WO2018214972A1 - 一种柔性全固态锂离子二次电池及其制备方法 - Google Patents

一种柔性全固态锂离子二次电池及其制备方法 Download PDF

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WO2018214972A1
WO2018214972A1 PCT/CN2018/088495 CN2018088495W WO2018214972A1 WO 2018214972 A1 WO2018214972 A1 WO 2018214972A1 CN 2018088495 W CN2018088495 W CN 2018088495W WO 2018214972 A1 WO2018214972 A1 WO 2018214972A1
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group
lithium
electrolyte
ether compound
solid
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PCT/CN2018/088495
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English (en)
French (fr)
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李林
刘凤泉
周建军
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北京师范大学
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Priority claimed from CN201710385193.0A external-priority patent/CN108933284B/zh
Priority claimed from CN201710386080.2A external-priority patent/CN108963389B/zh
Application filed by 北京师范大学 filed Critical 北京师范大学
Priority to JP2020515815A priority Critical patent/JP7166016B2/ja
Priority to EP18806570.0A priority patent/EP3637525A4/en
Priority to KR1020197035804A priority patent/KR102596721B1/ko
Publication of WO2018214972A1 publication Critical patent/WO2018214972A1/zh
Priority to US16/696,570 priority patent/US11557793B2/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/049—Processes for forming or storing electrodes in the battery container
    • 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
    • H01M10/052—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
    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention belongs to the technical field of lithium ion batteries, and in particular relates to a flexible all-solid lithium ion secondary battery and a preparation method thereof.
  • lithium-ion secondary batteries that provide electrical energy for daily-use electronic products.
  • lithium-ion secondary batteries also have potential safety hazards in their use, such as leakage of electrolytes. , burning, explosion, etc.
  • the battery must be safe in order to meet the normal production and life of human beings. Therefore, the safety of lithium-ion secondary batteries is also a hot topic explored by researchers.
  • the main solution to solve the electrolyte leakage of lithium ion secondary batteries is to use a solid electrolyte, which has the advantage that the liquid electrolyte cannot be compared, and is likely to become a technical way to solve the safety problem of the lithium ion secondary battery.
  • the all-solid-state lithium ion secondary battery has a huge advantage in widening the working temperature range, increasing the energy density of the battery, and prolonging the service life compared with the liquid lithium ion secondary battery.
  • the solid electrolyte can be classified into a polymer composite lithium ion electrolyte and an all solid state thin film lithium ion electrolyte.
  • the polymer composite lithium ion electrolyte mainly uses a high molecular polymer to form a coordination structure with a lithium salt, thereby realizing lithium ion conduction, and in order to increase the conductivity of lithium ions, a certain amount of silicon dioxide (SiO 2 ) is often added and oxidized.
  • An inorganic filler such as aluminum (Al 2 O 3 ) or zeolite.
  • the method for using a solid electrolyte in a lithium ion secondary battery is generally to place a solid electrolyte membrane between a positive electrode and a negative electrode, and such a preparation method can effectively block the contact between the positive electrode and the negative electrode, but cannot be overcome.
  • the all-solid lithium ion secondary batteries currently used are rigid, and have the disadvantages of heavy mass, easy crushing, poor strainability, poor recovery, poor electrochemical performance of the battery, poor cycle performance, and low endurance time.
  • the lithium ion secondary battery prepared by the method of the invention forms a conductive network inside the whole battery, so that the active material can fully function, and the internal resistance of the lithium ion secondary battery is greatly reduced, thereby improving the conductivity. Rate and rate performance can also solve the safety hazard caused by liquid electrolyte, and it has good strain, recovery, and is light and easy to carry.
  • an adjustable intensity and a formation time ie, a state of transition from a free-flowing liquid state to a non-flowable solid electrolyte state
  • the temperature of the transition and the transition temperature ie, the lowest temperature when the state of the non-flowable electrolyte changes to a free-flowing liquid state
  • the temperature of the transition and the transition temperature is adjustable, that is, solid electrolytes of different strengths can be prepared according to specific needs to meet different needs.
  • the solid electrolyte also has good reversibility, the fluidity of the solid electrolyte becomes stronger when the solid electrolyte transition temperature is reached, and the solid electrolyte is reformed when the temperature falls below the transition temperature. Not affected. Based on the above ideas, the present invention has been completed.
  • a first aspect of the present invention provides a method of preparing a flexible all-solid lithium ion secondary battery, the method comprising the steps of:
  • step 3a) injecting the gelable system of step 1a) into the all-solid-state battery before the liquid injection in step 2a), sealing, and standing to obtain an all-solid lithium ion secondary battery;
  • the gellable system comprises the following components: a lithium salt and an ether compound, the ether compound being selected from at least one of a cyclic ether compound or a linear ether compound; a gellable polymerization in the system
  • the mass percentage of the and/or gellable prepolymer is less than or equal to 1% by weight.
  • the all-solid battery before the liquid injection refers to the battery leaving the liquid inlet, that is, the dry battery; the method of assembly is a routine choice of those skilled in the art.
  • the solid-state pre-filled solid-state battery can be prepared by any method; for example, the positive electrode tab, the separator and the negative electrode tab are assembled into a solid-state pre-filled battery by lamination or winding; or The negative electrode, the separator and the positive electrode are integrally pressed in a battery pressing mold to form an all-solid battery before liquid injection.
  • a second aspect of the present invention provides a method of preparing a flexible all-solid lithium ion secondary battery, the method comprising the steps of:
  • step 3b compressing the positive electrode current collector and the positive electrode material into a positive electrode and then infiltrating into the gel system in step 1b); or applying the gelable system in step 1) to the positive electrode current collector and the positive electrode material.
  • step 4b) assembling the impregnated or coated negative electrode of the step 2b), the separator, and the impregnated or coated positive electrode of the step 3b) to obtain an all-solid lithium ion secondary battery before liquid injection; all solid lithium ions before liquid injection Injecting the gelable system of step 1b) into the secondary battery, sealing, and standing to obtain the all-solid lithium ion secondary battery;
  • step 4b' coating the gellable system of step 1b) on the surface of the substrate, the gelatinizable system solidifying on the surface of the substrate to form a solid electrolyte film; the impregnated or coated negative electrode, solid electrolyte film of step 2b), Step 3b) of the wetted or coated positive electrode assembly to obtain an all-solid lithium ion secondary battery; or
  • Step 4b) coating the gellable system of step 1b) on the surface of the substrate, the gellable system solidifying on the surface of the substrate to form a solid electrolyte film; the impregnated or coated negative electrode, solid electrolyte film of step 2b), Step 3b) the infiltrated or coated positive electrode assembly to obtain an all-solid lithium ion secondary battery before liquid injection; injecting the gelable system of step 1b) into the all-solid lithium ion secondary battery before liquid injection, sealing, and static Providing the all-solid lithium ion secondary battery;
  • the gellable system comprises the following components: a lithium salt and an ether compound, the ether compound being selected from at least one of a cyclic ether compound or a linear ether compound; a gellable polymerization in the system
  • the mass percentage of the and/or gellable prepolymer is less than or equal to 1% by weight.
  • the method of assembling is a conventional choice of those skilled in the art, and any method can be used to prepare an all-solid lithium ion secondary battery before liquid injection; exemplarily,
  • the impregnated or coated negative electrode of the step 2b), the separator, the impregnated or coated positive electrode of the step 3b) are assembled into a battery by lamination or winding, or the infiltration or coating of the step 2b)
  • the negative electrode, the separator, the impregnated or coated positive electrode of the step 3b) are integrally pressed in a battery pressing mold to form an all-solid lithium ion secondary battery before liquid injection.
  • the method of assembling is a conventional choice of those skilled in the art, and the all-solid lithium ion secondary battery can be prepared by any method; exemplarily, The impregnated or coated negative electrode, the solid electrolyte membrane of step 2b), the wetted or coated positive electrode of step 3b) are assembled into a battery by lamination or winding, or the like; or the wetting or coating of step 2b) The rear negative electrode, the solid electrolyte film, the impregnated or coated positive electrode of step 3b) are integrally pressed in a battery press mold to form an all-solid lithium ion secondary battery.
  • the method of assembly is a conventional choice of those skilled in the art, and any method can be used to prepare an all-solid lithium ion secondary battery before liquid injection; exemplarily , the impregnated or coated negative electrode of step 2b), the solid electrolyte membrane, the impregnated or coated positive electrode of step 3b) are assembled into a battery by lamination or winding; or, the infiltration or coating of step 2b)
  • the coated negative electrode, the solid electrolyte film, the impregnated or coated positive electrode of step 3b) are integrally pressed in a battery press mold to form an all-solid lithium ion secondary battery before liquid injection.
  • a third aspect of the present invention provides a method of preparing a flexible all-solid lithium ion secondary battery, the method comprising the steps of:
  • step 3c) preparing a negative electrode material, a conductive agent, a gellable system of step 1c), and optionally a binder, mixed with a solvent, and coated onto the surface of the negative current collector to prepare a negative electrode containing a gellable system;
  • Step 4c' coating the gellable system of step 1c) on the surface of the substrate, the gellable system solidifying on the surface of the substrate to form a solid electrolyte film; the positive electrode containing the gelable system of step 2c), a solid electrolyte film, Step 3c) assembling the negative electrode containing the gelable system to obtain an all-solid lithium ion secondary battery before liquid injection; injecting the gelable system of step 1c) into the all-solid lithium ion secondary battery before liquid injection, sealing, and standing Obtaining the all-solid lithium ion secondary battery; or
  • step 4c assembling the positive electrode containing the gellable system in step 2c), the separator, and the negative electrode containing the gel-forming system in step 3c) to obtain an all-solid lithium ion secondary battery before liquid injection; all solid lithium ions before liquid injection Injecting the gelable system of step 1c) into the secondary battery, sealing, and standing to obtain the all-solid lithium ion secondary battery;
  • the gellable system comprises the following components: a lithium salt and an ether compound, the ether compound being selected from at least one of a cyclic ether compound or a linear ether compound; a gellable polymerization in the system
  • the mass percentage of the and/or gellable prepolymer is less than or equal to 1% by weight.
  • the method of assembling is a conventional choice of those skilled in the art, and the all-solid lithium ion secondary battery can be prepared by any method; exemplarily, the steps are 2c) a positive electrode comprising a gellable system, a solid electrolyte membrane, and a step 3c) a negative electrode containing a gellable system assembled into a battery by lamination or winding; or, the gel-containing system of step 2c)
  • the positive electrode, the solid electrolyte membrane, and the negative electrode containing the gel-forming system in step 3c) are integrally pressed in a battery pressing mold to form an all-solid lithium ion secondary battery.
  • the method of assembly is a conventional choice of those skilled in the art, and any method can be used to prepare an all-solid lithium ion secondary battery before liquid injection; exemplarily , the positive electrode containing the gelable system of step 2c), the solid electrolyte membrane, and the negative electrode containing the gelable system of step 3c) are assembled into an all-solid lithium ion secondary battery by lamination or winding; or, step 2c
  • the positive electrode containing the gelable system, the solid electrolyte membrane, and the negative electrode containing the gelable system in step 3c) are integrally pressed in a battery pressing mold to form an all-solid lithium ion secondary battery.
  • the method of assembly is a conventional choice of those skilled in the art, and any method can be used to prepare an all-solid lithium ion secondary battery before liquid injection; exemplarily , the positive electrode containing the gellable system of step 2c), the separator, and the negative electrode containing the gelable system of step 3c) are assembled into an all-solid lithium ion secondary battery by lamination or winding; or, the step 2c)
  • the positive electrode containing the gelable system, the separator, and the negative electrode containing the gelable system in step 3c) are integrally pressed in a battery pressing mold to form an all-solid lithium ion secondary battery.
  • At least one of inorganic nanoparticles, other solvents and/or electrolytes, polyesters or blends thereof may also be included in the gellable system.
  • the sum of the weight percentages of the components in the gellable system is 100% by weight.
  • a solid electrolyte can be prepared, the lithium salt having a mass percentage of 5% by weight or more and 60% by weight or less; and the mass percentage of the ether compound 20% by weight or more and 60% by weight or less; the mass percentage of the other electrolyte or its solvent is 20% by weight or more and 755% by weight or less, and the mass percentage of the inorganic nanoparticles is 0% by weight or more and 30% or less.
  • the mass percentage of the additive is greater than or equal to 0% by weight and less than or equal to 30% by weight.
  • a solid electrolyte can be prepared, wherein the lithium salt has a mass percentage of 10% by weight or more and 40% by weight or less; and the mass percentage of the ether compound is greater than 20% by weight and 60% by weight or less; the mass percentage of the other electrolyte or its solvent is 20% by weight or more and 60% by weight or less, and the mass percentage of the inorganic nanoparticles is more than 0% by weight and less than or equal to 20% by weight.
  • the mass percentage of the additive is greater than 0 wt% and less than or equal to 20 wt%.
  • a gel electrolyte can be prepared, the lithium salt having a mass percentage of 5% by weight or more and 60% by weight or less; and the mass percentage of the ether compound
  • the content is more than 60% by weight and less than or equal to 90% by weight; the mass percentage of the other electrolyte or its solvent is 5% by weight or more and 30% by weight or less, and the mass percentage of the inorganic nanoparticles is greater than or equal to 0% by weight and less than or equal to 30% by weight.
  • the mass percentage of the additive is greater than or equal to 0% by weight and less than or equal to 30% by weight.
  • a gel electrolyte can be prepared, wherein the gelatinizable system has a mass percentage of the lithium salt of 10% by weight or more and 40% by weight or less;
  • the mass percentage of the ether compound is more than 60% by weight and less than or equal to 85 wt%; the mass percentage of the other electrolyte or its solvent is 5% by weight or more and 30% by weight or less, and the mass of the inorganic nanoparticle is 100%
  • the content of the component is more than 0% by weight and less than or equal to 20% by weight, and the mass percentage of the additive is more than 0% by weight and less than or equal to 20% by weight.
  • the preparation method of the gellable system specifically comprises the following steps:
  • the ether compound, the lithium salt and optionally other solvents and/or electrolytes, optionally inorganic nanoparticles, optionally additives, are mixed and stirred to give a mixed solution, ie the gellable system.
  • the preparation method of the gellable system specifically comprises the following steps:
  • Adding an ether compound to the lithium salt stirring to obtain a solution of the ether compound of the lithium salt, optionally adding other solvent and/or electrolyte and/or inorganic nanoparticles and/or additives to the linear ether of the lithium salt a compound solution, that is, the gellable system.
  • the ether compound, the lithium salt, optionally the inorganic nanoparticles, optionally other solvents and/or electrolytes and optionally additives are subjected to a pre-water removal treatment; preferably, molecular sieves and/or The method of vacuum drying pre-dehydrates the ether compound, the lithium salt, optionally the inorganic nanoparticles, optionally other solvents and/or electrolytes and optionally additives.
  • the process of pressing the positive electrode or the negative electrode into one body is carried out under dry conditions.
  • the coating is at least one selected from the group consisting of spraying, doctor blade coating, coating rolls, coating brushes, and the like.
  • the wetting time and the wetting temperature are not limited; when the wetting temperature is lower than a transition temperature of the solid electrolyte formed by the gellable system, the wetting time is preferably less than The time at which the gellable system forms a solid electrolyte; or, when the wetting temperature is higher than the transition temperature of the solid electrolyte formed by the gellable system, those skilled in the art can understand that the gelatinizable The system does not form a gel, so the infiltration time is not limited.
  • the selection of the conductive agent, the binder, the anode current collector, the anode material, the separator, the cathode material, and the cathode current collector is not limited, and those skilled in the art can understand that the flexibility is suitable for the present invention.
  • a solid state lithium ion secondary battery can be used.
  • the conductive agent is at least selected from the group consisting of conductive graphite, acetylene black, Super P, carbon nanotubes, graphene, graphene oxide, conductive carbon black, ketjen black, graphite (KS, SO), and SFG-6.
  • conductive graphite acetylene black
  • Super P carbon nanotubes
  • graphene graphene oxide
  • conductive carbon black ketjen black
  • SFG-6 graphite
  • the binder is selected from the group consisting of polyvinylidene fluoride (PVDF), acrylates and derivatives thereof, cyclodextrins and derivatives thereof, Carricks aromatic hydrocarbons and derivatives thereof, carboxymethyl cellulose and derivatives At least one of acrylic acid, acrylic acid and derivatives thereof, amino resin and derivatives thereof, polyimide, organic fluoropolymer, and organopolysiloxane.
  • PVDF polyvinylidene fluoride
  • acrylates and derivatives thereof cyclodextrins and derivatives thereof
  • Carricks aromatic hydrocarbons and derivatives thereof carboxymethyl cellulose and derivatives
  • carboxymethyl cellulose and derivatives At least one of acrylic acid, acrylic acid and derivatives thereof, amino resin and derivatives thereof, polyimide, organic fluoropolymer, and organopolysiloxane.
  • the anode current collector is at least one selected from the group consisting of copper foil, copper alloy, silver foil, stainless steel sheet, and carbon material.
  • the anode material is selected from at least one of a metal-based anode material (such as metal lithium, a lithium alloy, etc.), an inorganic non-metal anode material (such as a carbon material, a silicon material, and other different non-metal composite materials, etc.).
  • a metal-based anode material such as metal lithium, a lithium alloy, etc.
  • an inorganic non-metal anode material such as a carbon material, a silicon material, and other different non-metal composite materials, etc.
  • the separator is selected from the group consisting of a solid electrolyte membrane or a polyolefin porous membrane prepared by the gellable system of the present invention, such as at least one of a polyethylene microporous membrane, a polypropylene microporous membrane, and a three-layer composite membrane.
  • a solid electrolyte membrane or a polyolefin porous membrane prepared by the gellable system of the present invention such as at least one of a polyethylene microporous membrane, a polypropylene microporous membrane, and a three-layer composite membrane.
  • a polyethylene microporous membrane such as at least one of a polyethylene microporous membrane, a polypropylene microporous membrane, and a three-layer composite membrane.
  • the positive electrode material is selected from the group consisting of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, ternary material nickel cobalt manganese oxide, nano positive electrode material (such as nanocrystalline spinel LiMn 2 O 4 , barium magnesium manganese ore) Type MnO 2 nanofibers, polypyrrole coated spinel LiMn 2 O 4 nanotubes, polypyrrole/V 2 O 5 nanocomposites, etc.), blended electrodes, vanadium oxides, layered compounds (eg, modified by aniline) At least one of oxyferric chloride or the like after the sex.
  • nano positive electrode material such as nanocrystalline spinel LiMn 2 O 4 , barium magnesium manganese ore
  • Type MnO 2 nanofibers such as nanocrystalline spinel LiMn 2 O 4 , barium magnesium manganese ore
  • Type MnO 2 nanofibers such as nanocrystalline spinel LiMn 2 O 4 , barium magnesium manganese ore
  • the cathode current collector is at least one selected from the group consisting of aluminum foil and aluminum alloy.
  • the standing time is a formation time at which the gellable system used is converted into a solid electrolyte, and the standing temperature is room temperature.
  • a fourth aspect of the present invention provides a flexible all-solid lithium ion secondary battery which is produced by any of the above methods.
  • the lithium ion secondary battery includes a lithium ion battery, a lithium sulfur battery, a lithium air battery, and the like.
  • the present invention employs a gellable system as a solid electrolyte for a lithium ion secondary battery, which can be replaced by a binder in the original positive electrode and the negative electrode, or by infiltration or coating before it forms a solid electrolyte.
  • the method uses a positive electrode and a negative electrode for a lithium ion secondary battery in a gelable system in which a solid electrolyte is not formed, or a method of directly adding a gellable system to a lithium ion secondary battery, so that the positive and negative surfaces and the inside thereof It is wetted by the gellable system and enters into the voids inside the positive and negative electrodes. After the gel system is cured, it can form a solid electrolyte in situ on the positive and negative surfaces and inside.
  • the "all solid state” includes an all-solid state, that is, the electrolyte system does not contain any liquid in a flowable state; and includes a semi-solid state, that is, a certain liquid component is contained in the electrolyte system.
  • the resulting electrolyte is almost incapable of flowing.
  • the present invention provides a flexible all-solid lithium ion secondary battery, which is a method of replacing the binder in the original positive electrode and the negative electrode, or by infiltration or adoption, and a preparation method thereof.
  • the method of coating places the positive electrode and the negative electrode for a lithium ion secondary battery in a gellable system in which a solid electrolyte is not formed, or by directly adding a gellable system to a lithium ion secondary battery, so that the positive and negative electrodes
  • the surface and the interior are wetted by the gellable system and enter the voids inside the positive and negative electrodes. After the gel system reaches the solidified electrolyte, it can be in situ on the surface of the positive and negative electrodes and inside.
  • the lithium ion secondary battery prepared by the method can form a conductive network inside the entire battery, which can not only greatly reduce the internal resistance of the lithium ion secondary battery, thereby improving conductivity and rate performance. It can also solve the safety hazard caused by liquid electrolyte.
  • Fig. 1 is a graph showing the rate performance of a battery obtained by assembling in the second embodiment.
  • Fig. 2 is a graph showing the rate performance of the battery obtained by the assembly method in the fourth embodiment.
  • Fig. 3 is a graph showing the rate performance of the battery obtained by the assembly method in the sixth embodiment.
  • Fig. 4 is a graph showing the rate performance of the battery obtained by the assembly method in the seventh embodiment.
  • Fig. 5 is a graph showing the rate performance of the battery obtained by the assembly method in the eighth embodiment.
  • the gellable system of the present invention comprises a lithium salt, which may be selected from lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium trifluoromethanesulfonate, perfluorobutyl Lithium sulfonate, lithium bistrifluoromethanesulfonimide, lithium bisfluorosulfonimide, lithium aluminate, lithium chloroaluminate, lithium fluorosulfonimide, lithium chloride and lithium iodide Or more; preferably, the lithium salt is selected from one or both of lithium hexafluorophosphate, lithium perchlorate, and the like.
  • the gellable system of the present invention includes an ether compound selected from at least one of a cyclic ether compound or a linear ether compound.
  • the ether compound of the present invention may be selected from a cyclic ether compound selected from a cyclic ether compound containing one oxygen, two oxygen, three oxygen or more.
  • the cyclic ether compound is selected from a C 2 - C 20 cycloalkane having at least one oxygen atom (that is, 2 to 20 carbon atoms in the cyclic structure) or at least 1 oxygen atom.
  • the C 3 -C 20 cyclic olefin i.e., 3 to 20 carbon atoms in the cyclic structure contains at least one carbon-carbon double bond.
  • the cycloalkane or cycloalkene is a monocyclic ring, a fused ring (such as a bicyclic ring), a spiro ring or a bridged ring; when the cycloalkane or cycloalkene is a spiro ring or a bridged ring and contains two or more oxygen atoms
  • the oxygen atoms may be on one ring or on multiple rings.
  • the cyclic ether compound is selected from a C 2 to C 20 monocycloalkane having at least one oxygen atom, and is preferably selected from a C 3 to C 20 monocycloalkane having at least one oxygen atom.
  • first class compounds one of the following first class compounds:
  • the cyclic ether compound is selected from a C 4 to C 20 fused cycloalkane having at least one oxygen atom, and is, for example, one of the following second compounds:
  • the cyclic ether compound is selected from a C 4 to C 20 bridged cycloalkane having at least one oxygen atom, and is, for example, one of the following third types of compounds:
  • the cyclic ether compound is selected from a C 4 to C 20 spirocycloalkane having at least one oxygen atom, and is, for example, one of the following fourth compounds:
  • the carbon atom on the ring may be substituted by one or more R1 groups; the cycloalkane or cycloalkene is a bridged ring.
  • the non-bridged ring carbon atom may be substituted by one or more R1 groups; when the cycloalkane or cycloalkene is a spiro ring, the ring carbon atom may be substituted with one or more R1 groups;
  • the R1 group is selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, alkylthio, haloalkyl, cycloalkyl, cycloalkyloxy, cycloalkylthio ,heterocyclyl,heterocyclyloxy,heterocyclylthio,aryl,aryloxy,heteroaryl,heteroaryloxy,hydroxy,indolyl,nitro,carboxy,amino,ester,halogen , acyl group, aldehyde group.
  • the cyclic ether compound containing an oxygen is selected from a substituted or unsubstituted oxetane, a substituted or unsubstituted tetrahydrofuran, a substituted or unsubstituted tetrahydropyran;
  • the number may be one or more; the substituent is the above R1 group.
  • the cyclic ether compound containing one oxygen is selected from the group consisting of 3,3-dichloromethyloxetane, 2-chloromethyloxetane, and 2-chloromethylpropylene oxide. , 1,4-epoxycyclohexane, 1,3-epoxycyclohexane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, tetrahydropyran, 2-methyltetrahydropyran, oxygen Heterocycloheptane, oxacyclooctane, oxetan or oxetane.
  • the cyclic ether compound containing two oxygens is selected from substituted or unsubstituted 1,3-dioxolane (DOL), substituted or unsubstituted 1,4-dioxane;
  • DOL 1,3-dioxolane
  • the number of the substituents may be one or more; the substituent is the above R1 group.
  • the cyclic ether compound containing three oxygens is selected from substituted or unsubstituted paraformaldehyde; the number of the substituents may be one or more; and the substituent is the above R1 group. group.
  • the oxygen-containing ether compound is selected from the group consisting of substituted or unsubstituted 18-crown-6, substituted or unsubstituted 12-crown-4, substituted or unsubstituted 24-crown-8;
  • the number of the substituents may be one or more; the substituent is the above R1 group.
  • n is an integer greater than 0;
  • R 2 is selected from a linear or branched C 1 -C 6 alkylene group, a linear or branched C 2 -C 6 alkenylene group; the H on the carbon atom on R 2 can be At least one substitution in the group: alkenyl, alkynyl, alkoxy, alkylthio, cycloalkyl, cycloalkyloxy, cycloalkylthio, heterocyclyl, heterocyclyloxy, Heterocyclylthio, aryl, aryloxy, heteroaryl, heteroaryloxy, hydroxy, decyl, nitro, carboxy, amino, ester, halogen, acyl, aldehyde;
  • R 1 and R 3 are the same or different and are independently selected from one or more of a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, an alkynyl group; the carbon of the R 1 and R 3 H on an atom may be substituted by at least one of the following groups: alkenyl, alkynyl, alkoxy, alkylthio, cycloalkyl, cycloalkyloxy, cycloalkylthio, heterocyclic , heterocyclyloxy, heterocyclylthio, aryl, aryloxy, hydroxy, decyl, nitro, carboxy, amino, ester, halogen, acyl, aldehyde.
  • n is an integer between 1 and 6;
  • R 2 is selected from a linear or branched C 1 -C 4 alkylene group, a linear or branched C 2 -C 6 alkenylene group;
  • R 1 and R 3 are the same or different and are independently selected from a linear or branched C 1 -C 6 alkyl group.
  • R 2 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, vinyl;
  • R 1 and R 3 are the same or different and are independently selected from the group consisting of methyl, ethyl and propyl.
  • the linear ether compound is selected from the group consisting of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, 1,4-butanediol dimethyl ether, and 1,4-butanediol.
  • the linear ether compound is selected from the group consisting of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, 1,4-butanediol dimethyl ether, and 1,4-butanediol.
  • diethyl ether, 1,4-butanediol methyl ethyl ether and the like are examples of diethyl ether, 1,4-butanediol methyl ethyl ether and the like.
  • the linear ether compound is, for example, one of the following compounds:
  • the gellable system includes a lithium salt and an ether compound, and the ether compound is selected from a cyclic ether compound.
  • the gellable system includes a lithium salt, an ether compound, and other solvents and/or electrolytes, and the ether compound is selected from the group consisting of cyclic ether compounds.
  • the gellable system includes a lithium salt, an ether compound, and inorganic nanoparticles, and the ether compound is selected from a cyclic ether compound.
  • the gellable system includes a lithium salt, an ether compound, other solvents and/or an electrolyte, and inorganic nanoparticles, and the ether compound is selected from a cyclic ether compound.
  • the gellable system includes a lithium salt, an ether compound, and an additive, and the ether compound is selected from a cyclic ether compound.
  • the gellable system includes a lithium salt and an ether compound, and the ether compound is selected from a linear ether compound.
  • the gellable system includes a lithium salt, an ether compound, and other solvents and/or electrolytes, and the ether compound is selected from a linear ether compound.
  • the gellable system includes a lithium salt, an ether compound, and inorganic nanoparticles, and the ether compound is selected from a linear ether compound.
  • the gellable system includes a lithium salt, an ether compound, other solvents and/or an electrolyte, and inorganic nanoparticles, and the ether compound is selected from a linear ether compound.
  • the inorganic nanoparticles are selected from the group consisting of silica, alumina, silicon nitride, zinc oxide, titanium dioxide, silicon carbide, silicate, calcium carbonate, barium sulfate, clay, triiron tetroxide, antimony oxide, One or more of a nano carbon material, iron oxide, or the like; preferably, the inorganic nanoparticle is selected from one or more of the group consisting of silica, alumina, titania, and zinc oxide.
  • the gellable system further includes other solvents and/or electrolytes including an electrolyte for a lithium sulfur battery, a solvent for an electrolyte of a lithium sulfur battery. At least one of an electrolyte for a lithium ion battery, a solvent for an electrolyte of a lithium ion battery, a lithium air battery electrolyte, or a solvent thereof.
  • the lithium air battery electrolyte or solvent thereof includes an ether electrolyte and a solvent thereof, an ester electrolyte and a solvent thereof, an amide electrolyte and a solvent thereof, a nitrile electrolyte, a solvent thereof, and a sulfone. Electrolyte and its solvent.
  • the electrolyte for a lithium ion battery is selected from the group consisting of an ester mixture containing a lithium salt for a lithium ion battery, such as ethylene carbonate (EC) and dimethyl carbonate containing 1 M lithium hexafluorophosphate (LiPF 6 ).
  • a lithium salt for a lithium ion battery such as ethylene carbonate (EC) and dimethyl carbonate containing 1 M lithium hexafluorophosphate (LiPF 6 ).
  • EC ethylene carbonate
  • LiPF 6 lithium hexafluorophosphate
  • the solvent for the electrolyte of the lithium ion battery is selected from the group consisting of a cyclic nonaqueous organic solvent for an electrolyte of a lithium ion battery and a chain nonaqueous organic solvent for an electrolyte of a lithium ion battery. At least one of them.
  • the cyclic nonaqueous organic solvent for the electrolyte of the lithium ion battery is selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), fluoroethylene carbonate (FEC), and ⁇ -butane.
  • EC ethylene carbonate
  • PC propylene carbonate
  • FEC fluoroethylene carbonate
  • ⁇ -butane At least one of ester (GBL), vinyl sulfite (ES), propylene sulfite (PS), sulfolane (SL), and glycerol carbonate (GC).
  • the chain non-aqueous organic solvent for the electrolyte of the lithium ion battery is selected from the group consisting of diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and methyl propylene carbonate.
  • DEC diethyl carbonate
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • propylene carbonate methyl propylene carbonate
  • Ester dipropyl carbonate (DPC), ethyl propyl carbonate (EPC), ethyl acetate (EA), propyl acetate (PA), ethyl propionate (EP), ethyl butyrate (EB) Methyl butyrate (MB), dimethyl sulfite (DMS), diethyl sulfite (DES), ethyl methyl sulfite (EMS), dimethyl sulfone (MSM), dimethyl sulfoxide ( At least one of DMSO).
  • DPC dipropyl carbonate
  • EPC ethyl propyl carbonate
  • EA propyl acetate
  • PA propyl acetate
  • EP ethyl propionate
  • EB Methyl butyrate
  • MMS dimethyl sulfite
  • DES diethyl sulfite
  • EMS ethyl methyl sulfite
  • MSM di
  • the electrolyte for the lithium sulfur battery is selected from the group consisting of ether mixtures containing lithium salts, for example, 1,3-dioxolane containing 1 M lithium bistrifluoromethanesulfonimide (LiTFSI).
  • LiTFSI lithium bistrifluoromethanesulfonimide
  • the solvent for the electrolyte of the lithium sulfur battery is selected from the group consisting of 1,3-dioxolane, 1,2-dimethoxyethane, triethylene glycol dimethyl ether, and tetraethylene glycol.
  • 1,3-dioxolane 1,2-dimethoxyethane
  • triethylene glycol dimethyl ether triethylene glycol dimethyl ether
  • tetraethylene glycol triethylene glycol dimethyl ether
  • dimethyl ether, fluoroethylene carbonate, polyethylene glycol borate, 1,1', 2,2'-tetrafluoroethyl-2,2',3,3'-tetrafluoropropene ether 1,1', 2,2'-tetrafluoroethyl-2,2',3,3'-tetrafluoropropene etherkind or more.
  • the ester electrolyte is selected from the group consisting of a mixture of esters containing a lithium salt, such as a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) containing 1 M lithium hexafluorophosphate (LiPF 6 ), wherein The volume ratio of the ethylene carbonate (EC) to dimethyl carbonate (DMC) was 1:1.
  • a lithium salt such as a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) containing 1 M lithium hexafluorophosphate (LiPF 6 )
  • the solvent of the ester electrolyte solution is at least one selected from the group consisting of an ester cyclic nonaqueous organic solvent and an ester chain nonaqueous organic solvent.
  • the ester cyclic nonaqueous organic solvent is selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), fluoroethylene carbonate (FEC), ⁇ -butyrolactone (GBL), and sulfurous acid.
  • EC ethylene carbonate
  • PC propylene carbonate
  • FEC fluoroethylene carbonate
  • GBL ⁇ -butyrolactone
  • sulfurous acid At least one of vinyl ester (ES), propylene sulfite (PS), and glycerin carbonate (GC).
  • the chain non-aqueous organic solvent is selected from the group consisting of diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), methylpropyl carbonate (MPC), and dipropyl carbonate.
  • DEC diethyl carbonate
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • MPC methylpropyl carbonate
  • DPC dipropyl carbonate
  • EPC ethyl propyl carbonate
  • EA ethyl acetate
  • PA propyl acetate
  • EP ethyl propionate
  • EB ethyl butyrate
  • MB methyl butyrate
  • DMS dimethyl sulfite
  • DES diethyl sulfite
  • EMS ethyl methyl sulfite
  • the ether electrolyte is selected from the group consisting of ether mixtures containing lithium salts, for example, 1,3-dioxolane (DOL) containing 1 M lithium bistrifluoromethanesulfonimide (LiTFSI) and A mixed solution of ethylene glycol dimethyl ether (DME) in which the volume ratio of the 1,3-dioxolane (DOL) and ethylene glycol dimethyl ether (DME) is 1:1.
  • DOL 1,3-dioxolane
  • LiTFSI lithium bistrifluoromethanesulfonimide
  • DME ethylene glycol dimethyl ether
  • the solvent of the ether electrolyte is selected from the group consisting of 1,3-dioxolane, 1,2-dimethoxyethane, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
  • One or more of fluoroethylene carbonate, polyethylene glycol borate, 1,1', 2,2'-tetrafluoroethyl-2,2',3,3'-tetrafluoropropene ether is selected from the group consisting of 1,3-dioxolane, 1,2-dimethoxyethane, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
  • fluoroethylene carbonate polyethylene glycol borate
  • 1,1', 2,2'-tetrafluoroethyl-2,2',3,3'-tetrafluoropropene ether 1,1', 2,2'-tetrafluoroethyl-2,2',3,3'-tetrafluor
  • the amide-based electrolyte is selected from the group consisting of a mixture of amides containing a lithium salt, for example, a solution of 1 M lithium trifluoromethanesulfonate in N,N-dimethylacetamide.
  • the solvent of the amide-based electrolyte is selected from the group consisting of compounds containing an amide group
  • the solvent of the amide-based electrolyte is selected from the group consisting of C 1 - C 20 alkyl amides, C 1 - C 20 olefin amide nitriles, C 1 - C 20 alkynyl amides, C 1 - C 20 alkyl halides At least one of a amide, a C 1 -C 20 haloalkenylamide, a C 1 -C 20 haloalkynylamide, a C 7 -C 20 arylamide, and a C 1 -C 20 epoxy amide One.
  • the solvent of the amide-based electrolyte is selected from the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, benzamide, formamide, acetamide, succinimide, ortho Benzoimide, N-methyl-p-toluenesulfonamide, N-methylacetamide, 3-amino-6-methylbenzenesulfonamide, 2,2,2-trichloroacetamide, benzyl ester N- Ethyl p-toluenesulfonamide, 3-amino-2,2-dimethylpropanamide, erucamide, N-ethyl-5-methyl-2-(1-methylethyl)cyclohexanecarboxamide, 4-methoxybenzamide, 2,4-dihydroxybenzamide, N,N-diethyl-2-chloroacetamide, N-butylbenzenesulfonamide, N-ethylacetamide, chloride B Am
  • the nitrile electrolyte is selected from a nitrile mixture containing a lithium salt, for example, an acetonitrile solution containing 1 M lithium perchlorate.
  • the solvent of the nitrile electrolyte is selected from the group consisting of a nitrile group-containing compound
  • the solvent of the nitrile electrolyte is selected from the group consisting of C 1 - C 20 alkyl nitriles, C 1 - C 20 alkenyl nitriles, C 1 - C 20 alkynyl nitriles, C 1 - C 20 haloalkanes At least one of a nitrile, a C 1 -C 20 haloalkenyl nitrile, a C 1 -C 20 haloalkynyl nitrile, a C 7 -C 20 aryl nitrile, and a C 1 -C 20 epoxy nitrile One.
  • the solvent of the nitrile electrolyte is selected from the group consisting of acetonitrile and butyronitrile.
  • the sulfone-based electrolyte is selected from a sulfone-based mixture containing a lithium salt, for example, a dimethyl sulfoxide (DMSO) solution containing 1 M lithium perchlorate.
  • a lithium salt for example, a dimethyl sulfoxide (DMSO) solution containing 1 M lithium perchlorate.
  • the solvent of the sulfone-based electrolyte is selected from the group consisting of a compound containing a sulfone group;
  • the solvent of the nitrile electrolyte is selected from the group consisting of C 1 - C 20 alkyl sulfone, C 1 - C 20 alkenyl sulfone, C 1 - C 20 alkynyl sulfone, C 1 - C 20 alkyl halide a sulfone, a C 1 - C 20 haloalkenyl sulfone, a C 1 - C 20 haloalkynyl sulfone, a C 7 - C 20 aryl sulfone, and a C 1 - C 20 epoxy sulfone One.
  • the solvent of the sulfone-based electrolyte is selected from the group consisting of sulfolane (SL) and dimethyl sulfoxide.
  • the additive is selected from one or more of a polyester or a blend thereof; wherein the polyester is obtained by polycondensation of a polybasic acid or an acid anhydride with a polyol; the polybasic acid is selected from the group consisting of An acid, a tribasic acid or a polybasic acid selected from the group consisting of glycols, trihydric alcohols or polyhydric alcohols.
  • the polybasic acid is selected from one or two or three or more of the following polybasic acids which are substituted or unsubstituted: oxalic acid, malonic acid, succinic acid, butylene Acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, triglyceride; the number of said substituents may be one or more; when the substituent is When plural, it may form a ring; the substituent is one or more of an alkyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an amino group, an ester group, a halogen, an acyl group, an aldehyde group, a decyl group, an alkoxy group or the like.
  • oxalic acid malonic acid
  • succinic acid butylene Acid
  • glutaric acid adipic acid
  • pimelic acid suberic acid
  • the acid anhydride is selected from one or two or three or more than the following anhydrides which are substituted or unsubstituted: oxalic anhydride, malonic anhydride, succinic anhydride, butenedic anhydride, Glutaric anhydride, adipic anhydride, pimelic anhydride, suberic anhydride, sebacic anhydride, sebacic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride; the number of said substituents may be one or more; when said substitution When the base is plural, it may form a ring; the substituent is one of an alkyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an amino group, an ester group, a halogen, an acyl group, an aldehyde group, a decyl group, an alkoxy group or the like. Or a variety.
  • the polyol is selected from one or more of the following substituted or unsubstituted polyols: propylene glycol, butylene glycol, pentanediol, hexanediol, heptanediol, octanediol, hydrazine a diol, a decanediol, a polyethylene glycol, a glycerin; the number of the substituents may be one or more; when the substituent is plural, it may form a ring; the substituent is One or more of an alkyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an amino group, an ester group, a halogen, an acyl group, an aldehyde group, a decyl group, an alkoxy group and the like.
  • the polyol is selected from the group consisting of polyethylene glycol, or a combination of polyethylene glycol and one or more of the following polyols: propylene glycol, butylene glycol, pentanediol, hexanediol, g Glycol, octanediol, decanediol, decanediol.
  • the polyethylene glycol has a degree of polymerization of from 100 to 1,000, preferably from 150 to 800, and more preferably from 200 to 600.
  • the weight ratio of the polyethylene glycol to the other polyol is 1: (0 to 1), preferably 1: (0 to 0.9), and more preferably 1: (0 to 0.8).
  • gel in the present invention has a meaning well known in the art, and the term “gelling” also has the meanings well known in the art.
  • the gellable polymer and/or gellable prepolymer in the present invention means a polymer and/or a prepolymer which can form a gel or can be gelled under certain conditions.
  • the gellable polymer and/or gellable prepolymer of the present invention may be selected from the group consisting of polyethylene oxide (PEO), polyethylene glycol (PEG), and polyvinylidene fluoride (PVDF). ), polyvinyl chloride (PVC), polystyrene (PS), polyacrylonitrile (PAN), polyethyl acetate (PVAC), polyvinylpyrrolidone (PVP), polydivinyl sulfide (PVS), poly Sanya Methyl carbonate (PTMC), polymethyl methacrylate (PMMA), polyethylene glycol dimethacrylate (PEGDM), polyoxypropylene (PPO), polydimethylsiloxane (PDMSO) or One or more of a prepolymer, or a copolymer thereof, or a blend thereof.
  • PEO polyethylene oxide
  • PEG polyethylene glycol
  • PVDF polyvinylidene fluoride
  • PVC polyvinyl chlor
  • halogen means fluoro, chloro, bromo and iodo.
  • alkyl group used alone or as a suffix or prefix in the present invention is intended to include a branch having from 1 to 20, preferably from 1 to 6 carbon atoms (or a specific number if a specific number of carbon atoms is provided) Chain and linear saturated aliphatic hydrocarbon groups.
  • C 1-6 alkyl means a straight-chain or branched alkyl group having 1, 2, 3, 4, 5 or 6 carbon atoms.
  • alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl.
  • Haloalkyl or "alkyl halide”, as used alone or as a suffix or prefix, is intended to include having at least one halogen substituent and having from 1 to 20, preferably from 1 to 6 carbon atoms (or if provided)
  • the specific number of carbon atoms refers to the specific number of branched and linear saturated aliphatic hydrocarbon groups.
  • C 1-10 haloalkyl means a haloalkyl group having 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 carbon atoms.
  • haloalkyl groups include, but are not limited to, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, 1-fluoroethyl, 3-fluoropropyl, 2-chloropropyl, 3,4-di Fluorobutyl and the like.
  • alkenyl used alone or as a suffix or prefix in the present invention is intended to include the inclusion of 2 to 20, preferably 2 to 6 carbon atoms (or the specific number if a specific number of carbon atoms is provided) Branched and linear aliphatic hydrocarbon groups of alkenyl or olefin.
  • C 2-6 alkenyl means an alkenyl group having 2, 3, 4, 5 or 6 carbon atoms.
  • alkenyl groups include, but are not limited to, vinyl, allyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, 3 Methylbut-1-enyl, 1-pentenyl, 3-pentenyl and 4-hexenyl.
  • alkynyl used alone or as a suffix or prefix in the present invention is intended to include inclusions having from 2 to 20, preferably from 2 to 6 carbon atoms (or the specific number if a particular number of carbon atoms is provided) Branched and linear aliphatic hydrocarbon groups of alkynyl or alkyne.
  • ethynyl, propynyl eg, 1-propynyl, 2-propynyl
  • 3-butynyl pentynyl, hexynyl, and 1-methylpent-2-ynyl.
  • aryl as used herein means an aromatic ring structure composed of 5 to 20 carbon atoms.
  • an aromatic ring structure containing 5, 6, 7 and 8 carbon atoms may be a monocyclic aromatic group such as a phenyl group; a ring structure comprising 8, 9, 10, 11, 12, 13 or 14 carbon atoms It may be polycyclic such as naphthyl.
  • the aromatic ring may be substituted with one or more of the above substituents at one or more ring positions.
  • aryl also includes polycyclic ring systems having two or more rings wherein two or more carbons are shared by two adjacent rings (the ring is a "fused ring"), wherein at least One ring is aromatic and the other ring may be, for example, a cycloalkyl, cycloalkenyl, cycloalkynyl, aryl and/or heterocyclic group.
  • polycyclic rings include, but are not limited to, 2,3-dihydro-1,4-benzodioxadiene and 2,3-dihydro-1-benzofuran.
  • cycloalkyl as used herein is intended to include saturated cyclic groups having the indicated number of carbon atoms. These terms may include fused or bridged polycyclic systems.
  • the cycloalkyl group has 3 to 40 carbon atoms in its ring structure. In one embodiment, the cycloalkyl has 3, 4, 5 or 6 carbon atoms in its ring structure.
  • C 3-6 cycloalkyl means a group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group or a cyclohexyl group.
  • heteroaryl refers to a heteroaromatic heterocycle having at least one ring heteroatom such as sulfur, oxygen or nitrogen.
  • Heteroaryl groups include monocyclic systems and polycyclic systems (eg, having 2, 3 or 4 fused rings).
  • heteroaryl groups include, but are not limited to, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furyl, quinolyl, isoquinolinyl, thienyl, imidazolyl, thiazolyl, fluorene , pyrrolyl, oxazolyl, benzofuranyl, benzothienyl, benzothiazolyl, isoxazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, 1,2,4 -thiadiazolyl, isothiazolyl, benzothienyl, fluorenyl, oxazolyl, benzimidazolyl, benzoxazolyl, azabenzoxazolyl, imidazothiazolyl, benzo[1] 4] dioxolyl, benzo[1,3]dioxolyl and the
  • a heteroaryl has from 3 to 40 carbon atoms and in other embodiments from 3 to 20 carbon atoms. In some embodiments, a heteroaryl group contains 3 to 14, 4 to 14, 3 to 7, or 5 to 6 ring-forming atoms. In some embodiments, a heteroaryl has 1 to 4, 1 to 3 or 1 to 2 heteroatoms. In some embodiments, a heteroaryl has 1 heteroatom.
  • heterocyclyl refers to a saturated, unsaturated or partially saturated monocyclic, bicyclic or tricyclic ring containing from 3 to 20 atoms, wherein 1, 2, 3, 4 or 5 Ring atoms are selected from nitrogen, sulfur or oxygen, and unless otherwise indicated, may be attached by carbon or nitrogen, wherein the -CH 2 - group is optionally replaced by -C(O)-; and unless otherwise stated
  • the ring nitrogen atom or the ring sulfur atom is optionally oxidized to form an N-oxide or S-oxide or a ring nitrogen atom, optionally quaternized; wherein -NH in the ring is optionally acetyl, formyl, A Substituted with a methanesulfonyl group; and the ring is optionally substituted with one or more halogens.
  • heterocyclic group when the total number of S atoms and O atoms in the heterocyclic group exceeds 1, these hetero atoms are not adjacent to each other.
  • the heterocyclic group is bicyclic or tricyclic, at least one ring may be optionally a heteroaromatic or aromatic ring, provided that at least one ring is non-heteroaromatic. If the heterocyclic group is a monocyclic ring, it must not be aromatic. Examples of heterocyclic groups include, but are not limited to, piperidinyl, N-acetylpiperidinyl, N-methylpiperidinyl, N-formylpiperazinyl, N-methylsulfonylpiperazinyl, homopiperazinyl.
  • Lithium bistrifluoromethanesulfonimide LiTFSI: polyoxyethylene (PEO): tetraethylene glycol dimethyl ether (TEGDME): benzophenone (MBP) according to a ratio of 10:41.3:41.2:7.5
  • PEO polyoxyethylene
  • TEGDME tetraethylene glycol dimethyl ether
  • MBP benzophenone
  • the mixture was ground and mixed, and then uniformly coated on a plate of polytetrafluoroethylene to obtain a film, which was cross-linked by ultraviolet irradiation to obtain a solid electrolyte film having a room temperature conductivity of about 10 -3 S/cm.
  • a specific preparation method of the solid electrolyte membrane can be referred to in Luca Porcarelli et al. Super Soft All-Ethylene Oxide Polymer Electrolyte for Safe All-Solid Lithium Batteries. Scientific Reports, 2016, 6, 1-14.
  • the positive electrode of lithium ion battery uniformly mix lithium cobaltate with conductive graphite, conductive agent acetylene black (super p), binder polyvinylidene fluoride (PVDF) according to mass ratio of 85:5:5:5, with N- Methyl-pyrrolidone (NMP) was prepared into a slurry, uniformly coated on an aluminum foil, and dried in a vacuum oven at 120 ° C for 24 hours, standby; lithium ion battery negative electrode: lithium plate; positive electrode and negative electrode respectively The infiltrated positive electrode sheet and negative electrode sheet were taken out before being infiltrated into the electrolyte solution of the above-prepared unsolidified electrolyte before the formation of the solid electrolyte.
  • PVDF binder polyvinylidene fluoride
  • Diaphragm Polypropylene (PP) porous membrane; the separator is placed between the positive and negative electrodes infiltrated with the electrolyte, and then the electrolyte of the above-mentioned unsolidified electrolyte is injected into the interior of the battery, and the battery is pressed and packaged, and the electrolyte is left to be formed. After the solid electrolyte, the electrochemical performance of the battery was tested using a blue battery.
  • PP Polypropylene
  • the positive electrode of the lithium-sulfur battery the carbon-sulfur composite material and the conductive agent acetylene black (super p) and the binder polyvinylidene fluoride (PVDF) are uniformly mixed at a mass ratio of 8:1:1, and N-methyl-pyrrolidone is used. (NMP) the mixture was prepared into a slurry, uniformly coated on an aluminum foil, and dried in a vacuum oven at 60 ° C for 24 hours, and set aside;
  • the negative electrode of the lithium ion battery 90.5 parts of the negative electrode active material conductive graphite, 6 parts of acetylene black, 1 part of hydroxymethyl cellulose, and 2.5 parts of styrene-butadiene rubber binder are sufficiently mixed with an ethanol-water mixed solution to obtain a negative electrode slurry, and coated. Drying on a copper foil in a vacuum oven at 60 ° C for 24 hours, standby;
  • the positive electrode sheet and the negative electrode sheet obtained above were respectively impregnated into the electrolytic solution of the above-prepared non-solid electrolyte, and the infiltrated positive electrode sheet and negative electrode sheet were taken out before the solid electrolyte was formed.
  • Diaphragm Polypropylene (PP) porous membrane; the separator is placed between the positive and negative electrodes infiltrated with the electrolyte, and then the electrolyte of the above-mentioned unsolidified electrolyte is injected into the interior of the battery, and the battery is pressed and packaged, and the electrolyte is left to be formed. After the solid electrolyte, the electrochemical performance of the battery was tested using a blue battery. The performance parameters of the prepared solid electrolyte and battery were listed in Table 1.
  • the positive electrode and the negative electrode and the solid electrolyte were prepared in the same manner as in Example 1.
  • the positive and negative electrode sheets were also impregnated with the electrolyte solution before the solid electrolyte in Example 1, except that the solid electrolyte film prepared by the above Preparation Example 1 was used.
  • the electrolyte of the above-mentioned non-solid electrolyte was not injected into the interior of the battery, and the process of encapsulating the battery, stationary, and battery testing was the same as in Example 1, and the performance parameters of the battery are listed in Table 1.
  • the positive electrode and the negative electrode and the solid electrolyte were prepared in the same manner as in Example 2, and the positive and negative electrode sheets were also impregnated with the electrolyte solution before the solid electrolyte in Example 2, except that the solid electrolyte film prepared by the above Preparation Example 1 was used.
  • the electrolyte of the above-mentioned non-solid electrolyte was not injected into the interior of the battery, and the process of encapsulating the battery, stationary, and battery testing was the same as in Example 2, and the performance parameters of the battery are listed in Table 1.
  • the synthesis method of the positive electrode and the negative electrode and the solid electrolyte is the same as that in the embodiment 3 except that the positive and negative electrode sheets are not wetted into the electrolyte before the solid electrolyte, and the solid electrolyte film prepared in the above Preparation Example 1 is used instead.
  • the polypropylene separator, the electrolyte of the above-mentioned unsolidified electrolyte was not injected into the interior of the battery for assembly of the battery, and the processes of static and battery testing were exactly the same as in Example 3.
  • the performance parameters of the battery are listed in Table 1.
  • the synthesis method of the positive electrode and the negative electrode and the solid electrolyte is the same as that in the embodiment 4 except that the positive and negative electrode sheets are not wetted into the electrolyte before the solid electrolyte, and the solid electrolyte film prepared in the above Preparation Example 1 is used instead.
  • the polypropylene separator, the electrolyte of the above-mentioned unsolidified electrolyte was not injected into the interior of the battery for assembly of the battery, and the processes of static and battery testing were exactly the same as in Example 3.
  • the performance parameters of the battery are listed in Table 1.
  • 0.05 g of alumina was weighed into a reagent bottle, and 4.5 mL of 3,3-dichloromethyloxetane was added thereto, and the mixture was thoroughly mixed under magnetic stirring to obtain a mixed solution A. Further, 0.4 g of lithium fluorosulfonimide and 0.6 g of lithium perchlorate were placed in a reagent bottle, and 1.2 mL of a lithium sulfur battery conventional electrolyte was added thereto, and stirred until the lithium salt was completely dissolved to obtain a mixed solution B. The A and B solutions obtained above were thoroughly mixed, and the resulting mixture was thoroughly mixed and allowed to stand for use.
  • the positive electrode of lithium ion battery uniformly mix lithium iron phosphate with conductive graphite, conductive agent acetylene black (super p), binder polyvinylidene fluoride (PVDF) according to mass ratio of 85:5:5:5, with N- Methyl-pyrrolidone (NMP) to prepare a mixture into a slurry, uniformly coated on an aluminum foil, dried in a vacuum oven at 120 ° C for 24 hours, standby; lithium ion battery negative electrode: lithium plate;
  • the positive electrode sheet and the negative electrode sheet were respectively impregnated into the electrolytic solution of the above-prepared unsolidified electrolyte, and the infiltrated positive electrode sheet and negative electrode sheet were taken out before the solid electrolyte was formed.
  • the above gelable system is scraped onto a glass plate, allowed to stand, and after being polymerized into a solid electrolyte membrane, scraped off with a blade, placed between the positive and negative electrodes obtained above, and then the battery is pressed and packaged. After the electrolyte was allowed to stand to form a solid electrolyte, the electrochemical performance of the battery was tested using a blue battery.
  • the positive electrode of the lithium ion battery the lithium iron phosphate and the conductive graphite, the conductive agent acetylene black (super p), the gellizable system prepared in the above step (2) are uniformly mixed according to the mass ratio of 85:5:5:5, N-methyl-pyrrolidone (NMP) This mixture was prepared into a slurry, uniformly coated on an aluminum foil, and dried in a vacuum oven at 120 ° C for 24 hours, standby; lithium ion battery negative electrode: lithium plate; separator: polypropylene ( PP) porous film;
  • the separator is placed between the positive and negative electrodes infiltrated with the electrolyte, and then the electrolyte of the above-mentioned unsolidified electrolyte is injected into the interior of the battery, and the battery is pressed and packaged, and the electrolyte is allowed to stand to form a solid electrolyte, and then the blue battery pack is used for testing.
  • the electrochemical performance of the battery is not limited to the battery.
  • the positive electrode of lithium ion battery uniformly mix lithium iron phosphate with conductive graphite, conductive agent acetylene black (super p), binder polyvinylidene fluoride (PVDF) according to mass ratio of 85:5:5:5, with N- Methyl-pyrrolidone (NMP) This mixture was prepared into a slurry, uniformly coated on an aluminum foil, and dried in a vacuum oven at 120 ° C for 24 hours, standby; lithium ion battery negative electrode: lithium plate; separator: polypropylene (PP) Porous membrane
  • the separator is placed between the positive and negative electrodes, and then the precursor electrolyte of the quasi-solid electrolyte is injected into the interior of the battery, and the battery is pressed and packaged, and the electrolyte is allowed to stand to form a quasi-solid electrolyte, and then the battery is tested using a blue battery. Electrochemical performance.
  • 0.2 g of zinc oxide was weighed into a reagent bottle, and 6.0 mL of 1,3-dioxolane and 3.0 mL of tetrahydropyran were added thereto, and the mixture was thoroughly mixed under magnetic stirring to obtain a mixed solution A. Further, 0.5 g of lithium trifluoromethanesulfonate and 1.5 lithium hexafluoroarsenate were placed in a reagent bottle, 2.4 mL of dimethyl carbonate was added thereto, and the mixture was stirred until the lithium salt was completely dissolved to obtain a mixed solution B. The A and B solutions obtained above were thoroughly mixed, and the resulting mixture was obtained to obtain a gellable system;
  • the gellable system in step (1) is knife coated on a clean glass plate, allowed to stand, and after it is cured, it is gently peeled off with a blade and set aside.
  • the positive electrode of the lithium ion battery the lithium iron phosphate and the conductive graphite, the conductive agent acetylene black (super p), the gellable system obtained in the step (1) are uniformly mixed at a mass ratio of 85:5:5:5, and the mixture is mixed.
  • the solid electrolyte membrane was placed between the positive and negative electrode sheets containing the gellable system, and then the battery was compression-sealed, and after the electrolyte solution was allowed to stand to form a solid electrolyte, the electrochemical performance of the battery was tested using a blue battery.
  • the positive electrode of the lithium ion battery the lithium iron phosphate and the conductive graphite, the conductive agent acetylene black (super p), the gellable system obtained in the step (1) are uniformly mixed at a mass ratio of 85:5:5:5, and the mixture is mixed.
  • the separator is placed between the positive and negative electrode sheets containing the gellable system, and then the gelatinizable system obtained in the step (1) is injected, and then the battery is pressed and packaged, and the electrolyte is allowed to stand to form a semi-solid electrolyte, and then used.
  • the electrochemical performance of the battery was tested in a blue battery.
  • the performance parameters of the prepared quasi-solid electrolyte and battery were listed in Table 1.
  • Fig. 1 is a graph showing the rate performance of a battery obtained by assembling in the second embodiment. As can be seen from the figure, in the case of the positive and negative electrode sheets after the infiltration, when a certain amount of the electrolyte before the solid electrolyte is added, a good rate performance can be exhibited.
  • Fig. 2 is a graph showing the rate performance of the battery obtained by the assembly method in the fourth embodiment. As can be seen from the figure, the infiltrated positive and negative electrode sheets are separated by a solid electrolyte membrane, and the battery exhibits better rate performance.
  • Fig. 3 is a graph showing the rate performance of the battery obtained by the assembly method in the sixth embodiment.
  • the positive and negative electrode sheets are not wetted, and the positive and negative electrodes are separated by a simple solid electrolyte membrane, and the electric conductor serving as a surface has poor rate performance.
  • Fig. 4 is a graph showing the rate performance of the battery obtained by the assembly method in the seventh embodiment. It can be seen from the figure that the positive and negative gelation systems infiltrate, forming an ion-conducting network inside the battery, replacing the separator with a solid electrolyte, forming a solid-state battery, and having a good rate performance, even if it reaches 10C, it can exert good performance.
  • Fig. 5 is a graph showing the rate performance of a battery obtained by assembling in the eighth embodiment. It can be seen from the figure that in the preparation process, the gelatinizable system replaces the conventional binder in the preparation process, which not only improves the areal density of the active material, but also forms a good ion conductive network inside the electrode, and the battery exhibits excellent performance. Rate performance.
  • the battery assembled with the positive and negative electrodes infiltrated with the pre-solution of the solid electrolyte exhibits excellent rate performance compared to the un-infiltrated battery assembled with the positive and negative electrodes, indicating that the battery has been infiltrated.
  • the conductive network is formed inside the positive and negative electrodes, which is beneficial to the transmission of electrons and ions, and can withstand a large rate of charge and discharge.
  • the non-infiltrated positive and negative electrodes have no conductive network inside, and the electrochemical performance can only be achieved by electrodes and The contact portion of the solid electrolyte conducts electron and ion transport, so its rate performance is poor.

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Abstract

本发明公开了一种柔性全固态锂离子二次电池及其制备方法，所述柔性全固态锂离子二次电池是通过浸润或采用涂覆的方式将锂离子二次电池用正负极或任选地隔膜置于未形成固态电解质的可凝胶体系中，使得正负极表面及内部被可凝胶体系浸润，并进入到所述正负极内部的空隙中，待可凝胶体系达到形成固态电解质的经过固化之后，其可原位在正负极片表面及其内部形成固态电解质，采用所述方法制备得到的锂离子二次电池在整个电池内部即可形成导电网路，不仅可以极大地减小锂离子二次电池的内部的电阻，从而提高导电率和倍率性能，还可以解决液态电解液带来的安全隐患。

Description

一种柔性全固态锂离子二次电池及其制备方法 技术领域
本发明属于锂离子电池技术领域，具体涉及一种柔性全固态锂离子二次电池及其制备方法。
背景技术
科技的进步推动了为日用电子产品提供电能的锂离子二次电池的快速发展，然而，锂离子二次电池在其使用过程中也存在着不可小觑的安全隐患，例如：电解液的泄露、燃烧、爆炸等。电池在满足人类正常生产生活的前提必须是安全的，所以锂离子二次电池的安全性也是广大研究者所探索的热点课题。目前，解决锂离子二次电池电解液泄露的主要解决方法是采用固态电解质，其具有液体电解液无法比拟的优点，很有可能成为解决锂离子二次电池安全问题的技术途径。不仅如此，全固态锂离子二次电池相比于液态锂离子二次电池在拓宽工作温度区间、提高电池能量密度、延长使用寿命等方面均具有巨大的优势。
根据固态电解质组分的不同，固态电解质可分为聚合物复合锂离子电解质和全固态薄膜锂离子电解质。其中，聚合物复合锂离子电解质主要采用高分子聚合物与锂盐形成配位结构，从而实现锂离子的传导，为了提高锂离子的导电率往往加入一定量的二氧化硅(SiO 2)、氧化铝(Al 2O 3)、沸石等无机填料。
目前所报道的固态电解质在锂离子二次电池中的使用方法，一般都是将固态电解质膜放置在正极和负极之间，而这样的制备方法虽然可以有效阻隔正极和负极的接触，但是无法克服固态电解质和正极、固态电解质和负极之间的界面电阻，而且由于电解质是固态薄膜，使得电极片内部不能与固态电解质充分接触，故而造成制备得到的锂离子二次电池的导电性差、界面内阻大、倍率性能差等不足。
同时，目前所使用的全固态锂离子二次电池都是刚性的，其具有质量重、易压碎、应变性差、恢复性差、电池的电化学性能差、循环性能差、续航时间少等缺点。
发明内容
为了改善现有技术中存在的上述问题，本发明的目的是提供一种柔性全固态锂离子二次电池及其制备方法。采用本发明所述的方法制备得到的锂离子二次电池在整个电池内部形成导电网路，可以使得活性物质充分的发挥作用，极大地减小了锂离子二次电池内部的电阻，从而提高导电率和倍率性能，还可以解决液态电解液带来的安全隐患，并且具有很好的应变性、恢复性，而且轻便易携带。另外，通过控制制备所述固态电解质的可凝胶体系中各组分的种类和含量，可以得到强度可调、形成时间(即由可自由流动的液体状态转变成不可流动的固态电解质状态)可调、转变温度(即由不可流动的态电解质状态转变成可自由流动的液体状态时的最低温度)可调，即可以根据具体需要制备不同强度的固态电解质，以满足不同的需要。该固态电解质还具有很好的可逆性，在达到固态电解质转变温度以上时，所述固态电解质的流动性变强，而当温度降到转变温度以下时，所述固态电解质又重新形成，其性质并不受到影响。基于上述的思路，完成了本发明。
本发明目的是通过如下技术方案实现的：
本发明的第一个方面是提供一种柔性全固态锂离子二次电池的制备方法，所述方法包括如下步骤：
1a)配制可凝胶体系；
2a)将负极、隔膜、正极组装，得到注液前全固态电池；
3a)向步骤2a)的注液前全固态电池中注入步骤1a)的可凝胶体系，封口，静置，得到全固态锂离子二次电池；
其中，可凝胶体系包括以下组分：锂盐和醚类化合物，所述醚类化合物选自环状醚类化合物或直链醚类化合物中的至少一种；体系中可凝胶化的聚合物和/或可凝胶化的预聚物的质量百分含量小于等于1wt％。
根据本发明，所述步骤2a)中，所述的注液前全固态电池是指留有注液口的电池，即干燥的电芯；所述组装的方法为本领域技术人员的常规选择，采用任一种方法可以制备得到该注液前全固态电池即可；示例性地，将正极极片、隔膜和负极极片通过叠片或者卷绕等方式组装成注液前全固态电池；或者，负极、隔膜、正极在电池压制模具中压制成一体，形成注液前全固态电池。
本发明的第二个方面是提供一种柔性全固态锂离子二次电池的制备方法，所述方法包括如下步骤：
1b)配制可凝胶体系；
2b)将负极集流体、负极材料压制成负极后置于步骤1b)中的可凝胶体系中浸润；或者将步骤1)中的可凝胶体系涂覆到负极集流体、负极材料压制成的负极表面上；
3b)将正极集流体、正极材料压制成正极后置于步骤1b)中的可凝胶体系中浸润；或者将步骤1)中的可凝胶体系涂覆到正极集流体、正极材料压制成的正极表面上；
4)选自下述步骤中的一种：
4b)将步骤2b)的浸润或涂覆后的负极、隔膜、步骤3b)的浸润或涂覆后的正极组装，得到注液前全固态锂离子二次电池；向注液前全固态锂离子二次电池中注入步骤1b)的可凝胶体系，封口，静置，得到所述全固态锂离子二次电池；
4b’)将步骤1b)的可凝胶体系涂覆在基底表面，所述可凝胶体系在基底表面固化形成固态电解质薄膜；将步骤2b)的浸润或涂覆后的负极、固态电解质薄膜、步骤3b)的浸润或涂覆后的正极组装，得到全固态锂离子二次电池；或者，
4b”)将步骤1b)的可凝胶体系涂覆在基底表面，所述可凝胶体系在基底表面固化形成固态电解质薄膜；将步骤2b)的浸润或涂覆后的负极、固态电解质薄膜、步骤3b)的浸润或涂覆后的正极组装，得到注液前全固态锂离子二次电池；向注液前全固态锂离子二次电池中注入步骤1b)的可凝胶体系，封口，静置，得到所述全固态锂离子二次电池；
其中，可凝胶体系包括以下组分：锂盐和醚类化合物，所述醚类化合物选自环状醚类化合物或直链醚类化合物中的至少一种；体系中可凝胶化的聚合物和/或可凝胶化的预聚物的质量百分含量小于等于1wt％。
根据本发明，所述步骤4b)中，所述组装的方法为本领域技术人员的常规选择，采用任一种方法可以制备得到注液前全固态锂离子二次电池即可；示例性地，将步骤2b)的浸润或涂覆后的负极、隔膜、步骤3b)的浸润或涂覆后的正极通过叠片或者卷绕等方式组装成电池；或者，步骤2b)的浸润或涂覆后的负极、隔膜、步骤3b)的浸润或涂覆后的正极在电池压制模具中压制成一体，形成注液前全固态锂离子二次电池。
根据本发明，所述步骤4b’)中，所述组装的方法为本领域技术人员的常规选择，采用任一种方法可以制备得到该全固态锂离子二次电池即可；示例性地，将步骤2b)的浸润或涂覆后的负极、固态电解质薄膜、步骤3b)的浸润或涂覆后的正极通过叠片或者卷绕等方式组装成电池；或者，将步骤2b)的浸润或涂覆后的负极、固态电解质薄膜、步骤3b)的浸润或涂覆后的正极在电池压 制模具中压制成一体，形成全固态锂离子二次电池。
根据本发明，所述步骤4b”)中，所述组装的方法为本领域技术人员的常规选择，采用任一种方法可以制备得到注液前全固态锂离子二次电池即可；示例性地，将步骤2b)的浸润或涂覆后的负极、固态电解质薄膜、步骤3b)的浸润或涂覆后的正极通过叠片或者卷绕等方式组装成电池；或者，步骤2b)的浸润或涂覆后的负极、固态电解质薄膜、步骤3b)的浸润或涂覆后的正极在电池压制模具中压制成一体，形成注液前全固态锂离子二次电池。
本发明的第三个方面是提供一种柔性全固态锂离子二次电池的制备方法，所述方法包括如下步骤：
1c)配制可凝胶体系；
2c)将正极材料、导电剂、步骤1c)的可凝胶体系和任选地粘结剂，与溶剂混合打浆，并涂覆到正极集流体表面，制备得到含有可凝胶体系的正极；
3c)将负极材料、导电剂、步骤1c)的可凝胶体系和任选地粘结剂，与溶剂混合打浆，并涂覆到负极集流体表面，制备得到含有可凝胶体系的负极；
4)选自下述步骤中的一种：
4c)将步骤1c)的可凝胶体系涂覆在基底表面，所述可凝胶体系在基底表面固化形成固态电解质薄膜；将步骤2c)的含有可凝胶体系的正极、固态电解质薄膜、步骤3c)含有可凝胶体系的负极组装，得到全固态锂离子二次电池；或者，
4c’)将步骤1c)的可凝胶体系涂覆在基底表面，所述可凝胶体系在基底表面固化形成固态电解质薄膜；将步骤2c)的含有可凝胶体系的正极、固态电解质薄膜、步骤3c)含有可凝胶体系的负极组装，得到注液前全固态锂离子二次电池；向注液前全固态锂离子二次电池中注入步骤1c)的可凝胶体系，封口，静置，得到所述全固态锂离子二次电池；或者，
4c”)将步骤2c)的含有可凝胶体系的正极、隔膜、步骤3c)含有可凝胶体系的负极组装，得到注液前全固态锂离子二次电池；向注液前全固态锂离子二次电池中注入步骤1c)的可凝胶体系，封口，静置，得到所述全固态锂离子二次电池；
其中，可凝胶体系包括以下组分：锂盐和醚类化合物，所述醚类化合物选自环状醚类化合物或直链醚类化合物中的至少一种；体系中可凝胶化的聚合物和/或可凝胶化的预聚物的质量百分含量小于等于1wt％。
根据本发明，所述步骤4c)中，所述组装的方法为本领域技术人员的常规选择，采用任一种方法可以制备得到该全固态锂离子二次电池即可；示例性地，将步骤2c)的含有可凝胶体系的正极、固态电解质薄膜、步骤3c)含有可凝胶体系的负极通过叠片或者卷绕等方式组装成电池；或者，将步骤2c)的含有可凝胶体系的正极、固态电解质薄膜、步骤3c)含有可凝胶体系的负极在电池压制模具中压制成一体，形成全固态锂离子二次电池。
根据本发明，所述步骤4c’)中，所述组装的方法为本领域技术人员的常规选择，采用任一种方法可以制备得到注液前全固态锂离子二次电池即可；示例性地，将步骤2c)的含有可凝胶体系的正极、固态电解质薄膜、步骤3c)含有可凝胶体系的负极通过叠片或者卷绕等方式组装成全固态锂离子二次电池；或者，将步骤2c)的含有可凝胶体系的正极、固态电解质薄膜、步骤3c)含有可凝胶体系的负极在电池压制模具中压制成一体，形成全固态锂离子二次电池。
根据本发明，所述步骤4c”)中，所述组装的方法为本领域技术人员的常规选择，采用任一种方法可以制备得到注液前全固态锂离子二次电池即可；示例性地，将步骤2c)的含有可凝胶体系的正极、隔膜、步骤3c)含有可凝胶体系的负极通过叠片或者卷绕等方式组装成全固态锂离子二次电池；或者，将步骤2c)的含有可凝胶体系的正极、隔膜、步骤3c)含有可凝胶体系的负极 在电池压制模具中压制成一体，形成全固态锂离子二次电池。
根据本发明的第一方面到第三方面，所述可凝胶体系中还可以包括无机纳米颗粒、其他溶剂和/或电解液、聚酯或其共混物等添加剂中的至少一种。
根据本发明，在步骤1a)-步骤1c)中，所述可凝胶化体系中，各组分的重量百分比之和为100wt％。
根据本发明，所述可凝胶体系经凝胶后，可制备得到固态电解质，所述锂盐的质量百分含量大于等于5wt％且小于等于60wt％；所述醚类化合物的质量百分含量大于等于20wt％且小于等于60wt％；所述其他电解液或其溶剂的质量百分含量大于等于20wt％小于等于75wt％，所述无机纳米颗粒的质量百分含量大于等于0wt％且小于等于30wt％，所述添加剂的质量百分含量大于等于0wt％且小于等于30wt％。
优选地，所述可凝胶体系经凝胶后，可制备得到固态电解质，所述锂盐的质量百分含量大于等于10wt％且小于等于40wt％；所述醚类化合物的质量百分含量大于等于20wt％且小于等于60wt％；所述其他电解液或其溶剂的质量百分含量大于等于20wt％且小于等于60wt％，所述无机纳米颗粒的质量百分含量大于0wt％且小于等于20wt％，所述添加剂的质量百分含量大于0wt％且小于等于20wt％。
根据本发明，所述可凝胶体系经凝胶后，可制备得到凝胶电解质，所述锂盐的质量百分含量大于等于5wt％且小于等于60wt％；所述醚类化合物的质量百分含量大于60wt％且小于等于90wt％；所述其他电解液或其溶剂的质量百分含量大于等于5wt％小于等于30wt％，所述无机纳米颗粒的质量百分含量大于等于0wt％且小于等于30wt％，所述添加剂的质量百分含量大于等于0wt％且小于等于30wt％。
优选地，所述可凝胶体系经凝胶后，可制备得到凝胶电解质，所述的可凝胶化体系中，所述锂盐的质量百分含量大于等于10wt％且小于等于40wt％；所述醚类化合物的质量百分含量大于60wt％且小于等于85wt％；所述其他电解液或其溶剂的质量百分含量大于等于5wt％且小于等于30wt％，所述无机纳米颗粒的质量百分含量大于0wt％且小于等于20wt％，所述添加剂的质量百分含量大于0wt％且小于等于20wt％。
根据本发明的第一方面至第三方面，所述可凝胶化体系的制备方法具体包括如下步骤：
将醚类化合物、锂盐以及任选地其他溶剂和/或电解液、任选地无机纳米颗粒、任选地添加剂混合，搅拌下得到混合溶液，即所述可凝胶化体系。
优选地，所述可凝胶化体系的制备方法具体包括如下步骤：
将醚类化合物加入锂盐中，搅拌下得到锂盐的醚类化合物溶液，任选地将其他溶剂和/或电解液和/或无机纳米颗粒和/或添加剂加入到锂盐的直链醚类化合物溶液，即所述可凝胶化体系。
根据本发明，对所述醚类化合物、锂盐、任选地无机纳米颗粒、任选地其他溶剂和/或电解液和任选地添加剂进行预先除水处理；优选地，采用分子筛和/或真空干燥的方法对所述醚类化合物、锂盐、任选地无机纳米颗粒、任选地其他溶剂和/或电解液和任选地添加剂进行预先除水处理。
根据本发明第一方面至第三方面，所述正极或负极的压制成一体的过程是在干燥的条件下进行的。
根据本发明第一方面至第三方面，所述的涂覆选自喷涂、刮刀涂覆、涂布辊、涂布刷等方式中的至少一种。
根据本发明第二方面，所述的浸润时间和浸润温度没有限制；当所述浸润温度为低于所述可凝胶化体系形成的固态电解质的转变温度时，所述浸润时间优选为小于所述可凝胶化体系形成固态电解质的时间；或者，所述浸润温度为高于所述可凝胶化体系形成的固态电解质的转变温度时， 本领域技术人员可以理解，所述可凝胶化体系不能形成凝胶，故所述浸润时间没有限制。
根据本发明，对所述导电剂、粘结剂、负极集流体、负极材料、隔膜、正极材料和正极集流体的选择没有限定，本领域技术人员可以理解，适用于本发明所述的柔性全固态锂离子二次电池即可。
优选地，所述导电剂选自导电石墨、乙炔黑、Super P、碳纳米管、石墨烯、氧化石墨烯、导电炭黑、科琴黑、石墨(KS、SO)、SFG-6中的至少一种。
优选地，所述粘结剂选自聚偏氟乙烯(PVDF)、丙烯酸酯及其衍生物、环糊精及其衍生物、卡里克斯芳烃及其衍生物、羧甲基纤维素以及衍生物、丙烯酸及其衍生物、氨基树脂及其衍生物、聚酰亚胺、有机氟聚合物、有机聚硅氧烷中的至少一种。
优选地，所述负极集流体选自铜箔、铜合金、银箔、不锈钢片、碳材料中的至少一种。
优选地，所述负极材料选自金属类负极材料(如金属锂、锂合金等)、无机非金属类负极材料(如碳材料、硅材料以及其他不同非金属的复合材料等)中的至少一种。
优选地，所述隔膜选自本发明所述的可凝胶体系制备得到的固态电解质隔膜或聚烯烃多孔膜，如聚乙烯微孔膜、聚丙烯微孔膜、三层复合隔膜中的至少一种。
优选地，所述正极材料选自锂钴氧化物、锂镍氧化物、锂锰氧化物、三元材料镍钴锰氧、纳米正极材料(如纳米结晶尖晶石LiMn 2O 4、钡镁锰矿型MnO 2纳米纤维、聚吡咯包覆尖晶石型LiMn 2O 4纳米管、聚吡咯/V 2O 5纳米复合材料等)、共混电极、钒氧化物、层状化合物(如经过苯胺改性后的氧基氯化铁等)中的至少一种。
优选地，所述正极集流体选自铝箔、铝合金中的至少一种。
根据本发明，上述步骤中，所述静置的时间为所使用的可凝胶化体系转变为固态电解质的形成时间，所述静置的温度为室温。
本发明的第四方面是提供一种柔性全固态锂离子二次电池，所述锂离子二次电池是采用上述任一种方法制备得到的。
根据本发明，所述锂离子二次电池包括锂离子电池、锂硫电池、锂空气电池等等。
目前使用的固态锂离子二次电池中，往往是固态电解质代替常规的液体电解液，甚至是替换了隔膜，然而这样制备得到的固态锂离子二次电池中，由于固态电解质仅能与电极表面接触，故只能在电极表面形成导电网络，而无法在电极内部形成导电网络，不仅如此，没有与电极接触的内部还会形成巨大的界面电阻，正负极内部的活性材料不能得到充分的利用，严重限制了锂离子二次电池的电化学性能、循环稳定性和循环寿命。
本发明采用一种可凝胶体系作为锂离子二次电池用固态电解质，在其形成固态电解质之前，可通过替代原有正极和负极中的粘结剂的方式，或通过浸润或者采用涂覆的方式将锂离子二次电池用正极和负极置于未形成固态电解质的可凝胶体系中，或通过直接将可凝胶体系加入到锂离子二次电池中的方式，使得正、负极表面及内部被可凝胶体系浸润，并进入到所述正、负极内部的空隙中，待可凝胶体系经过固化之后，其可原位在正、负极表面及其内部形成固态电解质。
本发明中，所述的“全固态”包括全固态状态，即所述电解液体系内不含有任何可以流动状态的液体；还包括半固态状态，即在电解液体系中含有一定的液体组分，但是得到的电解液是几乎不能流动的。
本发明的有益效果：
本发明提供了一种柔性全固态锂离子二次电池及其制备方法，所述柔性全固态锂离子二次电池是通过替代原有正极和负极中的粘结剂的方式，或通过浸润或者采用涂覆的方式将锂离子二次电池用正极和负极置于未形成固态电解质的可凝胶体系中，或通过直接将可凝胶体系加入到锂离 子二次电池中的方式，使得正负极表面及内部被可凝胶体系浸润，并进入到所述正负极内部的空隙中，待可凝胶体系达到形成固态电解质的经过固化之后，其可原位在正负极片表面及其内部形成固态电解质，采用所述方法制备得到的锂离子二次电池在整个电池内部即可形成导电网路，不仅可以极大地减小锂离子二次电池的内部的电阻，从而提高导电率和倍率性能，还可以解决液态电解液带来的安全隐患。
附图说明
图1为实施例2中装配方式得到电池的倍率性能图。
图2为实施例4中装配方式得到电池的倍率性能图。
图3为实施例6中装配方式得到电池的倍率性能图。
图4为实施例7中装配方式得到电池的倍率性能图。
图5为实施例8中装配方式得到电池的倍率性能图。
具体实施方式
[锂盐]
本发明的可凝胶化体系中包括锂盐，所述锂盐可选自六氟磷酸锂、四氟硼酸锂、六氟砷酸锂、高氯酸锂、三氟甲基磺酸锂、全氟丁基磺酸锂、双三氟甲烷磺酰亚胺锂、双氟磺酰亚胺锂、铝酸锂、氯铝酸锂、氟代磺酰亚胺锂、氯化锂和碘化锂中的一种或多种；优选地，所述锂盐选自六氟磷酸锂、高氯酸锂等中的一种或两种。
[醚类化合物]
本发明的可凝胶化体系中包括醚类化合物，所述醚类化合物选自环状醚类化合物或直链醚类化合物中的至少一种。
[环状醚类化合物]
本发明的醚类化合物可选自环状醚类化合物，所述环状醚类化合物选自含有一个氧、两个氧、三个氧或更多氧的环状醚类化合物。
本发明中，所述环状醚类化合物选自至少含有1个氧原子的C 2～C 20环烷烃(即环状结构中的碳原子数为2-20个)或至少含有1个氧原子的C 3～C 20环烯烃(即环状结构中的碳原子数为3-20个)，其中至少含有一个碳碳双键。
本发明中，所述环烷烃或环烯烃为单环、稠合环(如双环)、螺环或桥环；当所述环烷烃或环烯烃为螺环或桥环且含有两个以上氧原子时，氧原子可以在一个环上，也可以在多个环上。
本发明中，所述环状醚类化合物选自至少含有1个氧原子的C 2～C 20的单环烷烃，优选选自至少含有1个氧原子的C 3～C 20的单环烷烃，例如为下述第一类化合物中的一种：
Figure PCTCN2018088495-appb-000001
本发明中，所述环状醚类化合物选自至少含有1个氧原子的C 4～C 20的稠合环烷烃，例如为下 述第二类化合物中的一种：
Figure PCTCN2018088495-appb-000002
本发明中，所述环状醚类化合物选自至少含有1个氧原子的C 4～C 20的桥环烷烃，例如为下述第三类化合物中的一种：
Figure PCTCN2018088495-appb-000003
本发明中，所述环状醚类化合物选自至少含有1个氧原子的C 4～C 20的螺环烷烃，例如为下述第四类化合物中的一种：
Figure PCTCN2018088495-appb-000004
Figure PCTCN2018088495-appb-000005
本发明中，上述四类化合物中的环结构上的C-C键至少有一个被C＝C替代且为稳定存在的化合物，则为上述的至少含有1个氧原子的C 3～C 20环烯烃，为本发明优选的环状醚类化合物的一种。
本发明中，所述环烷烃或环烯烃为单环或稠合环时，其所述环上的碳原子可以被1个或多个R1基团取代；所述环烷烃或环烯烃为桥环时，其非桥连环碳原子可以被1个或多个R1基团取代；所述环烷烃或环烯烃为螺环时，其环上碳原子上可以被1个或多个R1基团取代；所述R1基团选自下述基团的一种：烷基、烯基、炔基、烷氧基、烷硫基、卤代烷基、环烷基、环烷基氧基、环烷基硫基、杂环基、杂环基氧基、杂环基硫基、芳基、芳基氧基、杂芳基、杂芳基氧基、羟基、巯基、硝基、羧基、氨基、酯基、卤素、酰基、醛基。
本发明中，所述含有一个氧的环状醚类化合物选自取代或未取代的氧杂环丁烷、取代或未取代的四氢呋喃、取代或未取代的四氢吡喃；所述取代基的个数可以是一个或多个；所述取代基为上述的R1基团。
本发明中，所述含有一个氧的环状醚类化合物选自3,3-二氯甲基氧杂环丁烷、2-氯甲基氧杂环丁烷、2-氯甲基环氧丙烷、1,4-环氧环己烷、1,3-环氧环己烷、四氢呋喃、2-甲基四氢呋喃、3-甲基四氢呋喃、四氢吡喃、2-甲基四氢吡喃、氧杂环庚烷、氧杂环辛烷、氧杂环壬烷或氧杂环癸烷。
本发明中，所述含有两个氧的环状醚类化合物选自取代或未取代的1,3-二氧戊环(DOL)、取代或未取代的1,4-二氧六环；所述取代基的个数可以是一个或多个；所述取代基为上述的R1基团。
本发明中，所述含有三个氧的环状醚类化合物选自取代或未取代的三聚甲醛；所述取代基的个数可以是一个或多个；所述取代基为上述的R1基团。
本发明中，所述含有更多氧的醚类化合物选自取代或未取代的18-冠-6、取代或未取代的12-冠-4、取代或未取代的24-冠-8；所述取代基的个数可以是一个或多个；所述取代基为上述的R1基团。
[直链醚类化合物]
本发明中，所述直链醚类化合物的通式如式(1)所示：
R 1—O—(R 2—O) n—R 3      式(1)
其中，n为大于0的整数；
R 2选自直链或支链的C 1-C 6的亚烷基、直链或支链的C 2-C 6的亚烯基；所述R 2上的碳原子上的H可以被下述基团中的至少一种取代：烯基、炔基、烷氧基、烷硫基、环烷基、环烷基氧基、环烷基硫基、杂环基、杂环基氧基、杂环基硫基、芳基、芳基氧基、杂芳基、杂芳基氧基、羟基、巯基、硝基、羧基、氨基、酯基、卤素、酰基、醛基；
R 1和R 3相同或不同，彼此独立地选自氢原子、烷基、环烷基、杂环基、烯基、炔基中的一种或多种；所述R 1和R 3的碳原子上的H可以被下述基团中的至少一种取代：烯基、炔基、烷氧基、烷硫基、环烷基、环烷基氧基、环烷基硫基、杂环基、杂环基氧基、杂环基硫基、芳基、芳基氧基、羟基、巯基、硝基、羧基、氨基、酯基、卤素、酰基、醛基。
优选地，n为1～6之间的整数；
R 2选自直链或支链的C 1-C 4的亚烷基、直链或支链的C 2-C 6的亚烯基；
R 1和R 3相同或不同，彼此独立地选自直链或支链的C 1-C 6的烷基。
更优选地，R 2选自甲基、乙基、丙基、异丙基、丁基、异丁基、乙烯基；
R 1和R 3相同或不同，彼此独立地选自甲基、乙基、丙基。
还优选地，所述直链醚类化合物选自乙二醇二甲醚，乙二醇二乙醚，乙二醇甲乙醚，1,4-丁二醇二甲醚，1,4-丁二醇二乙醚，1,4-丁二醇甲乙醚等中的一种或多种。
本发明中，所述直链醚类化合物例如为下述化合物中的一种：
Figure PCTCN2018088495-appb-000006
[可凝胶化体系]
本发明中，所述可凝胶体系包括锂盐和醚类化合物，所述醚类化合物选自环状醚类化合物。
本发明中，所述可凝胶体系包括锂盐、醚类化合物、以及其他溶剂和/或电解液，所述醚类化合物选自环状醚类化合物。
本发明中，所述可凝胶体系包括锂盐、醚类化合物和无机纳米颗粒，所述醚类化合物选自环状醚类化合物。
本发明中，所述可凝胶体系包括锂盐、醚类化合物、其他溶剂和/或电解液、以及无机纳米颗粒，所述醚类化合物选自环状醚类化合物。
本发明中，所述可凝胶体系包括锂盐、醚类化合物和添加剂，所述醚类化合物选自环状醚类化合物。
本发明中，所述可凝胶体系包括锂盐和醚类化合物，所述醚类化合物选自直链醚类化合物。
本发明中，所述可凝胶体系包括锂盐、醚类化合物、以及其他溶剂和/或电解液，所述醚类化合物选自直链醚类化合物。
本发明中，所述可凝胶体系包括锂盐、醚类化合物和无机纳米颗粒，所述醚类化合物选自直 链醚类化合物。
本发明中，所述可凝胶体系包括锂盐、醚类化合物、其他溶剂和/或电解液、以及无机纳米颗粒，所述醚类化合物选自直链醚类化合物。
[无机纳米颗粒]
本发明中，所述无机纳米颗粒选自二氧化硅、氧化铝、氮化硅、氧化锌、二氧化钛、碳化硅、硅酸盐、碳酸钙、硫酸钡、黏土、四氧化三铁、氧化铈、纳米碳材料、氧化铁等中的一种或多种；优选地，所述无机纳米颗粒选自二氧化硅、氧化铝、二氧化钛、氧化锌中的一种或多种。
[其他溶剂和/或电解液]
本发明中，所述可凝胶化体系还包括其他溶剂和/或电解液，所述其他溶剂和/或电解液包括用于锂硫电池的电解液、用于锂硫电池的电解液的溶剂、用于锂离子电池的电解液、用于锂离子电池的电解液的溶剂、用于锂空气电池电解液或其溶剂中的至少一种。
本发明中，所述用于锂空气电池电解液或其溶剂包括醚类电解液及其溶剂、酯类电解液及其溶剂、酰胺类电解液及其溶剂、腈类电解液及其溶剂以及砜类电解液及其溶剂。
本发明中，所述用于锂离子电池的电解液选自含有用于锂离子电池的锂盐的酯类混合液，例如含1M六氟磷酸锂(LiPF 6)的碳酸乙烯酯(EC)和碳酸二甲酯(DMC)的混合液，其中，所述碳酸乙烯酯(EC)和碳酸二甲酯(DMC)的体积比为1:1。
本发明中，所述用于锂离子电池的电解液的溶剂选自用于锂离子电池的电解液的环状非水有机溶剂和用于锂离子电池的电解液的链状非水有机溶剂中的至少一种。
本发明中，所述用于锂离子电池的电解液的环状非水有机溶剂选自碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、氟代碳酸乙烯酯(FEC)、γ-丁内酯(GBL)、亚硫酸乙烯酯(ES)、亚硫酸丙烯酯(PS)、环丁砜(SL)、碳酸甘油酯(GC)中的至少一种。
本发明中，所述用于锂离子电池的电解液的链状非水有机溶剂选自碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、碳酸甲丙酯(MPC)、碳酸二丙酯(DPC)、碳酸乙丙酯(EPC)、乙酸乙酯(EA)、乙酸丙酯(PA)、丙酸乙酯(EP)、丁酸乙酯(EB)、丁酸甲酯(MB)、亚硫酸二甲酯(DMS)、亚硫酸二乙酯(DES)、亚硫酸甲乙酯(EMS)、二甲基砜(MSM)、二甲基亚砜(DMSO)中的至少一种。
本发明中，所述用于锂硫电池的电解液选自含有锂盐的醚类混合液，例如：含有1M双三氟甲烷磺酰亚胺锂(LiTFSI)的1,3-二氧戊环(DOL)和乙二醇二甲醚(DME)的混合液，其中，所述1,3-二氧戊环(DOL)和乙二醇二甲醚(DME)的体积比为1:1。
本发明中，所述用于锂硫电池的电解液的溶剂选自1,3-二氧戊环、1,2-二甲氧基乙烷、三乙二醇二甲醚、四乙二醇二甲醚、氟代碳酸乙烯酯、聚乙二醇硼酸酯、1,1’,2,2’-四氟乙基-2,2’,3,3’-四氟丙烯醚中的一种或多种。
本发明中，所述酯类电解液选自含有锂盐的酯类混合液，例如含1M六氟磷酸锂(LiPF 6)的碳酸乙烯酯(EC)和碳酸二甲酯(DMC)的混合液，其中，所述碳酸乙烯酯(EC)和碳酸二甲酯(DMC)的体积比为1:1。
本发明中，所述酯类电解液的溶剂选自酯类环状非水有机溶剂和酯类链状非水有机溶剂中的至少一种。
本发明中，所述酯类环状非水有机溶剂选自碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、氟代碳酸乙烯酯(FEC)、γ-丁内酯(GBL)、亚硫酸乙烯酯(ES)、亚硫酸丙烯酯(PS)、碳酸甘油酯(GC)中的至少一种。
本发明中，所述链状非水有机溶剂选自碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸甲乙 酯(EMC)、碳酸甲丙酯(MPC)、碳酸二丙酯(DPC)、碳酸乙丙酯(EPC)、乙酸乙酯(EA)、乙酸丙酯(PA)、丙酸乙酯(EP)、丁酸乙酯(EB)、丁酸甲酯(MB)、亚硫酸二甲酯(DMS)、亚硫酸二乙酯(DES)、亚硫酸甲乙酯(EMS)中的至少一种。
本发明中，所述醚类电解液选自含有锂盐的醚类混合液，例如：含有1M双三氟甲烷磺酰亚胺锂(LiTFSI)的1,3-二氧戊环(DOL)和乙二醇二甲醚(DME)的混合液，其中，所述1,3-二氧戊环(DOL)和乙二醇二甲醚(DME)的体积比为1:1。
本发明中，所述醚类电解液的溶剂选自1,3-二氧戊环、1,2-二甲氧基乙烷、三乙二醇二甲醚、四乙二醇二甲醚、氟代碳酸乙烯酯、聚乙二醇硼酸酯、1,1’,2,2’-四氟乙基-2,2’,3,3’-四氟丙烯醚中的一种或多种。
本发明中，所述酰胺类电解液选自含有锂盐的酰胺类混合液，例如：含1M三氟甲基磺酸锂的N,N-二甲基乙酰胺溶液。
本发明中，所述酰胺类电解液的溶剂选自含有酰胺基团的化合物；
优选地，所述酰胺类电解液的溶剂选自C 1～C 20的烷基酰胺、C 1～C 20的烯酰胺腈、C 1～C 20的炔基酰胺、C 1～C 20的卤代烷基酰胺、C 1～C 20的卤代烯基酰胺、C 1～C 20的卤代炔基酰胺、C 7～C 20的芳基酰胺、C 1～C 20的环氧基酰胺中的至少一种。
优选地，所述酰胺类电解液的溶剂选自N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、苯甲酰胺、甲酰胺、乙酰胺、丁二酰亚胺、邻苯二甲酰亚胺、N-甲基对甲苯磺酰胺、N-甲基乙酰胺、3-氨基-6-甲基苯磺酰胺、2,2,2-三氯乙酰胺、苄酯N-乙基对甲苯磺酰胺、3-氨基-2,2-二甲基丙酰胺、芥酸酰胺、N-乙基-5-甲基-2-(1-甲基乙基)环己甲酰胺、4-甲氧基苯甲酰胺、2,4-二羟基苯甲酰胺、N,N-二乙基-2-氯乙酰胺、N-丁基苯磺酰胺、N-乙基乙酰胺、氯乙酰胺、盐酸盐N-(2-氯苯基)乙酰胺、N,N'-乙撑双硬脂酰胺、戊酰胺、2-羟基异丁酰胺、乙氧酰胺、苯甲酯肉桂酰胺、L-(+)-樟脑内磺酰胺、丙二酰胺、磺酰胺、环丙磺酰胺、2-乙磺酰基咪唑并[1,2-a]吡啶-3-磺酰胺、N,N-二乙基乙酰胺、4-氯硫代苯甲酰胺、N,N’-二甲基草酰胺、N-甲氧基-N-甲基乙酰胺、苯甲酰胺、N-甲基己内酰胺、(S)-(-)-叔丁基亚磺酰胺、3-氨基-N-甲基苯甲酰胺、N,N’-亚甲基双丙烯酰胺、2,2-二溴-3-次氮基丙酰胺、N,N-二乙基十二酰胺、肼甲酰亚胺酰胺、一氯化氢硫代乙酰胺、氰乙酰胺、丙酰胺、苯甲酰胺、2-硝基苯磺酰胺、对氨基苯甲酰胺、异丁酰胺、己内酰胺、邻甲酸甲酯苯磺酰胺、N,N-二甲基乙酰胺、N-甲基甲酰胺、N-叔丁基丙烯酰胺、6-甲基烟酰胺、N,N-二甲基磺酰胺、2,3-二溴丙酰胺、2-氨基-5-甲基苯甲酰胺、左旋樟脑磺内酰胺、DL-氨基己内酰胺硬脂酰胺、1,1-环己基二乙酸单酰胺、环丙酰胺、对硝基苯甲酰胺、4-(2-氨乙基)苯磺酰胺、2-甲基-5-硝基苯磺酰胺、3,5-二羟基苯甲酰胺、2-丙烯酰胺基-2-甲基丙磺酸-N-甲基丁二酰胺、N,2,3-三甲基-2-异丙基丁酰胺、N,N-二甲基丙酰胺、N-乙烯基己内酰胺、2-碘乙酰胺、邻氨基苯磺酰胺、2,4-二氯-5-磺酰胺基苯甲酸-N-苯基马来酰亚胺、N-乙基马来酰亚胺、5-氯-2,4-二磺酰胺基苯胺邻氯苯磺酰胺、N,N-二甲基甘氨酰胺、2-氨基苯酚-5-(N,N-二甲基)磺酰胺、4-氨基-3,5-二硝基苯甲酰胺、4-氨基-N-甲基苯甲酰胺、2-苯乙酰胺、N-(叔丁氧羰基)对甲苯磺酰胺、4-氟苯甲酰胺、肟2-氨基丙二酰胺、双(四亚甲基)氟代甲酰胺、N-羟基-异丁酰胺、硫代丙酰胺、乙酯1-((氰基-1-甲基乙基)偶氮)甲酰胺、肉桂酰胺、4-氨基苯基-N-甲基甲烷磺酰胺、4-溴-3-氟苯磺酰胺、2,6-二氟苯磺酰胺、2-溴苯磺酰胺、4-氟苯磺酰胺、4-三氟甲氧基苯磺酰胺、4-氯苯磺酰胺、2,5-二氟苯磺酰胺、三氟甲磺酰胺、N-[双(甲硫基)亚甲基]对甲苯磺酰胺、4-氯-3-硝基-5-磺酰胺基苯甲酸、N-甲基二乙酰胺N-苯亚甲基苯磺酰胺、2-甲氧基-5-磺酰胺、3,5-二氯苯磺酰胺、2-氟苯磺酰胺、4-溴-2-氯苯磺胺、5-氯-2-氟苯磺酰、胺对甲氧基苯磺酰胺、4-氯水杨酸-5-磺酰胺、2-氨基-N-乙基-N-苯基苯磺酰胺、2-溴-4-氟苯磺酰胺、4-氟-2-甲基苯磺酰胺、2-氰基苯磺酰胺、4-[2-(5-氯-2-甲氧基苯甲酰氨基)乙基]苯磺 酰胺、3,4-二氟苯磺酰胺、DL-氨基己内酰胺、2,4,6-三氯苯磺酰胺、环丙烷磺酰胺、4-溴-3-(三氟甲基)苯磺胺、N-(4-氨基丁基)-乙酰胺神经酰胺、N-[(1R)-2-(3-氨基磺酰基-4-甲氧基)-1-甲基]乙酰胺、N-苄基-N-亚硝基-对甲苯磺酰胺、N-(2-氨基乙基)-4-甲基苯磺酰胺、(1R)-10-樟脑磺酰胺、4-氨基-6-(三氟甲基)苯-1,3-二磺酰胺、2-溴-4-(三氟甲基)苯磺酰胺、3-氟-4-甲基甲苯磺酰胺、2-溴-5-(三氟甲基)苯磺酰胺、萘-2-磺酰胺、(1S)-10-樟脑磺酰胺、(S)-(+)-对甲基苯亚磺酰胺、(1R)-反-N,N’-1,2-环己二基双(1,1,1-三氟甲磺酰胺)、N-(2-氟苯基)甲磺酰胺、(S)-N-(-)-对甲苯基亚磺酰基色胺、N-乙酰氧基-N-乙酰基-4-氯苯磺酰胺、2-(三甲基硅基)乙磺酰胺、N-(4-氨基苯)-磺酰胺-4-甲基苯(R)-(-)-4-甲基苯亚磺酰胺、N-乙基对甲苯磺酰胺、(R,R)-(+)-N,N’-双(Α-甲基苄基)磺酰胺、(S)-(-)-N-[1-(羟甲基)-2-苯基乙基]-4-甲基苯磺酰胺、环丙酰胺、2-氯-4-氟-5-氨磺酰基苯甲酸N-亚苄基-P,P-二苯基次膦酸酰胺、N-(4-氯苯亚甲基)-4-甲苯磺酰胺中至少一种。
本发明中，所述腈类电解液选自含有锂盐的腈类混合液，例如：含1M高氯酸锂的乙腈溶液。
本发明中，所述腈类电解液的溶剂选自含有腈基的化合物；
优选地，所述腈类电解液的溶剂选自C 1～C 20的烷基腈、C 1～C 20的烯基腈、C 1～C 20的炔基腈、C 1～C 20的卤代烷基腈、C 1～C 20的卤代烯基腈、C 1～C 20的卤代炔基腈、C 7～C 20的芳基腈、C 1～C 20的环氧基腈中的至少一种。
优选地，所述腈类电解液的溶剂选自乙腈、丁腈。
本发明中，砜类电解液选自含有锂盐的砜类混合液，例如：含1M高氯酸锂的二甲亚砜(DMSO)溶液。
本发明中，砜类电解液的溶剂选自含有砜基的化合物；
优选地，所述腈类电解液的溶剂选自C 1～C 20的烷基砜、C 1～C 20的烯基砜、C 1～C 20的炔基砜、C 1～C 20的卤代烷基砜、C 1～C 20的卤代烯基砜、C 1～C 20的卤代炔基砜、C 7～C 20的芳基砜、C 1～C 20的环氧基砜中的至少一种。
优选地，所述砜类电解液的溶剂选自环丁砜(SL)、二甲亚砜。
[添加剂]
本发明中，所述添加剂选自聚酯或其共混物中的一种或几种；其中，所述聚酯由多元酸或酸酐与多元醇缩聚而得；所述多元酸选自二元酸、三元酸或更多元酸，所述多元醇选自二元醇、三元醇或更多元醇。
本发明中，所述多元酸选自取代或未取代的下述多元酸中的一种或两种或三种或多于三种：乙二酸，丙二酸，丁二酸，丁烯二酸，戊二酸，己二酸，庚二酸，辛二酸，癸二酸，壬二酸，丙三酸；所述取代基的个数可以是一个或多个；当所述取代基为多个时，其可成环；所述取代基为烷基、环烷基、芳基、羟基、氨基、酯基、卤素、酰基、醛基、巯基、烷氧基等中的一种或多种。
本发明中，所述酸酐选自取代或未取代的下述酸酐中的一种或两种或三种或多于三种：乙二酸酐，丙二酸酐，丁二酸酐，丁烯二酸酐，戊二酸酐，己二酸酐，庚二酸酐，辛二酸酐，癸二酸酐，壬二酸酐，六氢苯酐，四氢苯酐；所述取代基的个数可以是一个或多个；当所述取代基为多个时，其可成环；所述取代基为烷基、环烷基、芳基、羟基、氨基、酯基、卤素、酰基、醛基、巯基、烷氧基等中的一种或多种。
本发明中，所述多元醇选自取代或未取代的下述多元醇中的一种或几种：丙二醇，丁二醇，戊二醇，己二醇，庚二醇，辛二醇，壬二醇，癸二醇，聚乙二醇，丙三醇；所述取代基的个数可以是一个或多个；当所述取代基为多个时，其可成环；所述取代基为烷基、环烷基、芳基、羟基、氨基、酯基、卤素、酰基、醛基、巯基、烷氧基等中的一种或多种。
本发明中，所述多元醇选自聚乙二醇，或者聚乙二醇与下述多元醇中的一种或几种的组合： 丙二醇，丁二醇，戊二醇，己二醇，庚二醇，辛二醇，壬二醇，癸二醇。
本发明中，所述聚乙二醇的聚合度为100-1000，优选为150-800，还优选为200-600。其中，所述聚乙二醇与其他多元醇的重量比为1:(0～1)，优选为1:(0～0.9)，还优选为1:(0～0.8)。
[术语和定义]
除非另有说明，本申请说明书和权利要求书中记载的基团和术语定义，包括其作为实例的定义、示例性的定义、优选的定义、表格中记载的定义、实施例中具体化合物的定义等，可以彼此之间任意组合和结合。这样的组合和结合后的基团定义及化合物结构，应当属于本申请保护的范围内。
本发明中的术语“凝胶”具有本领域公知的含义，术语“凝胶化”也具有本领域公知的含义。
本发明中的可凝胶化的聚合物和/或可凝胶化的预聚物是指在一定条件下可以形成凝胶或可以凝胶化的聚合物和/或预聚物。
不限制的，本发明所述可凝胶化的聚合物和/或可凝胶化的预聚物可选自聚氧化乙烯(PEO)、聚乙二醇(PEG)、聚偏氟乙烯(PVDF)、聚氯乙烯(PVC)、聚苯乙烯(PS)、聚丙烯腈(PAN)、聚乙酸乙酯(PVAC)、聚乙烯基吡咯烷酮(PVP)、聚二乙烯基硫(PVS)、聚三亚甲基碳酸酯(PTMC)、聚甲基丙烯酸甲酯(PMMA)、聚乙二醇二甲基丙烯酸酯(PEGDM)、聚氧化丙烯(PPO)、聚二甲基硅氧烷(PDMSO)或其预聚物，或其共聚物，或其共混物中的一种或多种。
本申请说明书和权利要求书记载的数值范围，当该数值范围被定义为“整数”时，应当理解为记载了该范围的两个端点以及该范围内的每一个整数。例如，“0～10的整数”应当理解为记载了0、1、2、3、4、5、6、7、8、9和10的每一个整数。当该数值范围被定义为“数”时，应当理解为记载了该范围的两个端点、该范围内的每一个整数以及该范围内的每一个小数。例如，“0～10的数”应当理解为不仅记载了0、1、2、3、4、5、6、7、8、9和10的每一个整数，还至少记载了其中每一个整数分别与0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9的和。
本发明使用的“卤素”指氟、氯、溴和碘。
本发明单独使用或用作后缀或前缀的“烷基”意在包括具有1至20个，优选1-6个碳原子(或若提供了碳原子的具体数目，则指该具体数目)的支链和直链饱和脂族烃基。例如，“C 1-6烷基”表示具有1、2、3、4、5或6个碳原子的直链和支链烷基。烷基的实例包括但不限于甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、戊基和己基。
本发明单独使用或用作后缀或前缀的“卤代烷基”或“烷基卤化物”意在包括具有至少一个卤素取代基且具有1-20个，优选1-6个碳原子(或若提供了碳原子的具体数目，则指该具体数目)的支链和直链饱和脂族烃基。例如，“C 1-10卤代烷基”表示具有0、1、2、3、4、5、6、7、8、9、10个碳原子的卤代烷基。卤代烷基的实例包括但不限于氟甲基、二氟甲基、三氟甲基、氯氟甲基、1-氟乙基、3-氟丙基、2-氯丙基、3,4-二氟丁基等。
本发明单独使用或用作后缀或前缀的“烯基”意在包括具有2至20个，优选2-6个碳原子(或若提供了碳原子的具体数目，则指该具体数目)的包含烯基或烯烃的支链和直链脂族烃基。例如，“C 2-6烯基”表示具有2、3、4、5或6个碳原子的烯基。烯基的实例包括但不限于乙烯基、烯丙基、1-丙烯基、1-丁烯基、2-丁烯基、3-丁烯基、2-甲基丁-2-烯基、3-甲基丁-1-烯基、1-戊烯基、3-戊烯基和4-己烯基。
本发明单独使用或用作后缀或前缀的“炔基”意在包括具有2至20个，优选2-6个碳原子(或若提供了碳原子的具体数目，则指该具体数目)的包含炔基或炔烃的支链和直链脂族烃基。例如乙炔基、丙炔基(例如l-丙炔基、2-丙炔基)、3-丁炔基、戊炔基、己炔基和1-甲基戊-2-炔基。
本发明使用的术语“芳基”指由5至20个碳原子构成的芳族环结构。例如：包含5、6、7和8个 碳原子的芳族环结构可以是单环芳族基团例如苯基；包含8、9、10、11、12、13或14个碳原子的环结构可以是多环的例如萘基。芳环可在一个或多个环位置取代有上述那些取代基。术语“芳基”还包括具有两个或更多个环的多环环系，其中两个或更多个碳为两个相邻环所共有(所述环为“稠环”)，其中至少一个环是芳族的且其它环例如可以是环烷基、环烯基、环炔基、芳基和/或杂环基。多环的实例包括但不限于2,3-二氢-1,4-苯并二氧杂环己二烯和2,3-二氢-1-苯并呋喃。
本发明使用的术语“环烷基”意在包括具有指定数目碳原子的饱和环基。这些术语可包括稠合或桥接的多环系统。环烷基在其环结构中具有3至40个碳原子。在一个实施方案中，环烷基在其环结构中具有3、4、5或6个碳原子。例如，“C 3-6环烷基”表示例如环丙基、环丁基、环戊基或环己基的基团。
本发明使用的“杂芳基”指具有至少一个环杂原子(例如硫、氧或氮)的杂芳族杂环。杂芳基包括单环系统和多环系统(例如具有2、3或4个稠环)。杂芳基的实例包括但不限于吡啶基、嘧啶基、吡嗪基、哒嗪基、三嗪基、呋喃基、喹啉基、异喹啉基、噻吩基、咪唑基、噻唑基、吲哚基、吡咯基、噁唑基、苯并呋喃基、苯并噻吩基、苯并噻唑基、异噁唑基、吡唑基、三唑基、四唑基、吲唑基、1,2,4-噻二唑基、异噻唑基、苯并噻吩基、嘌呤基、咔唑基、苯并咪唑基、苯并噁唑基、氮杂苯并噁唑基、咪唑并噻唑基、苯并[1,4]二氧杂环己烯基、苯并[1,3]二氧杂环戊烯基等。在一些实施方案中，杂芳基具有3至40个碳原子且在其它实施方案中具有3至20个碳原子。在一些实施方案中，杂芳基包含3至14个、4至14个、3至7个或5至6个成环原子。在一些实施方案中，杂芳基具有1至4个、1至3个或1至2个杂原子。在一些实施方案中，杂芳基具有1个杂原子。
除非另有说明，本发明使用的术语“杂环基”指包含3至20个原子的饱和、不饱和或部分饱和的单环、二环或三环，其中1、2、3、4或5个环原子选自氮、硫或氧，除非另有说明，其可通过碳或氮来连接，其中-CH 2-基团任选被-C(O)-代替；及其中除非另有相反说明，环氮原子或环硫原子任选被氧化以形成N-氧化物或S-氧化物或环氮原子任选被季铵化；其中环中的-NH任选被乙酰基、甲酰基、甲基或甲磺酰基取代；及环任选被一个或多个卤素取代。应该理解的是，当杂环基中S原子和O原子的总数超过1时，这些杂原子彼此不相邻。若所述杂环基为二环或三环，则至少一个环可任选为杂芳族环或芳族环，条件是至少一个环是非杂芳族的。若所述杂环基为单环，则其一定不是芳族的。杂环基的实例包括但不限于哌啶基、N-乙酰基哌啶基、N-甲基哌啶基、N-甲酰基哌嗪基、N-甲磺酰基哌嗪基、高哌嗪基、哌嗪基、氮杂环丁烷基、氧杂环丁烷基、吗啉基、四氢异喹啉基、四氢喹啉基、二氢吲哚基、四氢吡喃基、二氢-2H-吡喃基、四氢呋喃基、四氢噻喃基、四氢噻喃-1-氧化物、四氢噻喃-1,1-二氧化物、1H-吡啶-2-酮和2,5-二氧代咪唑烷基。
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是用于限制本发明的保护范围。此外，应理解，在阅读了本发明所记载的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落如本发明的保护范围。
制备例1
固态电解质薄膜的制备
将双三氟甲烷磺酰亚胺锂(LiTFSI)：聚氧乙烯(PEO)：四乙二醇二甲醚(TEGDME)：二苯甲酮(MBP)按照10:41.3:41.2:7.5的配比进行研磨混合，然后均匀的涂布在聚四氟乙烯的板子上，得到薄膜后，经过紫外辐照交联聚合，得到固态电解质薄膜，其室温导电率约10 -3S/cm。所述固态电解质薄膜的具体制备方法可参考Luca Porcarelli et al.Super Soft All-Ethylene Oxide Polymer Electrolyte for Safe All-Solid Lithium Batteries.Scientific Reports,2016,6,1-14.中所述的。
实施例1
(1)可凝胶体系的制备
称取1.2g的氟代磺酰亚胺锂固体于试剂瓶中，加入1.5mL的常规锂电池电解液(含1mol/L LiPF 6的碳酸二甲酯(DMC)和碳酸乙烯酯(EC)的混合溶液，所述碳酸二甲酯(DMC)和碳酸乙烯酯(EC)的体积比为1:1)，在磁力搅拌下使得锂盐完全溶解，然后加入5.5mL的四氢吡喃于上述混合溶液中，充分混合后，静置备用。
(2)电池材料的制备及电池的装配
锂离子电池的正极：将钴酸锂与导电石墨、导电剂乙炔黑(super p)、粘结剂聚偏二氟乙烯(PVDF)按照质量比85:5:5:5均匀混合，用N-甲基-吡咯烷酮(NMP)将此混合物调制成浆料，均匀涂敷在铝箔上，于120℃真空烘箱中干燥24小时，备用；锂离子电池的负极：锂片；将正极片和负极片分别浸润到上述制备的未成固态电解质的电解液溶液中，待其固态电解质形成之前，将浸润后的正极片和负极片取出。
隔膜：聚丙烯(PP)多孔膜；将隔膜放置在浸润了电解液的正负极片之间，再向电池内部注入上述未成固态电解质的电解液，将电池压制封装，静置待电解液形成固态电解质后，使用蓝电电池组测试电池的电化学性能。
制备得到的所述固体电解质和电池的性能参数列于表1中。
实施例2
(1)可凝胶体系的制备
称取0.75g氯铝酸锂和0.1g双氟磺酰亚胺锂于试剂瓶中，加入1.2mL三乙二醇二甲醚，在磁力搅拌下，使氯铝酸锂和双氟磺酰亚胺锂全部溶解，加入2.5mL四氢吡喃和1.2mL1,3-二氧戊环，充分混合后，静置备用。
(2)电池材料的制备及电池的装配
锂硫电池的正极：将碳硫复合材料与导电剂乙炔黑(super p)、粘结剂聚偏二氟乙烯(PVDF)按照质量比8:1:1均匀混合，用N-甲基-吡咯烷酮(NMP)将此混合物调制成浆料，均匀涂敷在铝箔上，于60℃真空烘箱中干燥24小时，备用；
锂离子电池的负极：负极活性物质导电石墨90.5份、乙炔黑6份、羟甲基纤维素1份、丁苯橡胶粘结剂2.5份用乙醇-水混合溶液充分混合得到负极浆料，涂布在铜箔上，于60℃真空烘箱中干燥24小时，备用；
将上述得到的正极片和负极片分别浸润到上述制备的未成固态电解质的电解液溶液中，待其固态电解质形成之前，将浸润后的正极片和负极片取出。
隔膜：聚丙烯(PP)多孔膜；将隔膜放置在浸润了电解液的正负极片之间，再向电池内部注入上述未成固态电解质的电解液，将电池压制封装，静置待电解液形成固态电解质后，使用蓝电电池组测试电池的电化学性能。制备得到的所述固体电解质和电池的性能参数列于表1中。
实施例3
正极和负极以及固态电解质的制备方法与实施例1相同，正负极片也用实施例1中的成固态电解质之前的电解液浸润，区别仅在于，采用上述制备例1制备得到的固态电解质薄膜来代替聚丙烯隔膜，上述未成固态电解质的电解液不注入电池内部，进行电池的封装，静止以及电池测试等过程与实施例1中相同，电池的性能参数列于表1中。
实施例4
正极和负极以及固态电解质的制备方法与实施例2相同，正负极片也用实施例2中的成固态电解质之前的电解液浸润，区别仅在于，采用上述制备例1制备得到的固态电解质薄膜来代替聚丙烯隔膜，上述未成固态电解质的电解液不注入电池内部，进行电池的封装，静止以及电池测试等 过程与实施例2中相同，电池的性能参数列于表1中。
实施例5
正极和负极以及固态电解质的合成方法与实施例3中的相同，区别仅在于，正负极片不浸润到成固态电解质之前的电解液中，采用上述制备例1制备得到的固态电解质薄膜来代替聚丙烯隔膜，上述未成固态电解质的电解液不注入电池内部进行电池的装配，静止以及电池测试等过程与实施例3完全相同，电池的性能参数列于表1中。
实施例6
正极和负极以及固态电解质的合成方法与实施例4中的相同，区别仅在于，正负极片不浸润到成固态电解质之前的电解液中，采用上述制备例1制备得到的固态电解质薄膜来代替聚丙烯隔膜，上述未成固态电解质的电解液不注入电池内部进行电池的装配，静止以及电池测试等过程与实施例3完全相同，电池的性能参数列于表1中。
实施例7
(1)可凝胶体系的制备
称取0.05g的氧化铝于试剂瓶中，向其中加入4.5mL的3,3-二氯甲基氧杂环丁烷，在磁力搅拌下使其充分混合均匀，得到混合液A。另取0.4g氟代磺酰亚胺锂和0.6g高氯酸锂于试剂瓶中，向其中加入1.2mL的锂硫电池常规电解液，搅拌直到锂盐完全溶解，得到混合液B。将上面得到的A和B溶液进行充分混合，得到的混合液，充分混合后，静置备用。
(2)电池材料的制备及电池的装配
锂离子电池的正极：将磷酸铁锂与导电石墨、导电剂乙炔黑(super p)、粘结剂聚偏二氟乙烯(PVDF)按照质量比85:5:5:5均匀混合，用N-甲基-吡咯烷酮(NMP)将此混合物调制成浆料，均匀涂敷在铝箔上，于120℃真空烘箱中干燥24小时，备用；锂离子电池的负极：锂片；
将正极片和负极片分别浸润到上述制备的未成固态电解质的电解液溶液中，待其固态电解质形成之前，将浸润后的正极片和负极片取出。
将上述的可凝胶化体系刮涂到玻璃板上，静置，待其聚合成固态电解质膜后，用刀片刮下，将其置于上面所得的正负极之间，再将电池压制封装，静置待电解液形成固态电解质后，使用蓝电电池组测试电池的电化学性能。
制备得到的所述固体电解质和电池的性能参数列于表1中。
实施例8
(1)聚酯的合成
称取15.0g戊二酸，10.0g丁烯二酸，20.0g聚乙二醇-400，10.0g1,4-丁二醇于三口烧瓶中，油浴加热至温度升至140℃，恒温1.5h，每隔20min升温20℃，直到温度升至220℃，恒温2h，加入0.2g催化剂钛酸四丁酯和0.2g阻聚剂对羟基苯酚，反应50min，抽真空1h，并降温得粗产物，加入三氯甲烷50.0mL，室温搅拌24h，至于乙醇中沉降，产物于60℃真空烘箱中干燥24h，得聚酯D，于手套箱中保存。
(2)可凝胶化体系和固体电解质的制备
量取1.0mL聚酯D，4.67mL四氢呋喃，搅拌使二者混合，得澄清透明液体，混匀之后加入1.0g氟代磺酰亚胺锂，搅拌1h，使氟代磺酰亚胺锂完全溶于上述混合液中，得到可凝胶化体系；继续搅拌2h，后静置备用。
(3)电池材料的制备及电池的装配
锂离子电池的正极：将磷酸铁锂与导电石墨、导电剂乙炔黑(super p)、上述步骤(2)制备得到的可凝胶化体系按照质量比85:5:5:5均匀混合，用N-甲基-吡咯烷酮(NMP)将此混合物调制 成浆料，均匀涂敷在铝箔上，于120℃真空烘箱中干燥24小时，备用；锂离子电池的负极：锂片；隔膜：聚丙烯(PP)多孔膜；
将隔膜放置在浸润了电解液的正负极片之间，再向电池内部注入上述未成固态电解质的电解液，将电池压制封装，静置待电解液形成固态电解质后，使用蓝电电池组测试电池的电化学性能。
制备得到的所述固体电解质和电池的性能参数列于表1中。
实施例9
(1)可凝胶化体系的制备
称取0.4g四氟硼酸锂于试剂瓶中，向其中加入2.0mL碳酸二甲酯和碳酸乙烯酯的混合液，搅拌使得锂盐完全溶解，将1.0mL四氢呋喃加入上述锂盐溶液中，搅拌充分混合后，得到可凝胶化体系；静止备用。
(2)电池材料的制备及电池的装配
锂离子电池的正极：将磷酸铁锂与导电石墨、导电剂乙炔黑(super p)、粘结剂聚偏二氟乙烯(PVDF)按照质量比85:5:5:5均匀混合，用N-甲基-吡咯烷酮(NMP)将此混合物调制成浆料，均匀涂敷在铝箔上，于120℃真空烘箱中干燥24小时，备用；锂离子电池的负极：锂片；隔膜：聚丙烯(PP)多孔膜；
将隔膜放置上述的正负极片之间，再向电池内部注入上述准固态电解质的前驱体电解液，将电池压制封装，静置待电解液形成准固态电解质后，使用蓝电电池组测试电池的电化学性能。
制备得到的所述准固体电解质和电池的性能参数列于表1中。
实施例10
(1)可凝胶化体系的制备
称取0.2g的氧化锌于试剂瓶中，向其中加入6.0mL1,3-二氧戊环和3.0mL四氢吡喃，在磁力搅拌下使其充分混合均匀，得到混合液A。另取0.5g三氟甲基磺酸锂和1.5六氟砷酸锂于试剂瓶中，向其中加入2.4mL的碳酸二甲酯，搅拌直到锂盐完全溶解，得到混合液B。将上面得到的A和B溶液进行充分混合，得到的混合液，得到可凝胶化体系；静置备用。
(2)固态电解质膜的制备
将步骤(1)中的可凝胶化体系刮涂在干净的玻璃板上，静置，待其固化后，用刀片轻轻的将其揭下，备用。
(3)电池材料的制备及电池的装配
锂离子电池的正极：将磷酸铁锂与导电石墨、导电剂乙炔黑(super p)、步骤(1)得到的可凝胶化体系按照质量比85:5:5:5均匀混合，将此混合物调制成浆料，均匀涂敷在铝箔上，于60℃真空烘箱中干燥24小时，备用；锂离子电池的负极：锂片；
将固态电解质膜放置上述含有可凝胶化体系的正负极片之间，然后将电池压制封装，静置待电解液形成固态电解质后，使用蓝电电池组测试电池的电化学性能。
制备得到的所述准固体电解质和电池的性能参数列于表1中。
实施例11
(1)可凝胶化体系的制备
称取0.2g的四氟硼酸锂、0.2g的双三氟甲烷磺酰亚胺锂和0.4g的双草酸硼酸锂固体于试剂瓶中，加入2.0mL的1,4-环氧环己烷和8.0mL四氢呋喃，在磁力搅拌下配制成锂盐含量为8wt％的四氟硼酸锂+双三氟甲烷磺酰亚胺锂+双草酸硼酸锂/1,4-环氧环己烷+四氢呋喃溶液，得到可凝胶化体系；持续搅拌直到锂盐完全溶解，静置备用。
(2)电池材料的制备及电池的装配
锂离子电池的正极：将磷酸铁锂与导电石墨、导电剂乙炔黑(super p)、步骤(1)得到的可凝胶化体系按照质量比85:5:5:5均匀混合，将此混合物调制成浆料，均匀涂敷在铝箔上，于60℃真空烘箱中干燥24小时，备用；锂离子电池的负极：锂片；隔膜：聚丙烯(PP)多孔膜；
将隔膜放置上述含有可凝胶化体系的正负极片之间，然后注入步骤(1)得到的可凝胶化体系，再将电池压制封装，静置待电解液形成半固态电解质后，使用蓝电电池组测试电池的电化学性能。制备得到的所述准固体电解质和电池的性能参数列于表1中。
表1 实施例1-9的固态电解质性质及制备得到的电池的性能参数
Figure PCTCN2018088495-appb-000007
图1为实施例2中装配方式得到电池的倍率性能图。由图可知，浸润后的正负极片，在有隔膜的情况下，补加一定量的未成固态电解质前的电解液后，可以表现出较好的倍率性能。
图2为实施例4中装配方式得到电池的倍率性能图。由图可知，浸润后的正负极片，以固态电解质膜将其隔开，该电池表现出较好的倍率性能。
图3为实施例6中装配方式得到电池的倍率性能图。由图可知，正负极片未经浸润，以单纯的固态电解质膜来隔开正负极，并且充当表面的导电体，其倍率性能较差。
图4为实施例7中装配方式得到的电池的倍率性能图。由图可知，正负极凝胶化体系浸润，在电池内部形成离子导电网络，用固态电解质代替隔膜，形成固态电池，具有很好的倍率性能，即使到10C，也能发挥出不错的性能。
图5为实施例8中装配方式得到的电池的倍率性能图。由图可知，正极极片在制备过程中，将可凝胶化体系代替传统的粘结剂，不仅提高了活性物质的面密度，而且在电极内部形成很好的离子导电网络，电池表现出优异的倍率性能。
由表1可以看出，相比于未浸润的正负极组装的电池而言，经过固态电解质的前溶液浸润的正负极组装而成的电池，表现出优异的倍率性能，说明进过浸润的正负极内部形成导电网络，有利于电子和离子的传输，可以承受较大的倍率充放电，而未经浸润的正负极内部没有导电网络，其电化学性能的发挥只能靠电极和固态电解质接触部分进行电子和离子的传输，所以其倍率性能较差。
以上，对本发明的实施方式进行了说明。但是，本发明不限定于上述实施方式。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种柔性全固态锂离子二次电池的制备方法，其特征在于，所述方法包括如下步骤：
    1a)配制可凝胶体系；
    2a)将负极、隔膜、正极组装，得到注液前全固态电池；
    3a)向步骤2a)的注液前全固态电池中注入步骤1a)的可凝胶体系，封口，静置，得到全固态锂离子二次电池；
    其中，可凝胶体系包括以下组分：锂盐和醚类化合物，所述醚类化合物选自环状醚类化合物或直链醚类化合物中的至少一种；体系中可凝胶化的聚合物和/或可凝胶化的预聚物的质量百分含量小于等于1wt％。
  2. 一种柔性全固态锂离子二次电池的制备方法，其特征在于，所述方法包括如下步骤：
    1b)配制可凝胶体系；
    2b)将负极集流体、负极材料压制成负极后置于步骤1b)中的可凝胶体系中浸润；或者将步骤1)中的可凝胶体系涂覆到负极集流体、负极材料压制成的负极表面上；
    3b)将正极集流体、正极材料压制成正极后置于步骤1b)中的可凝胶体系中浸润；或者将步骤1)中的可凝胶体系涂覆到正极集流体、正极材料压制成的正极表面上；
    4)选自下述步骤中的一种：
    4b)将步骤2b)的浸润或涂覆后的负极、隔膜、步骤3b)的浸润或涂覆后的正极组装，得到注液前全固态锂离子二次电池；向注液前全固态锂离子二次电池中注入步骤1b)的可凝胶体系，封口，静置，得到所述全固态锂离子二次电池；
    4b’)将步骤1b)的可凝胶体系涂覆在基底表面，所述可凝胶体系在基底表面固化形成固态电解质薄膜；将步骤2b)的浸润或涂覆后的负极、固态电解质薄膜、步骤3b)的浸润或涂覆后的正极组装，得到全固态锂离子二次电池；或者，
    4b”)将步骤1b)的可凝胶体系涂覆在基底表面，所述可凝胶体系在基底表面固化形成固态电解质薄膜；将步骤2b)的浸润或涂覆后的负极、固态电解质薄膜、步骤3b)的浸润或涂覆后的正极组装，得到注液前全固态锂离子二次电池；向注液前全固态锂离子二次电池中注入步骤1b)的可凝胶体系，封口，静置，得到所述全固态锂离子二次电池；
    其中，可凝胶体系包括以下组分：锂盐和醚类化合物，所述醚类化合物选自环状醚类化合物或直链醚类化合物中的至少一种；体系中可凝胶化的聚合物和/或可凝胶化的预聚物的质量百分含量小于等于1wt％。
  3. 一种柔性全固态锂离子二次电池的制备方法，其特征在于，所述方法包括如下步骤：
    1c)配制可凝胶体系；
    2c)将正极材料、导电剂、步骤1c)的可凝胶体系和任选地粘结剂，与溶剂混合打浆，并涂覆到正极集流体表面，制备得到含有可凝胶体系的正极；
    3c)将负极材料、导电剂、步骤1c)的可凝胶体系和任选地粘结剂，与溶剂混合打浆，并涂覆到负极集流体表面，制备得到含有可凝胶体系的负极；
    4)选自下述步骤中的一种：
    4c)将步骤1c)的可凝胶体系涂覆在基底表面，所述可凝胶体系在基底表面固化形成固态电解质薄膜；将步骤2c)的含有可凝胶体系的正极、固态电解质薄膜、步骤3c)含有可凝胶体系的负极组装，得到全固态锂离子二次电池；或者，
    4c’)将步骤1c)的可凝胶体系涂覆在基底表面，所述可凝胶体系在基底表面固化形成固态电解质薄膜；将步骤2c)的含有可凝胶体系的正极、固态电解质薄膜、步骤3c)含有可凝胶体系的负极组装，得到注液前全固态锂离子二次电池；向注液前全固态锂离子二次电池中注入步骤1c)的可凝胶体系，封口，静置，得到所述全固态锂离子二次电池；或者，
    4c”)将步骤2c)的含有可凝胶体系的正极、隔膜、步骤3c)含有可凝胶体系的负极组装，得到注液前全固态锂离子二次电池；向注液前全固态锂离子二次电池中注入步骤1c)的可凝胶体系，封口，静置，得到所述全固态锂离子二次电池；
    其中，可凝胶体系包括以下组分：锂盐和醚类化合物，所述醚类化合物选自环状醚类化合物或直链醚类化合物中的至少一种；体系中可凝胶化的聚合物和/或可凝胶化的预聚物的质量百分含量小于等于1wt％。
  4. 根据权利要求1-3中任一项所述的制备方法，其特征在于，所述可凝胶体系中还包括无机纳米颗粒、其他溶剂和/或电解液、聚酯或其共混物等添加剂中的至少一种。
    优选地，所述可凝胶体系中还包括无机纳米颗粒、其他溶剂和/或电解液、聚酯或其共混物等添加剂中的至少一种。
    优选地，所述可凝胶体系包括锂盐和醚类化合物，所述醚类化合物选自环状醚类化合物和直链醚类化合物中的至少一种。
    优选地，所述可凝胶体系包括锂盐、醚类化合物、以及其他溶剂和/或电解液，所述醚类化合物选自环状醚类化合物和直链醚类化合物中的至少一种。
    优选地，所述可凝胶体系包括锂盐、醚类化合物和无机纳米颗粒，所述醚类化合物选自环状醚类化合物和直链醚类化合物中的至少一种。
    优选地，所述可凝胶体系包括锂盐、醚类化合物、其他溶剂和/或电解液、以及无机纳米颗粒，所述醚类化合物选自环状醚类化合物和直链醚类化合物中的至少一种。
    优选地，所述可凝胶体系包括锂盐、醚类化合物、以及聚酯或其共混物等添加剂，所述醚类化合物选自环状醚类化合物。
    优选地，所述可凝胶体系经凝胶后，可制备得到固态电解质，所述锂盐的质量百分含量大于等于5wt％且小于等于60wt％；所述醚类化合物的质量百分含量大于等于20wt％且小于等于60wt％；所述其他电解液或其溶剂的质量百分含量大于等于20wt％小于等于75wt％，所述无机纳米颗粒的质量百分含量大于等于0wt％且小于等于30wt％，所述添加剂的质量百分含量大于等于0wt％且小于等于30wt％。
    优选地，所述可凝胶体系经凝胶后，可制备得到固态电解质，所述锂盐的质量百分含量大于等于10wt％且小于等于40wt％；所述醚类化合物的质量百分含量大于等于20wt％且小于等于60wt％；所述其他电解液或其溶剂的质量百分含量大于等于20wt％且小于等于60wt％，所述无机纳米颗粒的质量百分含量大于0wt％且小于等于20wt％，所述添加剂的质量百分含量大于0wt％且小于等于20wt％。
    优选地，所述可凝胶体系经凝胶后，可制备得到凝胶电解质，所述锂盐的质量百分含量大于等于5wt％且小于等于60wt％；所述醚类化合物的质量百分含量大于60wt％且小于等于90wt％；所述其他电解液或其溶剂的质量百分含量大于等于5wt％小于等于30wt％，所述无机纳米颗粒的质量百分含量大于等于0wt％且小于等于30wt％，所述添加剂的质量百分含量大于等于0wt％且小于等于30wt％。
    优选地，所述可凝胶体系经凝胶后，可制备得到凝胶电解质，所述的可凝胶化体系中，所述锂盐的质量百分含量大于等于10wt％且小于等于40wt％；所述醚类化合物的质量百分含量大于60wt％且小于等于85wt％；所述其他电解液或其溶剂的质量百分含量大于等于5wt％且小于等于30wt％，所述无机纳米颗粒的质量百分含量大于0wt％且小于等于20wt％，所述添加剂的质量百分含量大于0wt％且小于等于20wt％。
  5. 根据权利要求1-4任一项所述的制备方法，其特征在于，所述直链醚类化合物的通式如式(1)所示：
    R 1—O—(R 2—O) n—R 3  式(1)
    其中，n为大于0的整数；
    R 2选自直链或支链的C 1-C 6的亚烷基、直链或支链的C 2-C 6的亚烯基；所述R 2上的碳原子上的H可以被下述基团中的至少一种取代：烯基、炔基、烷氧基、烷硫基、环烷基、环烷基氧基、环烷基硫基、杂环基、 杂环基氧基、杂环基硫基、芳基、芳基氧基、杂芳基、杂芳基氧基、羟基、巯基、硝基、羧基、氨基、酯基、卤素、酰基、醛基；
    R 1和R 3相同或不同，彼此独立地选自氢原子、烷基、环烷基、杂环基、烯基、炔基中的一种或多种；所述R 1和R 3的碳原子上的H可以被下述基团中的至少一种取代：烯基、炔基、烷氧基、烷硫基、环烷基、环烷基氧基、环烷基硫基、杂环基、杂环基氧基、杂环基硫基、芳基、芳基氧基、羟基、巯基、硝基、羧基、氨基、酯基、卤素、酰基、醛基。
    优选地，n为1～6之间的整数；R 2选自直链或支链的C 1-C 4的亚烷基、直链或支链的C 2-C 6的亚烯基；R 1和R 3相同或不同，彼此独立地选自直链或支链的C 1-C 6的烷基。
    优选地，R 2选自甲基、乙基、丙基、异丙基、丁基、异丁基、乙烯基；R 1和R 3相同或不同，彼此独立地选自甲基、乙基、丙基。
    优选地，所述直链醚类化合物选自乙二醇二甲醚，乙二醇二乙醚，乙二醇甲乙醚，1,4-丁二醇二甲醚，1,4-丁二醇二乙醚，1,4-丁二醇甲乙醚等中的一种或多种。
    优选地，所述锂盐可选自六氟磷酸锂、四氟硼酸锂、六氟砷酸锂、高氯酸锂、三氟甲基磺酸锂、全氟丁基磺酸锂、双三氟甲烷磺酰亚胺锂、双氟磺酰亚胺锂、铝酸锂、氯铝酸锂、氟代磺酰亚胺锂、氯化锂和碘化锂中的一种或多种；优选地，所述锂盐选自六氟磷酸锂、高氯酸锂等中的一种或两种。
    优选地，所述可凝胶化体系还包括其他溶剂和/或电解液，所述其他溶剂和/或电解液包括用于锂硫电池的电解液、用于锂硫电池的电解液的溶剂、用于锂离子电池的电解液、用于锂离子电池的电解液的溶剂、用于锂空气电池电解液或其溶剂中的至少一种。
    优选地，所述用于锂空气电池电解液或其溶剂包括醚类电解液及其溶剂、酯类电解液及其溶剂、酰胺类电解液及其溶剂、腈类电解液及其溶剂以及砜类电解液及其溶剂。
    优选地，所述用于锂离子电池的电解液选自含有用于锂离子电池的锂盐的酯类混合液，例如含1M六氟磷酸锂(LiPF 6)的碳酸乙烯酯(EC)和碳酸二甲酯(DMC)的混合液，其中，所述碳酸乙烯酯(EC)和碳酸二甲酯(DMC)的体积比为1:1。
    优选地，所述用于锂离子电池的电解液的溶剂选自用于锂离子电池的电解液的环状非水有机溶剂和用于锂离子电池的电解液的链状非水有机溶剂中的至少一种。
    优选地，所述用于锂离子电池的电解液的环状非水有机溶剂选自碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、氟代碳酸乙烯酯(FEC)、γ-丁内酯(GBL)、亚硫酸乙烯酯(ES)、亚硫酸丙烯酯(PS)、环丁砜(SL)、碳酸甘油酯(GC)中的至少一种。
    优选地，所述用于锂离子电池的电解液的链状非水有机溶剂选自碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、碳酸甲丙酯(MPC)、碳酸二丙酯(DPC)、碳酸乙丙酯(EPC)、乙酸乙酯(EA)、乙酸丙酯(PA)、丙酸乙酯(EP)、丁酸乙酯(EB)、丁酸甲酯(MB)、亚硫酸二甲酯(DMS)、亚硫酸二乙酯(DES)、亚硫酸甲乙酯(EMS)、二甲基砜(MSM)、二甲基亚砜(DMSO)中的至少一种。
    优选地，所述用于锂硫电池的电解液选自含有锂盐的醚类混合液，例如：含有1M双三氟甲烷磺酰亚胺锂(LiTFSI)的1,3-二氧戊环(DOL)和乙二醇二甲醚(DME)的混合液，其中，所述1,3-二氧戊环(DOL)和乙二醇二甲醚(DME)的体积比为1:1。
    优选地，所述用于锂硫电池的电解液的溶剂选自1,3-二氧戊环、1,2-二甲氧基乙烷、三乙二醇二甲醚、四乙二醇二甲醚、氟代碳酸乙烯酯、聚乙二醇硼酸酯、1,1’,2,2’-四氟乙基-2,2’,3,3’-四氟丙烯醚中的一种或多种。
    优选地，所述酯类电解液选自含有锂盐的酯类混合液，例如含1M六氟磷酸锂(LiPF 6)的碳酸乙烯酯(EC)和碳酸二甲酯(DMC)的混合液，其中，所述碳酸乙烯酯(EC)和碳酸二甲酯(DMC)的体积比为1:1。
    优选地，所述酯类电解液的溶剂选自酯类环状非水有机溶剂和酯类链状非水有机溶剂中的至少一种。
    优选地，所述酯类环状非水有机溶剂选自碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、氟代碳酸乙烯酯(FEC)、γ-丁内酯(GBL)、亚硫酸乙烯酯(ES)、亚硫酸丙烯酯(PS)、碳酸甘油酯(GC)中的至少一种。
    优选地，所述链状非水有机溶剂选自碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、碳酸甲丙酯(MPC)、碳酸二丙酯(DPC)、碳酸乙丙酯(EPC)、乙酸乙酯(EA)、乙酸丙酯(PA)、丙酸乙酯(EP)、丁酸乙酯(EB)、丁酸甲酯(MB)、亚硫酸二甲酯(DMS)、亚硫酸二乙酯(DES)、亚硫酸甲乙酯(EMS)中的至少一种。
    优选地，所述醚类电解液选自含有锂盐的醚类混合液，例如：含有1M双三氟甲烷磺酰亚胺锂(LiTFSI)的1,3-二氧戊环(DOL)和乙二醇二甲醚(DME)的混合液，其中，所述1,3-二氧戊环(DOL)和乙二醇二甲醚(DME)的体积比为1:1。
    优选地，所述醚类电解液的溶剂选自1,3-二氧戊环、1,2-二甲氧基乙烷、三乙二醇二甲醚、四乙二醇二甲醚、氟代碳酸乙烯酯、聚乙二醇硼酸酯、1,1’,2,2’-四氟乙基-2,2’,3,3’-四氟丙烯醚中的一种或多种。
    优选地，所述酰胺类电解液选自含有锂盐的酰胺类混合液，例如：含1M三氟甲基磺酸锂的N,N-二甲基乙酰胺溶液。
    优选地，所述酰胺类电解液的溶剂选自含有酰胺基团的化合物；
    优选地，所述酰胺类电解液的溶剂选自C 1～C 20的烷基酰胺、C 1～C 20的烯酰胺腈、C 1～C 20的炔基酰胺、C 1～C 20的卤代烷基酰胺、C 1～C 20的卤代烯基酰胺、C 1～C 20的卤代炔基酰胺、C 7～C 20的芳基酰胺、C 1～C 20的环氧基酰胺中的至少一种。
    优选地，所述酰胺类电解液的溶剂选自N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、苯甲酰胺、甲酰胺、乙酰胺、丁二酰亚胺、邻苯二甲酰亚胺、N-甲基对甲苯磺酰胺、N-甲基乙酰胺、3-氨基-6-甲基苯磺酰胺、2,2,2-三氯乙酰胺、苄酯N-乙基对甲苯磺酰胺、3-氨基-2,2-二甲基丙酰胺、芥酸酰胺、N-乙基-5-甲基-2-(1-甲基乙基)环己甲酰胺、4-甲氧基苯甲酰胺、2,4-二羟基苯甲酰胺、N,N-二乙基-2-氯乙酰胺、N-丁基苯磺酰胺、N-乙基乙酰胺、氯乙酰胺、盐酸盐N-(2-氯苯基)乙酰胺、N,N'-乙撑双硬脂酰胺、戊酰胺、2-羟基异丁酰胺、乙氧酰胺、苯甲酯肉桂酰胺、L-(+)-樟脑内磺酰胺、丙二酰胺、磺酰胺、环丙磺酰胺、2-乙磺酰基咪唑并[1,2-a]吡啶-3-磺酰胺、N,N-二乙基乙酰胺、4-氯硫代苯甲酰胺、N,N’-二甲基草酰胺、N-甲氧基-N-甲基乙酰胺、苯甲酰胺、N-甲基己内酰胺、(S)-(-)-叔丁基亚磺酰胺、3-氨基-N-甲基苯甲酰胺、N,N’-亚甲基双丙烯酰胺、2,2-二溴-3-次氮基丙酰胺、N,N-二乙基十二酰胺、肼甲酰亚胺酰胺、一氯化氢硫代乙酰胺、氰乙酰胺、丙酰胺、苯甲酰胺、2-硝基苯磺酰胺、对氨基苯甲酰胺、异丁酰胺、己内酰胺、邻甲酸甲酯苯磺酰胺、N,N-二甲基乙酰胺、N-甲基甲酰胺、N-叔丁基丙烯酰胺、6-甲基烟酰胺、N,N-二甲基磺酰胺、2,3-二溴丙酰胺、2-氨基-5-甲基苯甲酰胺、左旋樟脑磺内酰胺、DL-氨基己内酰胺硬脂酰胺、1,1-环己基二乙酸单酰胺、环丙酰胺、对硝基苯甲酰胺、4-(2-氨乙基)苯磺酰胺、2-甲基-5-硝基苯磺酰胺、3,5-二羟基苯甲酰胺、2-丙烯酰胺基-2-甲基丙磺酸-N-甲基丁二酰胺、N,2,3-三甲基-2-异丙基丁酰胺、N,N-二甲基丙酰胺、N-乙烯基己内酰胺、2-碘乙酰胺、邻氨基苯磺酰胺、2,4-二氯-5-磺酰胺基苯甲酸-N-苯基马来酰亚胺、N-乙基马来酰亚胺、5-氯-2,4-二磺酰胺基苯胺邻氯苯磺酰胺、N,N-二甲基甘氨酰胺、2-氨基苯酚-5-(N,N-二甲基)磺酰胺、4-氨基-3,5-二硝基苯甲酰胺、4-氨基-N-甲基苯甲酰胺、2-苯乙酰胺、N-(叔丁氧羰基)对甲苯磺酰胺、4-氟苯甲酰胺、肟2-氨基丙二酰胺、双(四亚甲基)氟代甲酰胺、N-羟基-异丁酰胺、硫代丙酰胺、乙酯1-((氰基-1-甲基乙基)偶氮)甲酰胺、肉桂酰胺、4-氨基苯基-N-甲基甲烷磺酰胺、4-溴-3-氟苯磺酰胺、2,6-二氟苯磺酰胺、2-溴苯磺酰胺、4-氟苯磺酰胺、4-三氟甲氧基苯磺酰胺、4-氯苯磺酰胺、2,5-二氟苯磺酰胺、三氟甲磺酰胺、N-[双(甲硫基)亚甲基]对甲苯磺酰胺、4-氯-3-硝基-5-磺酰胺基苯甲酸、N-甲基二乙酰胺N-苯亚甲基苯磺酰胺、2-甲氧基-5-磺酰胺、3,5-二氯苯磺酰胺、2-氟苯磺酰胺、4-溴-2-氯苯磺胺、5-氯-2-氟苯磺酰、胺对甲氧基苯磺酰胺、4-氯水杨酸-5-磺酰胺、2-氨基-N-乙基-N-苯基苯磺酰胺、2-溴-4-氟苯磺酰胺、4-氟-2-甲基苯磺酰胺、2-氰基苯磺酰胺、4-[2-(5-氯-2-甲氧基苯甲酰氨基)乙基]苯磺酰胺、3,4-二氟苯磺酰胺、DL-氨基己内酰胺、2,4,6-三氯 苯磺酰胺、环丙烷磺酰胺、4-溴-3-(三氟甲基)苯磺胺、N-(4-氨基丁基)-乙酰胺神经酰胺、N-[(1R)-2-(3-氨基磺酰基-4-甲氧基)-1-甲基]乙酰胺、N-苄基-N-亚硝基-对甲苯磺酰胺、N-(2-氨基乙基)-4-甲基苯磺酰胺、(1R)-10-樟脑磺酰胺、4-氨基-6-(三氟甲基)苯-1,3-二磺酰胺、2-溴-4-(三氟甲基)苯磺酰胺、3-氟-4-甲基甲苯磺酰胺、2-溴-5-(三氟甲基)苯磺酰胺、萘-2-磺酰胺、(1S)-10-樟脑磺酰胺、(S)-(+)-对甲基苯亚磺酰胺、(1R)-反-N,N’-1,2-环己二基双(1,1,1-三氟甲磺酰胺)、N-(2-氟苯基)甲磺酰胺、(S)-N-(-)-对甲苯基亚磺酰基色胺、N-乙酰氧基-N-乙酰基-4-氯苯磺酰胺、2-(三甲基硅基)乙磺酰胺、N-(4-氨基苯)-磺酰胺-4-甲基苯(R)-(-)-4-甲基苯亚磺酰胺、N-乙基对甲苯磺酰胺、(R,R)-(+)-N,N’-双(Α-甲基苄基)磺酰胺、(S)-(-)-N-[1-(羟甲基)-2-苯基乙基]-4-甲基苯磺酰胺、环丙酰胺、2-氯-4-氟-5-氨磺酰基苯甲酸N-亚苄基-P,P-二苯基次膦酸酰胺、N-(4-氯苯亚甲基)-4-甲苯磺酰胺中至少一种。
    优选地，所述腈类电解液选自含有锂盐的腈类混合液，例如：含1M高氯酸锂的乙腈溶液。
    优选地，所述腈类电解液的溶剂选自含有腈基的化合物；
    优选地，所述腈类电解液的溶剂选自C 1～C 20的烷基腈、C 1～C 20的烯基腈、C 1～C 20的炔基腈、C 1～C 20的卤代烷基腈、C 1～C 20的卤代烯基腈、C 1～C 20的卤代炔基腈、C 7～C 20的芳基腈、C 1～C 20的环氧基腈中的至少一种。
    优选地，所述腈类电解液的溶剂选自乙腈、丁腈。
    优选地，砜类电解液选自含有锂盐的砜类混合液，例如：含1M高氯酸锂的二甲亚砜(DMSO)溶液。
    优选地，砜类电解液的溶剂选自含有砜基的化合物；
    优选地，所述腈类电解液的溶剂选自C 1～C 20的烷基砜、C 1～C 20的烯基砜、C 1～C 20的炔基砜、C 1～C 20的卤代烷基砜、C 1～C 20的卤代烯基砜、C 1～C 20的卤代炔基砜、C 7～C 20的芳基砜、C 1～C 20的环氧基砜中的至少一种。
    优选地，所述砜类电解液的溶剂选自环丁砜(SL)、二甲亚砜。
    优选地，所述添加剂选自聚酯或其共混物中的一种或几种；其中，所述聚酯由多元酸或酸酐与多元醇缩聚而得；所述多元酸选自二元酸、三元酸或更多元酸，所述多元醇选自二元醇、三元醇或更多元醇。
    优选地，所述多元酸选自取代或未取代的下述多元酸中的一种或两种或三种或多于三种：乙二酸，丙二酸，丁二酸，丁烯二酸，戊二酸，己二酸，庚二酸，辛二酸，癸二酸，壬二酸，丙三酸；所述取代基的个数可以是一个或多个；当所述取代基为多个时，其可成环；所述取代基为烷基、环烷基、芳基、羟基、氨基、酯基、卤素、酰基、醛基、巯基、烷氧基等中的一种或多种。
    优选地，所述酸酐选自取代或未取代的下述酸酐中的一种或两种或三种或多于三种：乙二酸酐，丙二酸酐，丁二酸酐，丁烯二酸酐，戊二酸酐，己二酸酐，庚二酸酐，辛二酸酐，癸二酸酐，壬二酸酐，六氢苯酐，四氢苯酐；所述取代基的个数可以是一个或多个；当所述取代基为多个时，其可成环；所述取代基为烷基、环烷基、芳基、羟基、氨基、酯基、卤素、酰基、醛基、巯基、烷氧基等中的一种或多种。
    优选地，所述多元醇选自取代或未取代的下述多元醇中的一种或几种：丙二醇，丁二醇，戊二醇，己二醇，庚二醇，辛二醇，壬二醇，癸二醇，聚乙二醇，丙三醇；所述取代基的个数可以是一个或多个；当所述取代基为多个时，其可成环；所述取代基为烷基、环烷基、芳基、羟基、氨基、酯基、卤素、酰基、醛基、巯基、烷氧基等中的一种或多种。
    优选地，所述多元醇选自聚乙二醇，或者聚乙二醇与下述多元醇中的一种或几种的组合：丙二醇，丁二醇，戊二醇，己二醇，庚二醇，辛二醇，壬二醇，癸二醇。
    优选地，所述聚乙二醇的聚合度为100-1000，优选为150-800，还优选为200-600。其中，所述聚乙二醇与其他多元醇的重量比为1:(0～1)，优选为1:(0～0.9)，还优选为1:(0～0.8)。
  6. 根据权利要求1-5任一项所述的制备方法，其特征在于，所述环状醚类化合物选自含有一个氧、两个氧、三个氧或更多氧的环状醚类化合物。
    优选地，所述环状醚类化合物可以是单环、稠合环(如双环)、螺环或桥环。
    优选地，所述环状醚类化合物选自至少含有1个氧原子的C 2～C 20环烷烃，即环状结构中的碳原子数为2-20 个；或至少含有1个氧原子的C 3～C 20环烯烃，即环状结构中的碳原子数为3-20个，其中至少含有一个碳碳双键。
    优选地，所述环烷烃或环烯烃为单环、稠合环(如双环)、螺环或桥环；当所述环烷烃或环烯烃为螺环或桥环且含有两个以上氧原子时，氧原子可以在一个环上，也可以在多个环上。
    优选地，所述环状醚类化合物选自至少含有1个氧原子的C 2～C 20的单环烷烃，优选选自至少含有1个氧原子的C 3～C 20的单环烷烃，例如为下述第一类化合物中的一种：
    Figure PCTCN2018088495-appb-100001
    优选地，所述环状醚类化合物选自至少含有1个氧原子的C 4～C 20的稠合环烷烃，例如为下述第二类化合物中的一种：
    Figure PCTCN2018088495-appb-100002
    Figure PCTCN2018088495-appb-100003
    优选地，所述环状醚类化合物选自至少含有1个氧原子的C 4～C 20的桥环烷烃，例如为下述第三类化合物中的一种：
    Figure PCTCN2018088495-appb-100004
    优选地，所述环状醚类化合物选自至少含有1个氧原子的C 4～C 20的螺环烷烃，例如为下述第四类化合物中的一种：
    Figure PCTCN2018088495-appb-100005
    Figure PCTCN2018088495-appb-100006
    优选地，上述四类化合物中的环结构上的C-C键至少有一个被C＝C替代且为稳定存在的化合物，则为上述的至少含有1个氧原子的C 3～C 20环烯烃，为本发明优选的环状醚类化合物的一种。
    优选地，所述环烷烃或环烯烃为单环或稠合环时，其所述环上的碳原子上可以被1个或多个R1基团取代；所述环烷烃或环烯烃为桥环时，其非桥连环碳原子可以被1个或多个R1基团取代；所述环烷烃或环烯烃为螺环时，其环上碳原子上可以被1个或多个R1基团取代；所述R1基团选自下述基团的一种：烷基、烯基、炔基、烷氧基、烷硫基、卤代烷基、环烷基、环烷基氧基、环烷基硫基、杂环基、杂环基氧基、杂环基硫基、芳基、芳基氧基、杂芳基、杂芳基氧基、羟基、巯基、硝基、羧基、氨基、酯基、卤素、酰基、醛基。
    优选地，所述含有一个氧的环状醚类化合物选自取代或未取代的氧杂环丁烷、取代或未取代的四氢呋喃、取代或未取代的四氢吡喃；所述取代基的个数可以是一个或多个；所述取代基为上述的R1基团。
    优选地，所述含有一个氧的环状醚类化合物选自3,3-二氯甲基氧杂环丁烷、2-氯甲基氧杂环丁烷、2-氯甲基环氧丙烷、1,4-环氧环己烷、1,3-环氧环己烷、四氢呋喃、2-甲基四氢呋喃、3-甲基四氢呋喃、四氢吡喃、2-甲基四氢吡喃、氧杂环庚烷、氧杂环辛烷、氧杂环壬烷或氧杂环癸烷。
    优选地，所述含有两个氧的环状醚类化合物选自取代或未取代的1,3-二氧戊环(DOL)、取代或未取代的1,4-二氧六环；所述取代基的个数可以是一个或多个；所述取代基为上述的R1基团。
    优选地，所述含有三个氧的环状醚类化合物选自取代或未取代的三聚甲醛；所述取代基的个数可以是一个或多个；所述取代基为上述的R1基团。
    优选地，所述含有更多氧的醚类化合物选自取代或未取代的18-冠-6、取代或未取代的12-冠-4、取代或未取代的24-冠-8；所述取代基的个数可以是一个或多个；所述取代基为上述的R1基团。
  7. 根据权利要求1-6中任一项所述的制备方法，其特征在于，在步骤1)中，所述可凝胶化体系的制备方法具体包括如下步骤：
    将醚类化合物、锂盐以及任选地其他溶剂和/或电解液、任选地无机纳米颗粒、任选地添加剂混合，搅拌下得到混合溶液，即所述可凝胶化体系。
    优选地，所述可凝胶化体系的制备方法具体包括如下步骤：
    将醚类化合物加入锂盐中，搅拌下得到锂盐的醚类化合物溶液，任选地将其他溶剂和/或电解液和/或无机纳米颗粒和/或添加剂加入到锂盐的直链醚类化合物溶液，即所述可凝胶化体系。
    优选地，对所述醚类化合物、锂盐、任选地无机纳米颗粒、任选地其他溶剂和/或电解液和任选地添加 剂进行预先除水处理；优选地，采用分子筛和/或真空干燥的方法对所述醚类化合物、锂盐、任选地无机纳米颗粒、任选地其他溶剂和/或电解液和任选地添加剂进行预先除水处理。
  8. 根据权利要求1-7中任一项所述的制备方法，其特征在于，所述正极或负极的压制成一体的过程是在干燥的条件下进行的。
    优选地，所述的涂覆选自喷涂、刮刀涂覆、涂布辊、涂布刷等方式中的至少一种。
    优选地，所述导电剂选自导电石墨、乙炔黑、Super P、碳纳米管、石墨烯、氧化石墨烯、导电炭黑、科琴黑、石墨(KS、SO)、SFG-6中的至少一种。
    优选地，所述粘结剂选自聚偏氟乙烯(PVDF)、丙烯酸酯及其衍生物、环糊精及其衍生物、卡里克斯芳烃及其衍生物、羧甲基纤维素以及衍生物、丙烯酸及其衍生物、氨基树脂及其衍生物、聚酰亚胺、有机氟聚合物、有机聚硅氧烷中的至少一种。
    优选地，所述负极集流体选自铜箔、铜合金、银箔、不锈钢片、碳材料中的至少一种。
    优选地，所述负极材料选自金属类负极材料(如金属锂、锂合金等)、无机非金属类负极材料(如碳材料、硅材料以及其他不同非金属的复合材料等)中的至少一种。
    优选地，所述隔膜选自本发明所述的可凝胶体系制备得到的固态电解质隔膜或聚烯烃多孔膜，如聚乙烯微孔膜、聚丙烯微孔膜、三层复合隔膜中的至少一种。
    优选地，所述正极材料选自锂钴氧化物、锂镍氧化物、锂锰氧化物、三元材料镍钴锰氧、纳米正极材料(如纳米结晶尖晶石LiMn 2O 4、钡镁锰矿型MnO 2纳米纤维、聚吡咯包覆尖晶石型LiMn 2O 4纳米管、聚吡咯/V 2O 5纳米复合材料等)、共混电极、钒氧化物、层状化合物(如经过苯胺改性后的氧基氯化铁等)中的至少一种。
    优选地，所述正极集流体选自铝箔、铝合金中的至少一种。
    优选地，所述静置的时间为所使用的可凝胶化体系转变为固态电解质的形成时间，所述静置的温度为室温。
  9. 一种柔性全固态锂离子二次电池，其特征在于，所述锂离子二次电池是采用权利要求1-8中任一项所述的方法制备得到的。
  10. 根据权利要求9所述的柔性全固态锂离子二次电池，其特征在于，所述锂离子二次电池包括锂离子电池、锂硫电池或锂空气电池。
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