WO2020220945A1 - 硫化物固态电池正极极片、硫化物固态电池及装置 - Google Patents

硫化物固态电池正极极片、硫化物固态电池及装置 Download PDF

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WO2020220945A1
WO2020220945A1 PCT/CN2020/083619 CN2020083619W WO2020220945A1 WO 2020220945 A1 WO2020220945 A1 WO 2020220945A1 CN 2020083619 W CN2020083619 W CN 2020083619W WO 2020220945 A1 WO2020220945 A1 WO 2020220945A1
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Prior art keywords
sulfide solid
state battery
pole piece
fso
positive pole
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English (en)
French (fr)
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刘成勇
郭永胜
付佳玮
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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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M10/056—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This application relates to the field of batteries, in particular to a sulfide solid-state battery positive pole piece, a sulfide solid-state battery and a device.
  • lithium-ion batteries With the continuous improvement of people's energy density requirements, traditional lithium-ion batteries have been difficult to meet the increasing demand for specific energy, and metal lithium electrodes with high specific capacity advantages have become a research hotspot.
  • the specific capacity of metallic lithium is 3860mAh/g
  • the electrochemical potential is -3.04V (vs standard hydrogen electrode)
  • the weight energy density of lithium metal batteries such as lithium-sulfur batteries and lithium-air batteries with lithium as the negative electrode can reach 400Wh/ Above kg.
  • the sulfide solid electrolyte material has an ion conductivity of 10 -2 S/cm at room temperature and a wide electrochemical window, which has excellent application prospects.
  • the thermal safety of sulfide solid-state batteries needs to be improved.
  • the purpose of this application is to provide a sulfide solid-state battery positive pole piece and a sulfide solid-state battery to improve the thermal safety of the sulfide solid-state battery.
  • the first aspect of the present application provides a positive electrode sheet for a sulfide solid state battery, which includes a positive electrode current collector and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector, the positive electrode active material layer It includes a positive electrode active material and a solid electrolyte, and the positive electrode active material layer further includes an added salt, and the added salt undergoes an endothermic phase change at 40-150°C.
  • the second aspect of the present application provides a sulfide solid state battery, which includes a positive pole piece, a negative pole piece, and a solid electrolyte membrane interposed between the positive pole piece and the negative pole piece.
  • the positive pole piece is the positive pole piece of the sulfide solid state battery provided in the first aspect of the application.
  • a device in the third aspect of the present application, includes the sulfide solid-state battery of the second aspect of the present application.
  • the positive pole piece of the sulfide solid-state battery provided in this application contains added salt that undergoes endothermic phase change at 40-150°C.
  • the endothermic effect of the added salt during the phase change can be used to absorb
  • the heat generated by the positive pole piece (such as the side reaction between the positive electrode and the sulfide solid electrolyte caused by the positive electrode active material, and the heat generated by the exothermic process such as the self-decomposition of the sulfide solid electrolyte), thereby reducing the sharp rise in battery temperature
  • the risk of thermal runaway caused by the battery will improve the thermal safety of the sulfide solid-state battery.
  • FIG. 1 is a schematic diagram of an embodiment of a sulfide solid-state battery
  • Fig. 2 is a schematic diagram of an embodiment of a battery module
  • FIG. 3 is a schematic diagram of an embodiment of the battery pack
  • Figure 4 is an exploded view of Figure 3;
  • Figure 5 is a schematic diagram of an embodiment of a device in which a sulfide solid-state battery is used as a power source;
  • the reference signs are described as follows: 1-battery pack, 2-upper case, 3-lower case, 4-battery module, 5 sulfide solid state battery.
  • the positive pole piece of the sulfide solid state battery of the first aspect of the present application includes a positive electrode current collector and a positive electrode active material layer provided on at least one surface of the positive electrode current collector.
  • the positive electrode active material layer includes a positive electrode active material, a solid electrolyte and an added salt, The added salt undergoes an endothermic phase change at 40-150°C.
  • the "endothermic phase change caused by the addition of salt” in the present application refers to the fact that the addition of salt absorbs heat and causes a solid-liquid phase transition or a solid phase transition (a change in the phase structure inside the solid phase).
  • the temperature range in which the salt undergoes endothermic phase transition can be measured by differential scanning calorimetry (DSC).
  • the sulfide solid state battery positive pole piece of the present application is added with an added salt that undergoes an endothermic phase change at 40 to 150°C.
  • the phase change endothermic effect of the added salt can be used to absorb the heat generated by the positive pole piece.
  • Heat (such as the side reaction between the positive electrode and the sulfide solid electrolyte caused by the positive electrode active material, the self-decomposition of the sulfide solid electrolyte and other reactions), thereby reducing the risk of battery thermal runaway caused by the rapid increase in battery temperature , Improve the thermal safety and cycle stability of the sulfide solid-state battery system.
  • the added salt undergoes an endothermic phase change at 60-110°C.
  • the decomposition temperature of the added salt is higher than 200°C, so as to avoid the decomposition side reaction of the added salt in the low temperature zone and the adverse effect of such side reaction on the performance of the sulfide solid state battery.
  • the added salt is selected from at least one of inorganic salts of alkali metals, organic salts of alkali metals, and organic-inorganic composite salts of alkali metals.
  • the added salt is selected from M-imide, where M is a cation selected from at least one of Li, Na, K, Rb, and Cs, and imide is a sulfonimide anion represented by formula (I) ,
  • n is selected from an integer of 0 to 4;
  • X and Y are each independently selected from one of F, Cl, Br, I, and a fluorinated alkyl group having 1 to 4 carbon atoms.
  • the added salt is selected from Li[(FSO 2 ) 2 N] (abbreviated LiFSI), Na[(FSO 2 ) 2 N] (abbreviated NaFSI), K[(FSO 2 ) 2 N] (abbreviated KFSI), Rb[(FSO 2 ) 2 N] (abbreviated RbFSI), Cs[(FSO 2 ) 2 N] (abbreviated CsFSI), Li[(FSO 2 )(CF 3 SO 2 )N] (abbreviated LiFTFSI), Na[(FSO 2 )(CF 3 SO 2 )N] (abbreviated NaFTFSI), K[(FSO 2 )(CF 3 SO 2 )N] (abbreviated KFTFSI), Rb[(FSO 2 )(CF 3 SO 2 ) N] (abbreviated RbFTFSI), Cs[(FSO 2 )(CF 3 SO 2 )N] (abbreviated CsFTFSI), Li[(FSO
  • the mass percentage content of the added salt in the positive electrode active material layer is 0.1-20%, preferably 1-10%.
  • controlling the content of added salt is very important for this application. The higher the content of added salt, the better the effect of improving safety performance. However, if the amount of added salt cannot be controlled In a reasonable range, even if the addition of salt can improve the safety performance, it is very likely to cause the performance of other aspects of the battery to decrease. Therefore, for the comprehensive performance of the battery, the content of the added salt is 0.1-20%, preferably 1 ⁇ 10%.
  • the type of the positive electrode current collector is not specifically limited, and can be selected according to actual needs.
  • the positive electrode current collector is usually a structure or part that can collect current, usually a layered body; the positive electrode current collector can be various materials in the field suitable for use as a positive electrode current collector of an electrochemical energy storage device, for example, it can include It is not limited to metal foil, and more specifically can be materials including but not limited to nickel foil, aluminum foil, carbon-coated aluminum foil or stainless steel.
  • the positive electrode active material layer may be provided on one surface of the positive electrode current collector, or may be provided on both surfaces of the positive electrode current collector.
  • the specific type of the positive electrode active material is not particularly limited, as long as it can accept and extract lithium ions.
  • it may be selected from at least one of olivine structure lithium metal oxide, layered structure lithium metal oxide, spinel structure lithium metal oxide, sulfur powder, and materials modified from the above materials.
  • the olivine structured lithium metal oxide can be selected from lithium iron phosphate (LiFePO 4 ), lithium cobalt phosphate (LiCoPO 4 ), lithium manganese phosphate (LiMnPO 4 ), lithium nickel phosphate (LiNiPO 4 ), iron phosphate ( FePO 4 ) and other lithium metal oxides.
  • the layered structure lithium metal oxide can be selected from lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ), ternary material LiNi s B t C( 1-st )O 2 (wherein B and C are independent Ground is selected from at least one of Co, Al, and Mn, and B and C are not the same, at least one of lithium metal oxides such as 0 ⁇ s ⁇ 1, 0 ⁇ t ⁇ 1).
  • the spinel structure lithium metal oxide may be selected from at least one of lithium metal oxides such as lithium manganate (LiMn 2 O 4 ) and lithium nickel manganate (LiNi 0.5 Mn 1.5 O 4 ).
  • the modified material can be selected from at least one of the above-mentioned materials after doping and coating treatment, and the doping and coating element can be selected from metal elements and non-metal elements, such as Li , N, F, Cl, S, B, P, Al, Si, Zr, Ti, Ge, Sn, Mg, Zn, Ce, W, V, etc.
  • metal elements and non-metal elements such as Li , N, F, Cl, S, B, P, Al, Si, Zr, Ti, Ge, Sn, Mg, Zn, Ce, W, V, etc.
  • the solid electrolyte may be selected from sulfide solid electrolyte.
  • the sulfide solid electrolyte may include lithium and sulfur, and may further include other elements. For example, it may include but not limited to at least one of P, Si, Ge, Sn, Al and other elements.
  • the general structural formula of the sulfide solid electrolyte can be expressed as yLi 2 S-(100-y)LS, where 0 ⁇ y ⁇ 100, and the LS can be but not limited to P 2 S 5 , SiS 2 , One or more of GeS 2 , SnS 2 , Al 2 S 3 and other substances, and the solid electrolyte system it constitutes may include but not limited to Li 2 SP 2 S 5 system, Li 2 S-SiS 2 system, Li 2 S-GeS 2 system, Li 2 S-SnS 2 system, Li 2 S-Al 2 S 3 system, one or more.
  • the state of the sulfide solid electrolyte may be a crystalline state, an amorphous state, or a crystalline-amorphous complex state.
  • the sulfide solid electrolyte may further include a doping material, and the doping material is preferably a lithium-containing compound LiQ.
  • the general formula of the doped sulfide electrolyte structure can be expressed as z(Li 2 S-LS)-(100-z)LiQ, where 90 ⁇ z ⁇ 100, and the doping material LiQ may include but not It is limited to a combination of one or more of lithium halide, lithium oxide, lithium nitride, lithium oxyacid salt, and the like.
  • the positive active material layer may also include a conductive agent and a binder.
  • the type and content of the conductive agent and the binder are not specifically limited, and can be based on actual needs. Make a selection.
  • the binder may be selected from at least one of SBS, SEBS, PVDF, PTFE, PAALi, styrene-butadiene rubber, nitrile rubber, butylene rubber, styrene rubber, and polyurethane;
  • the conductive agent may be selected from conductive carbon At least one of black (super-P), acetylene black, Vapor-grown carbon fiber (VGCF), carbon nanotubes, and graphene.
  • the second aspect of the application provides a sulfide solid-state battery.
  • the shape of the sulfide solid-state battery is not particularly limited in the application, and it can be cylindrical, square, or any other shape.
  • Fig. 1 shows a sulfide solid-state battery 5 with a square structure as an example.
  • the sulfide solid-state battery can be assembled into a battery module, and the number of the sulfide solid-state battery contained in the battery module can be multiple, and the specific number can be adjusted according to the application and capacity of the battery module.
  • Fig. 2 is a battery module 4 as an example.
  • a plurality of sulfide solid state batteries 5 may be arranged in sequence along the length direction of the battery module 4. Of course, it can also be arranged in any other manner. Furthermore, the plurality of sulfide solid-state batteries 5 can be fixed by fasteners.
  • the battery module 4 may further include a housing having an accommodation space, and a plurality of sulfide solid-state batteries 5 are accommodated in the accommodation space.
  • the above-mentioned battery modules can also be assembled into a battery pack, and the number of battery modules contained in the battery pack can be adjusted according to the application and capacity of the battery pack.
  • Figures 3 and 4 show the battery pack 1 as an example. 3 and 4, the battery pack 1 may include a battery box and a plurality of battery modules 4 provided in the battery box.
  • the battery box includes an upper box body 2 and a lower box body 3.
  • the upper box body 2 can be covered on the lower box body 3 and forms a closed space for accommodating the battery module 4.
  • Multiple battery modules 4 can be arranged in the battery box in any manner.
  • a device in the third aspect of the present application, includes the sulfide solid-state battery of the second aspect of the present application.
  • the sulfide solid-state battery provides power to the device.
  • the device can be, but is not limited to, mobile devices (such as mobile phones, laptop computers, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf Vehicles, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc.
  • the device can select a sulfide solid-state battery (Cell), a battery module (Module) or a battery pack (pack) according to its usage requirements.
  • Cell sulfide solid-state battery
  • Mode battery module
  • pack battery pack
  • Figure 5 is a device as an example.
  • the device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle.
  • battery packs or battery modules can be used.
  • the device may be a mobile phone, a tablet computer, a notebook computer, etc.
  • the device is usually thin and light, and can use sulfide solid-state batteries as a power source.
  • the positive electrode of the sulfide solid-state battery of the present application can be prepared by dry pressing or wet coating.
  • the following is an example of its preparation process.
  • the positive pole piece of the sulfide solid-state battery of the present invention can be prepared according to the following dry pressing method:
  • the mass percentages of the positive electrode active material, solid electrolyte, added salt, and conductive agent may be 50-95% (for example, 70-85%), 4.9, respectively. ⁇ 49.9% (for example, 10 to 29%), 0.1 to 20% (for example, 1 to 19%), 0 to 5% (for example, 0 to 2%).
  • the content of the positive electrode active material will affect the construction of the electronic and lithium ion conduction network in the positive pole piece: if the mass percentage of the positive electrode active material in the positive electrode active material layer is higher than 95%, it will cause the solid electrolyte and conductive additives If the content is too low, it is not conducive to the transfer of electrons and lithium ions; if the mass percentage of the positive electrode active material in the positive electrode active material layer is less than 50%, the capacity of the battery will be reduced and the energy density of the battery will be affected.
  • the hot pressing method may be one-step pressing or stepwise pressing.
  • the hot pressing pressure may be 0.1-500 MPa, preferably 100-400 MPa; the hot pressing temperature may be 25-160°C, preferably 60-120°C. If the hot pressing pressure is too low and the temperature is too low, the density of the diaphragm will be low. If the hot pressing pressure is too high, the equipment requirements will be high; if the hot pressing temperature is too high, the electrolyte will easily decompose.
  • the thickness of the positive electrode piece obtained by pressing is 10-200 ⁇ m. If the positive pole piece is too thin, the energy density of the battery will decrease; if the positive pole piece is too thick, it will increase the lithium ion transmission impedance in the positive pole piece and polarize the battery.
  • the positive pole piece of the sulfide solid-state battery of the present invention can also be prepared according to the following wet coating method:
  • the positive electrode active material, solid electrolyte, added salt, conductive agent, and binder are mixed in an organic solvent and dispersed to form a slurry.
  • the mass percentages of the positive electrode active material, solid electrolyte, added salt, conductive agent, and binder may be 50-95% (e.g. 70-80%), respectively. %), 4.7 to 39.9% (for example, 10 to 27%), 0.1 to 20% (for example, 1 to 10%), 0.1 to 5% (for example, 1 to 2%), 0.1 to 5% (for example, 1 to 2%) . If the content of the binder is too low, the strength and toughness of the electrolyte membrane will be poor; if the content of the binder is too high, it will affect the transfer of lithium ions and cause polarization of the battery.
  • the organic solvent used in the wet coating method needs not to react with the solid electrolyte, and can be selected from ether organic solvents, hydrocarbon organic solvents, ester organic solvents, nitrile organic solvents, amide organic solvents, and alcohols. At least one of quasi organic solvents and halogenated organic solvents.
  • the ether organic solvent is selected from at least one of diethyl ether, tetrahydrofuran, and ethylene glycol dimethyl ether;
  • the hydrocarbon organic solvent is selected from n-pentane, n-hexane, cyclohexane, toluene, xylene, and trimethylbenzene At least one of;
  • the ester organic solvent is selected from at least one of ethyl acetate, methyl formate and dimethyl phthalate,
  • the nitrile organic solvent is selected from acetonitrile, and the amide organic solvent is selected from N-methyl Pyrrolidone (NMP) and/or N,N-dimethylformamide (DMF)
  • alcoholic organic solvent is selected from ethanol;
  • halogenated organic solvent is selected from dichloromethane and/or 1,2-dichloroethane.
  • the viscosity of the slurry is controlled by an organic solvent, and the viscosity of the slurry is controlled to be 5000 to 200000 mPa ⁇ s, preferably 10000 to 50000 mPa ⁇ s. If the viscosity of the slurry is too high, it will increase the difficulty of making the electrolyte membrane; while the viscosity of the slurry is too low, it will easily lead to holes in the electrolyte membrane, which will increase the risk of short circuits in the battery to a certain extent.
  • the hot pressing method may be one-step pressing or stepwise pressing.
  • the hot pressing pressure may be 1 to 500 MPa, preferably 100 to 300 MPa; the hot pressing temperature may be 25 to 160°C, preferably 60 to 120°C. If the pressure is too small and the temperature is too low, the density of the diaphragm will be low. If the pressure is too high, the equipment requirements will be high. If the temperature is too high, the electrolyte and binder will be decomposed.
  • the sulfide solid state battery of the second aspect of the present invention includes a positive pole piece, a negative pole piece, and a solid electrolyte membrane spaced between the positive pole piece and the negative pole piece, wherein the positive pole piece is The positive pole piece of the sulfide solid state battery of the first aspect of the present invention.
  • the sulfide solid state battery of the present invention may be a laminated solid state battery.
  • the negative pole piece may include a negative current collector and a metal lithium or lithium alloy layer provided on the negative current collector.
  • the negative current collector may be selected from copper foil, carbon-coated copper foil and stainless steel foil. At least one of them. Among them, the thickness of the metallic lithium or lithium alloy layer may be 1 to 200 ⁇ m, preferably 5 to 100 ⁇ m.
  • the preparation method of the negative pole piece may be: attaching metallic lithium or a lithium alloy to the surface of the negative electrode current collector to form a negative pole piece.
  • the solid electrolyte membrane can be prepared from a solid electrolyte through a dry membrane method or a wet membrane method.
  • the solid electrolyte may also be selected from sulfide solid electrolytes, and the optional range of the sulfide solid electrolytes is the same as the solid electrolyte in the first aspect of the present invention.
  • the following is an example of the preparation process of the solid electrolyte membrane.
  • the dry film forming method is as follows: the solid electrolyte is placed in a mold and pressed to form a film.
  • the pressing method can be cold pressing or hot pressing.
  • the suppression method can be one-step suppression or stepwise suppression.
  • the hot pressing pressure is 0.1 to 500 MPa, preferably 100 to 400 MPa; the hot pressing temperature is 25 to 160°C, preferably 60 to 120°C. If the hot pressing pressure is too low and the temperature is too low, the resulting solid electrolyte membrane will have low density; however, if the hot pressing pressure is too high, the equipment requirements are high, and the hot pressing temperature is too high to easily cause the solid electrolyte to decompose.
  • the wet membrane production method is as follows: solid electrolyte and binder are mixed in an organic solvent and dispersed into a slurry; the slurry is coated on a glass substrate, dried and pressed to obtain a sulfide electrolyte membrane.
  • the optional range of the binder and the organic solvent may be the same as the binder and the organic solvent used in the preparation of the positive pole piece by the wet coating method in the first aspect of the present invention.
  • the mass percentage of solid electrolyte and binder can be 50% ⁇ 99%, 1% ⁇ 50%, and preferably 80% ⁇ 98%, 2% ⁇ 20% respectively .
  • the pressing method may be cold pressing or hot pressing; it may be one-step pressing or stepwise pressing.
  • the hot pressing pressure is 1 to 500 MPa, preferably 100 to 300 MPa; the hot pressing temperature is 25 to 160°C, preferably 60 to 120°C. If the pressure is too low and the temperature is too low, the density of the diaphragm will be low; if the pressure is too high, the equipment requirements are high, and the temperature is too high, which will easily cause the solid electrolyte and binder to decompose.
  • the sulfide solid-state battery of the second aspect of the present invention can be prepared by the following method:
  • the positive pole piece, solid electrolyte membrane, and negative pole piece are respectively sliced according to the required size, and the sliced positive pole piece, solid electrolyte membrane, and negative pole piece are aligned in the center and sequentially stacked into a sandwich layer unit.
  • the layer units are pressurized and compounded together at a certain temperature to obtain the cell of the sulfide solid-state battery.
  • the cell is cold-pressed and placed in an outer package for encapsulation to form the sulfide solid-state battery.
  • the pressing pressure can be 1 to 500 MPa, preferably 100 to 300 MPa;
  • the compaction temperature can be 20 to 160°C, preferably 60 to 120°C.
  • the positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O 2 , the sulfide solid electrolyte Li 3 PS 4 , the added salt Li[(FSO 2 )(CF 3 SO 2 )N], the conductive agent VGCF are 70% by weight. :24:5:1 After fully stirring and mixing uniformly, disperse it on the surface of aluminum foil and press at 100°C and 250MPa for 2min to obtain a positive pole piece with a thickness of 50 ⁇ m.
  • the sulfide solid electrolyte Li 3 PS 4 was pressed at 100° C. and 250 MPa for 2 min to obtain a solid electrolyte membrane with a thickness of 50 ⁇ m.
  • Example 2 It is basically the same as Example 1, except that the weight ratio of LiNi 0.8 Co 0.1 Mn 0.1 O 2 , Li 3 PS 4 , Li[(FSO 2 )(CF 3 SO 2 )N] and VGCF is changed from 70:24: 5:1 is adjusted to 70:29:0.1:0.9.
  • Example 2 It is basically the same as Example 1, except that the weight ratio of LiNi 0.8 Co 0.1 Mn 0.1 O 2 , Li 3 PS 4 , Li[(FSO 2 )(CF 3 SO 2 )N] and VGCF is changed from 70:24: 5:1 is adjusted to 70:28:1:1.
  • Example 2 It is basically the same as Example 1, except that the weight ratio of LiNi 0.8 Co 0.1 Mn 0.1 O 2 , Li 3 PS 4 , Li[(FSO 2 )(CF 3 SO 2 )N] and VGCF is changed from 70:24: 5:1 is adjusted to 70:19:10:1.
  • Example 2 It is basically the same as Example 1, except that the weight ratio of LiNi 0.8 Co 0.1 Mn 0.1 O 2 , Li 3 PS 4 , Li[(FSO 2 )(CF 3 SO 2 )N] and VGCF is changed from 70:24: 5:1 is adjusted to 70:9:20:1.
  • Example 2 It is basically the same as Example 1, except that the solid electrolyte in the positive pole piece is replaced by Li 3 PS 4 with Li 6 PS 5 Cl.
  • Example 2 It is basically the same as Example 1, except that the weight ratio of LiNi 0.8 Co 0.1 Mn 0.1 O 2 , Li 3 PS 4 , Li[(FSO 2 )(CF 3 SO 2 )N] and VGCF is changed from 70:24: 5:1 is adjusted to 70:20:5:5.
  • Example 2 It is basically the same as Example 1, except that the positive electrode active material is replaced by LiNi 0.8 Co 0.1 Mn 0.1 O 2 with LiNi 0.6 Co 0.2 Mn 0.2 O 2 .
  • Example 8 Basically the same as Example 8, the difference is: the added salt is replaced from Li[(FSO 2 )(CF 3 SO 2 )N] to Rb[(FSO 2 )(CF 3 SO 2 )N], and the hot pressing conditions Replaced from 100°C and 250MPa to 120°C and 250MPa.
  • Example 8 It is basically the same as Example 8, but the difference is that the added salt is replaced by Li[(FSO 2 )(CF 3 SO 2 )N] with Cs[(CF 3 SO 2 )(CF 3 SO 2 )N], and hot The pressure conditions were replaced from 100°C and 250MPa to 130°C and 250MPa.
  • the positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O 2 , the sulfide solid electrolyte Li 3 PS 4 , the added salt Li[(FSO 2 )(CF 3 SO 2 )N], the conductive agent VGCF, the binder Styrene butadiene rubber (number-average molecular weight is about 500,000) is mixed in THF solvent at a weight ratio of 70:22:5:1:2, fully stirred and mixed evenly, and then coated on the surface of aluminum foil, and dried naturally at 60°C After drying, cold pressing, and slicing, they were pressed at 100°C and 250 MPa for 2 minutes to obtain a positive electrode piece with a thickness of 50 ⁇ m.
  • the sulfide solid electrolyte Li 3 PS 4 and the binder styrene-butadiene rubber are mixed in a THF solvent at a weight ratio of 98:2 to prepare an electrolyte slurry, which is coated on the glass surface and dried at 60°C, at 50°C, 250MPa Press down for 2 min to obtain a solid electrolyte membrane with a thickness of 50 ⁇ m.
  • the 10-layer battery cell unit is placed in the outer package for encapsulation. , That is, a sulfide solid-state battery.
  • Example 11 It is basically the same as Example 11, but the difference is that the positive electrode active material is replaced by LiNi 0.8 Co 0.1 Mn 0.1 O 2 with LiNi 0.6 Co 0.2 Mn 0.2 O 2 .
  • Example 11 Basically the same as Example 11, the difference is that the added salt Li[(FSO 2 )(CF 3 SO 2 )N] in the positive pole piece is replaced with Li 0.8 Cs 0.2 [(FSO 2 )(CF 3 SO 2 ) N], and the hot pressing conditions are adjusted from 100°C and 250MPa to 50°C and 250MPa.
  • Example 11 It is basically the same as Example 11, but the difference is that the added salt Li[(FSO 2 )(CF 3 SO 2 )N] in the positive pole piece is replaced with Li[(FSO 2 ) 2 N] 0.5 [(FSO 2 ) (CF 3 SO 2 )N] 0.5 ; At the same time, the LiNi 0.8 Co 0.1 Mn 0.1 O 2 , Li 3 PS 4 , Li[(FSO 2 ) 2 N] 0.5 [(FSO 2 )(CF The weight ratio of 3 SO 2 )N] 0.5 , VGCF and styrene butadiene rubber is 50:39.9:0.1:5:5, and the hot pressing conditions are replaced from 100°C and 250MPa to 50°C and 250MPa.
  • Example 11 It is basically the same as Example 11, but the difference is that the added salt Li[(FSO 2 )(CF 3 SO 2 )N] in the positive pole piece is replaced with Li[(FSO 2 ) 2 N].
  • LiNi 0.8 Co The weight ratio of 0.1 Mn 0.1 O 2 , Li 3 PS 4 , Li[(FSO 2 ) 2 N], VGCF, and styrene butadiene rubber is adjusted to 95:4.7:0.1:0.1:0.1, and the hot pressing conditions are adjusted from 100°C, 250MPa Replace with 150°C, 250MPa.
  • Example 2 It is basically the same as Example 1, but the difference is that the positive pole piece does not contain added salt, and the weight ratio of LiNi 0.8 Co 0.1 Mn 0.1 O 2 , Li 3 PS 4 , and VGCF is 70:29:1.
  • Example 2 Basically the same as Example 1, the difference is: the positive pole piece does not contain added salt, and the solid electrolyte in the positive pole piece is replaced by Li 3 PS 4 with Li 6 PS 5 Cl, and LiNi 0.8 Co 0.1 Mn 0.1 O 2 The weight ratio of Li 6 PS 5 Cl and VGCF is 70:29:1.
  • the positive pole piece does not contain added salt, and the weight ratio of LiNi 0.8 Co 0.1 Mn 0.1 O 2 , Li 3 PS 4 , VGCF and styrene butadiene rubber is 70:27:1: 2.
  • phase transition temperature of the added salt in Table 1 refers to the starting temperature of the phase change of the added salt.
  • the performance test of the positive pole piece of the sulfide solid-state battery and the sulfide solid-state battery of the present invention is as follows:
  • the sulfide solid-state battery is charged for the first time and charged to 4.2V. After disassembling the test battery, a fully charged positive pole piece is obtained. A differential scanning calorimetry (DSC) test was performed on the positive pole piece in the fully charged state to detect the cumulative heating effect of the positive pole piece during the 25-300 °C process.
  • DSC differential scanning calorimetry
  • the test current is 0.1C (the current density is about 0.13mA/cm 2 ).
  • the temperature is 25°C.
  • Examples 1, 6, and 11 are compared with Comparative Examples 1, 2, and 3 respectively.
  • the difference is that the positive pole pieces of Examples 1, 6, and 11 are mixed with added salt, and The positive pole pieces of Comparative Examples 1, 2, and 3 do not contain added salt.
  • Table 2 that, compared with Comparative Examples 1, 2, and 3, the positive pole pieces of Examples 1, 6, and 11 have a significant reduction in the cumulative heat release under high voltage.
  • the heat absorption effect during the phase change of the added salt is used to absorb the heat generated by the positive pole piece (such as the positive electrode and sulfide promoted by the positive electrode active material).
  • the side reactions between solid electrolytes and the heat generated by exothermic processes such as the self-decomposition of sulfide solid electrolytes), thereby realizing the effective improvement of the thermal safety and cycle stability of the sulfide solid battery system.
  • Examples 1 to 5 adopt dry pressing process to prepare positive pole pieces, and the materials of the positive pole pieces, solid electrolyte and negative pole pieces are the same.
  • the difference between embodiments 1 to 5 is only the addition of salt The content is different. It can be seen from Table 1 and Table 2 that increasing the content of added salt can reduce the heat release of the system; but when the added salt content is too high (for example, reaching 20% in Example 5), due to the poor ionic conductivity of the added salt, It is not conducive to the rapid transfer of lithium ions in the positive electrode layer, which will cause a slight decrease in battery performance such as the first week specific capacity and first week efficiency of the battery.
  • the various added salts provided by the present invention can absorb the heat generated by the positive pole pieces and effectively improve the thermal safety and cycle stability of the sulfide solid-state battery system, when the salt material is added
  • the salt material is added
  • the lithium content in the battery system is slightly lower than that of the battery system where the added salt is a lithium material, resulting in a faster degradation of battery performance.
  • Example 6 a sulfide solid electrolyte material with high stability (for example, Example 6) and a positive electrode active material with better compatibility with the sulfide solid electrolyte (for example, Example 8) can be used. Further reduce the heat generated by the battery. If the content of conductive carbon in the battery system is too high, excessive conductive carbon will hinder the transfer of lithium ions in the solid-state battery and degrade the performance of the catalytic electrolyte, resulting in lower battery performance (for example, Example 7). Too high content of conductive agent and binder will also be detrimental to battery safety and battery performance (for example, Example 14).

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Abstract

本发明提供一种硫化物固态电池正极极片、硫化物固态电池及装置。所述硫化物固态电池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上的正极活性物质层，所述正极活性物质层包括正极活性材料、固态电解质以及添加盐，所述添加盐在40～150℃发生吸热相变。本发明还提供包括上述正极极片的硫化物固态电池。本发明的硫化物固态电池正极极片中添加了在40～150℃发生吸热相变的添加盐，在电池充放电过程中，可利用添加盐的相变吸热效应吸收正极极片中硫化物固态电解质的自身分解和副反应等放热过程产生的热量，从而降低由于电池温度急剧升高引发的热失控风险、提高硫化物固态电池体系的热安全性和循环稳定性。

Description

硫化物固态电池正极极片、硫化物固态电池及装置
本申请要求于2019年4月29日提交中国专利局、申请号为201910353583.9、申请名称为“硫化物固态电池正极极片及硫化物固态电池”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
本申请涉及电池领域，尤其涉及一种硫化物固态电池正极极片、硫化物固态电池及装置。
背景技术
随着人们对能量密度要求的不断提高，传统锂离子电池已经很难满足日益提高的比能量的需求，具有高比容量优势的金属锂电极成为研究热点。金属锂的比容量为3860mAh/g，电化学势为-3.04V(vs标准氢电极)，以锂作为负极的锂-硫电池、锂-空气电池等锂金属电池的重量能量密度可达到400Wh/kg以上。
早期开发的锂金属电池主要采用液态电解质材料，其中含有大量有机溶剂，导致液态锂金属电池安全隐患突出。采用固态电解质层代替液态电解液，可有望消除使用过程中的安全隐患，更符合电动汽车和规模储能领域未来发展的需求。因此，本领域内正大力开发全固态锂金属电池。目前，固态电解质种类繁多，按类型可分为有机聚合物、无机氧化物和无机硫化物等。其中，硫化物固态电解质材料在室温下的离子电导率在10 -2S/cm级别，且电化学窗口宽，具有优异的应用前景。但在实际使用过程中，硫化物固态电池的热安全性有待提升。
发明内容
鉴于背景技术中存在的问题，本申请的目的在于提供一种硫化物固态电池正极极片及硫化物固态电池，以提高硫化物固态电池的热安全性。
为了达到上述目的，本申请的第一方面提供了一种硫化物固态电池正极极片，其包括正极集流体以及设置在正极集流体至少一个表面上的正极活性物质层，所述正极活性物质层包括正极活性材料和固态电解质，所述正极活性物质层还包括添加盐，所述添加盐在40～150℃发生吸热相变。
本申请的第二方面提供了一种硫化物固态电池，其包括正极极片、负极极片、以及间隔设于所述正极极片和所述负极极片之间的固态电解质膜片，所述正极极片为本申请的第一方面所提供的硫化物固态电池正极极片。
在本申请的第三方面提供一种装置，所述装置包括本申请第二方面的硫化物固态电池。
相对于现有技术，本申请至少包括如下所述的有益效果：
本申请所提供的硫化物固态电池正极极片中，含有在40～150℃发生吸热相变的添加盐，在电池充放电过程中，可利用添加盐在相变过程中的吸热效应吸收正极极片产生的热量(如正极活性材料促发的正极与硫化物固态电解质之间的副反应、硫化物固态电解质的自身分解等放热过程产生的热量)，从而降低由于电池温度急剧升高引发的电池热失控风险、提高硫化物固态电池的热安全性。
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。
图1是硫化物固态电池的一实施方式的示意图；
图2是电池模块的一实施方式的示意图；
图3是电池包的一实施方式的示意图；
图4是图3的分解图；
图5是硫化物固态电池用作电源的装置的一实施方式的示意图；
其中，附图标记说明如下：1-电池包，2-上箱体，3-下箱体，4-电池模块，5硫化物固态电池。
具体实施方式
为使本申请实施例的目的、技术方案和优点更加清楚，下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
下面详细说明根据本申请的硫化物固态电池正极极片和硫化物固态电池。
本申请第一方面的硫化物固态电池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上的正极活性物质层，所述正极活性物质层包括正极活性材料、固态电解质以及添加盐，所述添加盐在40～150℃发生吸热相变。
本申请中所述的“添加盐发生吸热相变”是指：添加盐吸收热量、发生固-液相变或固态相变(固相内部的相结构的变化)。盐类发生吸热相变的温度区间可通过差示扫描量热法(DSC)测试所得。
本申请的硫化物固态电池正极极片中添加了在40～150℃发生吸热相变的添加盐，在电池充放电过程中，可利用添加盐的相变吸热效应吸收正极极片产生的热量(如正极活性材料促发的正极与硫化物固态电解质之间的副反应、硫化物固态电解质的自身分解等反应过程中的热量)，从而降低由于电池温度急剧升高引发的电池热失控风险、提高硫化物固态电池体系的热安全性和循环稳定性。
优选地，所述添加盐在60～110℃发生吸热相变。
优选地，所述添加盐的分解温度高于200℃，从而可避免添加盐在低温区发生自身的分解副反应以及该种副反应对硫化物固态电池性能的不利影响。
作为优选，所述添加盐选自碱金属的无机盐、碱金属的有机盐、碱金属的有机-无机复合盐中的至少一种。
进一步优选地，所述添加盐选自M-imide，其中，M为选自Li、Na、K、Rb、Cs中至少一种的阳离子，imide为式(I)所示的磺酰亚胺阴离子，
Figure PCTCN2020083619-appb-000001
式(I)中：n选自0～4的整数；X、Y各自独立地选自F、Cl、Br、I和碳原子数为1～4的含氟烷基中的一种。
更进一步优选地，所述添加盐选自Li[(FSO 2) 2N](简写LiFSI)、Na[(FSO 2) 2N](简写NaFSI)、K[(FSO 2) 2N](简写KFSI)、Rb[(FSO 2) 2N](简写RbFSI)、Cs[(FSO 2) 2N](简写CsFSI)、Li[(FSO 2)(CF 3SO 2)N](简写LiFTFSI)、Na[(FSO 2)(CF 3SO 2)N](简写NaFTFSI)、K[(FSO 2)(CF 3SO 2)N](简写KFTFSI)、Rb[(FSO 2)(CF 3SO 2)N](简写RbFTFSI)、Cs[(FSO 2)(CF 3SO 2)N](简写CsFTFSI)、Li 0.4K 0.6[(FSO 2) 2N](简写Li 0.4K 0.6FSI)、Li 0.4Cs 0.6[(FSO 2)(CF 3SO 2)N](简写Li 0.4Cs 0.6FTFSI)、Li 0.8Cs 0.2[(FSO 2)(CF 3SO 2)N](简写Li 0.8Cs 0.2FTFSI)中的至少一种。
优选地，所述添加盐在正极活性物质层中的质量百分含量为0.1～20％，优选为1～10％。在本申请的硫化物固态电池正极极片中，控制添加盐的含量对于本申请至关重要，添加盐的含量越高，对于改善安全性能的效果越好，但是，如果添加盐的量不能控制在合理的范围内，即使添加盐可以改善安全性能，但极有可能会造成电池其他方面的性能下降，因而，为了电池的综合性能考虑，添加盐的含量为0.1～20％，优选为1～10％。
在本申请的硫化物固态电池正极极片中，所述正极集流体的种类不受具体的限制，可根据实际需求进行选择。所述正极集流体通常是可以汇集电流的结构或零件，通常为层体；所述正极集流体可以是本领域各种适用于作为电化学储能装置正极集流体的材料，例如可以是包括但不限于金属箔，更具体可以是包括但不限于镍箔、铝箔、涂炭铝箔或不锈钢等材料。
在本申请的硫化物固态电池正极极片中，所述正极活性物质层可以设置在正极集流体的其中一个表面上，也可以设置在正极集流体的两个表面上。
在本申请的硫化物固态电池正极极片中，所述正极活性材料的具体种类没有特别的限制，只要能满足接受、脱出锂离子即可。例如可以选自橄 榄石结构锂金属氧化物、层状结构锂金属氧化物、尖晶石结构锂金属氧化物、硫粉及对以上材料进行改性后的材料中的至少一种。
具体地，所述橄榄石结构锂金属氧化物可选自磷酸铁锂(LiFePO 4)、磷酸钴锂(LiCoPO 4)、磷酸锰锂(LiMnPO 4)、磷酸镍锂(LiNiPO 4)、磷酸铁(FePO 4)等锂金属氧化物中的至少一种。所述层状结构锂金属氧化物可选自钴酸锂(LiCoO 2)、镍酸锂(LiNiO 2)、三元材料LiNi sB tC( 1-s-t)O 2(其中，B、C独立地选自Co、Al、Mn中的至少一种，且B和C不相同，0<s<1，0<t<1)等锂金属氧化物中的至少一种。所述尖晶石结构锂金属氧化物可选自锰酸锂(LiMn 2O 4)、镍锰酸锂(LiNi 0.5Mn 1.5O 4)等锂金属氧化物中的至少一种。所述改性后的材料可选自对上述各种材料进行掺杂与包覆处理后的材料中的至少一种，掺杂与包覆的元素可选自金属元素和非金属元素，如Li、N、F、Cl、S、B、P、Al、Si、Zr、Ti、Ge、Sn、Mg、Zn、Ce、W、V等。
在本申请的硫化物固态电池正极极片中，所述固态电解质可以选自硫化物固态电解质。所述硫化物固态电解质可以包括锂和硫，还可以进一步包括其他元素，例如，可以包括但不限于P、Si、Ge、Sn、Al等元素中的至少一种。
具体地，所述硫化物固态电解质的结构通式可以表述为yLi 2S-(100-y)LS，其中0<y<100，所述LS可以是但不限于P 2S 5、SiS 2、GeS 2、SnS 2、Al 2S 3等物质中的一种或多种，其所构成的固态电解质体系可以是包括但不限于Li 2S-P 2S 5体系、Li 2S-SiS 2体系、Li 2S-GeS 2体系、Li 2S-SnS 2体系、Li 2S-Al 2S 3体系中的一种或多种。所述硫化物固态电解质的状态可以为晶态、无定形态或晶态-无定形态的复合态。
进一步地，所述硫化物固态电解质还可以包括掺杂材料，所述掺杂材料优选为含锂元素的化合物LiQ。具体地，掺杂后的硫化物电解质结构通式可以表示为z(Li 2S-LS)-(100-z)LiQ，其中90≤z≤100，所述掺杂材料LiQ可以是包括但不限于卤化锂、锂的氧化物、锂的氮化物、锂的含氧酸盐等中的一种或多种的组合。其中，LiQ可以是包括但不限于LiF、LiCl、LiBr、LiI、Li 2O、Li 3N、LiAlO 2、Li 3PO 4、Li 2SO 4、Li 3BO 3、Li 4SiO 4、LiN(SO 2F) 2、LiN(SO 2R F) 2、LiN(SO 2F)(SO 2R F)(取代基R F＝C nF 2n+1，是饱和全氟烷基，n 为1～2的整数)等中的一种或多种。
在本申请的硫化物固态电池正极极片中，所述正极活性物质层还可以包括导电剂以及粘结剂，其中导电剂以及粘结剂的种类和含量不受具体的限制，可根据实际需求进行选择。具体地，粘结剂可以选自SBS、SEBS、PVDF、PTFE、PAALi、丁苯橡胶、丁腈橡胶、丁烯橡胶、苯乙烯橡胶和聚氨酯等中的至少一种；导电剂可以选自导电炭黑(super-P)、乙炔黑、气相生长炭纤维(Vapor-grown carbon fiber，简称VGCF)、碳纳米管和石墨烯中的至少一种。
本申请第二方面提供一种硫化物固态电池，本申请对硫化物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。如图1是作为一个示例的方形结构的硫化物固态电池5。
在一些实施例中，硫化物固态电池可以组装成电池模块，电池模块所含硫化物固态电池的数量可以为多个，具体数量可根据电池模块的应用和容量来调节。
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，多个硫化物固态电池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硫化物固态电池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壳体，多个硫化物固态电池5容纳于该容纳空间。
在一些实施例中，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根据电池包的应用和容量进行调节。
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。
在本申请的第三方面提供一种装置，所述装置包括本申请第二方面的硫化物固态电池。所述硫化物固态电池为所述装置提供电源。所述装置可以但不限于是移动设备(例如手机、笔记本电脑等)、电动车辆(例如纯电动车、 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)、电气列车、船舶及卫星、储能系统等。
所述装置可以根据其使用需求来选择硫化物固态电池(Cell)、电池模块(Module)或电池包(pack)。
图5是作为一个示例的装置。该装置为纯电动车、混合动力电动车、或插电式混合动力电动车等。为了满足该装置对硫化物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，可以采用硫化物固态电池作为电源。
本领域技术人员可以选择合适的方法制备本申请的硫化物固态电池正极极片，例如可以采用干法压制或湿法涂敷的方法进行制备。下面是对其制备过程的举例说明。
本发明的硫化物固态电池正极极片可以按照如下的干法压制法制备：
(1)将正极活性材料、固态电解质、添加盐、导电剂按比例分散混合，形成固体混合材料，分散工艺可以为手工、机械球磨等。其中，以形成正极活性物质层的原料的总质量为基准，正极活性材料、固态电解质、添加盐、导电剂的质量百分含量可以依次分别为50～95％(例如70～85％)、4.9～49.9％(例如10～29％)、0.1～20％(例如1～19％)、0～5％(例如0～2％)。正极活性材料的含量会影响到正极极片中电子和锂离子导通网络的构建：如果正极活性材料在正极活性物质层中的质量百分含量高于95％，会导致固态电解质、导电添加剂的含量过低，不利于电子和锂离子的传递；如果正极活性材料在正极活性物质层中的质量百分含量低于50％，会降低电池的容量，影响电池的能量密度。
(2)将上述固体混合材料分散于正极集流体表面，置于模具中进行热压，压制成膜，即得到硫化物固态电池正极极片。其中，热压方式可以是一步压制，也可以是分步压制。热压压力可以为0.1～500MPa，优选为100～400MPa；热压温度可以为25～160℃，优选为60～120℃。热压压力过小、温度过低则膜片致密度低，热压压力过大对设备要求高；热压温度过高则容易导致电解质分解。压制得到的正极极片的厚度为10～200μm。如 果正极极片过薄，则导致电池能量密度降低；如果正极极片过厚，则会增加正极极片内的锂离子传输阻抗，使电池发生极化。
本发明的硫化物固态电池正极极片也可以按照如下的湿法涂敷法制备：
(1)将正极活性材料、固态电解质、添加盐、导电剂、粘结剂混合于有机溶剂中，分散形成浆料。其中，以形成正极活性物质层的原料的总质量为基准，正极活性材料、固态电解质、添加盐、导电剂、粘结剂的质量百分含量可以依次分别为50～95％(例如70～80％)、4.7～39.9％(例如10～27％)、0.1～20％(例如1～10％)、0.1～5％(例如1～2％)、0.1～5％(例如1～2％)。如果粘结剂的含量过低，会导致电解质膜的强度和韧性差；如果粘结剂的含量过高，则会影响锂离子的传递，使电池发生极化。
另外，湿法涂敷法中所使用的有机溶剂需不与固态电解质发生反应，可选自醚类有机溶剂、烃类有机溶剂、酯类有机溶剂、腈类有机溶剂、酰胺类有机溶剂、醇类有机溶剂、卤代有机溶剂中的至少一种。具体地，醚类有机溶剂选自乙醚、四氢呋喃、乙二醇二甲醚中的至少一种；烃类有机溶剂选自正戊烷、正己烷、环己烷、甲苯、二甲苯、三甲苯中的至少一种；酯类有机溶剂选自乙酸乙酯、甲酸甲酯、邻苯二甲酸二甲酯中的至少一种，腈类有机溶剂选自乙腈，酰胺类有机溶剂选自N-甲基吡咯烷酮(NMP)和/或N,N-二甲基甲酰胺(DMF)，醇类有机溶剂选自乙醇；卤代有机溶剂选自二氯甲烷和/或1,2-二氯乙烷。利用有机溶剂对上述浆料的粘度进行调控，控制浆料的粘度为5000～200000mPa·s，优选为10000～50000mPa·s。如果浆料粘度过大，则会加大电解质膜制作难度；而浆料粘度过低，则易导致电解质膜出现孔洞，在一定程度上增加电池内短路的风险。
(2)将分散好的浆料均匀涂覆于铝箔表面，干燥后进行热压压制，即得到硫化物固态电池正极极片。其中，热压方式可以是一步压制，也可以是分步压制。热压压力可以为1～500MPa，优选为100～300MPa；热压温度可以为25～160℃，优选为60～120℃。压力过小、温度过低则膜片致密度低，压力过大对设备要求高，温度过高则容易导致电解质和粘结剂分解。
本发明第二方面的硫化物固态电池包括正极极片、负极极片、以及间隔设于所述正极极片和所述负极极片之间的固态电解质膜片，其中，所述正极极片为本发明第一方面的硫化物固态电池正极极片。
本发明的硫化物固态电池可以为叠片式固态电池。
在本发明的硫化物固态电池中，所述负极极片可以包括负极集流体和设于负极集流体上的金属锂或锂合金层，负极集流体可以选自铜箔、涂炭铜箔和不锈钢箔中的至少一种。其中，金属锂或锂合金层的厚度可以为1～200μm，优选为5～100μm。负极极片的制备方法可以为：将金属锂或锂合金贴于负极集流体表面，制成负极极片。
在本发明的硫化物固态电池中，所述固态电解质膜片可由固态电解质经干法制膜法或湿法制膜法制备。其中，固态电解质也可以选自硫化物固态电解质，所述硫化物固态电解质的可选范围与本发明第一方面中的固态电解质相同。下面是对固态电解质膜片的制备过程的举例说明。
干法制膜方法如下：将固态电解质置于模具中压制成膜。其中，压制方法可采用冷压或热压。压制方式可以是一步压制，也可以是分步压制。热压压力为0.1～500MPa，优选为100～400MPa；热压温度为25～160℃，优选为60～120℃。如果热压压力过小、温度过低则会导致制得的固态电解质膜片的致密度低；但热压压力过大对设备的要求高，热压温度过高则容易导致固态电解质分解。
湿法制膜方法如下：将固态电解质、粘结剂混合于有机溶剂中，分散成浆料；将浆料涂布于玻璃基材上，干燥后压制得到硫化物电解质膜片。其中，粘结剂、有机溶剂的可选范围可以与本发明第一方面中以湿法涂敷法制备正极极片时所用的粘结剂、有机溶剂相同。固态电解质和粘结剂的混合物中，固态电解质、粘结剂的质量百分含量可以分别为50％～99％、1％～50％；优选分别为80％～98％、2％～20％。如果粘结剂的含量过低，会导致电解质膜的强度和韧性差；如果粘结剂的含量过高，则会影响锂离子的传递，使电池发生极化。另外，压制方法可以采用冷压，也可以采用热压；可以是一步压制，也可以是分步压制。热压压力为1～500MPa，优选为100～300MPa；热压温度为25～160℃，优选为60～120℃。如压力过小、温度过低则膜片致密度低；如压力过大对设备要求高，温度过高则容易导固态电解质和粘结剂分解。
本发明第二方面的硫化物固态电池可以采用如下方法制备：
将正极极片、固态电解质膜片、负极极片分别按所需尺寸进行切片， 将切片后的正极极片、固态电解质膜片、负极极片按中心对齐、依次堆叠成夹心层单元，将夹心层单元在一定温度下加压复合在一起，即得到硫化物固态电池的电芯，将电芯冷压后置于外包装中封装成型，即得到硫化物固态电池。其中，加压压力可以为1～500MPa，优选为100～300MPa；压实温度可以为20～160℃，优选为60～120℃。
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。
实施例1
(1)干法制备正极极片
手套箱中，将正极活性物质LiNi 0.8Co 0.1Mn 0.1O 2、硫化物固态电解质Li 3PS 4、添加盐Li[(FSO 2)(CF 3SO 2)N]、导电剂VGCF按重量比70:24:5:1充分搅拌混合均匀后，分散于铝箔表面，在100℃、250MPa下压制2min后得到厚度为50μm的正极极片。
(2)制备固态电解质膜片
手套箱中，将硫化物固态电解质Li 3PS 4在100℃、250MPa下压制2min，得到厚度为50μm固态电解质膜片。
(3)制备负极极片
将25μm锂金属贴于铜箔表面，切片。
(4)制备硫化物固态电池
将上述正极片、固态电解质膜片、负极极片的中心对齐后依次叠放，在室温、250MPa下冷压2min得到电芯单元，将10层电芯单元冷压后置于外包装中封装成型，即得到固态锂金属电池。
实施例2
与实施例1基本相同，不同点在于：将LiNi 0.8Co 0.1Mn 0.1O 2、Li 3PS 4、Li[(FSO 2)(CF 3SO 2)N]、VGCF的重量比由70:24:5:1调整为70:29:0.1:0.9。
实施例3
与实施例1基本相同，不同点在于：将LiNi 0.8Co 0.1Mn 0.1O 2、Li 3PS 4、Li[(FSO 2)(CF 3SO 2)N]、VGCF的重量比由70:24:5:1调整为70:28:1:1。
实施例4
与实施例1基本相同，不同点在于：将LiNi 0.8Co 0.1Mn 0.1O 2、Li 3PS 4、Li[(FSO 2)(CF 3SO 2)N]、VGCF的重量比由70:24:5:1调整为70:19:10:1。
实施例5
与实施例1基本相同，不同点在于：将LiNi 0.8Co 0.1Mn 0.1O 2、Li 3PS 4、Li[(FSO 2)(CF 3SO 2)N]、VGCF的重量比由70:24:5:1调整为70:9:20:1。
实施例6
与实施例1基本相同，不同点在于：将正极极片中的固态电解质由Li 3PS 4替换为Li 6PS 5Cl。
实施例7
与实施例1基本相同，不同点在于：将LiNi 0.8Co 0.1Mn 0.1O 2、Li 3PS 4、Li[(FSO 2)(CF 3SO 2)N]、VGCF的重量比由70:24:5:1调整为70:20:5:5。
实施例8
与实施例1基本相同，不同点在于：将正极活性材料由LiNi 0.8Co 0.1Mn 0.1O 2替换为LiNi 0.6Co 0.2Mn 0.2O 2。
实施例9
与实施例8基本相同，不同点在于：将添加盐由Li[(FSO 2)(CF 3SO 2)N]替换为Rb[(FSO 2)(CF 3SO 2)N]，且热压条件由100℃、250MPa替换为120℃、250MPa。
实施例10
与实施例8基本相同，不同点在于：将添加盐由Li[(FSO 2)(CF 3SO 2)N]替换为Cs[(CF 3SO 2)(CF 3SO 2)N]，且热压条件由100℃、250MPa替换为130℃、250MPa。
实施例11
(1)湿法制备正极极片
手套箱中，将正极活性物质LiNi 0.8Co 0.1Mn 0.1O 2、硫化物固态电解质Li 3PS 4、添加盐Li[(FSO 2)(CF 3SO 2)N]、导电剂VGCF、粘结剂丁苯橡胶(数均分子量约为50万)按重量比70:22:5:1:2，混合于THF溶剂中，充分搅拌混合均匀后，涂覆于铝箔表面，自然晾干后经60℃烘干、冷压、切片后，在100℃、250MPa下压制2min，得到厚度为50μm的正极极片。
(2)制备固态电解质膜片
将硫化物固态电解质Li 3PS 4、粘结剂丁苯橡胶按重量比98:2，混合于THF溶剂中配制成电解质浆料，涂于玻璃表面，60℃下干燥后，在50℃、250MPa下压制2min，得到厚度为50μm固态电解质膜片。
(3)制备负极极片
将25μm锂金属贴于铜箔表面，切片。
(4)制备硫化物固态电池
将上述正极片、固态电解质膜片、负极极片的中心对齐后依次叠片，在室温、250MPa下冷压2min得到电芯单元，将10层电芯单元冷压后置于外包装中封装成型，即得到硫化物固态电池。
实施例12
与实施例11基本相同，不同点在于：将正极活性材料由LiNi 0.8Co 0.1Mn 0.1O 2替换为LiNi 0.6Co 0.2Mn 0.2O 2。
实施例13
与实施例11基本相同，不同点在于：将正极极片中的添加盐Li[(FSO 2)(CF 3SO 2)N]替换为Li 0.8Cs 0.2[(FSO 2)(CF 3SO 2)N]，且热压条件由100℃、250MPa调整为50℃、250MPa。
实施例14
与实施例11基本相同，不同点在于：将正极极片中的添加盐Li[(FSO 2)(CF 3SO 2)N]替换为Li[(FSO 2) 2N] 0.5[(FSO 2)(CF 3SO 2)N] 0.5；同时，还使正极极片中的LiNi 0.8Co 0.1Mn 0.1O 2、Li 3PS 4、Li[(FSO 2) 2N] 0.5[(FSO 2)(CF 3SO 2)N] 0.5、VGCF、丁苯橡胶的重量比为50:39.9:0.1:5:5，且热压条件由100℃、250MPa替换为50℃、250MPa。
实施例15
与实施例11基本相同，不同点在于：将正极极片中的添加盐Li[(FSO 2)(CF 3SO 2)N]替换为Li[(FSO 2) 2N]，同时，LiNi 0.8Co 0.1Mn 0.1O 2、Li 3PS 4、Li[(FSO 2) 2N]、VGCF、丁苯橡胶的重量比调整为95:4.7:0.1:0.1:0.1，且热压条件由100℃、250MPa替换为150℃、250MPa。
对比例1
与实施例1基本相同，不同点在于：正极极片中不含添加盐，且LiNi 0.8Co 0.1Mn 0.1O 2、Li 3PS 4、VGCF的重量比为70:29:1。
对比例2
与实施例1基本相同，不同点在于：正极极片中不含添加盐，且正极极片中的固态电解质由Li 3PS 4替换为Li 6PS 5Cl，同时LiNi 0.8Co 0.1Mn 0.1O 2、Li 6PS 5Cl、VGCF的重量比为70:29:1。
对比例3
与实施例11基本相同，不同点在于：正极极片中不含添加盐，且LiNi 0.8Co 0.1Mn 0.1O 2、Li 3PS 4、VGCF、丁苯橡胶的重量比为70:27:1:2。
下表1示出了实施例1～15和对比例1～3的具体参数：
Figure PCTCN2020083619-appb-000002
(注：表1中的添加盐相变温度是指：添加盐发生相变的起始温度。)
本发明的硫化物固态电池正极极片和硫化物固态电池的性能检测如下：
1、正极极片的累积热效应检测
对硫化物固态电池进行首次充电，充电至4.2V。将测试电池拆解后，得到满充状态的正极极片。对满充状态的正极极片进行差示扫描量热法(DSC)测试，检测正极极片在25～300℃过程中的累积热效应。
2、硫化物固态电池的性能测试
将硫化物固态电池的充放电工作电压范围设置为2.8V～4.2V，采用恒流充放电的方式进行循环测试，其中，测试电流为0.1C(电流密度约为0.13mA/cm 2)，测试温度为25℃。
(1)首周比容量：在0.1C充放电电流下，测试电池的首周放电比容量。
(2)首周库伦效率；在0.1C充放电电流下，测试电池的首周库伦效率；电池的首周库伦效率＝首周放电比容量/首周充电比容量×100％。
(3)循环测试：将电池分别循环50周和200周后，分别测试电池的容量保持率。容量保持率＝50周或200周放电比容量/首周放电比容量×100％。
下表2示出了实施例1～15和对比例1～3的性能检测结果：
Figure PCTCN2020083619-appb-000003
根据表1和表2，实施例1、6、11分别与对比例1、2、3相比，其区别在于，实施例1、6、11中的正极极片中掺入了添加盐，而对比例1、2、3的正极极片中不含有添加盐。从表2可以看到，相对于对比例1、2、3而言，实施例1、6、11的正极极片在高电压下的累积放热量存在显著降低。其原因就在于，在本发明的正极极片中引入添加盐后，利用添加盐相变过程中的吸热效应，吸收了正极极片产生的热量(如正极活性材料促发的正极与硫化物固态电解质之间的副反应、硫化物固态电解质的自身分解等放热过程产生的热量)，从而实现了对硫化物固态电池体系的热安全性和循环稳定性的有效提升。
关于添加盐的含量：实施例1～5均采用干法压制工艺制备正极极片，且正极极片、固态电解质和负极极片的材料相同，实施例1～5之间的区别仅在于添加盐的含量不同。结合表1、表2可知，提高添加盐的含量，可 降低体系放热量；但添加盐含量过高(例如实施例5中到达20％)的情况下，由于添加盐的离子导电性较差，是不利于正极层内锂离子的快速传递的，则会导致电池首周比容量及首周效率等电池性能轻微降低。
关于添加盐的种类：虽然本发明所提供的各种添加盐都能够吸收正极极片产生的热量、对硫化物固态电池体系的热安全性和循环稳定性进行有效提升，但是，当添加盐材料为非锂材料(例如实施例9和10中的Rb盐和Cs盐)时，电池体系内的锂含量相对于添加盐为锂材料的电池体系稍低，从而导致电池性能衰减稍快。
另外，从实施例5～15还可知，使用稳定性高的硫化物固态电解质材料(例如实施例6)、与硫化物固态电解质相容性更好的正极活性材料(例如实施例8)，可进一步降低电池发热量。如电池体系中的导电碳含量过高，过量的导电碳会阻碍固态电池中锂离子传递、催化电解质性能劣化，从而导致电池性能降低(例如实施例7)。导电剂、粘结剂含量过高也将不利于电池安全及电池性能发挥(例如实施例14)。
根据上述说明书的揭示和教导，本领域技术人员还可以对上述实施方式进行变更和修改。因此，本发明并不局限于上面揭示和描述的具体实施方式，对本发明的一些修改和变更也应当落入本发明的权利要求的保护范围内。此外，尽管本说明书中使用了一些特定的术语，但这些术语只是为了方便说明，并不对本发明构成任何限制。

Claims (15)

  1. 一种硫化物固态电池正极极片，其中，
    包括正极集流体以及设置在正极集流体至少一个表面上的正极活性物质层，所述正极活性物质层包括正极活性材料和固态电解质；
    所述正极活性物质层还包括添加盐，所述添加盐在40～150℃发生吸热相变。
  2. 根据权利要求1所述的硫化物固态电池正极极片，其中，所述添加盐在60～110℃发生吸热相变。
  3. 根据权利要求1或2所述的硫化物固态电池正极极片，其中，所述添加盐的分解温度高于200℃。
  4. 根据权利要求1-3任一项所述的硫化物固态电池正极极片，其中，所述添加盐选自碱金属的无机盐、碱金属的有机盐、碱金属的有机-无机复合盐中的至少一种。
  5. 根据权利要求4所述的硫化物固态电池正极极片，其中，所述添加盐选自M-imide；其中，M为选自Li、Na、K、Rb、Cs中至少一种的阳离子，imide为下式(I)所示的磺酰亚胺阴离子，
    Figure PCTCN2020083619-appb-100001
    式(I)中：
    n选自0～4的整数；
    X、Y各自独立地选自F、Cl、Br、I或碳原子数为1～4的含氟烷基。
  6. 根据权利要求4或5所述的硫化物固态电池正极极片，其中，所述添加盐选自Li[(FSO 2) 2N]、Na[(FSO 2) 2N]、K[(FSO 2) 2N]、Rb[(FSO 2) 2N]、Cs[(FSO 2) 2N]、Li[(FSO 2)(CF 3SO 2)N]、Na[(FSO 2)(CF 3SO 2)N]、K[(FSO 2)(CF 3SO 2)N]、Rb[(FSO 2)(CF 3SO 2)N]、Cs[(FSO 2)(CF 3SO 2)N]、Li 0.4K 0.6[(FSO 2) 2N]、Li 0.4Cs 0.6[(FSO 2)(CF 3SO 2)N]或Li 0.8Cs 0.2[(FSO 2)(CF 3SO 2)N]中的至少一种。
  7. 根据权利要求1-6任一项所述的硫化物固态电池正极极片，其中，所述添加盐在所述正极活性物质层中的质量百分含量为0.1％～20％。
  8. 根据权利要求7所述的硫化物固态电池正极极片，其中，所述添加盐在所述正极活性物质层中的质量百分含量为1％～10％。
  9. 根据权利要求1-8任一项所述的硫化物固态电池正极极片，其中，所述正极活性材料选自橄榄石结构锂金属氧化物、层状结构锂金属氧化物、尖晶石结构锂金属氧化物、硫粉或上述材料的改性材料中的至少一种。
  10. 根据权利要求1-9任一项所述的硫化物固态电池正极极片，其中，所述固态电解质选自硫化物固态电解质。
  11. 根据权利要求10所述的硫化物固态电池正极极片，其中，所述硫化物固态电解质的结构通式为yLi 2S-(100-y)LS，其中0<y<100，所述LS为P 2S 5、SiS 2、GeS 2、SnS 2和Al 2S 3中的一种或多种。
  12. 根据权利要求10或11所述的硫化物固态电池正极极片，其中，所述硫化物固态电解质中还包括掺杂材料，掺杂后的硫化物电解质结构通式为z(Li 2S-LS)-(100-z)LiQ，其中90≤z≤100，所述掺杂材料LiQ为卤化锂、锂的氧化物、锂的氮化物和锂的含氧酸盐中的一种或多种。
  13. 根据权利要求12任一项所述的硫化物固态电池正极极片，其中，所述通式z(Li 2S-LS)-(100-z)LiQ中，所述掺杂材料LiQ为LiF、LiCl、LiBr、LiI、Li 2O、Li 3N、LiAlO 2、Li 3PO 4、Li 2SO 4、Li 3BO 3、Li 4SiO 4、LiN(SO 2F) 2、LiN(SO 2R F) 2和LiN(SO 2F)(SO 2R F)中的一种或多种，其中，取代基R F是饱和全氟烷基，其通式为C nF 2n+1，n为1～2的整数。
  14. 一种硫化物固态电池，包括：正极极片、负极极片、以及间隔设于所述正极极片和所述负极极片之间的固态电解质膜片，其中，所述正极极片为权利要求1至13中任一项所述的硫化物固态电池正极极片。
  15. 一种装置，其中，所述装置包括权利要求14所述的硫化物固态电池。
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