crushed using a pre-crushing device to make its particle size reach the millimeter level.
  • inert gas such as Ar or N 2
  • the grinding results are shown in Figure 2. As shown in b and c, it can be seen from the figure that after adding the solvent, there is no hardening phenomenon in grinding, and the ball milling is very uniform.
  • the grinding ball is a zirconia grinding ball or a stainless steel grinding ball, and its diameter is in the range of 100mm-0.01mm.
  • the rotating speed of the ball mill is 1-9999 revolutions/min, and the ball milling time is 0.01-120h.
  • a certain amount of non-polar solvent is added as a wetting agent during the ball milling process, which can effectively prevent the RAP powder from adhering to the inner wall of the ball milling tank. Also, the heat generated during the ball milling evaporates the organic solvent, providing a protective atmosphere.
  • the RAP containing the non-polar solvent obtained after grinding is dried under vacuum or heating conditions; the vacuum conditions are maintained at 0.01-10 5 Pa for 0.01-120 hours.
  • the heating conditions are heating at 25-600°C for 0.01-120 hours.
  • the ball milling jar is opened in the glove box in an inert gas atmosphere, and the organic solvent is volatilized in a vacuum environment or under heating conditions.
  • the lithium salt solution wherein the lithium salt includes: lithium bis(trifluoromethylsulfonyl)imide, lithium bisfluorosulfonimide, aluminum perchlorate, tetrafluoroethylene Lithium borate, lithium hexafluorophosphate, lithium trifluoromethanesulfonate, tetraethylammonium tetrafluoroborate, lithium bis-oxalate borate, lithium difluorooxalate borate.
  • the lithium salt solution wherein the solvent is a lipid, ether solvent, specifically including but not limited to ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylene glycol dimethyl carbonate Ether (DME), 1,3 Dioxolane (DOL), Propylene Carbonate (PC), Ethyl Methyl Carbonate (EMC), Fluoroethylene Carbonate (FEC), Propyl Acetate (PA), Triethylene Dioxide Glycol dimethyl ether (TRIGLYME), vinylene carbonate (VC), 1,3-propane sultone (PS), ethylene ethylene carbonate (VEC), etc. one or a mixture of several. Or a mixed solvent obtained by mixing one or more of the above solvents with an organic solvent with a polarity value greater than 4.5.
  • a mixed solvent obtained by mixing one or more of the above solvents with an organic solvent with a polarity value greater than 4.5.
  • the concentration of the lithium salt solution may be 0.001-10 moles per liter (eg, 1 mole per liter).
  • the slurry can be coated on the substrate and dried to obtain a composite solid electrolyte membrane.
  • a coating device is used to coat a selected substrate at a certain speed to obtain a composite solid electrolyte wet film with a certain thickness, and then the composite solid electrolyte membrane is obtained by drying at a certain temperature.
  • the coating devices include but are not limited to extrusion coaters, knife coaters and cast coaters;
  • the substrates include Al foil, Cu foil, stainless steel foil, PI film, polytetrafluoroethylene Vinyl fluoride film, commercial lithium ion battery separator, lithium ion battery positive pole piece, negative pole piece.
  • the coating speed of the coating device may be 0.01 m/min to 10 m/min, 10 m/min to 50 m/min, 50 m/min to 100 m/min, 100 m/min to 100 m/min 150m/min, 150m/min to 200m/min.
  • the wet film thickness may be 1-50 microns, 50-100 microns, 100-200 microns, 200-400 microns, 400-600 microns, 600-800 microns, 800-1000 microns.
  • the temperature may be 30°C to 50°C, 50°C to 70°C, 70°C to 100°C, 100°C to 130°C, 130°C to 150°C, 150°C to 180°C, 180°C to 200°C.
  • the present invention also provides an all-solid-state battery, the all-solid-state battery includes an electrode sheet on which a solid electrolyte film is deposited.
  • the positive electrode can be used as the base, the composite solid electrolyte slurry can be coated on the positive electrode by a doctor blade coater, and the solid electrolyte film can be obtained after drying, and then the negative electrode can be contacted with it.
  • Solid state battery Solid state battery.
  • RAP Li 2 OHCl 0.5 Br 0.5 .
  • the obtained RAP powder was added to the sol under stirring to make it evenly dispersed, and then 3 ml of a lithium tetrafluoroborate solution with a concentration of 0.5 mol per liter and 0.5 ml of a lithium hexafluorophosphate solution with a concentration of 1 mol per liter were taken, Add it to the dispersion, continue to stir at high speed to make it evenly mixed, and obtain a composite solid electrolyte CPE slurry based on RAP.
  • the photo of the composite solid electrolyte CPE slurry after in-situ curing is shown in Figure 7.
  • nitrile rubber-based CPE slurry was coated on Cu foil, dried at 50 °C, and then cured at 70 °C to obtain a RAP-based composite solid electrolyte. CPE.
  • the ionic conductivity of different mass fractions of Li 2 OHCl 0.5 Br 0.5 /nitrile rubber CPE was tested. The results are shown in Figure 8. The ionic conductivity of the composite solid electrolyte is higher than that of the RAP solid electrolyte.
  • the RAP-based composite solid-state electrolyte CPE was prepared by the preparation method provided in Example 1, and then assembled into an all-solid-state battery. The performance of the battery was tested. The lithium symmetric battery cycle performance reached 490 times, as shown in Figure 9.
  • the coin-type all-solid - state battery assembled with LiFePO4 as the positive electrode and Li metal as the negative electrode showed a discharge capacity of 36% of the initial capacity after 50 cycles, as shown in Figure 10.
  • the charge-discharge plateau of LiFePO 4 is relatively stable during the first 10 cycles, as shown in Fig. 11.
  • the pouch-type all-solid - state battery assembled with LiFePO4 as the positive electrode and Li metal as the negative electrode showed a discharge capacity of 38% of the initial capacity after 10 cycles, as shown in Figure 12.
  • the charge-discharge plateau of LiFePO 4 is relatively stable during the first 6 cycles, as shown in Fig. 13.
  • the present invention provides a composite solid-state electrolyte slurry, a preparation method and a solid-state lithium battery.
  • the method includes: adding a polymer into a non-polar solvent, and mixing to obtain a sol; adding solid electrolyte powder and a lithium salt solution to the sol, and mixing to obtain a composite solid-state electrolyte slurry; the non-polar solvent is a non-polar solvent. an organic solvent that reacts with the solid electrolyte powder.
  • a sol is formed by mixing a polymer with a non-polar solvent, adding solid electrolyte powder and lithium salt to the sol, and mixing to obtain a composite solid electrolyte slurry; using the high shear force of the sol to disperse the solid electrolyte powder and the lithium salt solution , so that the solid electrolyte powder and the lithium salt solution are uniformly dispersed in the sol, and since the non-polar solvent used does not react with the solid electrolyte powder, the obtained composite solid electrolyte slurry has high stability.
  • the prepared composite solid electrolyte slurry is coated to form a film to obtain a composite solid electrolyte CPE, which is applied to an all-solid-state battery to improve the cycle performance of the battery.

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Abstract

本申请提供了一种复合固态电解质浆料、薄膜、制备方法及全固态电池。所述方法包括：将聚合物加入到非极性溶剂中，混合得到溶胶；向所述溶胶中加入固态电解质粉末及锂盐溶液，混合得到复合固态电解质浆料；所述非极性溶剂为不与所述固态电解质粉末发生反应的有机溶剂。通过将聚合物与非极性溶剂混合，形成溶胶，向该溶胶中加入固态电解质粉末及锂盐，混合后得到复合固态电解质浆料；利用溶胶的高剪切力分散固态电解质粉末及锂盐溶液，从而使得所述固态电解质粉末及锂盐溶液均匀分散在溶胶中，由于所使用的非极性溶剂不与固态电解质粉末发生反应，使得所得到的复合固态电解质浆料具有较高的稳定性。

Description

一种复合固态电解质浆料、薄膜、制备方法及全固态电池
本申请要求于2020年12月21日在中国知识产权局提交的、申请号为202011520126.3的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及全固态电池技术领域，具体涉及一种复合固态电解质浆料、薄膜、制备方法及全固态电池。
背景技术
目前，全固态电池领域主流采用干粉混合的方法压片制备全固态电池。但是，这种工艺仅仅适合基础研究，无法大规模生产。因此若要商业化，需要开发新型成膜工艺，与传统锂离子电池制备工艺相兼容。
然而，现有的固态电解质存在与多数有机溶剂发生反应，并且在浆料中难以分散均匀，难以得到适于制备固态电解质膜的浆料。
因此，现有技术还有待于进一步提升。
技术问题
本发明提供一种复合固态电解质浆料、制备方法及全固态电池，旨在一定程度上解决现有技术中固态电解质难以球磨，在浆料中难以分散均匀，难以得到适于制备化学稳定的固态电解质膜的浆料的技术问题。
技术解决方案
本发明解决上述技术问题的技术方案如下：
第一方面，一种复合固态电解质浆料的制备方法，其中，包括：
将聚合物加入到非极性溶剂中，混合得到溶胶；
向所述溶胶中加入固态电解质粉末及锂盐溶液，混合得到复合固态电解质浆料；
所述非极性溶剂为不与所述固态电解质粉末发生反应的有机溶剂。
可选地，所述的复合固态电解质浆料的制备方法，其中，所述聚合物选自丁苯橡胶、 丁腈橡胶、丁基橡胶、氢化丁晴橡胶、天然橡胶、异戊橡胶、顺丁橡胶、氯丁橡胶、硅橡胶、氟橡胶、聚硫橡胶、聚氨酯橡胶、氯醇橡胶、丙烯酸酯橡胶、乙丙橡胶中的一种或多种。
可选地，所述的复合固态电解质浆料的制备方法，其中，所述非极性溶剂为极性值小于5的有机溶剂；所述有机溶剂选自己烷、甲苯、邻二甲苯、对二甲苯、二氯甲烷、二溴甲烷中的一种或多种。
可选地，所述的复合固态电解质浆料的制备方法，其中，所述锂盐溶液中的锂盐选自双(三氟甲基磺酰)亚胺锂、双氟磺酰亚胺锂、高氯酸铝、四氟硼酸锂、六氟磷酸锂、三氟甲基磺酸锂、四乙基铵四氟硼酸盐、双草酸硼酸锂、二氟草酸硼酸锂中的一种或多种。
可选地，所述的复合固态电解质浆料的制备方法，其中，将固态电解质粉碎后得到所述固态电解质粉末，所述固态电解质选自反钙钛矿(RAP)、硫化物固态电解质、锂镧锆氧、磷酸钛铝锂、磷酸钛铝锂卤化物中的一种。
可选地，所述的复合固态电解质浆料的制备方法，其中，所述反钙钛矿，选自但不限于Li 3-xM xOX、Li 2-yM yOHX中的一种或多种，其中，0≤x≤3，0≤y≤2，M选自Na,K,Rb,Cs,Be,Ca,Mg,Al,Sr,Ba,Ga,In,Fe,Co,Ni,Y,La中的一种或多种，X选自F,Cl,Br,I,BF 4,BH 4,NH 2中的一种或多种。如Li 2.94Na 0.01Mg 0.01Al 0.01OCl 0.7Br 0.1I 0.1(BF 4) 0.1。
可选地，所述的复合固态电解质浆料的制备方法，其中，所述固态电解质为RAP，将所述RAP粉碎后得到RAP粉末，具体包括：
将RAP和所述非极性溶剂相混合，对包含有所述非极性溶剂的RAP进行研磨；
将研磨后得到的包含有所述非极性溶剂的RAP进行干燥，得到RAP粉末。
可选地，所述的复合固态电解质浆料的制备方法，其中，所述将RAP和所述非极性溶剂相混合，对包含有所述非极性溶剂的RAP进行研磨，具体包括：
在惰性气氛中，将所述RAP、研磨球及所述非极性溶剂加入球磨罐，在预定研磨条件下研磨；所述预定研磨条件包括：研磨时间，所述研磨时间为0.01-120小时。
可选地，所述的复合固态电解质浆料的制备方法，其中，所述将研磨后得到的包含有所述非极性溶剂的RAP进行干燥，得到RAP粉末，具体包括：
将研磨后得到的包含有所述非极性溶剂的RAP，在真空或加热条件下进行干燥；所述真空条件为在0.01-10 5Pa下保持0.01-120小时。
可选地，所述的复合固态电解质浆料的制备方法，其中，所述加热条件为在25-200℃加热0.01-120小时。
可选地，所述的复合固态电解质浆料的制备方法，其中，所述将聚合物加入到非极性溶剂中混合，得到溶胶，其中，所述聚合物与所述非极性溶剂的质量比0.001-99.999％。
可选地，所述的复合固态电解质浆料的制备方法，其中，所述向所述溶胶中加入固态电解质粉末及锂盐溶液，混合得到复合固态电解质浆料，其中，所述固态电解质粉末与所述溶胶中的聚合物的质量百分比为0.1-99.9％。
第二方面，一种复合固态电解质浆料，其中，采用上述所述的制备方法，制备得到。
第三方面，一种复合固态电解质薄膜，其中，采用上述所述的复合固态电解质浆料制备而成。
第四方面，一种全固态电池，包括正极极片，其中，所述正极极片上沉积有上述所述的固态电解质薄膜。
有益效果
本发明提供一种复合固态电解质浆料的制备方法，通过将聚合物与非极性溶剂混合，形成溶胶，向该溶胶中加入固态电解质粉末及锂盐，混合后得到复合固态电解质浆料；利用溶胶的高剪切力分散固态电解质粉末及锂盐溶液，从而使得所述固态电解质粉末及锂盐溶液均匀分散在溶胶中，由于所使用的非极性溶剂不与固态电解质粉末发生反应，使得所得到的复合固态电解质浆料具有较高的稳定性。
附图说明
图1为RAP在不同溶剂中的分散照片，其中，TEGDE：乙二醇二甲醚，Ethanol：乙醇，NMP：甲基吡咯烷酮，DBM：二溴甲烷，AN：乙腈，DMF：二甲基甲酰胺；
图2为RAP球磨后的照片，a不添加有机溶剂，发生板结，b,c添加溶剂后球磨效果，b球磨后含溶剂，c球磨后干燥，球磨后无板结现象，球磨均匀，图中白色小球为研磨球；
图3为本发明实施例提供的一种复合固态电解质浆料的制备方法流程图；
图4为本发明实施例提供的RAP基复合固态电解质的制备工艺流程图；
图5为本发明实施例提供的RAP粉末以及RAP/聚合物复合固态电解质的XRD图；
图6为本发明实施例提供的不同极性溶剂中混合RAP 24h后干燥粉末的XRD图；
图7为本发明实施例提供的原位固化后的RAP/聚合物复合固态电解质凝胶照片；
图8为本发明实施例提供的不同质量分数Li 2OHCl 0.5Br 0.5/丁腈橡胶复合固态电解质的变温锂离子电导率曲线；
图9为本发明实施例提供的全固态电池的锂对称电池循环性能测试结果；
图10为本发明实施例提供的纽扣型全固态电池的循环充放电性能曲线以及库伦效率；
图11为本发明实施例提供的纽扣型全固态电池的循环充放电过程中电压-容量曲线；
图12为本发明实施例提供的软包型全固态电池的循环充放电性能曲线；
图13为本发明实施例提供的软包型全固态电池的循环充放电过程中电压-时间曲线。
本发明的实施方式
为了便于理解本发明，下面将参照相关附图对本发明进行更全面的描述。附图中给出了本发明的较佳实施方式。但是，本发明可以通过许多不同的形式来实现，并不限于本文所描述的实施方式。相反地，提供这些实施方式的目的是使对本发明的公开内容理解的更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施方式的目的，不是旨在于限制本发明。
由于锂离子电池具有能量密度高、输出功率大、无记忆效应和低自放电等优点，在3C领域、新能源汽车以及储能电站等领域得到广泛的应用。但是，商用锂离子电池由于使用电解液，存在容易泄漏、易燃且稳定性差等缺点，容易带来安全事故，成为限制新能源汽车领域发展的主要技术障碍。
目前，固态电解质(SSE)主要分为聚合物SSE和无机SSE两大类。聚合物电解质使用有机物(如聚环氧乙烷PEO、PVDF-HFP等)。无机固态电解质包括氧化物(如锂镧锆氧Li 7La 3Zr 2O 12，LLZO、磷酸钛铝锂Li 1.4Al 0.4Ti 1.6(PO 4) 3)和硫化物(Li 7P 3S 11)。聚合物固态电解质柔性好、易加工、成本低廉，但是这类电解质的室温锂离子电导率低(10 -6S cm -1数量级)，机械强度差，不耐受锂枝晶，易导致电池短路。无机SSE锂离子电导率高(可达10 -2S cm -1数量级)，安全性好，但是氧化物SSE质地坚硬、较脆，不易加工成型，而硫化物与水接触后容易产生H 2S剧毒气体，带来安全隐患。通过将聚合物固态电解质与无机固态电解质混合，结合二者优点并且弥补各自不足，可以制备复合固态电解质(CPE)。 研究表明，无机固态电解质作为填料取代SiO 2或者Al 2O 3可以将CPE的锂离子电导率提高一个数量级。目前文献报道的CPE锂离子电导率最高可以达到10 -3S cm -1数量级，具有广阔的商业化前景。
RAP SSE具有较高的锂离子电导率(最高可达10 -3S cm -1)、较宽的电化学稳定窗口、制备温度低、成本低廉，容易大规模进行生产，具有广阔的商业化前景。目前RAP烧结后，无法制备颗粒均匀、粒径较小的粉末，主要是由于球磨后RAP在球磨罐内壁以及研磨球表面大量附着如图2中的a所示，大大降低了球磨的效果，并且粉末损失量大。如何减小RAP颗粒尺寸是该领域的技术难题之一。
目前，全固态电池领域主流采用干粉混合的方法压片制备全固态电池。但是，这种工艺仅仅适合基础研究，无法大规模生产。这种电池往往活性物质负载量小，能量密度低，失去了全固态电池高能量密度的先天优势；颗粒间接触不良，内阻大；界面稳定性差，SSE易发生分解；无柔性，不适合现实应用场景，受震动容易破碎；固态电解质用量大，成本高昂。所以，RAP若要商业化，需开发新型成膜工艺，与传统锂离子电池制备工艺进行兼容。但是，RAP与大多数有机溶剂发生反应(如图1所示)，难以机械精细粉碎，容易在机械力作用下在球磨罐中板结附着(如图2中的a所示)，并且在浆料中难以分散均匀。
基于此，本发明提供一种能够解决上述技术问题的方案，其详细内容将在后续实施例中得以阐述。
如图3至图4所示，本发明实施例提供一种复合固态电解质浆料的制备方法，方法包括如下步骤：
S10、将聚合物加入到非极性溶剂中，混合得到溶胶。
具体来说，所述聚合物是一类溶解在有机溶剂中具有粘结性的有机物，所述的聚合物可以为天然橡胶、合成橡胶，其包括但不限于丁苯橡胶、丁腈橡胶、丁基橡胶、氢化丁晴橡胶、天然橡胶、异戊橡胶、顺丁橡胶、氯丁橡胶、硅橡胶、氟橡胶、聚硫橡胶、聚氨酯橡胶、氯醇橡胶、丙烯酸酯橡胶、乙丙橡胶。需要说明的是，所述聚合物可以是单一的天然橡胶或合成橡胶，也可以是天然橡胶和合成橡胶的混合物。当为混合物时，天然橡胶和合成橡胶的混合比例不做限定。
在本实施例中，所述的非极性溶剂可以是所有极性小于5的有机溶剂机，其包括但不限于己烷、甲苯、邻二甲苯、对二甲苯、二氯甲烷、二溴甲烷。需要说明的是，所述非极 性溶剂可以是单一的极性小于5的有机溶剂，也可以是多个极性小于5的有机溶剂的混合物，如，可以是单一的甲苯、邻二甲苯、己烷等，也可以是甲苯和邻二甲苯的混合，还可以是甲苯、邻二甲苯、对二甲苯、二氯甲烷、二溴甲烷的混合。具体的混合比例以及混合的种类在此不做限定。
在本实施例中，作为举例，可以选用二氯甲烷作为溶剂，丁苯橡胶作为聚合物，将一定量的丁苯橡胶与一定的二氯甲烷加入到带搅拌功能的容器中，在加热的条件下以一定转速进行溶解(通过加热可以加快丁苯橡胶的溶解速度)，配制成溶胶。其中，丁苯橡胶与二氯甲烷的质量比可以是0.001％至1.0％，1.0％至10.0％，10.0％至20.0％，20.0％至40.0％，40.0％至60.0％，60.0％至80.0％，80.0％至90.0％，90.0％至99.999％。加热温度可以是25℃至50℃，50℃至80℃，80℃至120℃，120℃至140℃，140℃至160℃，160℃至180℃，180℃至200℃。需要说明的是，搅拌器的型号以及搅拌器的转速等，可以根据实际需要进行调节。
S20、向所述溶胶中加入固态电解质粉末及锂盐溶液，混合得到复合固态电解质浆料；所述非极性溶剂为不与所述固态电解质粉末发生反应的有机溶剂。
具体来说，可以选择在搅拌条件下，先将固态电解质粉末加入到溶胶中，使固态电解质粉末分散，得到包含有固态电解质粉末的分散液。接着将一定浓度的锂盐溶液加入到分散液中，进行分散得到复合固态电解质浆料。
在本实施例中，也可以选择将固态电解质粉末与一定浓度的锂盐溶液一起加入，然后进行分散，得到复合固态电解质浆料。需要说明的是，浆料在高速运动过程中对颗粒的剪切力与液体的粘度成正比。由于聚合物溶解在有机溶剂中以后形成粘稠的溶胶。聚合物的质量分数越高，溶胶的粘度越大，搅拌过程中剪切力就越大。
在本实施例中，通过利用溶胶的高剪切力，可以将合固态电解质粉末及锂盐溶液更好地分散在溶胶中。
在本实施例中，采用非极性有机液体作为溶剂来进行RAP球磨以及配制基于橡胶的聚合物电解质的基质，实现RAP球磨不粘壁且材料保持稳定，可以制备颗粒尺寸均匀且分散均匀的浆料。使用橡胶作为聚合物电解质的基质，与非极性溶剂和RAP都具有良好的化学相融性。
同时，利用原位聚合技术，在低于100℃条件下使聚合物发生原位聚合反应，进一步提升CPE材料的锂对称电池的循环性能。在CPE中添加适量LiPF 6电解液，利用LiPF 6在60-80℃条件下发生分解，释放PF 5气体。PF 5将起到引发剂的作用，将具有不饱和化学键的聚合物进行原位聚合反应。如下所示的丁苯橡胶发生原位聚合反应前的分子结构式：
Figure PCTCN2021100173-appb-000001
以及丁腈橡胶发生原位聚合反应前的分子结构式：
Figure PCTCN2021100173-appb-000002
其中均含有不饱和的碳碳双键。容易理解的是，分子结构式中的m、n、x、y均为正整数。
在本实施例一种实现方式中，所述固态电解质粉末为固态电解质粉碎后得到的。所述固态电解质包括但不限于RAP、富钠反钙钛矿、富钾反钙钛矿、硫化物固态电解质、锂镧锆氧、磷酸钛铝锂、磷酸钛铝锂卤化物，本发明特别适用于容易与常规有机溶剂发生化学反应的固态电解质。其中，所述的粉碎可以是采用研钵、机械粉碎机、万能粉碎机、固体粉碎机、磨粉机等进行粉碎。需要说明的是，为了使所得到的浆料具有更好的电化学性能，需要将电解质粉末尺寸降低到一定的粒径。
在本实施例中，当固态电解质为反钙钛矿时，其包括但不限于Li 3-xM xOX、Li 2-yM yOHX中的一种或多种，其中，0≤x≤3，0≤y≤2，M选自Na,K,Rb,Cs,Be,Ca,Mg,Al,Sr,Ba,Ga,In,Fe,Co,Ni,Y,La中的一种或多种,X选自F,Cl,Br,I,BF 4,BH 4,NH 2中的一种或多种。比如说，Li 2OHCl 0.5Br 0.5、Li 1.5Na 0.5OHCl 0.3Br 0.7、Li 2.75La 0.05Mg 0.05OCl 0.95(BF 4) 0.05、等。
在本实施例一种实现方式中，所述固态电解质为富锂钙钛矿，将RAP进行粉碎制备RAP粉末的具体步骤，可以包括：
S1、将RAP和所述非极性溶剂相混合，对包含有所述非极性溶剂的RAP进行研磨。
具体来说，在Ar或者N 2等惰性气体保护条件下，将固相反应制备的RAP使用预粉碎装置进行破碎，使其颗粒尺寸达到毫米级。在Ar或者N 2等惰性气体保护条件下，将预粉 碎RAP粉末和研磨球以及非极性溶剂以一定的比例放入球磨罐，调节球磨机转速，对RAP进行研磨，研磨结果如图2中的b、c所示，从图中可以看出在添加溶剂后，研磨无板结现象，且球磨很均匀。
在本实施例中，所述研磨球为氧化锆研磨球或者不锈钢研磨球，其直径在100mm-0.01mm范围内。所述的球磨机转速为1-9999转/min，球磨时间为0.01-120h。
在本实施例中，在球磨过程中添加一定量的非极性溶剂作为润湿剂，可以有效防止RAP粉末在球磨罐内壁的附着。并且，球磨过程中产生的热量蒸发有机溶剂，提供保护气氛。
S2、将研磨后得到的包含有所述非极性溶剂的RAP进行干燥，得到RAP粉末。
具体来说，将研磨后得到的包含有所述非极性溶剂的RAP，在真空或加热条件下进行干燥；所述真空条件为在0.01-10 5Pa下保持0.01-120小时。所述加热条件为在25-600℃加热0.01-120小时。
在本实施例中，在球磨结束后，在惰性气体氛围手套箱中打开球磨罐，在真空环境或者加热条件下使有机溶剂挥发。
在本实施例的一种实现方式中，所述锂盐溶液，其中锂盐包括：双(三氟甲基磺酰)亚胺锂、双氟磺酰亚胺锂、高氯酸铝、四氟硼酸锂、六氟磷酸锂、三氟甲基磺酸锂、四乙基铵四氟硼酸盐、双草酸硼酸锂、二氟草酸硼酸锂。所述锂盐溶液，其中溶剂为脂类、醚类溶剂，具体包括但不限制于碳酸乙烯酯(EC)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、乙二醇二甲醚(DME)、1,3二氧戊环(DOL)、碳酸丙烯酯(PC)、碳酸甲乙酯(EMC)、氟代碳酸乙烯酯(FEC)、乙酸丙酯(PA)、三乙二醇二甲醚(TRIGLYME)、、碳酸亚乙烯酯(VC)、1,3-丙磺酸内酯(PS)、碳酸乙烯亚乙酯(VEC)等其中一种或者几种的混合物。或者采用以上一种或者几种溶剂与极性值大于4.5的有机溶剂进行混合得到的混合溶剂。
在本实施例中，锂盐溶液的浓度可以是0.001-10摩尔每升(如1摩尔每升)。
在本实施例的一种实现方式中，在制备得到复合固态电解质浆料后，可以将该浆料涂覆在基体上，经干燥后得到复合固态电解质膜。
具体来说，使用涂布装置在选定的基底上以一定的速度进行涂布，得到具有一定厚度的复合固态电解质湿膜，然后在一定温度条件下干燥得到复合固态电解质膜。
在本实施例中，所述涂布装置包括但不限于挤压涂布机、刮刀涂布机和流延涂布机； 所述基底包括Al箔、Cu箔、不锈钢箔、PI膜、聚四氟乙烯膜、商用锂离子电池隔膜、锂离子电池正极极片、负极极片。
在本实施例中，涂布装置的涂布速度可以为0.01米/分钟至10米/分钟，10米/分钟至50米/分钟，50米/分钟至100米/分钟，100米/分钟至150米/分钟，150米/分钟至200米/分钟。所述湿膜厚度可以是1微米至50微米，50微米至100微米，100微米至200微米，200微米至400微米，400微米至600微米，600微米至800微米，800微米至1000微米。所述温度可以是30℃至50℃，50℃至70℃，70℃至100℃，100℃至130℃，130℃至150℃，150℃至180℃，180℃至200℃。
基于相同的发明构思，本发明还提供一种全固态电池，所述全固态电池包括电极片，在所述电极片上沉积有固态电解质薄膜。
具体来说，可以以正极极片为基底，采用刮刀涂布机在所述正极极片上涂覆复合固态电解质浆料，经干燥后得到固态电解质薄膜，然后将负极极片与之接触，组装成全固态电池。
下面通过具体的制备实施例来对本发明所提供复合固态电解质浆料及其制备方法做进一步的解释。
实施例1
将10毫升二氯甲烷与5克RAP进行混合，加入到球磨罐中，选择直径为5mm的氧化锆研磨球，对RAP进行研磨，球磨机的转速设为500转/min，球磨24小时。球磨结束后，在惰性气体氛围手套箱中，打开球磨罐，在真空条件下使溶剂挥发，得到RAP粉末，备用，其中，RAP为Li 2OHCl 0.5Br 0.5。
在氮气环境手套箱中，取30毫升的二氯甲烷作为溶剂，向其中加入5克的丁腈橡胶，使丁腈橡胶完全分散在二氯甲烷中，得到溶胶。
将所得到的RAP粉末在搅拌的调价下加入到溶胶中，使其分散均匀，然后取3毫升浓度为0.5摩尔每升的四氟硼酸锂溶液以及0.5毫升浓度为1摩尔每升的六氟磷酸锂溶液，加入到分散液中，继续高速搅拌，使其混合均匀，得到基于RAP的复合固态电解质CPE浆料，该复合固态电解质CPE浆料发生原位固化后的照片，如图7所示。
在氮气氛围中采用挤压涂布法，在Cu箔上涂布丁腈橡胶基CPE浆料，在50℃温度条件下干燥，然后在70℃温度条件下固化，得到的基于RAP的复合固态电解质CPE。
对所上述实施例制备得到的基于RAP的复合固态电解质CPE与溶剂接触后，测试XRD，结果如图5至图6所示，XRD显示无相变。
对不同质量分数Li 2OHCl 0.5Br 0.5/丁腈橡胶CPE进行离子电导率测试，结果如图8所示，复合固态电解质的离子电导率高于RAP固态电解质的离子电导率。
采用实施例1所提供的制备方法制备出基于RAP的复合固态电解质CPE，然后组装成全固态电池，对该电池进行性能测试，其中，锂对称电池循环性能达到490次，如图9所示。以LiFePO 4为正极，锂金属为负极组装的纽扣型全固态电池在循环50次后放电容量为初始容量的36％，如图10所示。前10次循环过程中LiFePO 4充放电平台较为稳定，如图11所示。以LiFePO 4为正极，锂金属为负极组装的软包型全固态电池在循环10次后放电容量为初始容量的38％，如图12所示。前6次循环过程中LiFePO 4充放电平台较为稳定，如图13所示。
综上所述，本发明提供了一种复合固态电解质浆料、制备方法及固态锂电池。所述方法包括：将聚合物加入到非极性溶剂中，混合得到溶胶；向所述溶胶中加入固态电解质粉末及锂盐溶液，混合得到复合固态电解质浆料；所述非极性溶剂为不与所述固态电解质粉末发生反应的有机溶剂。通过将聚合物与非极性溶剂混合，形成溶胶，向该溶胶中加入固态电解质粉末及锂盐，混合后得到复合固态电解质浆料；利用溶胶的高剪切力分散固态电解质粉末及锂盐溶液，从而使得所述固态电解质粉末及锂盐溶液均匀分散在溶胶中，由于所使用的非极性溶剂不与固态电解质粉末发生反应，使得所得到的复合固态电解质浆料具有较高的稳定性。将所制备的复合固态电解质浆料涂布成膜，得到复合固态电解质CPE，将其应用到全固态电池上，提升了电池的循环性能。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (14)

  1. 一种复合固态电解质浆料的制备方法，其特征在于，包括：
    将聚合物加入到非极性溶剂中，混合得到溶胶；
    向所述溶胶中加入固态电解质粉末及锂盐溶液，混合得到复合固态电解质浆料；
    所述非极性溶剂为不与所述固态电解质粉末发生反应的有机溶剂。
  2. 如权利要求1所述的复合固态电解质浆料的制备方法，其特征在于，所述聚合物选自丁苯橡胶、丁腈橡胶、丁基橡胶、氢化丁晴橡胶、天然橡胶、异戊橡胶、顺丁橡胶、氯丁橡胶、硅橡胶、氟橡胶、聚硫橡胶、聚氨酯橡胶、氯醇橡胶、丙烯酸酯橡胶、乙丙橡胶中的一种或多种。
  3. 如权利要求1所述的复合固态电解质浆料的制备方法，其特征在于，所述非极性溶剂为极性值小于5的有机溶剂；所述有机溶剂选自己烷、甲苯、邻二甲苯、对二甲苯、二氯甲烷、二溴甲烷中的一种或多种。
  4. 如权利要求1所述的复合固态电解质浆料的制备方法，其特征在于，在加热搅拌条件下，将所述聚合物与所述非极性溶剂混合，所述聚合物与所述非极性溶剂的质量比为0.001-99.999％，加热温度为25℃-200℃。
  5. 如权利要求1所述的复合固态电解质浆料的制备方法，其特征在于，将固态电解质粉碎后得到所述固态电解质粉末，所述固态电解质选自反钙钛矿、硫化物固态电解质、锂镧锆氧、磷酸钛铝锂、磷酸钛铝锂卤化物中的一种或多种。
  6. 如权利要求5所述的复合固态电解质浆料的制备方法，其特征在于，所述反钙钛矿选自Li 3-xM xOX、Li 2-yM yOHX中的一种或多种，其中，0≤x≤3，0≤y≤2，M选自Na,K,Rb,Cs,Be,Ca,Mg,Al,Sr,Ba,Ga,In,Fe,Co,Ni,Y,La中的一种或多种，X选自F,Cl,Br,I,BF 4,BH 4,NH 2中的一种或多种。
  7. 如权利要求5所述的复合固态电解质浆料的制备方法，其特征在于，所述固态电解质为反钙钛矿，将所述反钙钛矿粉碎后得到反钙钛矿粉末，具体包括：
    在惰性气氛中，将所述反钙钛矿、研磨球及所述非极性溶剂加入球磨罐，在预定研磨条件下研磨；
    将研磨后得到的包含有所述非极性溶剂的反钙钛矿，在真空或加热条件下进行干燥。
  8. 如权利要求7所述的复合固态电解质浆料的制备方法，其特征在于，所述预定研磨条件包括：球磨机转速为1-9999转/min，所述研磨时间为0.01-120小时。
  9. 如权利要求7所述的复合固态电解质浆料的制备方法，其特征在于，所述加热条件为在25-600℃下加热0.01-120小时；所述真空条件为在0.01-10 5Pa下保持0.01-120小时。
  10. 如权利要求1所述的复合固态电解质浆料的制备方法，其特征在于，所述锂盐溶液中的锂盐选自双(三氟甲基磺酰)亚胺锂、双氟磺酰亚胺锂、高氯酸铝、四氟硼酸锂、六氟磷酸锂、三氟甲基磺酸锂、四乙基铵四氟硼酸盐、双草酸硼酸锂、二氟草酸硼酸锂中的一种或多种。
  11. 如权利要求1所述的复合固态电解质浆料的制备方法，其特征在于，所述向所述溶胶中加入固态电解质粉末及锂盐溶液，混合得到复合固态电解质浆料，其中，所述固态电解质粉末与所述溶胶中的聚合物的质量比为1-99％。
  12. 一种复合固态电解质浆料，其特征在于，采用权利要求1-11任一所述的制备方法制备得到。
  13. 一种复合固态电解质薄膜，其特征在于，采用权利要求12所述的复合固态电解质浆料制备而成。
  14. 一种全固态电池，包括电极片，其特征在于，所述电极片上沉积有权利要求9所述的复合固态电解质薄膜；所述复合固态电解质薄膜的膜厚为10nm-1000μm。
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