WO2017128983A1 - 全固态锂离子电池正极复合材料及其制备方法和应用 - Google Patents

全固态锂离子电池正极复合材料及其制备方法和应用 Download PDF

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WO2017128983A1
WO2017128983A1 PCT/CN2017/071314 CN2017071314W WO2017128983A1 WO 2017128983 A1 WO2017128983 A1 WO 2017128983A1 CN 2017071314 W CN2017071314 W CN 2017071314W WO 2017128983 A1 WO2017128983 A1 WO 2017128983A1
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positive electrode
polymer electrolyte
lithium ion
ion battery
solid
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French (fr)
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谢静
马永军
易观贵
宋威
郭姿珠
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BYD Co Ltd
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BYD 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the field of lithium ion batteries, and particularly relates to an all-solid lithium ion battery cathode composite material and a preparation method thereof, a cathode material, a cathode and an all-solid lithium ion battery.
  • the preparation methods of the positive electrode of the all-solid lithium ion battery are generally classified into three types, namely, a powder tablet type, a vacuum coating type, and a coating type.
  • the powder tableting type is a method in which a positive electrode active material, an inorganic solid electrolyte powder and a conductive agent are mixed in a certain ratio and then pressed under a certain pressure. During the preparation of the method, volume expansion or volume shrinkage of the positive electrode active material occurs.
  • the effect causes the solid-solid contact interface effect between the positive active material and the inorganic solid electrolyte particles to deteriorate, and the solid-solid contact interface effect has a greater influence on the performance of the entire battery when the battery is subjected to external impact; vacuum coating type
  • the positive electrode active material is directly coated on the current collector by means of sputter coating, evaporation coating, pulsed laser deposition film or ion plating film. This method requires specific equipment, is expensive, and has low efficiency, which restricts to some extent. Commercial application; the coated positive electrode sheet is obtained by uniformly mixing a positive electrode active material, an inorganic solid electrolyte, a conductive agent and a binder in a specific solvent in a specific solvent, and then coating the mixed slurry on the current collector.
  • the method requires a binder to be added during coating, and the added binder component is non-lithium Conductor, will affect the conductivity of lithium ions inside the positive electrode, thus affecting the electrochemical performance of the battery.
  • the prior art discloses that the surface of the positive electrode material is coated with LiNbO 3 , SiO 2 , Al 2 O 3 , Ni 2 S 3 , Li 3 PS 4 or the like.
  • the methods of coating with oxides such as LiNbO 3 , SiO 2 , and Al 2 O 3 include fluidized bed method, pulsed laser deposition, etc. These methods are complicated in operation, expensive in equipment, and low in ion conductivity of the coating layer.
  • an object of the present invention is to provide an all-solid lithium ion battery positive electrode composite material and a preparation method thereof, a positive electrode material, a positive electrode, and an all solid state
  • the lithium ion battery can effectively solve the problem of the solid-solid interface layer existing between the cathode material and the sulfide solid electrolyte in the prior art and the problem of low ion conductivity.
  • the present invention provides an all-solid lithium ion battery positive electrode composite material having a core-shell structure, the core including a positive electrode active material, and the shell including a polymer electrolyte and a sulfide Solid electrolyte.
  • the present invention can reduce the direct contact between the positive electrode active material and the inorganic solid electrolyte by coating the surface of the positive electrode active material with the shell layer containing the polymer electrolyte and the inorganic solid electrolyte, thereby improving the interface problem between the positive electrode and the inorganic solid electrolyte;
  • the present invention uses a shell layer containing a polymer electrolyte and an inorganic solid electrolyte to coat a cathode active material to obtain a cathode composite material.
  • the inventors have also found that the polymer electrolyte contained in the shell layer not only has good lithium ion conductivity.
  • the polymer electrolyte component also has certain elastomeric properties, which can alleviate the positive electrode active material to a certain extent.
  • the volume expansion effect during charging and discharging; on the other hand, the sulfide solid electrolyte contained in the shell layer can not only improve the ionic conductivity of the shell polymer electrolyte, but also increase the electrochemical window of the shell polymer electrolyte, so that Positive electrode composites can match high ion power
  • the inorganic solid electrolyte and the negative electrode of the battery safety is higher, long cycle life.
  • the present invention also provides a method for preparing a solid-state lithium ion battery positive electrode composite material. According to an embodiment of the present invention, the method includes:
  • a positive electrode active material added to the emulsion of the step (2), wrapping the emulsion with the positive electrode composite material, and drying to obtain a positive electrode composite material having a core-shell structure, wherein the core includes a positive electrode active material A material comprising a polymer electrolyte and a sulfide solid electrolyte.
  • an all-solid lithium ion battery positive electrode material includes a positive electrode composite material and a positive electrode conductive agent, and the positive electrode composite The material is the all-solid lithium ion battery positive electrode composite material proposed by the invention.
  • the invention further provides an all-solid-state lithium ion battery positive electrode comprising a positive electrode material as set forth in the present application, in accordance with an embodiment of the present invention.
  • the present invention also provides an all-solid-state lithium ion battery, which according to an embodiment of the present invention includes a battery case and a battery cell located in the battery case, the battery core
  • the present invention includes a positive electrode, a negative electrode, and an inorganic solid electrolyte layer between the positive electrode and the negative electrode, wherein the positive electrode is the lithium ion proposed in the present application. Sub-cell positive.
  • FIG. 1 is a schematic structural view of a positive electrode composite material of an all-solid lithium ion battery according to the present application.
  • the present invention provides an all-solid lithium ion battery positive electrode composite material, according to an embodiment of the present invention, the positive electrode composite material has a core-shell structure, the core includes a positive electrode active material, The shell includes a polymer electrolyte and a sulfide solid electrolyte.
  • the polymer electrolyte in the solid-state lithium ion battery positive electrode composite material, may be selected from the group consisting of a polyoxyethylene polymer electrolyte, a polyvinylidene fluoride polymer electrolyte, a polyacrylonitrile-based polymer electrolyte, and a poly At least one of a methyl methacrylate-based polymer electrolyte and a polyvinyl polymer electrolyte; further preferably, the polymer electrolyte is selected from the group consisting of a polyoxyethylene polymer electrolyte, a polyvinylidene fluoride polymer electrolyte, At least one of polyacrylonitrile-based polymer electrolytes.
  • the lithium ion conductivity of the shell layer can be further improved, and at the same time, the shell has good bonding properties, thereby reducing the use of the nonionic conductivity component binder during the coating process of the cathode material.
  • the polymer electrolyte component also has certain elastomeric properties, which can alleviate the volume expansion effect of the positive active material during charge and discharge to a certain extent.
  • the polymer electrolyte of the present invention is a polymer electrolyte in the conventional sense in the prior art, that is, a complex of a polymer and a lithium salt formed by a complex reaction of a polymer and a lithium salt under certain conditions.
  • a positive electrode composite material for a positive electrode of a lithium ion battery is prepared by using a shell-coated positive electrode active material containing the above polymer electrolyte and a sulfide solid electrolyte, and the prepared battery has high safety. Performance and cycle performance; after repeated tests, it was found that the polyelectrolyte not only has good bonding property, but also has good ionic conductivity. After being mixed with a sulfide solid electrolyte, it is coated on the surface of the positive electrode active material.
  • the prepared positive electrode not only has a solid-solid interface effect with the inorganic solid electrolyte, but also has a good charge and discharge capacity of the positive electrode itself.
  • the glassy state of Li 2 SP 2 S 5 is selected from the group consisting of 70Li 2 S-30P 2 S 5 , 75Li 2 S-25P 2 S 5 , 80Li 2 S- At least one of 20P 2 S 5 ;
  • the glass-ceramic state of Li 2 SP 2 S 5 is selected from the group consisting of 70Li 2 S-30P 2 S 5 , 75Li 2 S-25P 2 S 5 , 80Li 2 S- in a glass-ceramic state At least one of 20P 2 S 5 ;
  • the crystalline state of Li x ' M y' PS z' is selected from the group consisting of Li 3 PS 4 , Li 4 SnS 4 , Li 4 GeS 4 , Li 10 SnP 2 S 12 , Li 10 At least one of GeP 2 S 12 and Li 10 SiP 2 S 12 .
  • the solid-state lithium ion battery positive electrode composite material preferably has a mass ratio of the polymer electrolyte to the sulfide solid electrolyte of 1:99 to 99:1; further preferably, the polymer electrolyte The mass ratio to the sulfide solid electrolyte is 2:8 to 1:99; or the mass ratio between the polymer electrolyte and the sulfide solid electrolyte is 8:2 to 99:1; still more preferably, the polymerization The mass ratio between the electrolyte of the substance and the solid electrolyte of the sulfide is 1:9 to 1:99; or the mass ratio between the polymer electrolyte and the sulfide solid electrolyte is 9:1 to 99:1.
  • the lithium ion conductivity of the shell layer can be further improved, and the adhesion property of the shell can be improved, and the use of the nonionic conductive component binder in the coating process of the cathode material can be reduced.
  • the ionic conductivity of the shell polymer electrolyte can be further improved, and the electrochemical window of the shell polymer electrolyte can be increased, so that the obtained cathode composite material can match the inorganic solid electrolyte and the anode with high ionic conductivity.
  • the battery is safer and has a long cycle life.
  • the all-solid lithium ion battery positive electrode composite material preferably has a mass ratio of the polymer electrolyte and the sulfide solid state electrolyte to the positive electrode active material of (40 to 5): (60 to 95) ).
  • the mass ratio of the total amount of the polymer electrolyte and the sulfide solid electrolyte to the positive electrode active material is (40 to 5): (60 to 95), which not only can well relieve the interface between the positive electrode and the inorganic solid electrolyte.
  • the impact problem can also ensure the charge and discharge efficiency of the positive electrode.
  • the corresponding negative electrode in the battery may be a negative electrode conventionally used in the art, such as a graphite negative electrode, a silicon carbon negative electrode, a metal lithium negative electrode or a lithium-indium alloy negative electrode.
  • the positive electrode active material is at least one selected from the group consisting of V 2 O 5 , MnO 2 , TiS 2 , and FeS 2 .
  • the corresponding negative electrode in the battery should be an anode active material capable of extracting lithium ions, for example, lithium metal can be used.
  • the present invention also provides a method for preparing an all-solid lithium ion battery positive electrode composite. According to an embodiment of the invention, the method comprises:
  • a positive electrode active material having a core-shell structure is obtained by adding a positive electrode active material to the emulsion of the step (2), wherein the core includes a positive electrode active material, and the shell includes a polymer electrolyte and a sulfide solid electrolyte.
  • the polymer in the step (1) is selected from the group consisting of polyoxyethylene, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate and poly At least one of ethylene;
  • the lithium salt is selected from the group consisting of LiPF 6 , LiAsF 6 , LiClO 4 , LiBF 6 , LiN(CF 3 SO 3 ) 2 , LiCF 3 SO 3 , LiC(CF 3 SO 3 ) 2 , LiN ( At least one of C 4 F 9 SO 2 )(CF 3 SO 3 ).
  • the polymer electrolyte prepared by using the above polymer and lithium salt can further improve the lithium ion conductivity of the shell layer, and at the same time, the shell has good bonding properties, thereby reducing non-ion conductance during coating of the cathode material.
  • the use of the component binder, and the polymer electrolyte component also has certain elastomeric properties, which can alleviate the volume expansion effect of the positive electrode active material during charging and discharging to some extent.
  • the step (1) comprises dissolving the polymer and the lithium salt in an organic ratio according to a ratio of (20 to 85): (80 to 15). After the solvent is stirred and mixed for 1-48 hours, the polymer and the lithium salt can be sufficiently subjected to a complexation reaction by using the above ratio and stirring for 1 to 48 hours, thereby efficiently preparing a polymer electrolyte.
  • the step (2) includes adding a sulfide solid electrolyte to the polymer electrolyte, and stirring and mixing for 1-48 hours to obtain an emulsion. Thereby, the polymer electrolyte can be uniformly mixed with the sulfide solid electrolyte.
  • the mass of the sulfide solid electrolyte added in the step (2) satisfies the mass ratio between the polymer electrolyte and the sulfide solid electrolyte.
  • the mass ratio between the polymer electrolyte and the sulfide solid electrolyte is 2:8 to 1:99; or the mass between the polymer electrolyte and the sulfide solid electrolyte a ratio of 8:2 to 99:1; still more preferably, the mass ratio between the polymer electrolyte and the sulfide solid electrolyte is 1:9 to 1:99; or the polymer electrolyte and the sulfide solid electrolyte The mass ratio between 9:1 and 99:1.
  • the lithium ion conductivity of the shell layer can be further improved, and the adhesion property of the shell can be improved, and the use of the nonionic conductive component binder in the coating process of the cathode material can be reduced.
  • the ionic conductivity of the shell polymer electrolyte can be further increased, and the electrochemical window of the shell polymer electrolyte can be increased, so that the obtained cathode composite can match the high ion.
  • the conductivity of the inorganic solid electrolyte and the negative electrode give the battery a higher safety and a longer cycle life.
  • the present invention further provides an all-solid lithium ion battery positive electrode material, comprising a positive electrode composite material and a positive electrode conductive material, wherein the positive electrode composite material is an all-solid lithium ion battery positive electrode composite material proposed by the present invention. .
  • the lithium ion positive electrode material proposed in the present application includes the positive electrode composite material described in the present application, the core of the positive electrode composite material includes a positive electrode active material, and the shell includes a polymer electrolyte and a sulfide solid electrolyte.
  • the above positive electrode material may also optionally comprise a positive electrode binder; since the polymer electrolyte of the shell layer of the positive electrode composite material provided by the present application not only has good ionic conductivity, but also has adhesive properties, and thus is used in the positive electrode material. It may be free of a positive binder or, optionally, a very small amount of a positive binder.
  • the positive electrode binder may be used as a binder in a positive electrode of a high-voltage lithium ion battery.
  • the positive electrode binder may be selected from a fluorine-containing resin and a polyolefin compound such as polyvinylidene fluoride (PVDF) and polytetraethylene. At least one of vinyl fluoride (PTFE) and styrene-butadiene rubber (SBR); preferably, the positive electrode binder is contained in an amount of from 0 to 5%.
  • the positive electrode conductive agent is a conductive agent used in a positive electrode of a high-voltage lithium ion battery.
  • the positive electrode conductive agent may be at least one selected from the group consisting of acetylene black, carbon nanotubes, HV, and carbon black.
  • a cathode material for a lithium ion battery according to the present invention is characterized in that the content of the positive electrode conductive agent is from 0.5% to 5% based on the mass of the positive electrode composite material.
  • the positive electrode composite material of the above embodiment of the present invention is used in the positive electrode material because the polymer electrolyte of the shell layer of the positive electrode composite material itself has good bonding properties, and therefore, the positive electrode material is prepared. In the process, it is only necessary to add a small amount of the positive electrode binder after adding the non-active positive electrode binder, and the corresponding addition amount of the positive electrode conductive agent in the positive electrode material can also be reduced.
  • the present application further provides an all-solid-state lithium ion battery positive electrode comprising the all-solid lithium ion battery positive electrode material of the above embodiment of the present invention.
  • the preparation method of the positive electrode of the present invention is not particularly limited, and is a method for preparing a positive electrode which is conventional in the art, comprising mixing the positive electrode composite material, the positive electrode conductive agent and the organic solvent according to the present invention to prepare a positive electrode slurry for coating the positive electrode current collector. Drying to obtain a positive electrode; or mixing the positive electrode composite material, the positive electrode binder and the positive electrode conductive agent described in the present application with an organic solvent to prepare a positive electrode slurry coated on the positive electrode current collector to be dried to obtain a positive electrode.
  • the positive electrode of the all-solid lithium ion battery described in the present application may also adopt the following methods, including:
  • the positive electrode active material and the positive electrode conductive agent are added to the surface of the step (2), and then coated on the surface of the positive electrode current collector to be dried to obtain the positive electrode described in the present application.
  • the polymer in the step (1) is at least one selected from the group consisting of polyoxyethylene, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate and polyethylene;
  • the lithium salt is selected from the group consisting of LiPF 6 , At least one of LiAsF 6 , LiClO 4 , LiBF 6 , LiN(CF 3 SO 3 ) 2 , LiCF 3 SO 3 , LiC(CF 3 SO 3 ) 2 , LiN(C 4 F 9 SO 2 )(CF 3 SO 3 ) One type;
  • the step (1) comprises dissolving the polymer and the lithium salt in an organic solvent according to a ratio of (20-85): (80-15), and stirring and mixing for 1-48 hours.
  • the polymer and the lithium salt are generated.
  • the complexation reaction results in a polymer electrolyte;
  • the step (2) comprises adding a sulfide solid electrolyte to the step (1), and stirring and mixing for 1-48 hours to obtain an emulsion;
  • the positive electrode conductive agent is well known to those skilled in the art.
  • the conductive agent in the positive electrode of the high-voltage lithium ion battery, wherein the positive electrode conductive agent may be at least one selected from the group consisting of acetylene black, carbon nanotubes, HV, and carbon black.
  • the mass of the sulfide solid electrolyte added in the step (2) satisfies the mass ratio between the polymer electrolyte and the sulfide solid electrolyte.
  • the mass ratio between the polymer electrolyte and the sulfide solid electrolyte is 2:8 to 1:99; or the mass between the polymer electrolyte and the sulfide solid electrolyte a ratio of 8:2 to 99:1; still more preferably, the mass ratio between the polymer electrolyte and the sulfide solid electrolyte is 1:9 to 1:99; or the polymer electrolyte and the sulfide solid electrolyte The mass ratio between 9:1 and 99:1.
  • the quality of the added positive electrode conductive agent satisfies: adding in step (3) based on the total mass of the obtained positive electrode material.
  • the content of the positive electrode conductive agent is from 1% to 5%.
  • the cathode current collector is a cathode current collector well known to those skilled in the art, and for example, may be selected from aluminum foil, carbon paper, carbon nanotube paper, graphene paper or stainless steel foil.
  • the present invention further provides an all-solid-state lithium ion battery comprising a battery case and a battery cell located in the battery case, the battery core including a positive electrode, a negative electrode, and a positive electrode and a negative electrode
  • an inorganic solid electrolyte layer which is the positive electrode proposed in the present application.
  • the inorganic solid electrolyte layer includes an inorganic solid electrolyte and a binder; the present invention has no special requirements on the inorganic solid electrolyte and the binder in the inorganic solid electrolyte layer, and the inorganic solid electrolyte and the binder which are conventional in the art can be used.
  • the binder is selected from at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and styrene butadiene rubber (SBR).
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • SBR styrene butadiene rubber
  • Negative electrode such as stone A negative electrode, a negative electrode silicon carbon, lithium metal or a lithium anode - the negative electrode can be indium alloy; Specifically, the negative electrode includes a negative current collector and a negative electrode material in said negative electrode current collector surface.
  • the negative current collector is a negative current collector known to those skilled in the art, for example, may be selected from copper foil.
  • the negative electrode material includes a negative electrode active material and a negative electrode binder;
  • the negative electrode active material may be a negative electrode active material conventional in the art; specifically, the negative electrode active material is selected from the group consisting of carbon materials, tin alloys, silicon alloys, silicon, At least one of tin and antimony; further, the carbon material may be selected from the group consisting of natural graphite, naturally modified graphite, artificial graphite, petroleum coke, organic cracked carbon, mesocarbon microbeads, carbon fiber, tin alloy, and silicon alloy.
  • the negative electrode active material may also be metal lithium, lithium-indium alloy or the like; generally, the negative electrode material may further contain a negative electrode conductive agent according to actual use.
  • the negative electrode conductive agent is not particularly limited and may be a conventional negative electrode conductive agent in the art, and may be, for example, at least one of carbon black, acetylene black, furnace black, carbon fiber VGCF, conductive carbon black, and conductive graphite;
  • the fourth binder is a binder known in the art for use in a negative electrode of a lithium ion battery. Specifically, the fourth binder may be selected from the group consisting of polythiophene and poly.
  • Oxide polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polystyrene, polyacrylamide, ethylene-propylene-diene copolymer resin, styrene butadiene rubber, polybutadiene, fluororubber, Polyethylene oxide, polyvinylpyrrolidone, polyester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxypropyl cellulose, ethyl cellulose, sodium carboxymethyl cellulose, styrene-butadiene latex At least one.
  • the content of the negative electrode active material and the negative electrode binder in the above negative electrode material is known to those skilled in the art, and specifically, the content of the negative electrode conductive agent is 0.5 to 10% by weight based on the weight of the negative electrode active material; The content of the negative electrode binder is 0.01 to 10% by weight.
  • the positive electrode active material is selected from at least one of V 2 O 5 , MnO 2 , TiS 2 , and FeS 2 ;
  • the negative electrode of lithium ion for example, lithium pre-calined graphite or a silicon negative electrode may be used, or metal lithium, lithium-indium alloy or the like may be used as it is; preferably, the corresponding negative electrode is metal lithium, lithium-indium alloy or the like.
  • the preparation method of the negative electrode of the battery in the present invention is not particularly limited, and the preparation method of the negative electrode conventional in the art may be used.
  • the negative electrode slurry containing the negative electrode active and negative electrode binder is coated on the negative electrode current collector.
  • a negative electrode material layer is formed on the negative electrode current collector.
  • the specific preparation method of lithium ion in the present invention is not particularly limited, and is a preparation method of an all-solid lithium ion battery which is conventional in the art; and the battery core is sealed in a battery case; the preparation of the battery core is conventional in the art.
  • the preparation method of the electric core in the all-solid lithium ion battery is not particularly limited; the preparation of the positive electrode is first prepared, and then the solid electrolyte layer is prepared on the surface of the positive electrode.
  • the solid electrolyte layer in the present application is an inorganic solid electrolyte layer;
  • the method of injecting an inorganic solid electrolyte layer comprises: drying an inorganic solid electrolyte slurry on a surface of the positive electrode to form an inorganic solid electrolyte layer on the surface of the positive electrode; the inorganic solid electrolyte slurry comprising an inorganic solid electrolyte and a binder;
  • the inorganic solid electrolyte is preferably a sulfide solid electrolyte; the kind of the binder and the ratio of the inorganic solid electrolyte to the binder are well known to those skilled in the art, and are not specifically limited herein.
  • the negative electrode is laminated on the solid electrolyte layer to obtain a lithium ion battery of the present application.
  • the positive electrode and the solid electrolyte are bonded together to obtain a lithium ion battery according to the present application.
  • the lithium ion battery provided by the present application adopts the positive electrode active material described in the present application, and the positive electrode has high ionic conductivity, and the interface between the positive electrode and the inorganic solid electrolyte layer has little influence, and the prepared battery has high safety. Good cycle performance.
  • step (1) (2) adding 750.0 g of LiNi 0.5 Mn 1.5 O 4 and 10.0 g of carbon nanotubes to the emulsion of step (1), and continuing magnetic stirring for 2 h, after forming a stable and uniform positive electrode slurry, coating on the aluminum foil current collector, and then After drying at 80 ° C, the positive electrode sheet A1 was obtained after being pressed by a roll press.
  • a positive electrode sheet and an all-solid lithium ion battery were prepared in the same manner as in Example 1, except that the glassy sulfide solid electrolyte 75Li 2 S-25P 2 S 5 was not added in the step (1); And an all-solid-state lithium-ion battery DS1.
  • a positive electrode sheet and an all-solid lithium ion battery were prepared in the same manner as in Example 1, except that the lithium salt LiN(CF 3 SO 3 ) 2 was not added in the step (1); the positive electrode sheet DA2 and the all solid lithium were prepared. Ion battery DS2.
  • a positive electrode sheet and an all-solid lithium ion battery were prepared in the same manner as in Example 1, except that step (1) used 7.0 g of polyvinylidene fluoride instead of polyoxyethylene, acetone was used instead of acetonitrile, and step (3) was added. 490.0 g of a glassy sulfide solid electrolyte 75Li 2 S-25P 2 S 5 ; A positive electrode sheet A3 and an all-solid lithium ion battery S3 were prepared.
  • a positive electrode sheet and an all-solid lithium ion battery were prepared in the same manner as in Example 1, except that step (1) used 7.0 g of polyacrylonitrile instead of polyoxyethylene, acetone was used instead of acetonitrile, and step (3) used 490.0.
  • step (1) used 7.0 g of polyacrylonitrile instead of polyoxyethylene
  • acetone was used instead of acetonitrile
  • step (3) used 490.0.
  • g Crystalline sulfide solid electrolyte Li 3 PS 4 replaces glassy sulfide solid electrolyte 75Li 2 S-25P 2 S 5 ;
  • a positive electrode sheet A4 and an all-solid lithium ion battery S4 were prepared.
  • a positive electrode sheet and an all-solid lithium ion battery were prepared in the same manner as in Example 1, except that step (1) used 7.0 g of polymethyl methacrylate instead of polyoxyethylene, and acetone was used instead of acetonitrile.
  • Step (3) A 228.0 g crystalline sulfide solid electrolyte Li 4 SnS 4 was used in place of the glassy sulfide solid electrolyte 75Li 2 S-25P 2 S 5 ; a positive electrode sheet A5 and an all-solid lithium ion battery S5 were prepared.
  • a positive electrode sheet and an all-solid lithium ion battery were prepared in the same manner as in Example 1, except that step (1) used 7.0 g of polyethylene instead of polyoxyethylene and 5.0 g of LiPF 6 instead of LiN (CF 3 SO 3 ). 2 ; A positive electrode sheet A6 and an all-solid lithium ion battery S6 were prepared.
  • a positive electrode sheet and an all-solid lithium ion battery were prepared in the same manner as in Example 1, except that 750.0 g of LiFePO 4 was used in place of LiNi 0.5 Mn 1.5 O 4 in the step (2); the positive electrode sheet A7 and the all solid lithium were prepared. Ion battery S7.
  • a positive electrode sheet and an all-solid lithium ion battery were prepared in the same manner as in Example 7, except that the sulfide solid electrolyte Li 2 SP 2 S 5 was not added in the step (1); the positive electrode sheet DA3 and the all solid lithium were prepared. Ion battery DS3.
  • a positive electrode sheet and an all-solid lithium ion battery were prepared in the same manner as in Example 7, except that the lithium salt LiN(CF 3 SO 3 ) 2 was not added in the step (1); the positive electrode sheet DA4 and the all solid lithium were prepared. Ion battery DS4.
  • a positive electrode sheet and an all-solid lithium ion battery were prepared in the same manner as in Example 1, except that 750.0 g of LiCoO 2 was used in place of LiNi 0.5 Mn 1.5 O 4 in the step (2); the positive electrode sheet A8 and the all solid lithium were prepared. Ion battery S8.
  • a positive electrode sheet and an all-solid lithium ion battery were prepared in the same manner as in Example 8, except that the sulfide solid electrolyte Li 2 SP 2 S 5 was not added in the step (1); the positive electrode sheet DA5 and the all solid lithium were prepared. Ion battery DS5.
  • a positive electrode sheet and an all-solid lithium ion battery were prepared in the same manner as in Example 8, except that the lithium salt LiN(CF 3 SO 3 ) 2 was not added in the step (1); the positive electrode sheet DA6 and the all solid lithium were prepared. Ion battery DS6.
  • a positive electrode sheet and an all-solid lithium ion battery were prepared in the same manner as in Example 1, except that 750.0 g of V 2 O 5 was used in place of LiNi 0.5 Mn 1.5 O 4 in the step (2); the positive electrode sheet A9 and the whole were prepared.
  • a positive electrode sheet and an all-solid lithium ion battery were prepared in the same manner as in Example 9, except that the sulfide solid electrolyte Li 2 SP 2 S 5 was not added in the step (1); the positive electrode sheet DA7 and the all solid lithium were prepared. Ion battery DS7.
  • a positive electrode sheet and an all-solid lithium ion battery were prepared in the same manner as in Example 9, except that the lithium salt LiN(CF 3 SO 3 ) 2 was not added in the step (1); the positive electrode sheet DA8 and the all solid lithium were prepared. Ion battery DS8.
  • a positive electrode sheet and an all-solid lithium ion battery were prepared in the same manner as in Example 1, except that 750.0 g of TiS 2 was used in place of LiNi 0.5 Mn 1.5 O 4 in the step (2); the positive electrode sheet A10 and the all solid lithium were prepared. Ion battery S10.
  • the frequency range is 100KHz-0.1Hz, the amplitude is 50mV; the impedance of all solid-state lithium-ion batteries S1-S10 and DS1-DS8 before charging and discharging is tested.
  • the test results are shown in Table 1;
  • the specific test conditions are: charging the batteries S1-S10 and DS1-DS8 constant current 0.01C to a certain voltage cut-off at 25 ⁇ 1°C (the cut-off voltage of the S1-S6 and DS1-DS2 batteries is set to 5.0V; S7) The cutoff voltage of the DS3 and DS4 batteries is set to 3.8V; the cutoff voltage of the S8, DS5 and DS6 batteries is set to 4.2V; the cutoff voltage of the S9, DS7 and DS8 batteries is set to 4.0V; the cutoff voltage of the S10 battery Set to 3.0V); set aside for 10 minutes; constant current 0.01C discharge to a certain voltage cutoff (S1-S8 and DS1-DS6 battery cut-off voltage is set to 3.0V; S9, S10, DS7 and DS8 battery cut-off voltage setting The cycle was set to 1.5 V. The battery was charged and discharged for 30 cycles, and the impedance after 30 cycles of the battery was recorded. The test results are shown
  • the batteries S1-S10 and DS1-DS8 were subjected to a charge and discharge cycle test at 0.01 C under conditions of 25 ⁇ 1 °C.
  • the specific test procedure is: set aside for 10 minutes, constant current 0.01C charge to a certain voltage cutoff (S1-S6 and DS1-DS2 battery cut-off voltage is set to 5.0V; S7, DS3 and DS4 battery cut-off voltage is set to 3.8V
  • the cutoff voltage of the S8, DS5, and DS6 batteries is set to 4.2V; the cutoff voltage of the S9, DS7, and DS8 batteries is set to 4.0V; the cutoff voltage of the S10 battery is set to 3.0V);; 10 minutes on hold; constant current Discharge to a certain voltage cutoff (S1-S8 and DS1-DS6 battery cut-off voltage is set to 3.0V; S9, S10, DS7 and DS8 battery cut-off voltage is set to 1.5
  • a mixture of a polymer electrolyte and a sulfide solid electrolyte is coated on the surface of the positive electrode active material.

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Abstract

本发明提出了一种全固态锂离子电池正极复合材料及其制备方法和应用，其中，正极复合材料具有核壳结构，所述核包括正极活性材料，所述壳包括聚合物电解质和硫化物固态电解质。本发明提供的全固态锂离子电池正极复合材料，制备工艺简单、且能有效改善锂离子电池正极与无机固体电解质之间的界面问题，利用其制备得到的全固态锂离子电池具有更好的循环寿命，安全性能更优。

Description

全固态锂离子电池正极复合材料及其制备方法和应用
优先权信息
本申请请求2016年01月29日向中国国家知识产权局提交的、专利申请号为201610063735.8的专利申请的优先权和权益，并且通过参照将其全文并入此处。
技术领域
本发明属于锂离子电池领域，尤其涉及全固态锂离子电池正极复合材料及其制备方法、正极材料、正极以及全固态锂离子电池。
背景技术
现有技术中，全固态锂离子电池正极的制备方法一般分为三种，即粉末压片型、真空镀膜型和涂覆型。粉末压片型是将正极活性材料、无机固体电解质粉末和导电剂按照一定的比例混合，然后在一定的压力下压制而成，该方法的制备过程中，正极活性材料发生的体积膨胀或体积收缩效应会导致正极活性材料与无机固体电解质颗粒之间的固-固接触界面效应恶化，此外当电池受到外部撞击时，这种固-固接触界面效应对整个电池性能的影响更大；真空镀膜型是采用溅射镀膜、蒸发镀膜、脉冲激光沉积膜或离子镀膜等方式直接将正极活性材料镀膜在集流体上，该种方法需要特定的设备，价格昂贵，效率较低，在一定程度上制约了商业化应用；涂覆型正极片是将正极活性材料、无机固体电解质、导电剂和粘接剂按照一定的比例在特定溶剂中混合均匀，然后将混合浆料均与地涂覆在集流体上，该种方法在涂覆时需要加入粘结剂，且加入的粘接剂组分为非锂离子导体，会影响正极内部锂离子的传导，从而影响电池的电化学性能。为了解决上述技术问题，现有技术公开了通过在正极材料表面包覆LiNbO3、SiO2、Al2O3、Ni2S3、Li3PS4等来解决。采用LiNbO3、SiO2、Al2O3等氧化物进行包覆的方法有流化床法、脉冲激光沉积等，这些方法操作手段复杂，设备昂贵，且包覆层的离子电导率较低，影响正极材料的倍率性能；而采用Ni2S3、Li3PS4等硫化物进行包覆时，虽然能够一定程度地提高离子电导率，但是仍然无法解决正极内正极活性材料与硫化物无机固体电解质之间固-固接触界面效应问题。
发明内容
本发明旨在至少在一定程度上解决相关技术中的技术问题之一。为此，本发明的一个目的在于提出了全固态锂离子电池正极复合材料及其制备方法、正极材料、正极以及全固态 锂离子电池，由此可以有效解决现有技术中正极材料与硫化物固态电解质之间存在的固-固界面层问题以及离子电导率低的问题。
根据本发明的一个方面，本发明提出了一种全固态锂离子电池正极复合材料，所述正极复合材料具有核壳结构，所述核包括正极活性材料，所述壳包括聚合物电解质和硫化物固态电解质。
本发明通过在正极活性材料表面包覆含有聚合物电解质和无机固态电解质的壳层，能够减少正极活性材料与无机固态电解质之间的直接接触，从而改善正极与无机固态电解质之间的界面问题；另外，本发明采用含有聚合物电解质和无机固态电解质的壳层包覆正极活性材料得到正极复合材料，一方面，发明人还发现，壳层含有的聚合物电解质不仅具有良好的锂离子传导性能，同时具有良好的粘结性能，能够减少正极材料涂覆过程中非离子电导组分粘结剂的使用，而且该聚合物电解质组分还有一定的弹性体性质，能够在一定程度缓解正极活性物质在充放电过程中的体积膨胀效应；另一方面，壳层含有的硫化物固态电解质不仅能够提高壳层聚合物电解质的离子电导率，还能够提高壳层聚合物电解质的电化学窗口，使得到的正极复合材料可以匹配高离子电导率的无机固态电解质和负极，得到的电池安全性更高，循环寿命长。
根据本发明的第二方面，本发明还提出了一种全固态锂离子电池正极复合材料的制备方法，根据本发明的实施例，该方法包括：
(1)将聚合物和锂盐按照(20～85):(80～15)的质量比溶于有机溶剂中，以便得到聚合物电解质；
(2)将步骤(1)中的聚合物电解质与硫化物固态电解质混合，以便得到乳液；
(3)向步骤(2)的乳液中加入正极活性材料，使所述乳液包裹所述正极复合材料，并进行烘干，以便得到具有核壳结构的正极复合材料，其中所述核包括正极活性材料，所述壳包括聚合物电解质和硫化物固态电解质。
根据本发明的第三方面，本发明进一步提出了一种全固态锂离子电池正极材料，根据本发明的实施例，全固态锂离子电池正极材料包括正极复合材料和正极导电剂，所述正极复合材料为本发明提出的全固态锂离子电池正极复合材料。
根据本发明的第四方面，本发明进一步提出了一种全固态锂离子电池正极，根据本发明的实施例，所述正极包括本申请提出的正极材料。
根据本发明的第五方面，本发明还提出了一种全固态锂离子电池，根据本发明的实施例，全固态锂离子电池包括电池壳体以及位于电池壳体内的电芯，所述电芯包括正极、负极以及位于正极和负极之间的无机固态电解质层，其特征在于，所述正极为本申请提出的锂离 子电池正极。
附图说明
图1为本申请提出的全固态锂离子电池正极复合材料的结构示意图。
具体实施方法
为了使本发明所解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
根据本发明的第一方面，本发明提出了一种全固态锂离子电池正极复合材料，根据本发明的实施例，所述正极复合材料具有核壳结构，所述核包括正极活性材料，所述壳包括聚合物电解质和硫化物固态电解质。
根据本发明的实施例，全固态锂离子电池正极复合材料中，聚合物电解质可以为选自聚氧乙烯基聚合物电解质、聚偏氟乙烯基聚合物电解质、聚丙烯腈基聚合物电解质、聚甲基丙烯酸甲酯基聚合物电解质、聚乙烯基聚合物电解质中的至少一种；进一步优选地，所述聚合物电解质选自聚氧乙烯基聚合物电解质、聚偏氟乙烯基聚合物电解质、聚丙烯腈基聚合物电解质中的至少一种。由此通过采用上述聚合物电解质可以进一步提高壳层的锂离子传导性能，同时使壳体具有良好的粘结性能，进而能够减少正极材料涂覆过程中非离子电导组分粘结剂的使用，而且该聚合物电解质组分还有一定的弹性体性质，能够在一定程度缓解正极活性物质在充放电过程中的体积膨胀效应。
本发明所述的聚合物电解质，为现有技术中常规意义上的聚合物电解质，即指聚合物和锂盐在一定条件下发生络合反应生成的聚合物与锂盐的络合物。
发明人在多次试验中发现，采用含有上述聚合物电解质与硫化物固态电解质的壳层包覆正极活性材料制备用于锂离子电池正极中的正极复合材料，制备得到的电池具有较高的安全性能和循环性能；后经过多次试验验证，发现该类聚合电解质不仅粘结性能好，且具有很好的离子导电性，在将其与硫化物固态电解质的混合包覆于正极活性材料表面后，制备得到的正极，不仅与无机固态电解质之间的固-固界面效应得到缓解，正极本身的充放电容量也得到了很好的提升。
根据本发明上述实施例的全固态锂离子电池正极复合材料中，优选地，所述硫化物固态电解质选自玻璃态的Li2S-P2S5、结晶态的Lix＇My＇PSz＇或玻璃陶瓷态的Li2S-P2S5中的至少一种，其中M为Si、Ge、Sn中的至少一种，x＇+4y＇+5＝2z＇,0≤y＇≤1。
根据本发明的具体实施例，进一步优选地，所述玻璃态的Li2S-P2S5选自玻璃态的 70Li2S-30P2S5、75Li2S-25P2S5、80Li2S-20P2S5中的至少一种；所述玻璃陶瓷态的Li2S-P2S5选自玻璃陶瓷态的70Li2S-30P2S5、75Li2S-25P2S5、80Li2S-20P2S5中的至少一种；所述结晶态的Lix＇My＇PSz＇选自Li3PS4、Li4SnS4、Li4GeS4、Li10SnP2S12、Li10GeP2S12、Li10SiP2S12中的至少一种。
根据本发明提出的全固态锂离子电池正极复合材料，优选地，所述聚合物电解质与硫化物固态电解质之间的质量比为1:99～99:1；进一步优选地，所述聚合物电解质与硫化物固态电解质之间的质量比为2:8～1:99；或者聚合物电解质与硫化物固态电解质之间的质量比为8:2～99:1；更进一步优选地，所述聚合物电解质与硫化物固态电解质之间的质量比为1:9～1:99；或者所述聚合物电解质与硫化物固态电解质之间的质量比为9:1～99:1。由此通过采用上述配比的聚合物电解质，可以进一步提高壳层的锂离子传导性能，同时提高壳体粘结性能，减少正极材料涂覆过程中非离子电导组分粘结剂的使用。另外，还可以进一步提高壳层聚合物电解质的离子电导率，还能够提高壳层聚合物电解质的电化学窗口，使得到的正极复合材料可以匹配高离子电导率的无机固态电解质和负极，得到的电池安全性更高，循环寿命长。
根据本发明提出的全固态锂离子电池正极复合材料，优选地，所述聚合物电解质和硫化物固态电解质的总质量与所述正极活性材料的质量比为(40～5):(60～95)。采用聚合物电解质与硫化物固态电解质的总量与所述正极活性材料的质量配比为(40～5):(60～95)，不仅能很好的缓解正极与无机固态电解质之间的界面影响问题，还能保证正极的充放电效率。
根据本发明提出的全固态锂离子电池正极复合材料，优选地，所述正极活性材料选自LiFexMnyMzPO4(0≤x≤1，0≤y≤1，0≤z≤1，x+y+z＝1，其中M为Al、Mg、Ga、Ti、Cr、Cu、Zn、Mo中的至少一种)、Li3V2(PO4)3、Li3V3(PO4)3、LiNi0.5-xMn1.5-yMx+yO4(-0.1≤x≤0.5,0≤y≤1.5，M为Li、Co、Fe、Al、Mg、Ca、Ti、Mo、Cr、Cu、Zn中的至少一种，)、LiVPO4F、Li1+xL1－y－zMyNzO2(L、M、N为Li、Co、Mn、Ni、Fe、Al、Mg、Ga、Ti、Cr、Cu、Zn、Mo、F、I、S、B中的至少一种，-0.1≤x≤0.2，0≤y≤1，0≤z≤1，0≤y+z≤1.0)、Li2CuO2、Li5FeO4中的至少一种；优选地，所述正极活性材料选自LiAl0.05Co0.15Ni0.80O2、LiCoO2、LiMn2O4、LiFePO4、LiMnPO4、LiNiPO4、LiCoPO4、LiNi0.5Mn1.5O4、Li3V3(PO4)3等中的至少一种。
当所述正极活性材料为上述锂盐活性材料时，电池中相对应的负极可以采用本领域常规使用的负极，如石墨负极、硅碳负极、金属锂负极或锂-铟合金负极均可。
根据本发明提出的全固态锂离子电池正极复合材料，优选地，所述正极活性材料选自V2O5、MnO2、TiS2、FeS2中的至少一种。
当所述正极活性材料为上述V2O5、MnO2、TiS2、FeS2中的至少一种时，电池中相对应的负极应采用可脱出锂离子的负极活性材料，例如可以采用金属锂负极或锂-铟合金负极。
根据本发明的第二方面，本发明还提出了一种全固态锂离子电池正极复合材料的制备方法。根据本发明的实施例，该方法包括：
(1)将聚合物和锂盐按照(20～85):(80～15)的质量比溶于有机溶剂中制备聚合物电解质；
(2)将步骤(1)中的聚合物电解质与硫化物固态电解质混合得到乳液；
(3)向步骤(2)的乳液中加入正极活性材料烘干制备得到具有核壳结构的正极复合材料，其中所述核包括正极活性材料，所述壳包括聚合物电解质和硫化物固态电解质。
根据本发明提出的锂离子电池正极复合材料的制备方法，优选地，所述步骤(1)中聚合物选自聚氧乙烯、聚偏氟乙烯、聚丙烯腈、聚甲基丙烯酸甲酯和聚乙烯中的至少一种；所述锂盐选自LiPF6、LiAsF6、LiClO4、LiBF6、LiN(CF3SO3)2、LiCF3SO3、LiC(CF3SO3)2、LiN(C4F9SO2)(CF3SO3)中的至少一种。
由此通过采用上述聚合物和锂盐制备得到的聚合物电解质可以进一步提高壳层的锂离子传导性能，同时使壳体具有良好的粘结性能，进而能够减少正极材料涂覆过程中非离子电导组分粘结剂的使用，而且该聚合物电解质组分还有一定的弹性体性质，能够在一定程度缓解正极活性物质在充放电过程中的体积膨胀效应。
根据本发明提出的锂离子电池正极复合材料的制备方法，优选地，所述步骤(1)中包括将聚合物和锂盐按照(20～85):(80～15)的配比溶于有机溶剂后搅拌混合1-48h，由此通过采用上述配比并搅拌混合1-48小时后，可以使得聚合物和锂盐充分发生络合反应，进而有效制备得到聚合物电解质。所述步骤(2)中包括向聚合物电解质中加入硫化物固态电解质后搅拌混合1-48h得到乳液。由此可以使得聚合物电解质与硫化物固态电解质混合均匀。
根据本发明提出的锂离子电池正极复合材料的制备方法，优选地，所述步骤(2)中加入的硫化物固态电解质的质量满足：所述聚合物电解质与硫化物固态电解质之间的质量比为1:99～99:1；进一步优选地，所述聚合物电解质与硫化物固态电解质之间的质量比为2:8～1:99；或者聚合物电解质与硫化物固态电解质之间的质量比为8:2～99:1；更进一步优选地，所述聚合物电解质与硫化物固态电解质之间的质量比为1:9～1:99；或者所述聚合物电解质与硫化物固态电解质之间的质量比为9:1～99:1。由此通过采用上述配比的聚合物电解质，可以进一步提高壳层的锂离子传导性能，同时提高壳体粘结性能，减少正极材料涂覆过程中非离子电导组分粘结剂的使用。另外，还可以进一步提高壳层聚合物电解质的离子电导率，还能够提高壳层聚合物电解质的电化学窗口，使得到的正极复合材料可以匹配高离子 电导率的无机固态电解质和负极，得到的电池安全性更高，循环寿命长。
根据本发明的第三方面，本发明进一步提出了一种全固态锂离子电池正极材料，包括正极复合材料和正极导电剂，所述正极复合材料为本发明提出的全固态锂离子电池正极复合材料。
本申请提出的锂离子正极材料，包括本申请所述的正极复合材料，该正极复合材料的核包括正极活性材料，所述壳包括聚合物电解质和硫化物固态电解质。
其中，上述正极材料也可以选择性的包含正极粘结剂；由于本申请提供的正极复合材料的壳层的聚合物电解质不仅具有良好的离子导电性，其还具备粘结性能，因此在正极材料中可以不含正极粘结剂，或者选择性的含有极少量的正极粘结剂。正极粘结剂可以采用用于高压锂离子电池正极中的粘结剂，具体地，所述正极粘结剂可以选自含氟树脂和聚烯烃化合物如聚偏二氟乙烯(PVDF)、聚四氟乙烯(PTFE)和丁苯橡胶(SBR)中的至少一种；优选地，所述正极粘结剂的含量为0-5％。
上述正极导电剂为用于高压锂离子电池正极中的导电剂，具体底，所述正极导电剂可以选自乙炔黑、碳纳米管、HV、碳黑中的至少一种。
根据本发明提出的锂离子电池正极材料，其特征在于，以所述正极复合材料的质量为基准，所述正极导电剂的含量为0.5％-5％。
根据本发明的实施例，正极材料中采用了本发明上述实施例的正极复合材料，因为该正极复合材料的壳层的聚合物电解质本身具备较好的粘结性能，因此，在制备正极材料的过程中，不需要加入非活性的正极粘结剂后仅需加入及少量的正极粘结剂，相对应的也可以减少正极导电剂在正极材料中的添加量。
根据本发明的第四方面，本申请进一步提出了一种全固态锂离子电池正极，所述正极包括本发明上述实施例的全固态锂离子电池正极材料。
本发明对正极的制备方法不作特殊限定，为本领域常规的正极的制备方法，包括将本发明所述的正极复合材料、正极导电剂与有机溶剂混合制备成正极浆料涂覆于正极集流体上烘干得到正极；或将本申请所述的正极复合材料、正极粘结剂和正极导电剂与有机溶剂混合制备成正极浆料涂覆于正极集流体上烘干得到正极。
本申请所述的全固态锂离子电池的正极也可以采用以下方法，包括：
(1)将聚合物和锂盐按照(20～85):(80～15)的配比溶于有机溶剂中制备聚合物电解质；
(2)将步骤(1)中的聚合物电解质与硫化物固态电解质混合得到乳液；
(3)向步骤(2)乳液中加入正极活性材料和正极导电剂后涂覆于正极集流体的表面烘干得到本申请所述的正极。
其中，所述步骤(1)中聚合物选自聚氧乙烯、聚偏氟乙烯、聚丙烯腈、聚甲基丙烯酸甲酯和聚乙烯中的至少一种；所述锂盐选自LiPF6、LiAsF6、LiClO4、LiBF6、LiN(CF3SO3)2、LiCF3SO3、LiC(CF3SO3)2、LiN(C4F9SO2)(CF3SO3)中的至少一种；
所述步骤(1)中包括将聚合物和锂盐按照(20～85):(80～15)的配比溶于有机溶剂后搅拌混合1-48h，该过程中，聚合物与锂盐发生络合反应得到聚合物电解质；所述步骤(2)中包括向步骤(1)中加入硫化物固态电解质后搅拌混合1-48h得到乳液；所述正极导电剂为本领域技术人员公知的用于高压锂离子电池正极中的导电剂，具体底，所述正极导电剂可以选自乙炔黑、碳纳米管、HV、碳黑中的至少一种。
根据本发明提出的全固态锂离子电池正极的制备方法，优选地，所述步骤(2)中加入的硫化物固态电解质的质量满足：所述聚合物电解质与硫化物固态电解质之间的质量比为1:99～99:1；进一步优选地，所述聚合物电解质与硫化物固态电解质之间的质量比为2:8～1:99；或者聚合物电解质与硫化物固态电解质之间的质量比为8:2～99:1；更进一步优选地，所述聚合物电解质与硫化物固态电解质之间的质量比为1:9～1:99；或者所述聚合物电解质与硫化物固态电解质之间的质量比为9:1～99:1。
根据本发明的实施例，上述全固态锂离子电池正极的制备方法，优选地，所述加入的正极导电剂的质量满足：以所得到的正极材料的总质量为基准，步骤(3)中加入的正极导电剂的含量为1％-5％。
所述正极集流体为本领域技术人员公知的正极集流体，例如，可以选自铝箔、碳纸、碳纳米管纸、石墨烯纸或不锈钢箔。
根据本发明的第五方面，本发明还提出了一种全固态锂离子电池，包括电池壳体以及位于电池壳体内的电芯，所述电芯包括正极、负极以及位于正极和负极之间的无机固态电解质层，所述正极为本申请提出的正极。
所述无机固态电解质层包括无机固态电解质和粘结剂；本发明对无机固态电解质层中的无机固态电解质和粘结剂均没有特殊要求，为本领域常规的无机固态电解质和粘结剂即可，优选地，所述无机固态电解质选自硫化物固态电解质；优选地，所述硫化物固态电解质选自玻璃态的Li2S-P2S5、结晶态的Lix＇My＇PSz＇或玻璃陶瓷态的Li2S-P2S5中的至少一种，其中M为Si、Ge、Sn中的至少一种，x＇+4y＇+5＝2z＇,0≤y＇≤1；进一步优选地，所述玻璃态的Li2S-P2S5选自玻璃态的70Li2S-30P2S5、75Li2S-25P2S5、80Li2S-20P2S5中的至少一种；所述玻璃陶瓷态的Li2S-P2S5选自玻璃陶瓷态的70Li2S-30P2S5、75Li2S-25P2S5、80Li2S-20P2S5中的至少一种；所述结晶态的Lix＇My＇PSz＇选自Li3PS4、Li4SnS4、Li4GeS4、Li10SnP2S12、Li10GeP2S12、Li10SiP2S12中的至少一种。所述粘结剂选自聚偏二氟乙烯(PVDF)、 聚四氟乙烯(PTFE)和丁苯橡胶(SBR)中的至少一种。本发明对无机固态电解质层的厚度以及无机固态电解质层中无机固态电解质与粘结剂的配比也没有特殊要求，为本领域常规的无机固态电解质层的厚度以及常规的无机固态电解质层中无机固态电解质与粘结剂的配比，本申请不作赘述。
根据本发明提出的全固态锂离子电池，优选地，所述正极活性材料选自LiFexMnyMzPO4(0≤x≤1，0≤y≤1，0≤z≤1，x+y+z＝1，其中M为Al、Mg、Ga、Ti、Cr、Cu、Zn、Mo中的至少一种)、Li3V2(PO4)3、Li3V3(PO4)3、LiNi0.5-xMn1.5-yMx+yO4(-0.1≤x≤0.5,0≤y≤1.5，M为Li、Co、Fe、Al、Mg、Ca、Ti、Mo、Cr、Cu、Zn中的至少一种，)、LiVPO4F、Li1+xL1－y－zMyNzO2(L、M、N为Li、Co、Mn、Ni、Fe、Al、Mg、Ga、Ti、Cr、Cu、Zn、Mo、F、I、S、B中的至少一种，-0.1≤x≤0.2，0≤y≤1，0≤z≤1，0≤y+z≤1.0)、Li2CuO2、Li5FeO4中的至少一种；优选地，所述正极活性材料选自LiAl0.05Co0.15Ni0.80O2、LiCoO2、LiMn2O4、LiFePO4、LiMnPO4、LiNiPO4、LiCoPO4、LiNi0.5Mn1.5O4、Li3V3(PO4)3等中的至少一种；此时负极不作特殊限定，电池中相对应的负极可以采用本领域常规使用的负极，如石墨负极、硅碳负极、金属锂负极或锂-铟合金负极均可；具体的，所述负极包括负极集流体和位于所述负极集流体表面的负极材料。所述负极集流体为本领域技术人员公知的负极集流体，例如，可以选自铜箔。
所述负极材料包括负极活性物质和负极粘结剂；所述负极活性物质可以为本领域常规的负极活性物质；具体的，所述负极活性物质选自碳材料、锡合金、硅合金、硅、锡、锗中的至少一种；进一步地，所述碳材料可以选自天然石墨、天然改性石墨、人造石墨、石油焦、有机裂解碳、中间相碳微球、碳纤维、锡合金和硅合金中的至少一种，优选人造石墨和天然改性石墨；同时，负极活性物质也可以为金属锂、锂-铟合金等；通常，根据实际使用情况，所述负极材料中还可以含有负极导电剂，所述的负极导电剂没有特别限制，可以为本领域常规的负极导电剂，例如可以为碳黑、乙炔黑、炉黑、碳纤维VGCF、导电炭黑和导电石墨中的至少一种；所述的第四粘结剂为本领域公知的用于锂离子电池负极中的粘结剂，具体地，所述第四粘结剂可以选自聚噻吩、聚吡咯、聚四氟乙烯、聚偏氟乙烯、聚乙烯、聚丙烯、聚苯乙烯、聚丙烯酰胺、乙烯-丙烯-二烯共聚树脂、苯乙烯丁二烯橡胶、聚丁二烯、氟橡胶、聚环氧乙烯、聚乙烯吡咯烷酮、聚酯树脂、丙烯酸树脂、酚醛树脂、环氧树脂、聚乙烯醇、羧丙基纤维素、乙基纤维素、羧甲基纤维素钠、丁苯胶乳中的至少一种。
上述负极材料中，负极活性物质以及负极粘结剂的含量为本领域技术人员公知，具体地，以所述负极活性物质的重量为基准，所述负极导电剂的含量为0.5-10wt％；所述负极粘结剂的含量为0.01-10wt％。
根据本发明提出的全固态锂离子电池，优选地，所述正极活性材料选自V2O5、MnO2、TiS2、FeS2中的至少一种；此时相对应的负极应采用能够脱出锂离子的负极，例如可以采用预嵌锂的石墨或硅负极，或直接采用金属锂、锂-铟合金等；优选地，相对应的负极为金属锂、锂-铟合金等。
本发明中对电池负极的制备方法不作特殊限定，采用本领域常规的负极的制备方法即可，优选地，包括将含有负极活性、负极粘结剂的负极浆料涂覆于负极集流体上在负极集流体上形成负极材料层。
本发明中对锂离子的具体制备方法不作特殊限定，为本领域常规的全固态锂离子电池的制备方法；包括将电芯密封于电池壳体中得到；所述电芯的制备为本领域常规的全固态锂离子电池中的电芯的制备方法，不作特殊限定；包括先制备得到正极，然后在正极表面制备固态电解质层，本申请中的固态电解质层为无机固态电解质层；在正极表面制备无机固态电解质层的方法包括在正极表面涂覆无机固态电解质浆料后烘干，从而在正极表面形成无机固态电解质层；所述无机固态电解质浆料包括无机固态电解质和粘结剂；本申请中，无机固态电解质优选为硫化物固态电解质；粘结剂的种类及无机固态电解质与粘结剂的配比为本领域技术人员公知，本申请不作特殊限定。
在正极表面形成无机固态电解质层之后，将负极贴合在固态电解质层上压合即得到本申请所述锂离子电池。
本申请也可以先在负极表面形成固态电解质层后，将正极与固态电解质贴合进行压合得到本申请所述的锂离子电池。
本申请提供的锂离子电池，采用了本申请所述的正极活性材料，不仅正极具有较高的离子电导率，且正极与无机固态电解质层之间的界面影响小，制备得到的电池安全性高、循环性能好。
以下通过实施例对本发明进行进一步详细的说明。
实施例1
(1)称取7.0g聚氧乙烯(分子量60万)溶于无水乙腈中，随后向其中加入5.0g的LiN(CF3SO3)2，然后在室温下磁力搅拌20h后，向其中加入228.0g玻璃态硫化物固体电解质75Li2S-25P2S5(玻璃态硫化物固体电解质75Li2S-25P2S5预先通过高能球磨的方式制备得到)，然后室温下磁力搅拌6h得到乳液；
(2)在步骤(1)的乳液中加入750.0g LiNi0.5Mn1.5O4和10.0g碳纳米管，继续磁力搅拌2h，待形成稳定均一的正极浆料后涂覆在铝箔集流体上，然后80℃烘干，经过辊压机压片后得到正极片A1。
(3)将490g硫化物固体电解质Li10SnP2S12和10g SBR加入到无水正庚烷中，然后在真空搅拌机中搅拌，形成稳定均一的电解质浆料；将该电解质浆料均匀地间歇涂布在上述制备的正极片A1上，转入烘箱中80℃下烘干，在正极表面形成无机固态电解质层；将锂箔贴合在无机固态电解质层表面，并施加240MPa的压力以压紧，随后进行封装即得到全固态锂离子电池S1。
实施例2
(1)称取7.0gPEO(分子量60万)溶于无水乙腈中，随后向其中加入5.0g的LiN(CF3SO3)2，然后在室温下磁力搅拌20h后，向其中加入228.0g玻璃态硫化物固体电解质75Li2S-25P2S5(玻璃态硫化物固体电解质75Li2S-25P2S5预先通过高能球磨的方式制备得到)，然后室温下磁力搅拌6h得到乳液；
(2)在步骤(1)的乳液中加入750.0g LiNi0.5Mn1.5O4，磁力搅拌2h，烘干得到球磨得到正极活性材料B；取该正极活性材料B490.0g加入到有机溶剂无水乙腈中，然后加入5.0g碳纳米管，充分分散后得到正极浆料，将正极浆料涂覆在铝箔集流体上，然后80℃烘干，经过辊压机压片后得到正极片A2。
(3)将490.0g硫化物固体电解质Li10SnP2S12和10.0g SBR加入到无水正庚烷中，然后在真空搅拌机中搅拌，形成稳定均一的电解质浆料；将该电解质浆料均匀地间歇涂布在上述制备的正极片A1上，转入烘箱中80℃下烘干，在正极表面形成无机固态电解质层；将锂箔贴合在无机固态电解质层表面，并施加240MPa的压力以压紧，随后进行封装即得到全固态锂离子电池S2。
对比例1
采用与实施例1相同的方法制备正极片以及全固态锂离子电池，不同之处在于，步骤(1)中不加入玻璃态硫化物固体电解质75Li2S-25P2S5；制备得到正极片DA1以及全固态锂离子电池DS1。
对比例2
采用与实施例1相同的方法制备正极片以及全固态锂离子电池，不同之处在于，步骤(1)中不加入锂盐LiN(CF3SO3)2；制备得到正极片DA2以及全固态锂离子电池DS2。
实施例3
采用与实施例1相同的方法制备正极片以及全固态锂离子电池，不同之处在于，步骤(1)采用7.0g聚偏氟乙烯取代聚氧乙烯，采用丙酮代替乙腈，步骤(3)中加入490.0g玻璃态硫化物固体电解质75Li2S-25P2S5；制备得到正极片A3以及全固态锂离子电池S3。
实施例4
采用与实施例1相同的方法制备正极片以及全固态锂离子电池，不同之处在于，步骤(1)采用7.0g聚丙烯腈取代聚氧乙烯，采用丙酮代替乙腈，步骤(3)中采用490.0g结晶态硫化物固体电解质Li3PS4取代玻璃态硫化物固体电解质75Li2S-25P2S5；制备得到正极片A4以及全固态锂离子电池S4。
实施例5
采用与实施例1相同的方法制备正极片以及全固态锂离子电池，不同之处在于，步骤(1)采用7.0g聚甲基丙烯酸甲酯取代聚氧乙烯，采用丙酮代替乙腈，步骤(3)中采用228.0g结晶态硫化物固体电解质Li4SnS4取代玻璃态硫化物固体电解质75Li2S-25P2S5；制备得到正极片A5以及全固态锂离子电池S5。
实施例6
采用与实施例1相同的方法制备正极片以及全固态锂离子电池，不同之处在于，步骤(1)采用7.0g聚乙烯取代聚氧乙烯以及采用5.0g LiPF6取代LiN(CF3SO3)2；制备得到正极片A6以及全固态锂离子电池S6。
实施例7
采用与实施例1相同的方法制备正极片以及全固态锂离子电池，不同之处在于，步骤(2)中采用750.0g LiFePO4取代LiNi0.5Mn1.5O4；制备得到正极片A7以及全固态锂离子电池S7。
对比例3
采用与实施例7相同的方法制备正极片以及全固态锂离子电池，不同之处在于，步骤(1)中不加入硫化物固体电解质Li2S-P2S5；制备得到正极片DA3以及全固态锂离子电池DS3。
对比例4
采用与实施例7相同的方法制备正极片以及全固态锂离子电池，不同之处在于，步骤(1)中不加入锂盐LiN(CF3SO3)2；制备得到正极片DA4以及全固态锂离子电池DS4。
实施例8
采用与实施例1相同的方法制备正极片以及全固态锂离子电池，不同之处在于，步骤(2)中采用750.0g LiCoO2取代LiNi0.5Mn1.5O4；制备得到正极片A8以及全固态锂离子电池S8。
对比例5
采用与实施例8相同的方法制备正极片以及全固态锂离子电池，不同之处在于，步骤(1) 中不加入硫化物固体电解质Li2S-P2S5；制备得到正极片DA5以及全固态锂离子电池DS5。
对比例6
采用与实施例8相同的方法制备正极片以及全固态锂离子电池，不同之处在于，步骤(1)中不加入锂盐LiN(CF3SO3)2；制备得到正极片DA6以及全固态锂离子电池DS6。
实施例9
采用与实施例1相同的方法制备正极片以及全固态锂离子电池，不同之处在于，步骤(2)中采用750.0g V2O5取代LiNi0.5Mn1.5O4；制备得到正极片A9以及全固态锂离子电池S9。
对比例7
采用与实施例9相同的方法制备正极片以及全固态锂离子电池，不同之处在于，步骤(1)中不加入硫化物固体电解质Li2S-P2S5；制备得到正极片DA7以及全固态锂离子电池DS7。
对比例8
采用与实施例9相同的方法制备正极片以及全固态锂离子电池，不同之处在于，步骤(1)中不加入锂盐LiN(CF3SO3)2；制备得到正极片DA8以及全固态锂离子电池DS8。
实施例10
采用与实施例1相同的方法制备正极片以及全固态锂离子电池，不同之处在于，步骤(2)中采用750.0g TiS2取代LiNi0.5Mn1.5O4；制备得到正极片A10以及全固态锂离子电池S10。
性能测试
(1)交流阻抗测试
开路电位下，频率范围100KHz-0.1Hz，振幅50mV；测试全固态锂离子电池S1-S10以及DS1-DS8在充放电前的阻抗大小，测试结果见表1；
具体测试条件为：在25±1℃条件下，将电池S1-S10以及DS1-DS8恒流0.01C充电至一定电压截止(S1-S6和DS1-DS2电池的截止电压设定为5.0V；S7、DS3和DS4电池的截止电压设定为3.8V；S8、DS5和DS6电池的截止电压设定为4.2V；S9、DS7和DS8电池的截止电压设定为4.0V；S10电池的该截止电压设定为3.0V)；搁置10分钟；恒流0.01C放电至一定电压截止(S1-S8和DS1-DS6电池的截止电压设定为3.0V；S9、S10、DS7和DS8电池的截止电压设定为1.5V)为1次循环，如此对电池进行充放电30次循环，记录电池循环30次后的阻抗大小，测试结果见表1。
表1
Figure PCTCN2017071314-appb-000001
(2)充放电循环测试
采用LAND CT2001C二次电池性能检测装置，25±1℃条件下，将电池S1-S10以及DS1-DS8以0.01C进行充放电循环测试。具体测试步骤为：搁置10分钟，恒流0.01C充电至一定电压截止(S1-S6和DS1-DS2电池的截止电压设定为5.0V；S7、DS3和DS4电池的截止电压设定为3.8V；S8、DS5和DS6电池的截止电压设定为4.2V；S9、DS7和DS8电池的截止电压设定为4.0V；S10电池的截止电压设定为3.0V)；；搁置10分钟；恒流放电至一定电压截止(S1-S8和DS1-DS6电池的截止电压设定为3.0V；S9、S10、DS7和DS8电池的截止电压设定为1.5V)，即为1次循环，如此对电池进行充放电30次循环，记录首 次充放电容量，并计算库仑效率(％)。30次循环后，记录第30次循环的放电容量，计算循环后容量保持率(％)＝第30次循环的放电容量/首次放电容量×100％；测试结果见表2。
表2
Figure PCTCN2017071314-appb-000002
由图1可以看出，聚合物电解质和硫化物固态电解质的混合包覆于正极活性材料表面。
由表1可以看出，实施例1-10中电池S1-S10的初始阻抗值和循环后的阻抗值均小于相应对比实施例DS1-DS8的阻抗值，表明经过复合电解质的包覆后，电池正极内部的极化减小。
由表2可以看出，实施例1-10中电池S1-S10的放电比容量和充放电循环稳定性能也均优于相应对比实施例DS1-DS8的放电比容量和充放电循环稳定性能，表明复合型电解质不 仅很好地充当锂离子传输的导体，提高正极活性材料的活性，而且能有效缓解正极活性材料在充放电过程中的体积收缩膨胀效应，改善正极活性材料与电解质材料之间的动态接触界面，达到了预期的效果。
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本发明的限制，本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。

Claims (19)

  1. 一种全固态锂离子电池正极复合材料，所述正极复合材料具有核壳结构，其特征在于，所述核包括正极活性材料，所述壳包括聚合物电解质和硫化物固态电解质。
  2. 根据权利要求1所述的正极复合材料，其特征在于，所述聚合物电解质为选自聚氧乙烯基聚合物电解质、聚偏氟乙烯基聚合物电解质、聚丙烯腈基聚合物电解质、聚甲基丙烯酸甲酯基聚合物电解质和聚乙烯基聚合物电解质中的至少一种。
  3. 根据权利要求2所述的正极复合材料，其特征在于，所述聚合物电解质为选自聚氧乙烯基聚合物电解质、聚偏氟乙烯基聚合物电解质和聚丙烯腈基聚合物电解质中的至少一种。
  4. 根据权利要求1-3任意一项所述的正极复合材料，其特征在于，所述硫化物固态电解质为选自玻璃态的Li2S-P2S5、结晶态的Lix＇My＇PSz＇和玻璃陶瓷态的Li2S-P2S5中的至少一种，其中结晶态的Lix＇My＇PSz＇中，M为Si、Ge和Sn中的至少一种，x＇+4y＇+5＝2z＇，0≤y＇≤1。
  5. 根据权利要求4所述的正极复合材料，其特征在于，所述玻璃态的Li2S-P2S5为选自玻璃态的70Li2S-30P2S5、75Li2S-25P2S5和80Li2S-20P2S5中的至少一种；所述玻璃陶瓷态的Li2S-P2S5为选自玻璃陶瓷态的70Li2S-30P2S5、75Li2S-25P2S5和80Li2S-20P2S5中的至少一种；所述结晶态的Lix＇My＇PSz＇为选自Li3PS4、Li4SnS4、Li4GeS4、Li10SnP2S12、Li10GeP2S12和Li10SiP2S12中的至少一种。
  6. 根据权利要求1-5任意一项所述的正极复合材料，其特征在于，所述聚合物电解质与硫化物固态电解质之间的质量比为1:99～99:1。
  7. 根据权利要求6所述的正极复合材料，其特征在于，所述聚合物电解质与硫化物固态电解质之间的质量比为1:9～1:99。
  8. 根据权利要求6所述的正极复合材料，其特征在于，所述聚合物电解质与硫化物固态电解质之间的质量比为9:1～99:1。
  9. 根据权利要求1-8任意一项所述的正极复合材料，其特征在于，所述聚合物电解质和所述硫化物固态电解质的总质量与所述正极活性材料的质量比为(40～5):(60～95)。
  10. 根据权利要求1-9任意一项所述的正极复合材料，其特征在于，所述正极活性材料为选自LiFexMnyMzPO4、Li3V2(PO4)3、Li3V3(PO4)3、LiNi0.5-xMn1.5-yMx+yO4、LiVPO4F、Li1+ xL1－y－zMyNzO2、Li2CuO2和Li5FeO4中的至少一种，
    其中，所述LiFexMnyMzPO4中，0≤x≤1，0≤y≤1，0≤z≤1，x+y+z＝1，其中M为选 自Al、Mg、Ga、Ti、Cr、Cu、Zn和Mo中的至少一种；
    所述LiNi0.5-xMn1.5-yMx+yO4中，-0.1≤x≤0.5,0≤y≤1.5，M为选自Li、Co、Fe、Al、Mg、Ca、Ti、Mo、Cr、Cu和Zn中的至少一种；
    所述Li1+xL1－y－zMyNzO2中，L、M、N分别独立地为选自Li、Co、Mn、Ni、Fe、Al、Mg、Ga、Ti、Cr、Cu、Zn、Mo、F、I、S和B中的至少一种，-0.1≤x≤0.2，0≤y≤1，0≤z≤1，0≤y+z≤1.0。
  11. 根据权利要求1-9任意一项所述的正极复合材料，其特征在于，所述正极活性材料为选自V2O5、MnO2、TiS2、FeS2中的至少一种。
  12. 一种制备权利要求1-11任意一项所述全固态锂离子电池正极复合材料的方法，包括：
    (1)将聚合物和锂盐按照(20～85):(80～15)的质量比溶于有机溶剂中，以便得到聚合物电解质；
    (2)将所述聚合物电解质与硫化物固态电解质混合，以便得到乳液；
    (3)向所述乳液中加入正极活性材料，使所述乳液包裹所述正极复合材料，并进行烘干，以便得到具有核壳结构的正极复合材料，其中所述核包括正极活性材料，所述壳包括聚合物电解质和硫化物固态电解质。
  13. 根据权利要求12所述的方法，其特征在于，所述聚合物为选自聚氧乙烯、聚偏氟乙烯、聚丙烯腈、聚甲基丙烯酸甲酯和聚乙烯中的至少一种；所述锂盐为选自LiPF6、LiAsF6、LiClO4、LiBF6、LiN(CF3SO3)2、LiCF3SO3、LiC(CF3SO3)2、LiN(C4F9SO2)(CF3SO3)中的至少一种。
  14. 一种全固态锂离子电池正极材料，包括正极复合材料和正极导电剂，其特征在于，所述正极复合材料为权利要求1-11任意一项所述正极复合材料。
  15. 根据权利要求14所述的正极材料，其特征在于，以所述正极复合材料的质量为基准，所述正极导电剂的含量为0.5％-5％。
  16. 一种全固态锂离子电池正极，其特征在于，所述正极包括权利要求14-15任意一项所述的正极材料。
  17. 一种全固态锂离子电池，包括电池壳体以及位于电池壳体内的电芯，所述电芯包括正极、负极以及位于正极和负极之间的无机固态电解质层，其特征在于，所述正极为权利要求16所述的正极。
  18. 根据权利要求17所述的全固态锂离子电池，其特征在于，所述无机固态电解质层中的无机固态电解质选自硫化物固态电解质。
  19. 根据权利要求17或18所述的全固态锂离子电池，其特征在于，所述正极活性材料选自V2O5、MnO2、TiS2、FeS2中的一种或多种；所述负极为金属锂或锂-铟合金。
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