WO2024227391A1 - 固态电解质膜及其制备方法、固态电池、用电装置 - Google Patents

固态电解质膜及其制备方法、固态电池、用电装置 Download PDF

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WO2024227391A1
WO2024227391A1 PCT/CN2024/086391 CN2024086391W WO2024227391A1 WO 2024227391 A1 WO2024227391 A1 WO 2024227391A1 CN 2024086391 W CN2024086391 W CN 2024086391W WO 2024227391 A1 WO2024227391 A1 WO 2024227391A1
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solid electrolyte
electrolyte membrane
solid
fiber
membrane according
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French (fr)
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WO2024227391A9 (zh
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宁子杨
刘成勇
胡波兵
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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Priority to JP2025536072A priority Critical patent/JP2026500037A/ja
Priority to EP24799849.5A priority patent/EP4621905A4/en
Publication of WO2024227391A1 publication Critical patent/WO2024227391A1/zh
Publication of WO2024227391A9 publication Critical patent/WO2024227391A9/zh
Priority to US19/277,867 priority patent/US20250349977A1/en
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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
    • 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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/454—Separators, membranes or diaphragms characterised by the material having a layered structure comprising a non-fibrous layer and a fibrous layer superimposed on one another
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • 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
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • 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
    • H01M50/44—Fibrous 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • 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
    • 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
    • H01M2300/0074—Ion conductive at high temperature
    • H01M2300/0077—Ion conductive at high temperature based on zirconium oxide
    • 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
    • H01M2300/008—Halides
    • 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
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • 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 present application relates to the field of battery technology, and in particular to a solid electrolyte membrane and a preparation method thereof, a solid-state battery, and an electrical device.
  • solid electrolytes can be divided into polymer solid electrolytes and inorganic ceramic solid electrolytes.
  • the fragile mechanical properties of inorganic ceramic solid electrolytes are the core bottleneck of the application of this type of solid electrolytes.
  • the present application provides a solid electrolyte membrane and a preparation method thereof, a solid-state battery, and an electrical device.
  • the solid electrolyte membrane has good mechanical properties.
  • a solid electrolyte membrane comprising a solid electrolyte material layer and a phase change toughening agent and a fiber material dispersed in the solid electrolyte material layer, wherein the solid electrolyte material layer comprises an inorganic ceramic solid electrolyte material.
  • the above-mentioned solid electrolyte membrane can effectively improve the mechanical properties, especially the fracture toughness, of the solid electrolyte membrane through the synergistic effect between the phase change toughening agent and the fiber material in the solid electrolyte material layer, thereby reducing problems such as dendrites and short circuits caused by fracture of the solid electrolyte membrane.
  • the phase change toughening agent includes metastable ZrO 2 ; optionally, the phase change toughening agent includes one or more of yttria stabilized zirconia (YSZ), scandia stabilized zirconia (SSZ), magnesia stabilized zirconia (MSZ), calcia stabilized zirconia (CSZ) and cesium oxide stabilized zirconia (CsSZ).
  • YSZ yttria stabilized zirconia
  • SSZ scandia stabilized zirconia
  • MSZ magnesia stabilized zirconia
  • CSZ calcia stabilized zirconia
  • CsSZ cesium oxide stabilized zirconia
  • the fiber material comprises ceramic fiber; alternatively, the fiber material comprises silicon carbide One or more of fibers, silicon nitride fibers, boron nitride fibers, alumina fibers and silica fibers.
  • the total volume of the phase change toughening agent and the fiber material in the solid electrolyte material layer is 5% to 20% by volume; alternatively, the volume percentage is 8% to 12%.
  • the volume ratio of the phase change toughening agent to the fiber material is 1:(0.25-4); optionally, the volume ratio is 1:(0.5-1.5).
  • the phase change toughening agent has a D 50 of 50 nm to 100 nm.
  • the fiber material has a diameter of 0.5 ⁇ m to 5 ⁇ m and a length of 10 ⁇ m to 30 ⁇ m.
  • the inorganic ceramic solid electrolyte material includes a lithium ion solid electrolyte material, a sodium ion solid electrolyte material or a potassium ion solid electrolyte material.
  • the solid electrolyte membrane has one or more of the following features (1) to (2):
  • the fracture toughness of the solid electrolyte membrane is ⁇ 0.25 MPa ⁇ m 1/2 ;
  • the fracture toughness of the solid electrolyte membrane is ⁇ 1.5 MPa ⁇ m 1/2 ;
  • the critical current density of the solid electrolyte membrane is ⁇ 1.5 mA/cm 2 ; optionally, the critical current density of the solid electrolyte membrane is ⁇ 2 mA/cm 2 .
  • the second aspect of the present application provides a method for preparing the solid electrolyte membrane according to the first aspect, comprising the following steps:
  • the mixed material is subjected to molding treatment to prepare the solid electrolyte membrane.
  • the preparation method of the solid electrolyte membrane has simple steps and is easy to promote and apply in industry.
  • the mixing is dry mixing.
  • the molding process is a pressurization process; optionally, the pressure of the pressurization process is 300MPa to 600MPa.
  • the mixing is wet mixing.
  • the molding process comprises coating the mixture into a film, and a drying step; optionally, the solvent used in the wet mixing comprises one or more of toluene, p-xylene, o-xylene, m-xylene, trimethylbenzene, ethyl acetate, butyl butyrate, n-butyl ether, anisole, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and n-butane.
  • the solvent used in the wet mixing comprises one or more of toluene, p-xylene, o-xylene, m-xylene, trimethylbenzene, ethyl acetate, butyl butyrate, n-butyl ether, anisole, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and n-butane.
  • a third aspect of the present application provides a solid-state battery, comprising the solid-state electrolyte membrane described in the first aspect.
  • the fourth aspect of the present application provides an electrical device comprising the solid-state battery described in the third aspect.
  • FIG1 is a schematic diagram of a solid-state battery according to an embodiment of the present application.
  • FIG2 is a schematic diagram of a battery module according to an embodiment of the present application.
  • FIG3 is a schematic diagram of a battery pack according to an embodiment of the present application.
  • FIG4 is an exploded view of the battery pack according to an embodiment of the present application shown in FIG3 ;
  • FIG5 is a schematic diagram of an electrical device using a solid-state battery as a power source according to an embodiment of the present application
  • FIG6 is a cross-sectional scanning electron microscope image of a solid electrolyte membrane prepared in one embodiment of the present application.
  • “Scope” disclosed in the present application is limited in the form of lower limit and upper limit, and a given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a special range.
  • the scope limited in this way can be including end values or not including end values, and can be arbitrarily combined, that is, any lower limit can form a scope with any upper limit combination. For example, if the scope of 60-120 and 80-110 is listed for a specific parameter, it is understood that the scope of 60-110 and 80-120 is also expected.
  • the numerical range "a-b" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers.
  • the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations.
  • a parameter is expressed as an integer ⁇ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.
  • the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially.
  • the method may also include step (c), which means Step (c) may be added to the method in any order.
  • the method may include steps (a), (b) and (c), or steps (a), (c) and (b), or steps (c), (a) and (b), etc.
  • the “include” and “comprising” mentioned in this application are open-ended or closed-ended.
  • the “include” and “comprising” may mean that other components not listed may also be included or only the listed components may be included or only the listed components may be included.
  • the term "or” is inclusive.
  • the phrase “A or B” means “A, B, or both A and B”. More specifically, any of the following conditions satisfies the condition "A or B”: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).
  • Fracture toughness is a parameter that describes the material's ability to absorb strain energy before fracture. Higher fracture toughness represents a stronger barrier to crack propagation. It also reflects the solid electrolyte membrane's ability to resist cracking and short circuits caused by dendrites. There are four-point bending test, Vickers cone indentation test and other test methods for fracture toughness. In this application, the Vickers cone indentation test is used to obtain the fracture toughness.
  • Test method The prepared solid electrolyte membrane is polished with sandpaper in an argon atmosphere, from 800 mesh, to 2000 mesh, to 4000 mesh, to 8000 mesh, until the electrolyte surface presents mirror properties without obvious defects. Then, the polished surface is indented by a Vickers cone indentation tester. The indentation tester is driven with an appropriate load until radial cracks appear at the four corners of the cone indentation. According to the indentation load P, the extension length C of the radial crack, the Young's modulus E and the microhardness HV, the fracture toughness value K IC can be calculated by the following formula:
  • Critical current density refers to the minimum current density at which dendrites and short circuits will occur when the solid electrolyte membrane is electrochemically deposited with the corresponding alkali metal electrode. In other words, when the solid electrolyte membrane is electrochemically deposited below the critical current density, dendrites and short circuits will not occur.
  • Critical current density is the core indicator that describes the ability of solid electrolyte membranes to suppress dendrites and short circuits.
  • Test method The critical current density of the solid electrolyte membrane is measured by the traditional symmetrical battery step-by-step increase current density cycle method. Take the lithium-ion solid electrolyte as an example, and take the prepared solid electrolyte membrane. Two 8 mm dendrites and 50 ⁇ m thick lithium metal discs are placed in the center of the two symmetrical sides of the electrolyte. Mechanical pressure will make the lithium metal and the electrolyte sheet fit closely to form a lithium/solid electrolyte/lithium precipitation pool.
  • the lithium/solid electrolyte/lithium symmetrical battery starts from 0.25 milliamperes per square centimeter (mA/cm 2 ), and 1 milliampere per square centimeter (mAh/cm 2 ) of lithium is deposited and stripped on one side, and then the current is increased to 0.5mA/cm 2.
  • the surface capacity is deposited and stripped, and then the current is successively increased from 0.75mA/cm 2 , 1.0mA/cm 2 , 1.25mA/cm 2 ... to 10mA/cm 2 and the voltage is suddenly reduced sharply.
  • the lower current density is recorded as the critical current density.
  • some examples of the present application provide a solid electrolyte membrane, including a solid electrolyte material layer and a phase change toughening agent and a fiber material dispersed in the solid electrolyte material layer, wherein the solid electrolyte material layer includes an inorganic ceramic solid electrolyte material.
  • the above-mentioned solid electrolyte membrane disperses phase change toughening agent and fiber material in the solid electrolyte material layer.
  • phase change toughening agent and the fiber material to form an internal structure similar to "reinforced concrete", which can effectively improve the mechanical properties of the solid electrolyte membrane, especially the fracture toughness, thereby reducing problems such as dendrites and short circuits caused by fracture.
  • phase change toughening agents and fiber materials Furthermore, by rationally selecting the types of phase change toughening agents and fiber materials, the synergistic effect of phase change toughening and fiber toughening can be maximized, thereby achieving higher fracture toughness and critical current density.
  • the phase change toughening agent includes metastable ZrO 2. Further, the phase change toughening agent includes one or more of yttria stabilized zirconia (YSZ), scandia stabilized zirconia (SSZ), magnesia stabilized zirconia (MSZ), calcia stabilized zirconia (CSZ) and cesium oxide stabilized zirconia (CsSZ). Further, the phase change toughening agent includes yttria stabilized zirconia (YSZ). By properly selecting the type of phase change toughening agent, higher fracture toughness and critical current density can be achieved.
  • YSZ yttria stabilized zirconia
  • the fiber material includes ceramic fibers.
  • ceramic fibers themselves have no ion conduction capability, and also reduce the occurrence of fiber-induced deposition in conventional methods.
  • the fiber material includes one or more of silicon carbide fibers, silicon nitride fibers, boron nitride fibers, alumina fibers, and silica fibers.
  • the fiber material includes one or more of silicon carbide fibers, silicon nitride fibers, alumina fibers, and silica fibers.
  • the critical current density can be improved while achieving a better fracture toughness improvement effect by controlling the influence of the phase change toughening agent and the fiber material on the ion conduction and permeation in the solid electrolyte material.
  • the total volume of the phase change toughening agent and the fiber material in the solid electrolyte material layer is 5% to 20% by volume.
  • the volume percentage includes but is not limited to: 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20% or a range between any two of the foregoing values. Further, the volume percentage is 8% to 12%.
  • the volume ratio of the phase change toughening agent to the fiber material is 1:(0.25-4). Specifically, the volume ratio includes but is not limited to: 1:0.25, 1:0.5, 1:0.8, 1:1, 1:1.2, 1:1.5, 1:2, 1:3, 1:35, 4 or a range between any two of the foregoing values. Further, the volume ratio is 1:(0.5-1.5).
  • phase change toughening agent and the fiber material
  • a multi-scale structural toughening and dendrite inhibition structure can be formed to achieve better fracture toughness and critical current density levels.
  • the phase change toughening agent has a D 50 of 50 nm to 100 nm. Specifically, the phase change toughening agent has a D 50 of 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, 100 nm, or a range between any two of the foregoing values.
  • the diameter of the fiber material is 0.5 micrometers ( ⁇ m) to 5 ⁇ m, and the length is 10 ⁇ m to 30 ⁇ m.
  • the diameter of the fiber material includes but is not limited to: 0.5 ⁇ m, 1 ⁇ m, 1.5 ⁇ m, 2 ⁇ m, 2.5 ⁇ m, 3 ⁇ m, 3.5 ⁇ m, 4 ⁇ m, 4.5 ⁇ m, 5 ⁇ m or a range between any two of the foregoing values.
  • the length of the fiber material includes but is not limited to: 10 ⁇ m, 15 ⁇ m, 20 ⁇ m, 25 ⁇ m, 30 ⁇ m or a range between any two of the foregoing values.
  • the diameter of the fiber material is 0.5 ⁇ m to 3 ⁇ m, and the length is 15 ⁇ m to 30 ⁇ m.
  • the inorganic ceramic solid electrolyte material includes a lithium ion solid electrolyte material, a sodium ion solid electrolyte material or a potassium ion solid electrolyte material. Further, the inorganic ceramic solid electrolyte material includes a sulfide-based solid electrolyte material.
  • the lithium ion solid electrolyte includes one or more of a LISICON type solid electrolyte, a NASICON type lithium ion solid electrolyte, a Garnet type solid electrolyte, a LIPON type solid electrolyte, a Perovskite type solid electrolyte, an Anti-Perovskite type lithium ion solid electrolyte, a Thio-LiSICON type solid electrolyte, a Li 10 GeP 2 S 12 type solid electrolyte, a (100-e)Li 2 S ⁇ e(F2) ⁇ f(G2) type solid electrolyte, an Argyrodite type solid electrolyte, a Halide type solid electrolyte and a Hydride type lithium ion solid electrolyte; wherein, in the (100-e)Li 2 S ⁇ e(F2) ⁇ f(G2) type solid electrolyte, 20 ⁇ e ⁇ 30, 0 ⁇ f ⁇ 50, and F2 includes B 2 S S ⁇
  • the sodium ion solid electrolyte includes one or more of a NASICON sodium ion solid electrolyte, a Na- ⁇ -Alumina type solid electrolyte, a Na 3 PS 4 type solid electrolyte, a Na 11 Sn 2 PS 12 type solid electrolyte, an antiperovskite type solid electrolyte and a Hydride type sodium ion solid electrolyte.
  • the potassium ion solid electrolyte includes one or more of a ⁇ -Alumina type potassium ion solid electrolyte, an Anti-Perovskite type potassium ion solid electrolyte, a K 2 Fe 4 O 7 type solid electrolyte and a KSi 2 P 3 type solid electrolyte.
  • the Garnet-type solid electrolyte includes Li 7-a La 3 Zr 2-a (A2) a O 12 ; wherein 0 ⁇ a ⁇ 1; A2 includes Sb, One or more of Nb, Ta, Te and W.
  • Thio-LiSICON type solid electrolyte includes Li 3+b (B2) c (C2) 1-c (D2) 4-d (E2) d ; wherein, -1 ⁇ b ⁇ 2, 0 ⁇ c ⁇ 1, 0 ⁇ d ⁇ 2; B2 includes one or more of B, Al, In, Si, Ge, Sn, Ti, W and Mo; C2 includes one or more of P, As, Sb and Bi; D2 includes one or more of S and Se; E2 includes one or more of F, Cl, Br and I.
  • Argyrodite-type solid electrolytes include Li 6+g (H2) h (I2) 1-h (J2) 5-i (K2) 1+i ; wherein, -1 ⁇ g ⁇ 1, 0 ⁇ h ⁇ 1, -1 ⁇ i ⁇ 1; H2 includes one or more of B, Al, In, Si, Ge, Sn, Ti, W and Mo; I2 includes one or more of P, As, Sb and Bi; J2 represents one or more of S and Se; K2 includes one or more of F, Cl, Br and I.
  • the LISICON type solid electrolyte includes ⁇ -Li 3 PO 4 .
  • the NASICON-type lithium-ion solid electrolyte includes Li 1+j (L2) j (M2) 2-j (PO 4 ) 3 , wherein 0 ⁇ j ⁇ 1; L2 includes one or more of Al, Cr, Ba, Fe, Sc, In, Lu, Y and La; and M2 includes one or more of Ti and Ge.
  • the Perovskite-type solid electrolyte includes Li 3k (N2) 2/3-k (Q2)O 3 , wherein 0.04 ⁇ k ⁇ 0.17; N2 includes one or more of La, Sr, Ba and Nd; and Q2 includes one or more of Al, Ti and Ge.
  • the anti-Perovskite type lithium ion solid electrolyte includes Li 3 OCl.
  • the Li 10 GeP 2 S 12 type solid electrolyte includes Li 10+l (R2) 1+m (S2) 2-m (T2) 12-n (U2) n , wherein -2 ⁇ l ⁇ 2, 0 ⁇ m ⁇ 2, 0 ⁇ n ⁇ 2, R2 includes one or more of B, Al, In, Si, Ge, Sn, Ti, W and Mo; S2 includes one or more of P, As, Sb and Bi; T2 includes one or more of S and Se; U2 includes one or more of F, Cl, Br and I.
  • the Halide-type solid electrolyte includes one or more of Li 3 (V2)(W2) 6 and Li 2 Sc 2/3 (W2) 4 ; wherein V2 includes one or more of Y, Er, In, Sc and Ga; and W2 includes one or more of F, Cl, Br and I.
  • the hydride-type lithium-ion solid electrolyte includes one or more of LiBH 4 and pLi(CB 9 H 10 ) ⁇ (1-p)Li(CB 11 H 12 ); wherein 0 ⁇ p ⁇ 1.
  • the NASICON sodium ion solid electrolyte includes Na 1+t+2u Zr 2-u (A3) u P 3-t Si t O 12 ; wherein 0 ⁇ t ⁇ 3, 0 ⁇ u ⁇ 1, and A3 includes one or more of Zn, Mg and Ca.
  • the Na- ⁇ -Alumina type solid electrolyte includes one or more of Na 2 O ⁇ (5-7)Al 2 O 3 and Na 2 O ⁇ (8-11)Al 2 O 3 .
  • Na 3 PS 4 type solid electrolyte includes Na 3+x (B3) v (C3) 1-v (D3) 4-w (E3) w , where -1 ⁇ x ⁇ 2, 0 ⁇ v ⁇ 1, 0 ⁇ w ⁇ 2, B3 includes one or more of B, Al, In, Si, Ge, Sn, Ti, W and Mo; C3 includes one or more of P, As, Sb and Bi; D3 includes one or more of S and Se; E3 represents one or more of F, Cl, Br and I.
  • the Na 11 Sn 2 PS 12 type solid electrolyte includes Na 11+(x1) (F3) 2-y (G3) 1+y (H3) 12-z (J3) z , where -1 ⁇ x1 ⁇ 1, 0 ⁇ y ⁇ 2, 0 ⁇ z ⁇ 2, F3 includes one or more of B, Al, In, Si, Ge, Sn, Ti, W and Mo; G3 includes one or more of P, As, Sb and Bi; H3 includes one or more of S and Se; J3 includes one or more of F, Cl, Br and I.
  • the antiperovskite solid electrolyte includes Na 3 O (K3), wherein K3 includes one or more of Cl, Br, I and BH 4 .
  • the ⁇ -Alumina type potassium ion solid electrolyte includes K 2 O ⁇ (8-11)Al 2 O 3 .
  • the anti-Perovskite type potassium ion solid electrolyte includes K 3 OI.
  • the K 2 Fe 4 O 7 type solid electrolyte includes K 2 Fe 4 O 7 .
  • the KSi 2 P 3 type solid electrolyte includes KSi 2 P 3 .
  • the fracture toughness of the solid electrolyte membrane can be effectively improved by the above-mentioned membrane layer design.
  • the fracture toughness of the solid electrolyte membrane is ⁇ 0.25MPa ⁇ m 1/2 .
  • the fracture toughness of the solid electrolyte membrane is ⁇ 1.5MPa ⁇ m 1/2 .
  • the fracture toughness of the solid electrolyte membrane includes but is not limited to: 1.67MPa ⁇ m 1/2 , 2.17MPa ⁇ m 1/2 , 2.37MPa ⁇ m 1/2 , 2.79MPa ⁇ m 1/2 , 2.83MPa ⁇ m 1/2 , 2.91MPa ⁇ m 1/2 , 3.02MPa ⁇ m 1/2 , 3.07MPa ⁇ m 1/2 , 3.09MPa ⁇ m 1/2 , 3.11MPa ⁇ m 1/2 , 3.17MPa ⁇ m 1/2 , 3.19MPa ⁇ m 1/2 , 3.23MPa ⁇ m 1/2 , 3.32MPa ⁇ m 1/2 , 3.44MPa ⁇ m 1/2 , 3.69MPa ⁇ m 1/2 , 4.76MPa ⁇ m 1/2 , 5.32MPa ⁇ m1 /2 , 6.231MPa ⁇ m1 /2 .
  • the fracture toughness is related to the specific type of solid electrolyte material.
  • the inorganic ceramic solid electrolyte material includes a sulfide-based solid electrolyte material
  • the above performance can be met
  • the solid electrolyte material is other types of materials
  • the fracture toughness may also be less than 0.25MPa ⁇ m1 /2 , but when the solid electrolyte material used is the same, the use of the above example of the present application can improve the fracture toughness of the solid electrolyte membrane.
  • the critical current density of the solid electrolyte membrane can be effectively improved.
  • the critical current density of the solid electrolyte membrane is ⁇ 1.5mA/ cm2 .
  • the critical current density of the solid electrolyte membrane is ⁇ 2mA/ cm2 .
  • the critical current density of the solid electrolyte membrane includes but is not limited to: 3.75mA/ cm2 , 4.25mA/ cm2 , 4.50mA/ cm2 , 5.0mA/ cm2 , 5.25mA/cm2, 5.50mA/ cm2 , 5.75mA / cm2 , 6.0mA/ cm2 , 6.02mA/ cm2 , 6.25mA/ cm2 , 7.25mA/ cm2 .
  • the critical current density is related to the specific type of solid electrolyte material.
  • the inorganic ceramic solid electrolyte material includes a sulfide-based solid electrolyte material
  • the above performance can be met, and when the solid electrolyte material is other types of materials, the critical current density may also be less than 1.5 mA/cm 2 , but when the solid electrolyte material used is the same, the critical current density of the solid electrolyte membrane can be improved by using the solution exemplified above in the present application.
  • Some other examples of the present application provide a method for preparing the solid electrolyte membrane as described above, comprising the following steps:
  • the mixed material is subjected to molding treatment to prepare the solid electrolyte membrane.
  • the preparation method of the solid electrolyte membrane has simple steps and is easy to promote and apply in industry.
  • the mixing is dry mixing.
  • the molding process is a pressurization process.
  • the pressure of the pressurization process is 300 MPa to 600 MPa.
  • the mixing is wet mixing.
  • the molding process step includes coating the mixture into a film, and a drying step.
  • the solvent used in the wet mixing includes one or more of toluene, p-xylene, o-xylene, m-xylene, trimethylbenzene, ethyl acetate, butyl butyrate, n-butyl ether, anisole, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and n-butane.
  • a solid-state battery is provided.
  • a solid-state battery includes a positive electrode sheet, a negative electrode sheet, and an electrolyte.
  • active ions are embedded and extracted back and forth between the positive electrode sheet and the negative electrode sheet.
  • the electrolyte plays the role of conducting ions between the positive electrode sheet and the negative electrode sheet.
  • the electrolyte adopts the solid electrolyte layer as described above.
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer arranged on at least one surface of the positive electrode current collector, and the positive electrode active material layer includes the positive electrode active material of the first aspect of the present application.
  • the positive electrode current collector has two surfaces facing each other in its thickness direction, and the positive electrode active material layer is disposed on any one or both of the two facing surfaces of the positive electrode current collector.
  • the positive electrode current collector may be a metal foil or a composite current collector.
  • aluminum foil may be used as the metal foil.
  • the composite current collector may include a polymer material base and a metal layer formed on at least one surface of the polymer material base.
  • the composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the positive electrode active material may be a positive electrode active material for a battery known in the art.
  • the positive electrode active material may include at least one of the following materials: an olivine-structured lithium-containing phosphate, a lithium transition metal oxide, and their respective modified compounds.
  • the present application is not limited to these materials, and other traditional materials that can be used as positive electrode active materials for batteries may also be used. These positive electrode active materials may be used alone or in combination of two or more.
  • lithium transition metal oxides include, but are not limited to, lithium cobalt oxide (such as LiCoO 2 ), lithium nickel oxide (such as LiNiO 2 ), lithium manganese oxide (such as LiMnO 2 , LiMn 2 O 4 ), lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (such as LiNi 1/3 Co 1/3 Mn 1/3 O 2 (also referred to as NCM 333 ), LiNi 0.5 Co 0.2 Mn 0.3 O 2 (also referred to as NCM 523 ), LiNi 0.5 Co 0.25 Mn 0.25 O 2 (also referred to as NCM 211 ), LiNi 0.6 Co 0.2 Mn 0.2 O 2 (also referred to as NCM 622 ), LiNi 0.8 Co 0.1 Mn 0.1 O 2 (also referred to as NCM 811 ) , and LiNi 0.8 Co 0.2 Mn 0.2 O 2 (also referred to as NCM 811 ,
  • lithium-containing phosphates with an olivine structure may include, but are not limited to, at least one of lithium iron phosphate (such as LiFePO 4 (also referred to as LFP)), a composite material of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO 4 ), a composite material of lithium manganese phosphate and carbon, lithium iron manganese phosphate, and a composite material of lithium iron manganese phosphate and carbon.
  • lithium iron phosphate such as LiFePO 4 (also referred to as LFP)
  • LiMnPO 4 lithium manganese phosphate
  • LiMnPO 4 lithium manganese phosphate
  • LiMnPO 4 lithium manganese phosphate and carbon
  • the positive electrode active material layer may further include a binder.
  • the binder may include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride, polyvinylide ... At least one of ethylene-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer and fluorine-containing acrylate resin.
  • the positive electrode active material layer may further include a conductive agent.
  • the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
  • the positive electrode sheet can be prepared in the following manner: the components for preparing the positive electrode sheet, such as the positive electrode active material, the conductive agent, the binder and any other components are dispersed in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry; the positive electrode slurry is coated on the positive electrode collector, and after drying, cold pressing and other processes, the positive electrode sheet can be obtained.
  • a solvent such as N-methylpyrrolidone
  • the negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer disposed on at least one surface of the negative electrode current collector, wherein the negative electrode active material layer includes a negative electrode active material.
  • the negative electrode current collector has two surfaces facing each other in its thickness direction, and the negative electrode active material layer is disposed on any one or both of the two facing surfaces of the negative electrode current collector.
  • the negative electrode current collector may be a metal foil or a composite current collector.
  • a metal foil a copper foil may be used.
  • the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material substrate.
  • the composite current collector may be formed by forming a metal material (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the negative electrode active material may adopt the negative electrode active material for batteries known in the art.
  • the negative electrode active material may include at least one of the following materials: lithium metal, lithium-containing alloys, lithium-containing composites, artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, etc.
  • the silicon-based material can be selected from at least one of elemental silicon, silicon oxide compounds, silicon-carbon composites, silicon-nitrogen composites, and silicon alloys.
  • the tin-based material can be selected from at least one of elemental tin, tin oxide compounds, and tin alloys.
  • the present application is not limited to these materials, and other traditional materials that can be used as negative electrode active materials for batteries can also be used. These negative electrode active materials can be used alone or in combination of two or more.
  • the negative electrode active material includes one or more of lithium metal, lithium-containing alloys, and lithium-containing composites.
  • the negative electrode active material layer may further include a binder.
  • the binder may be selected from at least one of styrene-butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), polymethacrylic acid (PMAA) and carboxymethyl chitosan (CMCS).
  • the negative electrode active material layer may further include a conductive agent, which may be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • a conductive agent which may be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the negative electrode active material layer may further include other additives, such as a thickener (eg, sodium carboxymethyl cellulose (CMC-Na)).
  • a thickener eg, sodium carboxymethyl cellulose (CMC-Na)
  • the negative electrode sheet can be prepared in the following manner: the components for preparing the negative electrode sheet, such as the negative electrode active material, the conductive agent, the binder and any other components are dispersed in a solvent (such as deionized water) to form a negative electrode slurry; the negative electrode slurry is coated on the negative electrode collector, and after drying, cold pressing and other processes, the negative electrode sheet can be obtained.
  • a solvent such as deionized water
  • the positive electrode sheet, the negative electrode sheet and the solid electrolyte membrane can be made into an electrode assembly by a winding process or a lamination process.
  • the solid-state battery may include an outer packaging that can be used to encapsulate the electrode assembly and the electrolyte.
  • the outer packaging of the solid-state battery can be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc.
  • the outer packaging of the solid-state battery can also be a soft package, such as a bag-type soft package.
  • the material of the soft package can be plastic, and as the plastic, polypropylene, polybutylene terephthalate, and polybutylene succinate can be listed.
  • FIG1 is a solid-state battery 5 of a square structure as an example.
  • solid-state batteries may be assembled into a battery module.
  • the number of solid-state batteries contained in the battery module may be one or more, and the specific number may be selected by those skilled in the art according to the application and capacity of the battery module.
  • FIG2 is a battery module 4 as an example.
  • a plurality of solid-state batteries 5 may be arranged in sequence along the length direction of the battery module 4. Of course, they may also be arranged in any other manner. Further, the plurality of solid-state batteries 5 may be fixed by fasteners.
  • the battery module 4 may further include a housing having a receiving space, and the plurality of solid-state batteries 5 are received in the receiving space.
  • the battery modules may be assembled into a battery pack.
  • the battery pack may contain one or more battery modules. The specific number may be selected by those skilled in the art according to the application and capacity of the battery pack.
  • FIG3 and FIG4 are battery packs 1 as an example.
  • the battery pack 1 may include a battery box and a plurality of battery modules 4 disposed in the battery box.
  • the battery box includes an upper box body 2 and a lower box body 3, and the upper box body 2 can be covered on the lower box body 3 to form a closed space for accommodating the battery modules 4.
  • the plurality of battery modules 4 can be arranged in the battery box in any manner.
  • the present application also provides an electrical device, which includes at least one of the solid-state batteries, battery modules, or battery packs provided in the present application.
  • the solid-state battery, battery module, or battery pack can be used as a power source for the electrical device, or as an energy storage unit for the electrical device.
  • the electrical device may include mobile devices, electric vehicles, electric trains, ships and satellites, energy storage systems, etc., but are not limited to these.
  • the mobile device may be, for example, a mobile phone, a laptop computer, etc.;
  • the electric vehicle may be, for example, a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf cart, an electric truck, etc., but are not limited to these.
  • a solid-state battery, battery module or battery pack can be selected according to its usage requirements.
  • FIG5 is an example of an electric device 5.
  • the electric device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle, etc.
  • a battery pack or a battery module may be used.
  • Another example device may be a mobile phone, a tablet computer, a laptop computer, etc. Such a device is usually required to be thin and light, and a solid-state battery may be used as a power source.
  • the uniformly mixed composite solid electrolyte powder is pressed into a solid electrolyte disc with a thickness of 1 mm and a diameter of 5 mm using a 5 mm stainless steel mold at a pressure of 500 MPa.
  • the cross-sectional scanning electron microscope image of the solid electrolyte membrane prepared in Example 1 is shown in FIG6 , and it can be seen that the phase change toughening agent and the fiber form a structure similar to "reinforced concrete".
  • Examples 2 to 19 and Comparative Examples 1 to 3 change the type or volume percentage or D50 of the phase change toughening agent, the type or volume percentage or diameter*length of the fiber on the basis of Example 1, and the remaining steps are the same as Example 1, as shown in Table 1.
  • the embodiment can improve the mechanical properties and critical current density of the solid electrolyte membrane by combining the phase change toughening agent and the fiber material.

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Abstract

一种固态电解质膜及其制备方法、固态电池、用电装置。所述固态电解质膜包括固态电解质材料层以及分散在固态电解质材料层中的相变增韧剂和纤维材料，所述固态电解质材料层包括无机陶瓷固态电解质材料。上述固态电解质膜在固态电解质材料层通过相变增韧剂和纤维材料之间的协同作用，能够有效提升固态电解质膜的力学性能，特别是断裂韧性，进而减少断裂导致的枝晶和短路等问题。

Description

固态电解质膜及其制备方法、固态电池、用电装置
交叉引用
本申请引用于2023年05月04日递交的名称为“固态电解质膜及其制备方法、固态电池、用电装置”的第2023104881248号中国专利申请，其通过引用被全部并入本申请。
技术领域
本申请涉及电池技术领域，特别是涉及一种固态电解质膜及其制备方法、固态电池、用电装置。
背景技术
近年来，随着电池的应用范围越来越广泛，电池广泛应用于水力、火力、风力和太阳能电站等储能电源系统，以及电动工具、电动自行车、电动摩托车、电动汽车、军事装备、航空航天等多个领域。随着电池研究的进展，固态电池应运而生，且近年来已被视为可以继承锂离子电池地位的电池。固态锂电池技术以固态电解质替代电解液，可以大大提升锂电池的能量密度。
目前，固态电解质可以分为聚合物类固态电解质和无机陶瓷类固态电解质。其中相比较聚合物类固态电解质，无机陶瓷类固态电解质脆弱的力学性能是此类固态电解质应用的核心瓶颈。
发明内容
基于此，本申请提供一种固态电解质膜及其制备方法、固态电池、用电装置。该固态电解质膜具有良好的力学性能。
本申请的第一方面，提供一种固态电解质膜，包括固态电解质材料层以及分散在固态电解质材料层中的相变增韧剂和纤维材料，所述固态电解质材料层包括无机陶瓷固态电解质材料。
上述固态电解质膜在固态电解质材料层通过相变增韧剂和纤维材料之间的协同作用，能够有效提升固态电解质膜的力学性能，特别是断裂韧性，进而减少固态电解质膜因断裂导致的枝晶和短路等问题。
在其中一个实施例中，所述相变增韧剂包括介稳状态的ZrO2；可选地，所述相变增韧剂包括氧化钇稳定氧化锆(YSZ)、氧化钪稳定氧化锆(SSZ)、氧化镁稳定氧化锆(MSZ)、氧化钙稳定氧化锆(CSZ)和氧化铯稳定氧化锆(CsSZ)中的一种或多种。
在其中一个实施例中，所述纤维材料包括陶瓷纤维；可选地，所述纤维材料包括碳化硅 纤维、氮化硅纤维、氮化硼纤维、氧化铝纤维和二氧化硅纤维中的一种或多种。
在其中一个实施例中，所述相变增韧剂和纤维材料的总体积在所述固态电解质材料层中的体积百分比为5％～20％；可选地，所述体积百分比为8％～12％。
在其中一个实施例中，所述相变增韧剂与所述纤维材料的体积比为1:(0.25～4)；可选地，所述体积比为1:(0.5～1.5)。
在其中一个实施例中，所述相变增韧剂的D50＝50nm～100nm。
在其中一个实施例中，所述纤维材料的直径为0.5μm～5μm，长度为10μm～30μm。
在其中一个实施例中，所述无机陶瓷固态电解质材料包括锂离子固态电解质材料、钠离子固态电解质材料或钾离子固态电解质材料。
在其中一个实施例中，所述固态电解质膜具有如下(1)～(2)所示特征中的一项或多项：
(1)所述固态电解质膜的断裂韧性≥0.25MPa·m1/2；可选地，所述固态电解质膜的断裂韧性≥1.5MPa·m1/2；
(2)所述固态电解质膜的临界电流密度≥1.5mA/cm2；可选地，所述固态电解质膜的临界电流密度≥2mA/cm2。
本申请的第二方面，提供第一方面所述的固态电解质膜的制备方法，包括如下步骤：
将所述无机陶瓷固态电解质材料、相变增韧剂和纤维材料混合，制备混合料；
将所述混合料进行成型处理，制备所述固态电解质膜。
上述固态电解质膜的制备方法步骤简单，便于工业化推广应用。
在其中一个实施例中，所述混合为干法混合。
在其中一个实施例中，所述成型处理为加压处理；可选地，所述加压处理的压力为300MPa～600MPa。
在其中一个实施例中，所述混合为湿法混合。
在其中一个实施例中，所述成型处理的步骤包括将所述混合料涂布成膜，以及干燥的步骤；可选地，所述湿法混合采用的溶剂包括甲苯、对二甲苯、邻二甲苯、间二甲苯、三甲苯、乙酸乙酯、丁酸丁酯、正丁醚、苯甲醚、乙二醇二甲醚、乙二醇二乙醚和正丁烷中的一种或多种。
本申请的第三方面，提供一种固态电池，包括第一方面所述的固态电解质膜。
本申请的第四方面，提供一种用电装置，包括第三方面所述的固态电池。
附图说明
为了更清楚地说明本申请实施例的技术方案，下面将对本申请实施例中所需要使用的附图作简单地介绍，显而易见地，下面所描述的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据附图获得其他的附图。在附 图中：
图1为本申请一实施方式的固态电池的示意图；
图2为本申请一实施方式的电池模块的示意图；
图3为本申请一实施方式的电池包的示意图；
图4为图3所示的本申请一实施方式的电池包的分解图；
图5为本申请一实施方式的固态电池用作电源的用电装置的示意图；
图6为本申请一实施例制备得到的固态电解质膜的断面扫描电子显微镜图像；
附图标记说明：
1：电池包；2：上箱体；3：下箱体；4：电池模块；5：固态电池；6：用电装置。
具体实施方式
以下，适当地参照附图详细说明具体公开了本申请的固态电解质膜及其制备方法、固态电池、用电装置的实施方式。但是会有省略不必要的详细说明的情况。例如，有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长，便于本领域技术人员的理解。此外，附图及以下说明是为了本领域技术人员充分理解本申请而提供的，并不旨在限定权利要求书所记载的主题。
本申请所公开的“范围”以下限和上限的形式来限定，给定范围是通过选定一个下限和一个上限进行限定的，选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的，并且可以进行任意地组合，即任何下限可以与任何上限组合形成一个范围。例如，如果针对特定参数列出了60-120和80-110的范围，理解为60-110和80-120的范围也是预料到的。此外，如果列出的最小范围值1和2，和如果列出了最大范围值3，4和5，则下面的范围可全部预料到：1-3、1-4、1-5、2-3、2-4和2-5。在本申请中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本文中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。另外，当表述某个参数为≥2的整数，则相当于公开了该参数为例如整数2、3、4、5、6、7、8、9、10、11、12等。
如果没有特别的说明，本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有技术特征以及可选技术特征可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有步骤可以顺序进行，也可以随机进行，在一些示例中是顺序进行的。例如，所述方法包括步骤(a)和(b)，表示所述方法可包括顺序进行的步骤(a)和(b)，也可以包括顺序进行的步骤(b)和(a)。例如，所述提到所述方法还可包括步骤(c)，表示 步骤(c)可以任意顺序加入到所述方法，例如，所述方法可以包括步骤(a)、(b)和(c)，也可包括步骤(a)、(c)和(b)，也可以包括步骤(c)、(a)和(b)等。
如果没有特别的说明，本申请所提到的“包括”和“包含”表示开放式，也可以是封闭式。例如，所述“包括”和“包含”可以表示还可以包括或包含没有列出的其他组分，也可以仅包括或包含列出的组分。
如果没有特别的说明，在本申请中，术语“或”是包括性的。举例来说，短语“A或B”表示“A，B，或A和B两者”。更具体地，以下任一条件均满足条件“A或B”：A为真(或存在)并且B为假(或不存在)；A为假(或不存在)而B为真(或存在)；或A和B都为真(或存在)。
在本申请中，断裂韧性的定义及测试方法如下：
定义：断裂韧性是描述材料在发生断裂前对应变能的吸收能力的参数，更高的断裂韧性代表着对裂纹传播更强的阻碍能力。在这里也反映固态电解质膜对枝晶导致的开裂和短路的抵抗能力。断裂韧性有四点弯曲实验、Vickers锥型压痕实验等测试方法，在本申请中选用Vickers锥形压痕实验来得出。
测试方法：将制备得到的固态电解质膜在氩气氛围内对固态电解质片的表面用砂纸进行抛光，从800目，到2000目，到4000目，到8000目，直至电解质表面呈现镜面特性无明显缺陷。之后通过Vickers锥形压痕测试仪，对抛光面进行压痕测试。以适当载荷驱动压痕测试仪直至锥形压痕的四角出现辐射状裂纹。根据压痕载荷P、辐射状裂纹的扩展长度C，杨氏模量E和显微硬度HV可通过下方公式计算出断裂韧性数值KIC：
在本申请中，临界电流密度的定义及测试方法如下：
定义：临界电流密度指固态电解质膜与对应碱金属电极搭配会发生电化学沉积时，会发生枝晶和短路的最低电流密度，也即固态电解质膜在低于临界电流密度发生电化学沉积时，不会发生枝晶和短路。临界电流密度是描述固态电解质膜对枝晶和短路抑制能力的核心指标。
测试方法：固态电解质膜的临界电流密度通过传统的对称电池阶梯式增长电流密度循环的方式来测出。以锂离子固态电解质为例，取制备得到的固态电解质膜。将两片8毫米(mm)枝晶，50微米(μm)厚的锂金属圆片置于电解质两侧对称的中心的位置，会通过机械压力让锂金属与电解质片紧密贴合，组成锂/固态电解质/锂对沉淀池。将对称电池组装并封装后，使锂/固态电解质/锂对称电池从0.25毫安每平方厘米(mA/cm2)开始，在一侧依次沉积和剥离1毫安时每平方厘米(mAh/cm2)锂后提高电流至0.5mA/cm2，保持1mAh/cm2面容量沉积剥离后，依次在0.75mA/cm2，1.0mA/cm2，1.25mA/cm2……至10mA/cm2并将电压突然大幅降 低的电流密度记为临界电流密度。
目前，由于无机陶瓷类固态电解质脆弱的力学性能，使得其容易碎裂，并容易在负极侧沉积时产生枝晶和短路。传统方法中通过在固态电解质中引入纤维以提升固态电解质膜的力学性能，进而减少因断裂出现的枝晶和短路现象。但是这种方式对于力学性能的提升有限。
基于此，本申请一些示例提供一种固态电解质膜，包括固态电解质材料层以及分散在固态电解质材料层中的相变增韧剂和纤维材料，所述固态电解质材料层包括无机陶瓷固态电解质材料。
上述固态电解质膜在固态电解质材料层的中分散相变增韧剂和纤维材料，相变增韧剂和纤维材料之间存在协同作用，形成类似于“钢筋混凝土”的内部结构，能够有效提升固态电解质膜的力学性能，特别是断裂韧性，进而减少断裂导致的枝晶和短路等问题。
另外在研究过程中还发现，在该固态电解质产生缺陷和生成枝晶时，局部膨胀产生的拉应力还会使得周围的相变增韧剂原位发生相变，并产生压应力以进一步减少缺陷和枝晶的生成，在提高固态电解质膜力学性能的同时大幅提高固态电解质的临界电流密度。
进一步地，通过合理选择相变增韧剂与纤维材料的种类，可以最大化相变增韧与纤维增韧的协同效果，从而达到更高的断裂韧性和临界电流密度。
在其中一些示例中，所述相变增韧剂包括介稳状态的ZrO2。进一步地，所述相变增韧剂包括氧化钇稳定氧化锆(YSZ)、氧化钪稳定氧化锆(SSZ)、氧化镁稳定氧化锆(MSZ)、氧化钙稳定氧化锆(CSZ)和氧化铯稳定氧化锆(CsSZ)中的一种或多种。更进一步地，所述相变增韧剂包括氧化钇稳定氧化锆(YSZ)。通过合理选择相变增韧剂的种类，可以达到更高的断裂韧性和临界电流密度。
在其中一些示例中，所述纤维材料包括陶瓷纤维。除了优化断裂韧性和临界电流密度之外，陶瓷纤维本身没有离子传导的能力，也减少了传统方法中纤维诱导沉积的现象出现。进一步地，所述纤维材料包括碳化硅纤维、氮化硅纤维、氮化硼纤维、氧化铝纤维和二氧化硅纤维中的一种或多种。更进一步地，所述纤维材料包括碳化硅纤维、氮化硅纤维、氧化铝纤维和二氧化硅纤维中的一种或多种。通过合理选择纤维材料的种类，可以达到更高的断裂韧性和临界电流密度。
进一步地，通过合理选择相变增韧剂与纤维材料在固态电解质材料层中的总体积占比，可以通过控制相变增韧剂与纤维材料对固态电解质材料中离子传导渗流的影响从而在达到较优的断裂韧性提升效果的同时，还可以提升临界电流密度。
在其中一些示例中，所述相变增韧剂和纤维材料的总体积在所述固态电解质材料层中的体积百分比为5％～20％。具体地，所述体积百分比包括但不限于：5％、6％、7％、8％、9％、10％、11％、12％、13％、14％、15％、16％、17％、18％、19％、20％或前述任两个数值之间的范围值。进一步地，所述体积百分比为8％～12％。
进一步地，通过合理选择相变增韧剂与纤维材料的体积比，可以达到更优的断裂韧性及临界电流密度水平。
在其中一些示例中，所述相变增韧剂与所述纤维材料的体积比为1:(0.25～4)。具体地，所述体积比包括但不限于：1:0.25、1:0.5、1:0.8、1:1、1:1.2、1:1.5、1:2、1:3、1:35、4或前述任两个数值之间的范围值。进一步地，所述体积比为1:(0.5～1.5)。
进一步地，通过合理选择所述相变增韧剂和纤维材料的比例和尺寸，能够形成多尺度的结构增韧与枝晶抑制结构，实现更优的断裂韧性及临界电流密度水平。
在其中一些示例中，所述相变增韧剂的D50＝50纳米(nm)～100nm。具体地，所述相变增韧剂的D50包括但不限于：50nm、55nm、60nm、65nm、70nm、75nm、80nm、85nm、90nm、95nm、100nm或前述任两个数值之间的范围值。
在其中一些示例中，所述纤维材料的直径为0.5微米(μm)～5μm，长度为10μm～30μm。具体地，所述纤维材料的直径包括但不限于：0.5μm、1μm、1.5μm、2μm、2.5μm、3μm、3.5μm、4μm、4.5μm、5μm或前述任两个数值之间的范围值。所述纤维材料的长度包括但不限于：10μm、15μm、20μm、25μm、30μm或前述任两个数值之间的范围值。进一步地，所述纤维材料的直径为0.5μm～3μm，长度为15μm～30μm。
在其中一些示例中，所述无机陶瓷固态电解质材料包括锂离子固态电解质材料、钠离子固态电解质材料或钾离子固态电解质材料。进一步地，所述无机陶瓷固态电解质材料包括硫化物系固态电解质材料。
不作限制地，所述锂离子固态电解质包括LISICON型固态电解质、NASICON型锂离子固态电解质、Garnet型固态电解质、LIPON型固态电解质、Perovskite型固态电解质、Anti-Perovskite型锂离子固态电解质、Thio-LiSICON型固态电解质、Li10GeP2S12型固态电解质、(100-e)Li2S·e(F2)·f(G2)型固态电解质、Argyrodite型固态电解质、Halide型固态电解质和Hydride型锂离子固态电解质中的一种或多种；其中，所述(100-e)Li2S·e(F2)·f(G2)型固态电解质中20≤e≤30，0≤f≤50，F2包括B2S3、Al2S3、In2S3、SiS2、GeS2、SnS2、P2S5、As2S3、Sb2S5、Bi2S3、WS2和MoS2中的一种或多种，G2包括B2O3、Al2O3、In2O3、SiO2、GeO2、SnO2、P2O5、Sb2O5、Bi2O3、WO2、WO3、MoO2、MoO3、Fe2O3、ZnO、MgO、CuO、CaO、LiN、Li2O、LiF、LiCl、LiBr和LiI中的一种或多种。
钠离子固态电解质包括NASICON型钠离子固态电解质、Na-β-Alumina型固态电解质、Na3PS4型固态电解质、Na11Sn2PS12型固态电解质、反钙钛矿型固态电解质和Hydride型钠离子固态电解质中的一种或多种。
钾离子固态电解质包括β-Alumina型钾离子固态电解质、Anti-Perovskite型钾离子固态电解质、K2Fe4O7型固态电解质和KSi2P3型固态电解质中的一种或多种。
作为示例，Garnet型固态电解质包括Li7-aLa3Zr2-a(A2)aO12；其中，0≤a<1；A2包括Sb、 Nb、Ta、Te和W中的一种或多种。
Thio-LiSICON型固态电解质包括Li3+b(B2)c(C2)1-c(D2)4-d(E2)d；其中，-1<b<2，0≤c≤1，0≤d≤2；B2包括B、Al、In、Si、Ge、Sn、Ti、W和Mo中的一种或多种；C2包括P、As、Sb和Bi中的一种或多种；D2包括S和Se中的一种或多种；E2包括F、Cl、Br和I中的一种或多种。
Argyrodite型固态电解质包括Li6+g(H2)h(I2)1-h(J2)5-i(K2)1+i；其中，-1≤g≤1，0≤h≤1，-1<i≤1；H2包括B、Al、In、Si、Ge、Sn、Ti、W和Mo中的一种或多种；I2包括P、As、Sb和Bi中的一种或多种；J2表示S和Se中的一种或多种；K2包括F、Cl、Br和I中的一种或多种。
LISICON型固态电解质包括γ-Li3PO4。
NASICON型锂离子固态电解质包括Li1+j(L2)j(M2)2-j(PO4)3，其中，0≤j<1；L2包括Al、Cr、Ba、Fe、Sc、In、Lu、Y和La中的一种或多种；M2包括Ti和Ge中的一种或多种。
Perovskite型固态电解质包括Li3k(N2)2/3-k(Q2)O3，其中0.04<k<0.17；N2包括La、Sr、Ba和Nd中的一种或多种；Q2包括Al、Ti和Ge中的一种或多种。
Anti-Perovskite型锂离子固态电解质包括Li3OCl。
Li10GeP2S12型固态电解质包括Li10+l(R2)1+m(S2)2-m(T2)12-n(U2)n，其中-2<l<2，0≤m≤2，0≤n≤2，R2包括B、Al、In、Si、Ge、Sn、Ti、W和Mo中的一种或多种；S2包括P、As、Sb和Bi中的一种或多种；T2包括S和Se中的一种或多种；U2包括F、Cl、Br和I中的一种或多种。
Halide型固态电解质包括Li3(V2)(W2)6和Li2Sc2/3(W2)4中的一种或多种；其中，V2包括Y、Er、In、Sc和Ga中的一种或多种；W2包括F、Cl、Br和I中的一种或多种。
Hydride型锂离子固态电解质包括LiBH4和pLi(CB9H10)·(1-p)Li(CB11H12)中的一种或多种；其中，0<p<1。
LIPON型固态电解质包括LixPOyNz等；其中(2y+3z-x＝5，x≥1，y≥1，z≥0)。
NASICON型钠离子固态电解质包括Na1+t+2uZr2-u(A3)uP3-tSitO12；其中，0≤t≤3，0≤u≤1，A3包括Zn、Mg和Ca中的一种或多种。
Na-β-Alumina型固态电解质包括Na2O·(5-7)Al2O3和Na2O·(8-11)Al2O3中的一种或多种。
Na3PS4型固态电解质包括Na3+x(B3)v(C3)1-v(D3)4-w(E3)w，其中-1<x<2，0≤v≤1，0≤w≤2,B3包括B、Al、In、Si、Ge、Sn、Ti、W和Mo中的一种或多种；C3包括P、As、Sb和Bi中的一种或多种；D3包括S和Se中的一种或多种；E3表示F、Cl、Br和I中的一种或多种。
Na11Sn2PS12型固态电解质包括Na11+(x1)(F3)2-y(G3)1+y(H3)12-z(J3)z，其中-1<x1<1，0≤y≤2，0≤z≤2，F3包括B、Al、In、Si、Ge、Sn、Ti、W和Mo中的一种或多种；G3包括P、As、Sb和Bi中的一种或多种；H3包括S和Se中的一种或多种；J3包括F、Cl、Br和I中的一种或多种。
反钙钛矿型固态电解质包括Na3O(K3)，其中，K3包括Cl、Br、I和BH4中的一种或多种。
Hydride型钠离子固态电解质包括Na2C(b1)B(a1)-(b1)H(b1)和Na(BH4)0.5(NH2)0.5等，其中，其中，a1＝10或12，b1＝0或1。
β-Alumina型钾离子固态电解质包括K2O·(8-11)Al2O3。
Anti-Perovskite型钾离子固态电解质包括K3OI。
K2Fe4O7型固态电解质包括K2Fe4O7。
KSi2P3型固态电解质包括KSi2P3。
进一步地，通过上述的膜层设计，可以有效提高固态电解质膜的断裂韧性。在其中一些示例中，所述固态电解质膜的断裂韧性≥0.25MPa·m1/2。进一步地，所述固态电解质膜的断裂韧性≥1.5MPa·m1/2。具体地，所述固态电解质膜的断裂韧性包括但不限于：1.67MPa·m1/2、2.17MPa·m1/2、2.37MPa·m1/2、2.79MPa·m1/2、2.83MPa·m1/2、2.91MPa·m1/2、3.02MPa·m1/2、3.07MPa·m1/2、3.09MPa·m1/2、3.11MPa·m1/2、3.17MPa·m1/2、3.19MPa·m1/2、3.23MPa·m1/2、3.32MPa·m1/2、3.44MPa·m1/2、3.69MPa·m1/2、4.76MPa·m1/2、5.32MPa·m1/2、6.231MPa·m1/2。同时可以理解地，断裂韧性与固态电解质材料的具体类型有关。在本申请的一些示例中，比如所述无机陶瓷固态电解质材料包括硫化物系固态电解质材料时，可以满足如上性能，而当固态电解质材料为其它类型材料时，断裂韧性也可能小于0.25MPa·m1/2，但采用的固态电解质材料相同的情况下，采用本申请如上示例的方案能够提高所述固态电解质膜的断裂韧性。
通过上述的膜层设计，可以有效提高固态电解质膜的临界电流密度。在其中一些示例中，所述固态电解质膜的临界电流密度≥1.5mA/cm2。进一步地，所述固态电解质膜的临界电流密度≥2mA/cm2。具体地，所述固态电解质膜的临界电流密度包括但不限于：3.75mA/cm2、4.25mA/cm2、4.50mA/cm2、5.0mA/cm2、5.25mA/cm2、5.50mA/cm2、5.75mA/cm2、6.0mA/cm2、6.02mA/cm2、6.25mA/cm2、7.25mA/cm2。同时可以理解地，临界电流密度与固态电解质材料的具体类型有关。在本申请的一些示例中，比如所述无机陶瓷固态电解质材料包括硫化物系固态电解质材料时，可以满足如上性能，而当固态电解质材料为其它类型材料时，临界电流密度也可能小于1.5mA/cm2，但采用的固态电解质材料相同的情况下，采用本申请如上示例的方案能够提高所述固态电解质膜的临界电流密度。
本申请的另一些示例提供如上所述的固态电解质膜的制备方法，包括如下步骤：
将所述无机陶瓷固态电解质材料、相变增韧剂和纤维材料混合，制备混合料；
将所述混合料进行成型处理，制备所述固态电解质膜。
上述固态电解质膜的制备方法步骤简单，便于工业化推广应用。
在其中一些示例中，所述混合为干法混合。进一步地，与干法混合相配合地，所述成型处理为加压处理。不作限制地，所述加压处理的压力为300MPa～600MPa。
在其中一些示例中，所述混合为湿法混合。进一步地，与湿法混合相配合地，所述成型处理的步骤包括将所述混合料涂布成膜，以及干燥的步骤。不作限制地，所述湿法混合采用的溶剂包括甲苯、对二甲苯、邻二甲苯、间二甲苯、三甲苯、乙酸乙酯、丁酸丁酯、正丁醚、苯甲醚、乙二醇二甲醚、乙二醇二乙醚和正丁烷中的一种或多种。
另外，以下适当参照附图对本申请的固态电池、电池模块、电池包和用电装置进行说明。
本申请的一个实施方式中，提供一种固态电池。
通常情况下，固态电池包括正极极片、负极极片和电解质。在电池充放电过程中，活性离子在正极极片和负极极片之间往返嵌入和脱出。电解质在正极极片和负极极片之间起到传导离子的作用，具体地，所述电解质采用如上所述的固态电解质层。
正极极片包括正极集流体以及设置在正极集流体至少一个表面的正极活性材料层，正极活性材料层包括本申请第一方面的正极活性材料。
作为示例，正极集流体具有在其自身厚度方向相对的两个表面，正极活性材料层设置在正极集流体相对的两个表面的其中任意一者或两者上。
在其中一些实施例中，正极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可采用铝箔。复合集流体可包括高分子材料基层和形成于高分子材料基层至少一个表面上的金属层。复合集流体可通过将金属材料(铝、铝合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
在其中一些实施例中，正极活性材料可采用本领域公知的用于电池的正极活性材料。作为示例，正极活性材料可包括以下材料中的至少一种：橄榄石结构的含锂磷酸盐、锂过渡金属氧化物及其各自的改性化合物。但本申请并不限定于这些材料，还可以使用其他可被用作电池正极活性材料的传统材料。这些正极活性材料可以仅单独使用一种，也可以将两种以上组合使用。其中，锂过渡金属氧化物的示例可包括但不限于锂钴氧化物(如LiCoO2)、锂镍氧化物(如LiNiO2)、锂锰氧化物(如LiMnO2、LiMn2O4)、锂镍钴氧化物、锂锰钴氧化物、锂镍锰氧化物、锂镍钴锰氧化物(如LiNi1/3Co1/3Mn1/3O2(也可以简称为NCM333)、LiNi0.5Co0.2Mn0.3O2(也可以简称为NCM523)、LiNi0.5Co0.25Mn0.25O2(也可以简称为NCM211)、LiNi0.6Co0.2Mn0.2O2(也可以简称为NCM622)、LiNi0.8Co0.1Mn0.1O2(也可以简称为NCM811)、锂镍钴铝氧化物(如LiNi0.85Co0.15Al0.05O2)及其改性化合物等中的至少一种。橄榄石结构的含锂磷酸盐的示例可包括但不限于磷酸铁锂(如LiFePO4(也可以简称为LFP))、磷酸铁锂与碳的复合材料、磷酸锰锂(如LiMnPO4)、磷酸锰锂与碳的复合材料、磷酸锰铁锂、磷酸锰铁锂与碳的复合材料中的至少一种。
在其中一些实施例中，正极活性材料层还可选地包括粘结剂。作为示例，粘结剂可以包括聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、偏氟乙烯-四氟乙烯-丙烯三元共聚物、偏氟乙 烯-六氟丙烯-四氟乙烯三元共聚物、四氟乙烯-六氟丙烯共聚物及含氟丙烯酸酯树脂中的至少一种。
在其中一些实施例中，正极活性材料层还可选地包括导电剂。作为示例，导电剂可以包括超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在其中一些实施例中，可以通过以下方式制备正极极片：将上述用于制备正极极片的组分，例如正极活性材料、导电剂、粘结剂和任意其他的组分分散于溶剂(例如N-甲基吡咯烷酮)中，形成正极浆料；将正极浆料涂覆在正极集流体上，经烘干、冷压等工序后，即可得到正极极片。
负极极片包括负极集流体以及设置在负极集流体至少一个表面上的负极活性材料层，负极活性材料层包括负极活性材料。
作为示例，负极集流体具有在其自身厚度方向相对的两个表面，负极活性材料层设置在负极集流体相对的两个表面中的任意一者或两者上。
在其中一些实施例中，负极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可以采用铜箔。复合集流体可包括高分子材料基层和形成于高分子材料基材至少一个表面上的金属层。复合集流体可通过将金属材料(铜、铜合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
在其中一些实施例中，负极活性材料可采用本领域公知的用于电池的负极活性材料。作为示例，负极活性材料可包括以下材料中的至少一种：锂金属、含锂合金、含锂复合物、人造石墨、天然石墨、软炭、硬炭、硅基材料、锡基材料和钛酸锂等。硅基材料可选自单质硅、硅氧化合物、硅碳复合物、硅氮复合物以及硅合金中的至少一种。锡基材料可选自单质锡、锡氧化合物以及锡合金中的至少一种。但本申请并不限定于这些材料，还可以使用其他可被用作电池负极活性材料的传统材料。这些负极活性材料可以仅单独使用一种，也可以将两种以上组合使用。
在其中一些实施例中，负极活性材料包括锂金属、含锂合金和含锂复合物中的一种或多种。
在其中一些实施例中，负极活性材料层还可选地包括粘结剂。粘结剂可选自丁苯橡胶(SBR)、聚丙烯酸(PAA)、聚丙烯酸钠(PAAS)、聚丙烯酰胺(PAM)、聚乙烯醇(PVA)、海藻酸钠(SA)、聚甲基丙烯酸(PMAA)及羧甲基壳聚糖(CMCS)中的至少一种。
在其中一些实施例中，负极活性材料层还可选地包括导电剂。导电剂可选自超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在其中一些实施例中，负极活性材料层还可选地包括其他助剂，例如增稠剂(如羧甲基纤维素钠(CMC-Na))等。
在其中一些实施例中，可以通过以下方式制备负极极片：将上述用于制备负极极片的组分，例如负极活性材料、导电剂、粘结剂和任意其他组分分散于溶剂(例如去离子水)中，形成负极浆料；将负极浆料涂覆在负极集流体上，经烘干、冷压等工序后，即可得到负极极片。
在其中一些实施例中，正极极片、负极极片和固态电解质膜可通过卷绕工艺或叠片工艺制成电极组件。
在其中一些实施例中，固态电池可包括外包装。该外包装可用于封装上述电极组件及电解质。
在其中一些实施例中，固态电池的外包装可以是硬壳，例如硬塑料壳、铝壳、钢壳等。固态电池的外包装也可以是软包，例如袋式软包。软包的材质可以是塑料，作为塑料，可列举出聚丙烯、聚对苯二甲酸丁二醇酯以及聚丁二酸丁二醇酯等。
本申请对固态电池的形状没有特别的限制，其可以是圆柱形、方形或其他任意的形状。例如，图1是作为一个示例的方形结构的固态电池5。
在其中一些实施例中，固态电池可以组装成电池模块，电池模块所含固态电池的数量可以为一个或多个，具体数量本领域技术人员可根据电池模块的应用和容量进行选择。
图2是作为一个示例的电池模块4。参照图2，在电池模块4中，多个固态电池5可以是沿电池模块4的长度方向依次排列设置。当然，也可以按照其他任意的方式进行排布。进一步可以通过紧固件将该多个固态电池5进行固定。
可选地，电池模块4还可以包括具有容纳空间的外壳，多个固态电池5容纳于该容纳空间。
在其中一些实施例中，上述电池模块还可以组装成电池包，电池包所含电池模块的数量可以为一个或多个，具体数量本领域技术人员可根据电池包的应用和容量进行选择。
图3和图4是作为一个示例的电池包1。参照图3和图4，在电池包1中可以包括电池箱和设置于电池箱中的多个电池模块4。电池箱包括上箱体2和下箱体3，上箱体2能够盖设于下箱体3，并形成用于容纳电池模块4的封闭空间。多个电池模块4可以按照任意的方式排布于电池箱中。
另外，本申请还提供一种用电装置，用电装置包括本申请提供的固态电池、电池模块、或电池包中的至少一种。固态电池、电池模块、或电池包可以用作用电装置的电源，也可以用作用电装置的能量存储单元。用电装置可以包括移动设备、电动车辆、电气列车、船舶及卫星、储能系统等，但不限于此。其中，移动设备例如可以是手机、笔记本电脑等；电动车辆例如可以是纯电动车、混合动力电动车、插电式混合动力电动车、电动自行车、电动踏板车、电动高尔夫球车、电动卡车等，但不限于此。
作为用电装置，可以根据其使用需求来选择固态电池、电池模块或电池包。
图5是作为一个示例的用电装置5。该用电装置为纯电动车、混合动力电动车、或插电式混合动力电动车等。为了满足该用电装置对固态电池的高功率和高能量密度的需求，可以采用电池包或电池模块。
作为另一个示例的装置可以是手机、平板电脑、笔记本电脑等。该装置通常要求轻薄化，可以采用固态电池作为电源。
以下，说明本申请的实施例。下面描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
实施例1
(1)将YSZ(D50＝50nm)、Al2O3纤维(1μm直径，20μm长)与Li6PS5Cl固态电解质粉体混合；其中，YSZ占Li6PS5Cl固态电解质粉体的体积比为5％，SiO2纤维占Li6PS5Cl固态电解质粉体的体积比为5％；
(2)将混合均匀的复合固态电解质粉体，在模具中以500MPa压力压制成型。
具体在制备测试用固态电解质膜片时，将混合均匀的复合固态电解质粉体使用5mm的不锈钢模具，在500MPa压力下压制成厚度1mm、直径5mm的固态电解质圆片。实施例1制备得到的固态电解质膜的断面扫描电子显微镜图像如图6所示，可见相变增韧剂与纤维形成类似“钢筋混凝土”结构。
实施例2～19和对比例1～3在实施例1的基础上改变相变增韧剂的种类或体积占比或D50、纤维的种类或体积占比或直径*长度，其余步骤与实施例1相同，具体如表1所示。
表1

由表1可知，相比较对比例，实施例通过采用相变增韧剂和纤维材料相配合，能够改善固态电解质膜力学性能以及临界电流密度。
需要说明的是，本申请不限定于上述实施方式。上述实施方式仅为示例，在本申请的技术方案范围内具有与技术思想实质相同的构成、发挥相同作用效果的实施方式均包含在本申请的技术范围内。此外，在不脱离本申请主旨的范围内，对实施方式施加本领域技术人员能够想到的各种变形、将实施方式中的一部分构成要素加以组合而构筑的其它方式也包含在本申请的范围内。

Claims (16)

  1. 一种固态电解质膜，包括固态电解质材料层以及分散在固态电解质材料层中的相变增韧剂和纤维材料，所述固态电解质材料层包括无机陶瓷固态电解质材料。
  2. 根据权利要求1所述的固态电解质膜，其中，所述相变增韧剂包括介稳状态的ZrO2；可选地，所述相变增韧剂包括氧化钇稳定氧化锆、氧化钪稳定氧化锆、氧化镁稳定氧化锆、氧化钙稳定氧化锆和氧化铯稳定氧化锆中的一种或多种。
  3. 根据权利要求1或2所述的固态电解质膜，其中，所述纤维材料包括陶瓷纤维；可选地，所述纤维材料包括碳化硅纤维、氮化硅纤维、氮化硼纤维、氧化铝纤维和二氧化硅纤维中的一种或多种。
  4. 根据权利要求1～3任一项所述的固态电解质膜，其中，所述相变增韧剂和纤维材料的总体积在所述固态电解质材料层中的体积百分比为5％～20％；可选地，所述体积百分比为8％～12％。
  5. 根据权利要求1～4任一项所述的固态电解质膜，其中，所述相变增韧剂与所述纤维材料的体积比为1:(0.25～4)；可选地，所述体积比为1:(0.5～1.5)。
  6. 根据权利要求1～5任一项所述的固态电解质膜，其中，所述相变增韧剂的D50＝50nm～100nm。
  7. 根据权利要求1～6任一项所述的固态电解质膜，其中，所述纤维材料的直径为0.5μm～5μm，长度为10μm～30μm。
  8. 根据权利要求1～7任一项所述的固态电解质膜，其中，所述无机陶瓷固态电解质材料包括锂离子固态电解质材料、钠离子固态电解质材料或钾离子固态电解质材料。
  9. 根据权利要求1～8任一项所述的固态电解质膜，其中，所述固态电解质膜具有如下(1)～(2)所示特征中的一项或多项：
    (1)所述固态电解质膜的断裂韧性≥0.25MPa·m1/2；可选地，所述固态电解质膜的断裂韧性≥1.5MPa·m1/2；
    (2)所述固态电解质膜的临界电流密度≥1.5mA/cm2；可选地，所述固态电解质膜的临界电流密度≥2mA/cm2。
  10. 权利要求1～9任一项所述的固态电解质膜的制备方法，包括如下步骤：
    将所述无机陶瓷固态电解质材料、相变增韧剂和纤维材料混合，制备混合料；
    将所述混合料进行成型处理，制备所述固态电解质膜。
  11. 根据权利要求10所述的固态电解质膜的制备方法，其中，所述混合为干法混合。
  12. 根据权利要求11所述的固态电解质膜的制备方法，其中，所述成型处理为加压处理；可选地，所述加压处理的压力为300MPa～600MPa。
  13. 根据权利要求10所述的固态电解质膜的制备方法，其中，所述混合为湿法混合。
  14. 根据权利要求13所述的固态电解质膜的制备方法，其中，所述成型处理的步骤包括将所述混合料涂布成膜，以及干燥的步骤；可选地，所述湿法混合采用的溶剂包括甲苯、对二甲苯、邻二甲苯、间二甲苯、三甲苯、乙酸乙酯、丁酸丁酯、正丁醚、苯甲醚、乙二醇二甲醚、乙二醇二乙醚和正丁烷中的一种或多种。
  15. 一种固态电池，包括权利要求1～9中任一项所述的固态电解质膜。
  16. 一种用电装置，包括权利要求15所述的固态电池。
PCT/CN2024/086391 2023-05-04 2024-04-07 固态电解质膜及其制备方法、固态电池、用电装置 Ceased WO2024227391A1 (zh)

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