WO2018214973A1 - 一种可凝胶化体系及在锂空气电池、有机体系的超级电容器或电容电池中的应用 - Google Patents

一种可凝胶化体系及在锂空气电池、有机体系的超级电容器或电容电池中的应用 Download PDF

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WO2018214973A1
WO2018214973A1 PCT/CN2018/088496 CN2018088496W WO2018214973A1 WO 2018214973 A1 WO2018214973 A1 WO 2018214973A1 CN 2018088496 W CN2018088496 W CN 2018088496W WO 2018214973 A1 WO2018214973 A1 WO 2018214973A1
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weight
group
electrolyte
lithium
mass percentage
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PCT/CN2018/088496
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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 CN201710386081.7A external-priority patent/CN108962627B/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 JP2020515816A priority Critical patent/JP7173617B2/ja
Priority to EP18805899.4A priority patent/EP3637524A4/en
Priority to KR1020197035816A priority patent/KR102636304B1/ko
Publication of WO2018214973A1 publication Critical patent/WO2018214973A1/zh
Priority to US16/696,615 priority patent/US11545696B2/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
    • H01M10/0565—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
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/60—Liquid electrolytes characterised by the solvent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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
    • 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
    • Y02E60/13—Energy storage using capacitors
    • 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 gel electrolytes, and in particular relates to a gellable system and application in a lithium air battery, an ultracapacitor or a capacitor battery of an organic system.
  • Lithium-ion batteries have attracted more and more attention because of their higher energy density than lithium-ion batteries.
  • Lithium-air batteries are mainly made of porous carbon because of their cathode materials, and oxygen can be continuously obtained from the environment without being stored in the battery, so that it has the characteristics of light weight and the like.
  • the anode of the conventional lithium air battery is infiltrated in the organic electrolyte, and the air is infiltrated in the aqueous electrolyte.
  • the organic electrolyte and the aqueous electrolyte are separated by the separator to prevent mixing of the two electrolytes, and the battery can be reacted.
  • Li 2 O lithium oxide
  • the positive electrode active material oxygen of the lithium air battery is not stored in the battery but is directly taken from the air.
  • other components in the air such as H 2 O and CO 2 , have a significant impact on the performance of lithium-air batteries.
  • H 2 O reacts with the negative metal lithium to form H 2 , which poses a serious safety problem
  • CO 2 reacts with the discharge product Li 2 O 2 of the positive electrode to form a hardly decomposable Li 2 CO 3 , thereby blocking the oxygen transmission channel. , seriously affecting the performance of the battery.
  • the performance of the battery is often studied in a dry pure oxygen environment. Strictly speaking, the system can be temporarily called a "lithium oxygen battery.”
  • the system can be temporarily called a "lithium oxygen battery.”
  • the oxygen tank for the battery, because this will seriously reduce the energy density of the lithium-air battery.
  • the ultimate goal of the system is to be able to work in an air environment. Therefore, the use of a gel electrolyte system and a solid electrolyte system is very necessary in a lithium air battery.
  • the safety of lithium-air batteries also restricts its further development.
  • the safety issues mainly involve the dissolution of the anode material, the piercing of the separator, and the volatilization and leakage of the liquid organic or aqueous electrolyte. Therefore, problems such as leakage of volatile electrolyte, flammability of the battery, and overpotential decomposition seriously restrict the safety of the lithium-air battery.
  • These lithium batteries are far less than supercapacitors in terms of fast charge and discharge performance and service life.
  • Supercapacitor also known as Electrochemical Capacitor (EC)
  • EC Electrochemical Capacitor
  • supercapacitors can be divided into aqueous supercapacitors and organic supercapacitors; supercapacitors of aqueous systems mostly use strong acidity or strong alkali as electrolytes, but their decomposition voltage is low, generally 1.2V, which is extremely large. The degree affects the energy density of the device; the supercapacitor of the organic system mostly uses a volatile organic solvent as the electrolyte; similarly, the electrolyte of the capacitor battery is mostly an organic system.
  • the safety problems caused by electrolytes such as combustion and explosion in organic system electrolytes also restrict its further development.
  • the safety of supercapacitors and capacitor batteries in organic systems mainly involves the volatilization, leakage and thermal explosion of liquid organic electrolytes. , electrolyte decomposition and other issues. Therefore, the leakage of volatile electrolytes, battery flammability and overpotential decomposition seriously restrict the safety of supercapacitors.
  • inorganic solid electrolytes In order to overcome the problems of liquid electrolyte leakage and flammability, inorganic solid electrolytes, polymer solid electrolytes, and polymer gel electrolytes have been extensively studied, wherein the inorganic solid electrolyte is a lithium salt containing inorganic superionic conductivity;
  • the polymer solid electrolyte is a conductive solid composed of a polymer and a lithium salt.
  • the current reported solid electrolyte has poor electrical conductivity, which seriously affects the cycle performance of the prepared battery.
  • the polymer gel electrolyte has good conductivity and its porous structure can effectively inhibit the volatilization and leakage of the electrolyte
  • the current reported polymerization of the gel electrolyte is introduced into the polymer or synthetic step from the raw material.
  • a relatively complex small-molecule organogel factor is used in a conventional electrolyte, and the obtained polymer gel electrolyte needs to be in a flowing state at a relatively high temperature, and is in a gel state at a low temperature, which makes it necessary to inject liquid.
  • the use of high temperature injection increases the complexity of the experimental operation.
  • the transition temperature of the prepared polymer gel electrolyte is relatively low, and the gel state is relatively easily destroyed. Once the gel is destroyed, it cannot be reused. , greatly increasing the cost.
  • Another object of the present invention is to provide a gel or solid electrolyte prepared by gelation of a gellable system for a lithium air battery, and a preparation method and application of the gel or solid electrolyte.
  • a third object of the present invention is to provide a supercapacitor of an organic system and a capacitor battery of an organic system.
  • a gellable system for a lithium air battery comprising the following components: (a) a lithium salt, (b) an ether compound, and (c) an electrolyte for a lithium air battery or a solvent thereof;
  • the ether compound is selected from at least one of a cyclic ether compound or a linear ether compound;
  • the electrolyte for a lithium air battery or a solvent thereof is selected from the group consisting of an ester electrolyte and a solvent thereof, and an ether type electrolysis Liquid and solvent thereof, amide electrolyte and solvent thereof, nitrile electrolyte and solvent thereof, sulfone electrolyte and solvent thereof; gellizable polymer and/or gellizable prepolymer in system
  • the mass percentage is less than or equal to 1% by weight.
  • the mass percentage of the ether compound is 20% by weight or more and 60% by weight or less;
  • the mass percentage of the electrolyte or the solvent thereof for the lithium air battery is 20% by weight or more and 75% by weight or less, the inorganic
  • the mass percentage of the nanoparticles is 0% by weight or more and 30% by weight or less
  • the mass percentage of the additive is 0% by weight or more and 30% by weight or less.
  • the mass percentage of the ether compound is more than 60% by weight and less than or equal to 90% by weight;
  • the mass percentage of the electrolyte or the solvent thereof for the lithium air battery is 5% by weight or more and 30% by weight or less, the inorganic nanometer
  • the mass percentage of the particles is greater than or equal to 0% by weight and less than or equal to 30% by weight, and 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 comprising the gel described above.
  • a lithium air battery comprising a gel electrolyte and/or a solid electrolyte prepared by a gellable system; the gellable system comprising the following a component: (a) a lithium salt, (b) an ether compound, and (c) an electrolyte for a lithium air battery or a solvent thereof;
  • the ether compound is selected from the group consisting of a cyclic ether compound and a linear ether compound At least one of; the gelatinizable polymer and/or the gellable prepolymer in the system has a mass percentage of less than or equal to 1% by weight.
  • a gelation system the gellable system comprises the following components: (a) a lithium salt and (b) an ether compound selected from the group consisting of a cyclic ether compound and a linear ether compound At least one of; the gelatinizable polymer and/or the gellable prepolymer in the system has a mass percentage of less than or equal to 1% by weight.
  • the present invention provides a gellable system for a lithium air battery and a gel and/or solid electrolyte prepared therefrom, and a method and application thereof.
  • the present invention also provides an ultracapacitor or capacitor battery of an organic system.
  • a lithium salt and a small molecular ether compound one of a cyclic ether compound or a linear ether compound
  • ring-opening polymerization or polycondensation of small molecular ether compounds can form a gel system or a solid system; supercapacitors for lithium air batteries and organic systems are added to the gel system or solid state system.
  • the prepared system not only has the safety of use superior to the ordinary gel system or the solid system, but also by adjusting the content and type of each component in the gellable system,
  • the strength of the gel system or solid system, the formation time of the gel system or the solid system, the transition temperature of the gel system or the solid system, the change in strength can cause the gel system to expand to In solid-state systems, the application range of the gel system is further expanded.
  • the gel system or the solid system is also reversible, that is, the gel system or the solid system can be prepared at a temperature lower than the transition temperature, and after the high temperature treatment (heating to above the transition temperature), the gel system Or the solid state system will become able to flow, but after it is left to cool down (below the transition temperature), it can be restored to the original gel system or solid state system, and the properties will not change.
  • the gel system or the solid state system can not only meet the safety of the supercapacitor or the capacitor battery of the battery, the organic system, and the normal use of the battery, but also prepare the raw materials generally, and the preparation process is simple, and does not involve complicated and lengthy experimental steps.
  • the gel and solid electrolyte prepared by the gellable system for a lithium air battery according to the present invention, or the gel and solid electrolyte of the supercapacitor or capacitor battery of the organic system are adjustable in strength
  • the formation time ie, transition from a free-flowing liquid state to a non-flowable gel state and/or a solid electrolyte state
  • the transition temperature ie, from a non-flowable gel state and/or a solid electrolyte state to a
  • the lowest temperature in the free-flowing liquid state is adjustable, that is, different strength gels and solid electrolytes can be prepared according to specific needs to meet different needs.
  • the gel and the solid electrolyte have strong impact resistance.
  • the gel and the solid electrolyte can not only effectively solve the problem of leakage of the liquid electrolyte solution, but also make
  • the lithium air battery has higher charging and discharging efficiency and better impact resistance, so that the supercapacitor or the capacitor battery of the organic system has higher safety of use; and the growth thorn of lithium dendrites can be better prevented. Breaking the diaphragm or the solid electrolyte causes a short circuit of the battery, so that the lithium air battery has higher safety of use.
  • the gel and solid electrolyte prepared by the gellable system for a lithium air battery according to the present invention, or the gel and solid electrolyte in the supercapacitor or capacitor battery of the organic system are higher
  • the transition temperature is also reversible.
  • the gel or solid electrolyte When used at a temperature higher than its transition temperature, the gel and the solid electrolyte become flowable, but after cooling it below the transition temperature, it is reversible and can be re-formed into a gel. It can be reused as a solid electrolyte; because of its high transition temperature and reversibility, it can delay the service life and save costs, making it a new green gel material.
  • the gel and solid electrolyte of the present invention are simple in preparation, mild in reaction conditions, short in reaction cycle, high in product yield, low in preparation cost, and easy to realize industrial production.
  • the gel and solid electrolyte prepared by the gellable system of the present invention, or the gel and solid electrolyte in the supercapacitor or capacitor battery of the organic system can exhibit a better gel at low temperature.
  • the state or the state of the solid electrolyte, that is, the gel state or the solid electrolyte state can be maintained below the transition temperature of the gel or solid electrolyte, and the strength of the gel and the solid electrolyte is better at a low temperature.
  • the gel or solid electrolyte prepared by the gellizable system of the present invention can be applied to a lithium air battery, an ultracapacitor or a capacitor battery of an organic system, and can still be used at high and low temperatures.
  • Fig. 1 is a graph showing the cycle performance of a gel electrolyte obtained in Example 1-1 as a lithium air battery electrolyte assembled into a battery.
  • Example 2 is a cycle performance diagram of the solid electrolyte obtained in Example 1-3 assembled into a battery as a lithium air battery electrolyte.
  • Fig. 3 is a graph showing the first three charge and discharge data of the gel electrolyte obtained in Example 2-1 as a supercapacitor electrolyte of an organic system assembled into a supercapacitor.
  • Example 4 is a cycle performance diagram of a solid state electrolyte obtained in Example 2-6 as a capacitor battery electrolyte of an organic system assembled into a capacitor battery.
  • Fig. 5 is a nuclear magnetic resonance spectrum of the gel electrolyte purified product obtained in Example 1-1.
  • a first aspect of the present invention provides a gellable system for a lithium air battery, the system comprising the following components: (a) a lithium salt, (b) an ether compound, and (c) for lithium An electrolyte of an air battery or a solvent thereof;
  • the ether compound is at least one selected from the group consisting of a cyclic ether compound or a linear ether compound;
  • the electrolyte for a lithium air battery or a solvent thereof is selected from the group consisting of amides Electrolyte and solvent thereof, nitrile electrolyte and solvent thereof, sulfone electrolyte and solvent thereof; mass percentage of gellable polymer and/or gellable prepolymer in system is less than or equal to 1wt %.
  • the sum of the weight percentages of the components is 100% by weight.
  • the mass percentage of the lithium salt is 5% by weight or more and 60% by weight or less; and the mass percentage of the ether compound is greater than or equal to 20% by weight and 90% by weight or less; the mass percentage of the electrolyte or the solvent thereof for the lithium air battery is 5% by weight or more and 75% by weight or less.
  • the mass percentage of the lithium salt is 10% by weight or more and 40% by weight or less; and the mass percentage of the ether compound is 20% by weight or more. And less than or equal to 60% by weight; the mass percentage of the electrolyte or the solvent thereof for the lithium air battery is 20% by weight or more and 60% by weight or less.
  • the lithium salt has a mass percentage of 10% by weight or more and 40% by weight or less; and the ether compound has a mass percentage of more than 60% by weight and 85 wt% or less; the mass percentage of the electrolyte or the solvent thereof for the lithium air battery is 5% by weight or more and 30% by weight or less.
  • the lithium salt may be selected from lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium perfluorobutylsulfonate, lithium aluminate, chlorine One or more of lithium aluminate, lithium fluorosulfonimide, lithium chloride and lithium iodide; preferably, the lithium salt is selected from one or both of lithium hexafluorophosphate, lithium perchlorate, and the like. .
  • inorganic nanoparticles are further included in the gellable system.
  • the inorganic nanoparticles have a mass percentage of greater than or equal to 0% by weight and less than or equal to 30% by weight.
  • the inorganic nanoparticles have a mass percentage of more than 0% by weight and less than or equal to 20% by weight.
  • the gellizable system further comprises (e) an additive selected from one or more of a polyester or a blend thereof; wherein the polyester is composed of a polybasic acid or an acid anhydride Polycondensed with a polyhydric alcohol selected from the group consisting of dibasic acids, tribasic acids or polybasic acids selected from the group consisting of glycols, trihydric alcohols or polyhydric alcohols.
  • the additive has a mass percentage of greater than or equal to 0% by weight and less than or equal to 30% by weight.
  • the additive has a mass percentage of more than 0% by weight and less than or equal to 20% by weight.
  • a second aspect of the present invention provides a gel obtained by gelling a gellizable system for a lithium air battery as described above; wherein the lithium salt has a mass percentage of 5% by weight or more And 60% by weight or less; the mass percentage of the ether compound is 20% by weight or more and 60% by weight or less; the mass percentage of the electrolyte or the solvent thereof for the lithium air battery is 20% by weight or more or less.
  • the inorganic nanoparticles have a mass percentage of greater than or equal to 0 wt% and less than or equal to 30 wt%, and the mass percent of the additive is greater than or equal to 0 wt% and less than or equal to 30 wt%.
  • the mass percentage of the lithium salt is 10% by weight or more and 40% by weight or less; and the mass percentage of the ether compound is 20% by weight or more. And less than or equal to 60% by weight; the mass percentage of the electrolyte for the lithium air battery or the solvent thereof 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 more than 0% by weight and less than or equal to 20% by weight.
  • the gel has a transition temperature of 40 to 90 ° C, preferably 60 to 75 ° C.
  • the gel has a conductivity of 10 -6 to 10 -1 S/cm, preferably 10 -5 to 5 ⁇ 10 -2 S/cm.
  • a third aspect of the present invention provides a method for producing the above gel, comprising the steps of:
  • the gelation process needs to be completed under standing conditions.
  • the gel is formed at a temperature lower than the transition temperature of the gel, and the gel is formed for a time of 30 seconds to 300 hours.
  • an electrolyte for a lithium air battery or a solvent thereof, a lithium salt and an ether compound are subjected to a pre-water removal treatment; preferably, an electrolyte for a lithium air battery is used by a molecular sieve and/or a vacuum drying method. Or its solvent, lithium salt and ether compound are subjected to pre-water removal treatment.
  • a fourth aspect of the present invention provides a solid electrolyte obtained by gelling a gellizable system for a lithium air battery described above; wherein the lithium salt has a mass percentage of 5% by weight or more And the content of the ether compound is greater than 60% by weight and less than or equal to 90% by weight; the mass percentage of the electrolyte for the lithium air battery or the solvent thereof is 5% by weight or more and 30% or less.
  • the inorganic nanoparticle has a mass percentage of greater than or equal to 0% by weight and less than or equal to 30% by weight
  • the additive has a mass percentage of greater than or equal to 0% by weight and less than or equal to 30% by weight.
  • the lithium salt has a mass percentage of 10% by weight or more and 40% by weight or less; and the ether compound has a mass percentage of more than 60% by weight and 85 wt% or less; the mass percentage of the electrolyte or the solvent thereof for the lithium air battery is 5% by weight or more and 30% by weight or less, and the mass percentage of the inorganic nanoparticles is more than 0 wt% and less than or equal to 20 wt% %, the mass percentage of the additive is more than 0% by weight and less than or equal to 20% by weight.
  • the solid electrolyte has a transition temperature of 65 to 130 ° C, preferably 75 to 120 ° C.
  • the solid electrolyte has a conductivity of 10 -7 to 10 -3 S/cm, preferably 10 -6 to 10 -3 S/cm.
  • a fifth aspect of the present invention provides a method for producing the above solid electrolyte, comprising the steps of:
  • the gelation process needs to be completed under standing conditions.
  • the solid electrolyte is formed at a temperature lower than a transition temperature of the solid electrolyte, and the solid electrolyte is formed for a time of 30 minutes to 150 hours.
  • an electrolyte for a lithium air battery or a solvent thereof, a lithium salt and an ether compound are subjected to a pre-water removal treatment; preferably, an electrolyte for a lithium air battery is used by a molecular sieve and/or a vacuum drying method. Or its solvent, lithium salt and ether compound are subjected to pre-water removal treatment.
  • a sixth aspect of the invention provides a gel electrolyte comprising the gel described above.
  • a seventh aspect of the present invention provides the use of the above gel, the above solid electrolyte, and the above gel electrolyte, which is used in the field of lithium air batteries and the like.
  • An eighth aspect of the present invention provides a lithium air battery comprising a gel electrolyte and/or a solid electrolyte prepared by a gellable system;
  • the gelling system comprises the following components: (a) a lithium salt, (b) an ether compound, and (c) an electrolyte for a lithium air battery or a solvent thereof;
  • the ether compound is selected from the group consisting of a cyclic ether compound and a straight At least one of the chain ether compounds;
  • the gelatinizable polymer and/or the gellable prepolymer in the system has a mass percentage of 1% by weight or less.
  • a ninth aspect of the present invention provides a supercapacitor of an organic system comprising a gel electrolyte and/or a solid electrolyte prepared by a gellable system;
  • the gellable system comprises the following components: (a) a lithium salt and (b) an ether compound, the ether compound being selected from at least one of a cyclic ether compound and a linear ether compound;
  • the gelled polymer and/or gellable prepolymer has a mass percentage of less than or equal to 1% by weight.
  • a tenth aspect of the present invention provides a capacitor battery of an organic system comprising a gel electrolyte and/or a solid electrolyte prepared by a gellable system;
  • the gellable system comprises the following components: (a) a lithium salt and (b) an ether compound, the ether compound being selected from at least one of a cyclic ether compound and a linear ether compound;
  • the gelled polymer and/or gellable prepolymer has a mass percentage of less than or equal to 1% by weight.
  • the sum of the weight percentages of the components is 100% by weight.
  • the lithium salt has a mass percentage of 2% by weight or more and 50% by weight or less; and the ether compound has a mass percentage of 50% by weight or more and 98% by weight or less.
  • the lithium salt has a mass percentage of 5% by weight or more and less than 20% by weight; or, the lithium salt has a mass percentage of 20% by weight or more and 30% by weight or less.
  • the lithium salt may be selected from lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium perfluorobutylsulfonate, bistrifluoromethanesulfonate.
  • the gel process system further includes (c) an electrolyte for a supercapacitor or a capacitor battery of an organic system or a solvent thereof.
  • the mass percentage of the electrolyte of the supercapacitor or the capacitor battery for the organic system or the solvent thereof is 0% by weight or more and 48% by weight or less.
  • the mass percentage of the electrolyte of the supercapacitor or the capacitor battery for the organic system or the solvent thereof is more than 0% by weight and less than or equal to 40% by weight.
  • inorganic nanoparticles are further included in the gellable system.
  • the inorganic nanoparticles have a mass percentage of greater than or equal to 0% by weight and less than or equal to 30% by weight.
  • the inorganic nanoparticles have a mass percentage of more than 0% by weight and less than or equal to 20% by weight.
  • the gellizable system further comprises (e) an additive selected from one or more of a polyester or a blend thereof; wherein the polyester is composed of a polybasic acid or An acid anhydride is obtained by polycondensation of a polybasic acid selected from the group consisting of a dibasic acid, a tribasic acid or a polybasic acid, and the polyhydric alcohol is selected from the group consisting of a dihydric alcohol, a trihydric alcohol or a polyhydric alcohol.
  • the additive has a mass percentage of greater than or equal to 0% by weight and less than or equal to 30% by weight.
  • the additive has a mass percentage of more than 0% by weight and less than or equal to 20% by weight.
  • the gel electrolyte is prepared by a gellizable system, wherein the lithium salt has a mass percentage of 2% by weight or more and less than 20% by weight;
  • the mass percentage of the compound is greater than 50% by weight and less than or equal to 98% by weight;
  • the mass percentage of the electrolyte or solvent of the supercapacitor or capacitor battery for the organic system is greater than or equal to 0% by weight and less than or equal to 48% by weight;
  • 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.
  • the lithium salt has a mass percentage of 5% by weight or more and less than 20% by weight; the ether compound has a mass percentage of more than 55% by weight and less than or equal to 95% by weight; the supercapacitor or capacitor for the organic system
  • the mass percentage of the electrolyte of the battery or the solvent thereof is greater than 0 wt% and less than or equal to 40 wt%; the mass percentage of the inorganic nanoparticles is greater than 0 wt% and less than or equal to 20 wt%; the mass percentage of the additive is greater than 0 wt. % and less than or equal to 20% by weight.
  • the gel electrolyte has a transition temperature of 40 to 95 ° C, preferably 45 to 85 ° C.
  • the gel electrolyte has a conductivity of 10 -5 to 10 -1 S/cm, preferably 10 -4 to 10 -2 S/cm.
  • the solid electrolyte is prepared by a gellizable system, wherein the lithium salt has a mass percentage of 20% by weight or more and 50% by weight or less;
  • the mass percentage of the compound is 50% by weight or more and 80% by weight or less;
  • the mass percentage of the electrolyte of the supercapacitor or the capacitor battery for the organic system or the solvent thereof is 0% by weight or more and 30% by weight or less;
  • the mass percentage of the inorganic nanoparticles is 0% by weight or more and 30% by weight or less;
  • the mass percentage of the additive is 0% by weight or more and 30% by weight or less.
  • the mass percentage of the lithium salt is 20 wt% or more and 30 wt% or less; the mass percentage of the ether compound is 55 wt% or more and 80 wt% or less; the supercapacitor for an organic system Or the mass percentage of the electrolyte of the capacitor battery or the solvent thereof is greater than 0 wt% and less than or equal to 25 wt%; the mass percentage of the inorganic nanoparticles is greater than 0 wt% and less than or equal to 20 wt%; the mass percentage of the additive More than 0% by weight and less than or equal to 20% by weight.
  • the solid electrolyte has a transition temperature of 60 to 130 ° C, preferably 80 to 110 ° C.
  • the solid electrolyte has a conductivity of 10 -7 to 10 -3 S/cm, preferably 10 -6 to 10 -4 S/cm.
  • An eleventh aspect of the present invention provides a method for producing the above gel electrolyte, comprising the steps of:
  • An ether compound, a lithium salt, and an electrolyte of a supercapacitor or a capacitor battery, optionally used in an organic system, or a solvent thereof, and optionally an inorganic nanoparticle and optionally an additive, are stirred to obtain an ether compound of a lithium salt
  • the preparation method of the gel electrolyte specifically comprises the following steps:
  • Adding an ether compound to a lithium salt stirring to obtain a solution of a lithium salt ether compound, optionally using an electrolyte for a supercapacitor or a capacitor battery of an organic system or a solvent thereof and/or inorganic nanoparticles and/or additives
  • the solution of the ether compound added to the lithium salt that is, the gellable system, is continuously stirred, and gelled to obtain the gel electrolyte.
  • the lithium salt, an ether compound, an electrolyte of a supercapacitor or a capacitor battery for an organic system or a solvent thereof, and inorganic nanoparticles and additives are optionally subjected to water removal treatment; preferably, The molecular sieve and/or vacuum drying method pre-dehydrates the lithium salt, the ether compound, an electrolyte of a supercapacitor or a capacitor battery for an organic system or a solvent thereof, and inorganic nanoparticles and additives.
  • the gelation process needs to be completed under standing conditions.
  • the gel electrolyte is formed at a temperature lower than a transition temperature of the gel electrolyte, and the gel electrolyte is formed for a time of 5 seconds to 300 hours.
  • a twelfth aspect of the present invention provides a method for producing the above solid electrolyte, comprising the steps of:
  • An ether compound, a lithium salt, and an electrolyte of a supercapacitor or a capacitor battery, optionally used in an organic system, or a solvent thereof, and optionally an inorganic nanoparticle and optionally an additive, are stirred to obtain an ether compound of a lithium salt
  • the method for preparing the solid electrolyte specifically comprises the following steps:
  • Adding an ether compound to a lithium salt stirring to obtain a solution of a lithium salt ether compound, optionally using an electrolyte for a supercapacitor or a capacitor battery of an organic system or a solvent thereof and/or inorganic nanoparticles and/or additives
  • the solution of the ether compound added to the lithium salt that is, the gellable system, is continuously stirred, and the solid electrolyte is obtained by gelation.
  • the lithium salt, an ether compound, an electrolyte of a supercapacitor or a capacitor battery for an organic system or a solvent thereof, and inorganic nanoparticles and additives are optionally subjected to water removal treatment; preferably, The molecular sieve and/or vacuum drying method pre-dehydrates the lithium salt, the ether compound, an electrolyte of a supercapacitor or a capacitor battery for an organic system or a solvent thereof, and inorganic nanoparticles and additives.
  • the gelation process needs to be completed under standing conditions.
  • the solid electrolyte is formed at a temperature lower than a transition temperature of the solid electrolyte, and the solid electrolyte is formed for a time of 30 minutes to 100 hours.
  • the lithium salt, an ether compound, an electrolyte of a supercapacitor or a capacitor battery for an organic system or a solvent thereof, and inorganic nanoparticles and additives are optionally subjected to water removal treatment; preferably, The molecular sieve and/or vacuum drying method pre-dehydrates the lithium salt, the ether compound, an electrolyte of a supercapacitor or a capacitor battery for an organic system or a solvent thereof, and inorganic nanoparticles and additives.
  • 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;
  • 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 and ethyl. , 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 cyclic ether compound is selected from cyclic ether compounds containing one oxygen, two oxygen, three oxygen or more.
  • the cyclic ether compound may be a monocyclic ring, a fused ring (such as a bicyclic ring), a spiro ring or a bridged ring.
  • 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.
  • the electrolyte for a lithium air battery, a supercapacitor or a capacitor battery for an organic system or a solvent thereof includes an ether electrolyte and a solvent thereof, an ester electrolyte and a solvent thereof, an amide electrolyte, and The solvent, the nitrile electrolyte and the solvent thereof, and the sulfone electrolyte and the solvent thereof.
  • 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; preferably, the solvent of the amide-based electrolyte is selected from the group consisting of C 1 - C 20 alkyl amides, C 1 - C 20 Alkylamonitrile, C 1 -C 20 alkynyl amide, C 1 -C 20 haloalkylamide, C 1 -C 20 haloalkenylamide, C 1 -C 20 haloalkynylamide, C 7 ⁇ C 20 aryl amide group, an epoxy group at least one C 1 ⁇ C 20 amide in.
  • 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; preferably, 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 to C 20 alkynyl nitriles, C 1 to C 20 haloalkyl nitriles, C 1 to C 20 haloalkenyl nitriles, C 1 to C 20 haloalkynyl nitriles, C 7 to C 20 aryl At least one of a nitrile and a C 1 -C 20 epoxy nitrile.
  • the solvent of the nitrile electrolyt is selected from the
  • 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 electrolyte is selected from the group consisting of a compound containing a sulfone group; preferably, 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 haloalkyl sulfone of 1 ⁇ C 20, C haloalkenyl sulfone group of 1 ⁇ C 20, C haloalkynyl sulfone of 1 ⁇ C 20, C aryl sulfone group of 7 ⁇ C 20 And at least one of C 1 to C 20 epoxy sulfones.
  • 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.
  • 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 a dibasic acid, a tribasic acid or a polybasic acid
  • the polyhydric alcohol is selected from the group consisting of a glycol, a triol or a polyhydric alcohol.
  • 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 polyethylene glycol, or a combination of polyethylene glycol and one or more of the following polyols: propylene glycol, butanediol, pentanediol, hexanediol, glycol 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).
  • PVC polyvinyl chloride
  • PS polystyrene
  • PAN polyacrylonitrile
  • PAN polyethyl acetate
  • PVAC polyvinylpyrrolidone
  • PVS polydivinyl sulfide
  • PTMC poly Sanya Methyl carbonate
  • PMMA polymethyl methacrylate
  • PEGDM polyethylene glycol dimethacrylate
  • PPO polyoxypropylene
  • PDMSO polydimethylsiloxane
  • 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.
  • 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.
  • 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.
  • the conductivity described in this example was obtained using an electrochemical workstation of the Model 1000 model from Gamry, Inc., and the test scanning frequency was from 1.0 Hz to 100 kHz.
  • the test of the battery described in this embodiment is a blue battery pack.
  • the test of the supercapacitor or capacitor battery of the organic system is in the blue electric tester.
  • the ether compound is subjected to water removal treatment via molecular sieve before use.
  • the electrolyte for the lithium air battery or its solvent is dried by water removal through a molecular sieve before use.
  • the electrolyte of the supercapacitor or capacitor battery for an organic system or a solvent thereof is dried by a molecular sieve to remove water before use.
  • the negative electrode was a lithium plate; the electrolytic solution: a gel electrolyte or a solid electrolyte prepared in each example; a separator: Whatman separator.
  • the mass percentage of the lithium salt is 12% by weight; the mass percentage of the ether compound is 58% by weight; and the mass percentage of the electrolytic solution for the lithium air battery or the solvent thereof is 30% by weight.
  • the performance parameters of the gel were tested in Table 1.
  • the gel When the prepared gel is heated above the transition temperature of the gel, the gel begins to become sticky. When the reagent bottle is inverted, the gel is observed to flow downward, indicating that the temperature has reached the gel transition temperature, and when the temperature is reached. Upon falling below the transition temperature of the gel, the gel reformed again, indicating that the prepared gel has good reversibility.
  • the gel prepared above was applied as a gel electrolyte to a lithium air battery, and the electrochemical performance of the button battery was tested using a blue battery (test results are shown in Table 1).
  • the assembly process of the lithium air battery is carried out in the glove box.
  • the Swagelok removable and washable battery mold is used.
  • the mold, diaphragm, air electrode and other tools need to be vacuum dried in a vacuum oven at 100 ° C for 24 hours before use.
  • the gloss is first assembled when the battery is assembled. A good lithium sheet is placed in the center of the mold base, and then an appropriate amount of electrolyte, separator, and graphene air electrode are sequentially added to assemble a lithium air battery, and the gelled system is allowed to stand to become a gel electrolyte.
  • the mass percentage of the lithium salt is 15% by weight; the mass percentage of the ether compound is 68% by weight; and the mass percentage of the electrolyte for the lithium air battery or the solvent thereof is 17% by weight.
  • the performance parameters of the solid electrolyte were tested in Table 1.
  • the solid electrolyte prepared above was applied to a lithium air battery, and the electrochemical performance of the button battery was tested using a blue battery (test results are shown in Table 1).
  • the assembly process of the lithium air battery is carried out in the glove box.
  • the Swagelok removable and washable battery mold is used.
  • the mold, diaphragm, air electrode and other tools need to be vacuum dried in a vacuum oven at 100 ° C for 24 hours before use.
  • the gloss is first assembled when the battery is assembled. A good lithium sheet is placed in the center of the mold base, and then an appropriate amount of electrolyte, separator, and graphene air electrode are sequentially added to assemble a lithium air battery, and the gelatinizable system is allowed to stand into a solid electrolyte.
  • alumina 0.1 g was weighed into a reagent bottle, and 4.5 mL of 1,3-dioxolane was added thereto, and the mixture was thoroughly mixed under magnetic stirring to obtain a mixed solution A. Further, 0.4 g of lithium trifluoromethanesulfonate and 0.6 g of lithium perchlorate were placed in a reagent bottle, 1.2 mL of dimethyl sulfoxide (DMSO) 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; it was allowed to stand for a while to form a solid electrolyte.
  • DMSO dimethyl sulfoxide
  • the solid electrolyte When the prepared solid electrolyte is heated above the gel transition temperature of the solid electrolyte gel, the solid electrolyte begins to become sticky, and when the reagent bottle is inverted, the solid electrolyte flows downward, indicating that the temperature has reached the transition temperature of the solid electrolyte. When the temperature drops below the gel transition temperature, the solid electrolyte is reformed again, indicating that the prepared solid electrolyte has good reversibility.
  • the solid electrolyte prepared above was applied to a lithium air battery, and the electrochemical performance of the button battery was tested using a blue battery (test results are shown in Table 1).
  • the assembly process of the lithium air battery is carried out in the glove box.
  • the Swagelok removable and washable battery mold is used.
  • the mold, diaphragm, air electrode and other tools need to be vacuum dried in a vacuum oven at 100 ° C for 24 hours before use.
  • the gloss is first assembled when the battery is assembled. A good lithium sheet is placed in the center of the mold base, and then an appropriate amount of electrolyte, separator, and graphene air electrode are sequentially added to assemble a lithium air battery, and the gelatinizable system is allowed to stand into a solid electrolyte.
  • the mass percentage of the lithium salt is 22% by weight; the mass percentage of the ether compound is 45 wt%; the mass percentage of the polyester additive is 21 wt%; the solvent and/or electrolysis of the lithium air battery
  • the mass percentage of the liquid was 11% by weight; the mass percentage of silica was 1% by weight.
  • the performance parameters of the gel electrolyte were tested in Table 1.
  • the gel When the prepared gel is heated above 60 ° C, the gel becomes able to flow. When the reagent bottle is inverted, the gel is found to flow downward, indicating that the gel transition temperature has been reached, and when the temperature drops to 60 ° C. In the following, the gel was reformed again, indicating that the prepared gel has good reversibility.
  • the gel prepared above was applied as a gel electrolyte to a lithium air battery, and the electrochemical performance of the button battery was tested using a blue battery (test results are shown in Table 1).
  • the assembly process of the lithium air battery is carried out in the glove box.
  • the Swagelok removable and washable battery mold is used.
  • the mold, diaphragm, air electrode and other tools need to be vacuum dried in a vacuum oven at 100 ° C for 24 hours before use.
  • the gloss is first assembled when the battery is assembled. A good lithium sheet is placed in the center of the mold base, and then an appropriate amount of electrolyte, separator, and graphene air electrode are sequentially added to assemble a lithium air battery, and the gelled system is allowed to stand to become a gel electrolyte.
  • trioxane 0.8 g of lithium chloride and 0.8 g of lithium perchlorate were weighed into a reagent bottle, 1.1 mL of acetonitrile was added thereto, and the lithium salt and the paraformaldehyde were completely dissolved under magnetic stirring, and added thereto.
  • 3.5 mL of 1,4-dioxane was stirred for thorough mixing to give a gellable system; for a period of time, a solid electrolyte was formed.
  • the mass percentage of the lithium salt is 23% by weight; the mass percentage of the ether compound is 61% by weight; and the mass percentage of the electrolyte for the lithium air battery or the solvent thereof is 16wt %.
  • the performance parameters of the solid electrolyte were tested in Table 1.
  • the solid electrolyte prepared above was applied to a lithium air battery, and the electrochemical performance of the button battery was tested using a blue battery (test results are shown in Table 1).
  • the assembly process of the lithium air battery is carried out in the glove box.
  • the Swagelok removable and washable battery mold is used.
  • the mold, diaphragm, air electrode and other tools need to be vacuum dried in a vacuum oven at 100 ° C for 24 hours before use.
  • the gloss is first assembled when the battery is assembled. A good lithium sheet is placed in the center of the mold base, and then an appropriate amount of electrolyte, separator, and graphene air electrode are sequentially added to assemble a lithium air battery, and the gelatinizable system is allowed to stand into a solid electrolyte.
  • the mass percentage of the lithium salt is 17% by weight; the mass percentage of the ether compound is 50% by weight; and the mass percentage of the electrolytic solution for the lithium air battery or the solvent thereof is 33% by weight.
  • the performance parameters of the gel electrolyte were tested in Table 1.
  • the gel When the prepared gel is heated above the transition temperature of the gel, the gel begins to become sticky. When the reagent bottle is inverted, the gel is observed to flow downward, indicating that the temperature has reached the gel transition temperature, and when the temperature is reached. Upon lowering below the transition temperature of the gel, the gel reformed again, indicating that the prepared gel has good reversibility.
  • 0.05 g of silica was weighed into a reagent bottle, 3.0 mL of tetrahydrofuran was added thereto, and the mixture was thoroughly mixed under magnetic stirring to obtain a mixed solution A. Further, 1.0 g of lithium tetrafluoroborate was placed in a reagent bottle, 3.0 mL of dimethyl sulfoxide (DMSO) 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; it was allowed to stand for a while to form a gel.
  • DMSO dimethyl sulfoxide
  • the mass percentage of the lithium salt is 14 wt%; the mass percentage of the ether compound is 42.6 wt%; the mass percentage of the inorganic nanoparticles is 0.8 wt%; the lithium air battery solvent and / Or the mass percentage of the electrolyte is 42.6 wt%.
  • the performance parameters of the gel electrolyte were tested in Table 1.
  • the gel When the prepared gel is heated above the transition temperature of the gel, the gel begins to become sticky, and when the reagent bottle is inverted, the gel is observed to flow downward, indicating that the temperature has reached the transition temperature of the gel, and When the temperature drops below the transition temperature of the gel, the gel re-forms, indicating that the prepared gel has good reversibility.
  • the gel prepared above was applied as a gel electrolyte to a lithium air battery, and the electrochemical performance of the button battery was tested using a blue battery (test results are shown in Table 1).
  • the assembly process of the lithium air battery is carried out in the glove box.
  • the Swagelok removable and washable battery mold is used.
  • the mold, diaphragm, air electrode and other tools need to be vacuum dried in a vacuum oven at 100 ° C for 24 hours before use.
  • the gloss is first assembled when the battery is assembled. A good lithium sheet is placed in the center of the mold base, and then an appropriate amount of electrolyte, separator, and graphene air electrode are sequentially added to assemble a lithium air battery, and the gelled system is allowed to stand to become a gel electrolyte.
  • trioxane 0.5 g of lithium trifluoromethanesulfonate and 1.0 g of lithium bis(oxalate)borate in a reagent bottle, and add 1.0 mL of dimethyl carbonate thereto to make lithium salt and trioxane under magnetic stirring.
  • solution A 0.1 g of carbon nitride was weighed, and 3.8 mL of tetrahydrofuran was added thereto, and stirred to sufficiently mix to obtain a solution B.
  • the solution A and the solution B were uniformly mixed to obtain a gellable system; for a while, a solid electrolyte was formed.
  • the mass percentage of the lithium salt is 20.5 wt%; the mass percentage of the ether compound is 64.3 wt%; the mass percentage of the inorganic nanoparticles is 1.4 wt%; The mass percentage of the electrolyte of the air battery or its solvent was 13.8% by weight.
  • the performance parameters of the solid electrolyte were tested in Table 1.
  • the solid electrolyte prepared above was applied to a lithium air battery, and the electrochemical performance of the button battery was tested using a blue battery (test results are shown in Table 1).
  • the assembly process of the lithium air battery is carried out in the glove box.
  • the Swagelok removable and washable battery mold is used.
  • the mold, diaphragm, air electrode and other tools need to be vacuum dried in a vacuum oven at 100 ° C for 24 hours before use.
  • the gloss is first assembled when the battery is assembled. A good lithium sheet is placed in the center of the mold base, and then an appropriate amount of electrolyte, separator, and graphene air electrode are sequentially added to assemble a lithium air battery, and the gelatinizable system is allowed to stand into a solid electrolyte.
  • Fig. 1 is a graph showing the cycle performance of a gel electrolyte obtained in Example 1-1 as a lithium air battery electrolyte assembled into a battery. As can be seen from the figure, the gel electrolyte exhibits excellent cycle performance in a lithium air battery, and the discharge specific capacity decays very slowly, and remains substantially unchanged in the latter stage, exhibiting stable cycle performance.
  • the gel When the prepared gel is heated above the transition temperature of the gel, the gel begins to become sticky. When the reagent bottle is inverted, the gel is observed to flow downward, indicating that the temperature has reached the gel transition temperature, and when the temperature is reached. Upon falling below the transition temperature of the gel, the gel reformed again, indicating that the prepared gel has good reversibility.
  • the method for preparing the supercapacitor comprises: placing a separator between the positive electrode and the negative electrode, filling the gelatinizable system prepared in the step (1) between the three, packing and compacting, and assembling into a CR2032 button type super capacitor. The gellable system is allowed to stand to become a gel electrolyte.
  • the gel When the prepared gel is heated above the transition temperature of the gel, the gel begins to become sticky. When the reagent bottle is inverted, the gel is observed to flow downward, indicating that the temperature has reached the gel transition temperature, and when the temperature is reached. Upon falling below the transition temperature of the gel, the gel reformed again, indicating that the prepared gel has good reversibility.
  • Capacitor battery positive electrode The lithium manganate electrode material is uniformly mixed with conductive graphite, conductive agent Ketjen black, and binder polyvinylidene fluoride (PVDF) according to a mass ratio of 85:5:5:5, using N-methyl- Pyrrolidone (NMP) to prepare a mixture into a slurry, uniformly coated on an aluminum foil, and dried in a vacuum oven at 120 ° C for 24 hours, ready for use;
  • PVDF polyvinylidene fluoride
  • Capacitor battery anode The lithium titanate electrode material and the conductive agent Ketchen Black, the binder polyvinylidene fluoride (PVDF) are uniformly mixed at a mass ratio of 85:8:7, and N-methyl-pyrrolidone (NMP) will be used. The mixture was prepared into a slurry, uniformly coated on an aluminum foil, and dried in a vacuum oven at 120 ° C for 24 hours, and used;
  • the capacitor battery is prepared by placing a separator between the positive electrode and the negative electrode, and filling the gelatinizable system prepared in the step (1) between the three, packing and compacting, and assembling into a CR2032 type button capacitor battery. The gellable system is allowed to stand to become a gel electrolyte.
  • the solid electrolyte When the prepared solid electrolyte is heated above the transition temperature of the solid electrolyte, the solid electrolyte begins to become sticky, and when the reagent bottle is inverted, the solid electrolyte flows downward, indicating that the temperature has reached the transition temperature of the solid electrolyte, and when the temperature When the temperature drops below the transition temperature of the solid electrolyte, the solid electrolyte is reformed again, indicating that the prepared solid electrolyte has good reversibility.
  • Supercapacitor anode The iron-cobalt-nickel composite supercapacitor material, the conductive agent Ketchen black, and the binder polyvinylidene fluoride (PVDF) are uniformly mixed at a mass ratio of 8:1:1, and N-methyl-pyrrolidone (NMP) is used. The mixture is prepared into a slurry, uniformly coated on an aluminum foil, and dried in a vacuum oven at 60 ° C for 24 hours, and used;
  • PVDF polyvinylidene fluoride
  • NMP N-methyl-pyrrolidone
  • the solid electrolyte When the prepared solid electrolyte is heated above the transition temperature of the solid electrolyte, the solid electrolyte begins to become sticky, and when the reagent bottle is inverted, the solid electrolyte flows downward, indicating that the temperature has reached the transition temperature of the solid electrolyte, and when the temperature When the temperature drops below the transition temperature of the solid electrolyte, the solid electrolyte is reformed again, indicating that the prepared solid electrolyte has good reversibility.
  • Capacitor battery anode The preparation process is the same as the preparation process of the negative electrode of the capacitor of Example 2-2.
  • the solid electrolyte prepared above was applied to a capacitor battery, and assembled into a capacitor battery with the above-mentioned capacitor battery positive electrode and capacitor battery negative electrode, and the electrochemical performance of the capacitor battery was tested using a blue electric tester (test results are shown in Table 2).
  • the capacitor battery is prepared by placing a separator between the positive electrode and the negative electrode, and filling the gelatinizable system prepared in the step (1) between the three, packing and compacting, and assembling into a CR2032 type button capacitor battery.
  • the gellable system is allowed to stand to become a solid electrolyte.
  • the mass percentage of the lithium salt is 15% by weight; the mass percentage of the ether compound is 40% by weight; and the mass percentage of the electrolyte for the lithium ion battery or the solvent thereof is 45 wt% .
  • the performance parameters of the gel electrolyte were tested in Table 2.
  • the gel electrolyte When the prepared gel electrolyte is heated above the transition temperature of the gel electrolyte, the gel electrolyte begins to become sticky, and the gel electrolyte is observed to flow downward when the reagent bottle is inverted, indicating that the temperature has reached the transition of the gel electrolyte. The temperature, and when the temperature drops below the transition temperature of the gel electrolyte, the gel electrolyte is reformed again, indicating that the prepared gel electrolyte has good reversibility.
  • Capacitor battery positive electrode The preparation process is the same as that in Example 2-2.
  • Capacitor battery anode The preparation process is the same as the preparation process of the negative electrode of the capacitor of Example 2-2.
  • the capacitor battery is prepared by placing a separator between the positive electrode and the negative electrode, and filling the gelatinizable system prepared in the step (1) between the three, packing and compacting, and assembling into a CR2032 type button capacitor battery. The gellable system is allowed to stand to become a gel electrolyte.
  • the solid electrolyte When the prepared solid electrolyte is heated above the transition temperature of the solid electrolyte, the solid electrolyte begins to become sticky, and when the reagent bottle is inverted, the solid electrolyte flows downward, indicating that the temperature has reached the transition temperature of the solid electrolyte, and when the temperature When the temperature drops below the transition temperature of the solid electrolyte, the solid electrolyte is reformed again, indicating that the prepared solid electrolyte has good reversibility.
  • Capacitor battery positive electrode The preparation process is the same as that in Example 2-2.
  • Capacitor battery anode The preparation process is the same as the preparation process of the negative electrode of the capacitor of Example 2-2.
  • lithium perfluorobutanesulfonate 1.2 g was weighed into a reagent bottle, 4 mL of 1,4-epoxycyclohexane and 4 mL of 2-chloromethyloxetane were added thereto, and 0.8 g of an additive was added thereto, followed by stirring to sufficiently mix.
  • Gelatinizable system static for a period of time to form a gel electrolyte.
  • the mass percentage of the lithium salt is 12% by weight; the mass percentage of the ether compound is 80% by weight; and the mass percentage of the additive is 8% by weight.
  • the performance parameters of the gel electrolyte were tested in Table 2.
  • the gel electrolyte When the prepared gel electrolyte is heated above the transition temperature of the gel electrolyte, the gel electrolyte begins to become sticky, and the gel electrolyte is observed to flow downward when the reagent bottle is inverted, indicating that the temperature has reached the transition of the gel electrolyte. The temperature, and when the temperature drops below the transition temperature of the gel electrolyte, the gel electrolyte is reformed again, indicating that the prepared gel electrolyte has good reversibility.
  • Supercapacitor positive electrode The preparation process was the same as that of Example 2-1 supercapacitor positive electrode preparation process.
  • Supercapacitor negative electrode the preparation process is the same as that of the embodiment 2-1 supercapacitor negative electrode preparation process;
  • the method for preparing the supercapacitor comprises: placing a separator between the positive electrode and the negative electrode, filling the gelatinizable system prepared in the step (1) between the three, packing and compacting, and assembling into a CR2032 button type super capacitor. The gellable system is allowed to stand to become a gel electrolyte.
  • the gel When the prepared gel is heated above the transition temperature of the gel, the gel begins to become sticky. When the reagent bottle is inverted, the gel is observed to flow downward, indicating that the temperature has reached the gel transition temperature, and when the temperature is reached. Upon falling below the transition temperature of the gel, the gel reformed again, indicating that the prepared gel has good reversibility.
  • Supercapacitor positive electrode The preparation process was the same as that of Example 2-1 supercapacitor positive electrode preparation process.
  • the method for preparing the supercapacitor comprises: placing a separator between the positive electrode and the negative electrode, filling the gelatinizable system prepared in the step (1) between the three, packing and compacting, and assembling into a CR2032 button type super capacitor. The gellable system is allowed to stand to become a gel electrolyte.
  • the mass percentage of the lithium salt is 21% by weight; the mass percentage of the ether compound is 74% by weight; the mass percentage of the electrolyte for the supercapacitor or the solvent thereof is 3% by weight, the additive The mass percentage is 2% by weight.
  • the performance parameters of the solid electrolyte were tested in Table 2.
  • the solid electrolyte When the prepared solid electrolyte is heated above the transition temperature of the solid electrolyte, the solid electrolyte begins to become sticky, and when the reagent bottle is inverted, the solid electrolyte flows downward, indicating that the temperature has reached the transition temperature of the solid electrolyte, and when the temperature When the temperature drops below the transition temperature of the solid electrolyte, the solid electrolyte is reformed again, indicating that the prepared solid electrolyte has good reversibility.
  • Supercapacitor positive electrode The preparation process was the same as that of the example 2-1 supercapacitor positive electrode preparation process, and the obtained pole piece was immersed in the precursor solution of the above solid electrolyte.
  • Supercapacitor Negative The preparation process was the same as in Example 2-2. The supercapacitor negative electrode preparation process was performed, and the obtained pole piece was immersed in the precursor solution of the above solid electrolyte.
  • the above solid electrolyte precursor was blade coated on a glass plate, and after it was cured, it was gently peeled off with a blade to obtain a solid electrolyte film.
  • the solid electrolyte membrane prepared above was placed between the above-mentioned supercapacitor positive electrode and the supercapacitor negative electrode, assembled into a supercapacitor, and the electrochemical performance of the supercapacitor was tested using a blue electric tester (test results are shown in Table 2).
  • the method for preparing the supercapacitor comprises: placing a separator between the positive electrode and the negative electrode, filling the gelatinizable system prepared in the step (1) between the three, packing and compacting, and assembling into a CR2032 button type super capacitor. The gellable system is allowed to stand to become a solid electrolyte.
  • 1.5 mL of the above polyester was weighed, 1.5 mL of dimethyl carbonate, 1.5 mL of propylene carbonate and 3.5 mL of 1,2-epoxycyclohexane were added, and the mixture was uniformly stirred under magnetic stirring to obtain a clear solution, and weighed.
  • 1.8 g of lithium tetrafluoroborate solid was added to the above mixture, and after sufficiently dissolved, a gellable system was obtained; and the gel electrolyte was formed at rest for a while.
  • the mass percentage of the lithium salt is 18 wt%; the mass percentage of the ether compound is 35.7 wt%; the mass percentage of the polyester additive is 15.3%; for the lithium ion battery
  • the mass percentage of the electrolyte or its solvent was 31% by weight.
  • the performance parameters of the gel electrolyte were tested in Table 2.
  • Table 2 The performance parameters of the gel electrolyte were tested in Table 2.
  • the gel electrolyte When the prepared gel electrolyte is heated above the transition temperature of the gel electrolyte, the gel electrolyte begins to become sticky, and the gel electrolyte is observed to flow downward when the reagent bottle is inverted, indicating that the temperature has reached the transition of the gel electrolyte. The temperature, and when the temperature drops below the transition temperature of the gel electrolyte, the gel electrolyte is reformed again, indicating that the prepared gel electrolyte has good reversibility.
  • Capacitor battery positive electrode the lithium manganate electrode material and conductive graphite, conductive agent Ketchen black, the above gelatinizable system is uniformly mixed according to the mass ratio of 85:5:5:5, and N-methyl-pyrrolidone (NMP) will be used.
  • the mixture is prepared into a slurry, uniformly coated on an aluminum foil, and dried in a vacuum oven at 120 ° C for 24 hours, and used; the negative electrode of the capacitor battery: the lithium titanate electrode material and the conductive agent Ketchen Black, the gelatinizable system described above
  • the mass ratio was uniformly mixed at 85:8:7, and the mixture was prepared into a slurry by N-methyl-pyrrolidone (NMP), uniformly coated on an aluminum foil, and dried in a vacuum oven at 120 ° C for 24 hours, and was used.
  • NMP N-methyl-pyrrolidone
  • the capacitor battery is prepared by placing a separator between the positive electrode and the negative electrode, and filling the gelatinizable system prepared in the step (1) between the three, packing and compacting, and assembling into a CR2032 type button capacitor battery. The gellable system is allowed to stand to become a gel electrolyte.
  • the mass percentage of the lithium salt is 33% by weight; the mass percentage of the ether compound is 0% by weight; and the mass percentage of the electrolytic solution of the supercapacitor for the organic system or the solvent thereof is 67% by weight.
  • Fig. 3 is a view showing the first three charge and discharge diagrams of the gel electrolyte obtained in Example 2-1 as a supercapacitor electrolyte of an organic system assembled into a supercapacitor.
  • the gel electrolyte as an organic system supercapacitor electrolyte can make the supercapacitor charge and discharge normally, and the active material in the electrolyte can fully function, and the supercapacitor has a high specific capacity.

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Abstract

本发明公开了一种可凝胶化体系及在锂空气电池、有机体系的超级电容器或电容电池中的应用。所述有机体系的超级电容器或电容电池包括凝胶电解质和/或固态电解质，其由可凝胶化体系制备得到的，所述可凝胶化体系包括如下组分，(a)锂盐，(b)醚类化合物；所述用于锂空气电池的可凝胶化体系还包括(c)用于锂空气电池的电解液或其溶剂；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％；通过调节所述体系中各组分含量和种类，可以制备得到强度可调、形成时间可调、转变温度可调，同时也具有可逆性的凝胶和/或固态电解质；所述制备方法简单、反应条件温和、反应周期短、产物收率高、制备成本低、易于实现工业化生产。

Description

一种可凝胶化体系及在锂空气电池、有机体系的超级电容器或电容电池中的应用 技术领域
本发明属于凝胶电解质技术领域，具体涉及一种可凝胶化体系及在锂空气电池、有机体系的超级电容器或电容电池中的应用。
背景技术
近年来，化石能源的过度消耗造成了能源危机和环境问题，大量的汽车尾气排放造成全球变暖和雾霾天气的日益加重，这些问题都严重影响了人类的生产生活。电能是一种清洁能源并且可以通过可充电电池实现循环使用，锂电池由于具有高电压平台、高能量密度、循环寿命长以及低自放电等优势，其不仅可以应用在便携式电子设备，例如：数码相机和便携式计算机等设备中，而且在电动工具、电动车等方面也有着广泛的应用。
目前最常用的锂电池为锂离子电池、锂硫电池和锂空气电池等，由于锂空气电池比锂离子电池具有更高的能量密度的新型锂电池，其越来越受到人们的关注。锂空气电池因其阴极材料主要以多孔碳为主，且氧气可以从环境中不断获取而不需要存储在电池内，因而具有质量轻便等特点。常规的锂空气电池的负极浸润在有机电解液中，空气极浸润在水性电解液中，有机电解液和水性电解液通过隔膜分隔开，防止两电解液发生混合，而且能促进电池发生反应，也能够防止正极的固体反应生成物——氧化锂(Li 2O)的析出。然而，锂空气电池的正极活性物质氧气并不储存在电池内，而是直接从空气中获取。但是，空气中的其他成分，譬如H 2O和CO 2，对锂空气电池的性能有显著影响。H 2O会和负极金属锂反应生成H 2，从而带来严重的安全问题，而CO 2会与正极的放电产物Li 2O 2反应，生成难分解的Li 2CO 3，从而堵塞氧气传输通道，严重影响电池的性能。为了避免H 2O、CO 2等气体的干扰，目前往往在干燥的纯氧环境内进行电池性能的研究。严格来说，该体系可以暂时称为“锂氧气电池”。但是，在未来锂空气电池的实际应用中，并不可能为电池专门配置氧气罐，因为此举会严重降低锂空气电池的能量密度。该体系的最终目标是能够在空气环境中工作。所以使用凝胶电解质体系和固态电解质体系在锂空气电池中是十分必要的。另外锂空气电池的安全问题也制约其进一步的发展，其安全问题主要涉及到负极材料的溶解、隔膜的刺穿和液态有机或水性电解液的挥发和泄露等问题。因此，挥发性电解液的泄露、电池可燃和过电势分解等问题严重制约着锂空气电池的安全性。而这些锂电池在快速充放电性能和使用寿命上远不及超级电容器，超级电容器(Supercapacitor,Ultracapacitor)又叫电化学电容器(Electrochemical Capacitor,EC)，是一种电化学元件，通过极化电解质来储能，且储能的过程并不发生化学反应，始终是物理过程，因此性能稳定；这种储能过程是可逆的，也正因为此超级电容器可以反复充放电数十万次，其使用寿命得到了大大的延长；不仅如此，当外加电压加到超级电容器的两个极板上时，正极板存储正电荷，负极板存储负电荷，在超级电容器的两极板上电荷产生的电场作用下，在电解液与电极间的界面上形成相反的电荷，以平衡电解液的内电场，这种正电荷与负电荷在两个不同相之间的接触面上，以正负电荷之间极短间隙排列在相反的位置上，因此存储的电容量非常大。然而，单纯的超级电容器虽然具有很高的功率密度，但能量密度仍有待进一步提高。通过研究发现，在电池两端并联大容量电容器能缓冲大电流对电池的冲击，从而延长电池的循环寿命，由此电容型锂离子电池便应运而生。后期，人们又采用内连接的方式，使每个电池材料颗粒都处于电容器的保护之中，由此产生电容电池的这一电子器件，其兼具有电池高能量密度和超级电容高功率密度的特点。
按电解质类型分类，超级电容器可以分为水性体系超级电容器和有机体系超级电容器；水性体系的超级电容器多采用强酸性或强碱性作电解质，但其分解电压较低，一般在1.2V，极大程度影响了器件的能量密度；有机体系的超级电容器则多采用可挥发性有机溶剂作电解质；同样，电容电池的电解液也多为有机体系。然而，有机体系电解液带来的诸如燃烧、爆炸等安全问题也制约其进一步的发展，有机体系的超级电容器及电容电池的安全问题主要涉及到液态有机电解液的挥发、泄露以及遇热着火爆炸，电解液分解等问题。因此，挥发性电解液的泄露、电池可燃和过电势分解等问题严重制约着超级电容器的安全性。
为了克服液态电解液的泄露和可燃等问题，无机固态电解质、聚合物固态电解质以及聚合物凝胶电解质等已经被广泛研究，其中，无机固态电解质是一种含有无机超离子导电性的锂盐；聚合物固态电解质是聚合物和锂盐构成的具有导电性的固体，但是，目前报道的固态电解质的导电性均不好，这严重影响了制备得到的电池的循环性能。
聚合物凝胶电解质虽然具有较好的导电性，而且其多孔结构可以有效的抑制电解液的挥发和泄露，然而，目前报道的聚合凝胶电解质的制备都是从原料上引入高分子或者合成步骤比较复杂的小分子有机凝胶因子于常规电解液中，并且得到的聚合物凝胶电解质都需要在较高温度下才能呈现流动状态，在低温下为凝胶态，这就使得注液时要采用高温注液，增加了实验操作的复杂性，另外，制备得到的聚合物凝胶电解质的转变温度也都相对比较低，凝胶状态比较容易被破坏，一旦凝胶被破坏后，无法再次利用，大大增加了成本。
发明内容
为了解决现有技术的不足，本发明的目的之一是提供一种用于锂空气电池的可凝胶化体系。
本发明的目的之二是提供一种上述用于锂空气电池的可凝胶化体系经凝胶化制备得到的凝胶或固态电解质，及所述凝胶或固态电解质的制备方法和应用。
本发明的目的之三是提供一种有机体系的超级电容器和有机体系的电容电池。
本发明目的是通过如下技术方案实现的：
一种用于锂空气电池的可凝胶化体系，该体系中包括以下组分：(a)锂盐，(b)醚类化合物和(c)用于锂空气电池的电解液或其溶剂；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；所述用于锂空气电池的电解液或其溶剂选自酯类电解液及其溶剂、醚类电解液及其溶剂、酰胺类电解液及其溶剂、腈类电解液及其溶剂、砜类电解液及其溶剂；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％。
一种凝胶，所述凝胶由上述的用于锂离子电池的可凝胶化体系经凝胶化得到；其中，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％；所述用于锂空气电池的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％。
一种固态电解质，所述固态电解质由上述的用于锂离子电池的可凝胶化体系经凝胶化得到；其中，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％；所述用于锂空气电池的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％。
一种凝胶电解质，所述凝胶电解质包括上述的凝胶。
一种锂空气电池，所述锂空气电池包括凝胶电解质和/或固态电解质，所述凝胶电解质和/或 固态电解质由可凝胶化体系制备得到的；所述可凝胶化体系包括如下组分：(a)锂盐，(b)醚类化合物和(c)用于锂空气电池的电解液或其溶剂；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；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％。
一种有机体系的超级电容器或有机体系的电容电池，所述有机体系的超级电容器或有机体系的电容电池包括凝胶电解质和/或固态电解质，所述凝胶电解质和/或固态电解质由可凝胶化体系制备得到的；所述可凝胶化体系包括如下组分：(a)锂盐和(b)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；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％。
本发明的有益效果：
1.本发明提供了一种用于锂空气电池的可凝胶化体系及其制备得到的凝胶和/或固态电解质、及其制备方法和应用。另外，本发明还提供了一种有机体系的超级电容器或电容电池。申请人在研究中发现，将锂盐和小分子醚类化合物(环状醚类化合物或直链醚类化合物中的一种)混合，通过二者的相互作用(例如生成新的络合物或自组装作用等)和小分子醚类化合物的开环聚合或缩聚等方式可形成凝胶体系或固态体系；在所述凝胶体系或固态体系中加入用于锂空气电池、有机体系的超级电容器或电容电池的电解液或其溶剂，使得制备得到的体系不仅具备优于普通凝胶体系或固态体系的使用安全性，而且通过调节所述可凝胶化体系中各组分的含量和种类，可以有效控制所述凝胶体系或固态体系的强度，所述凝胶体系或固态体系的形成时间，所述凝胶体系或固态体系的转变温度，所述强度的改变可使得凝胶体系扩展到固态体系中，从而更加扩大凝胶体系的应用范围。另外，所述凝胶体系或固态体系还具有可逆性，即凝胶体系或固态体系在低于转变温度时可以制备得到，而经过高温处理(加热至转变温度以上)后，所述凝胶体系或固态体系会变得可以流动，但将其重新静置冷却(降至转变温度以下)后，又能够恢复成原来的凝胶体系或固态体系，并且性质不会发生变化。所述凝胶体系或固态体系不但可以满足电池、有机体系的超级电容器或电容电池的安全性和电池的正常使用，而且制备原料普遍，制备过程简单，不涉及繁琐冗长的实验步骤
2.本发明所述的用于锂空气电池的可凝胶化体系制备得到的凝胶和固态电解质、或者是所述的有机体系的超级电容器或电容电池中的凝胶和固态电解质强度可调、形成时间(即由可自由流动的液体状态转变成不可流动的凝胶状态和/或固态电解质状态)可调、转变温度(即由不可流动的凝胶状态和/或固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凝胶和固态电解质，以满足不同的需要。所述凝胶和固态电解质具有较强的抗冲击能力，在应用于锂空气电池、有机体系的超级电容器或电容电池等领域中时，不仅可以有效解决液体电解液溶液泄露等问题，还可以使得锂空气电池具有更高的充放电效率、更好的耐冲击性，使所述有机体系的超级电容器或电容电池具有更高的使用安全性；同样可以更好地防止由于锂枝晶的生长刺破隔膜或者固态电解质而引起电池短路，使所述锂空气电池具有更高的使用安全性。
3.本发明所述的用于锂空气电池的可凝胶化体系制备得到的凝胶和固态电解质，或者是所述的有机体系的超级电容器或电容电池中的凝胶和固态电解质具有较高的转变温度，同时也具有可逆性。当所述凝胶或固态电解质的使用温度高于其转变温度后，凝胶和固态电解质变得可以流动，但是将其冷却至低于转变温度后，其具有可逆性，又可重新形成凝胶或固态电解质而被重新使用；由于其具有较高的转变温度和可逆性，可以延缓使用寿命，节约成本，使其成为一个绿色环保的新型凝胶材料。
4.本发明所述的凝胶和固态电解液的制备方法简单、反应条件温和、反应周期短、产物收率高、制备成本低、易于实现工业化生产。
5.本发明所述的可凝胶体系制备得到的凝胶和固态电解质，或者是所述的有机体系的超级电容器或电容电池中的凝胶和固态电解质可在低温展现出更好的凝胶状态或固态电解质状态，即在所述凝胶或固态电解质的转变温度以下均可以保持很好的凝胶状态或固态电解质状态，且低温下所述凝胶和固态电解质的强度更佳。
6.本发明所述的可凝胶化体系制备得到的凝胶或固态电解质可应用于锂空气电池、有机体系的超级电容器或电容电池中，且在高低温下仍然能够使用。
附图说明
图1为实施例1-1中得到的凝胶电解质作为锂空气电池电解液组装成电池的循环性能图。
图2为实施例1-3中得到的固态电解质作为锂空气电池电解质组装成电池的循环性能图。
图3为实施例2-1中得到的凝胶电解质作为有机体系的超级电容器电解液组装成超级电容器的前三次充放电数据图。
图4为实施例2-6中得到的固态电解质作为有机体系的电容电池电解质组装成电容电池的循环性能图。
图5为实施例1-1中得到的凝胶电解质提纯物的核磁共振氢谱。
具体实施方式
[锂空气电池]
本发明的第一个方面是提供一种用于锂空气电池的可凝胶化体系，该体系中包括以下组分：(a)锂盐，(b)醚类化合物和(c)用于锂空气电池的电解液或其溶剂；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；所述用于锂空气电池的电解液或其溶剂选自酰胺类电解液及其溶剂、腈类电解液及其溶剂、砜类电解液及其溶剂；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％。
所述用于锂空气电池的可凝胶化体系中，各组分的重量百分比之和为100wt％。
本发明中，所述用于锂空气电池的可凝胶化体系中，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90wt％；所述用于锂空气电池的电解液或其溶剂的质量百分含量大于等于5wt％小于等于75wt％。
其中，所述用于锂空气电池的可凝胶化体系中，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等于20wt％且小于等于60wt％；所述用于锂空气电池的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％。
其中，所述用于锂空气电池的可凝胶化体系中，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％；所述用于锂空气电池的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％。
本发明中，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、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。
本发明中，所述可凝胶化体系中还包括(d)无机纳米颗粒。所述可凝胶化体系中，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％。优选地，所述可凝胶化体系中，所述无机纳米颗粒的质量百分含量大于0wt％且小于等于20wt％。
本发明中，所述可凝胶化体系中进一步包括(e)添加剂，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。所述可凝胶化体系中，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，所述可凝胶化体系中，所述添加剂的质量百分含量大于0wt％且小于等于20wt％。
本发明的第二个方面是提供一种凝胶，其由上述的用于锂空气电池的可凝胶化体系经凝胶化得到；其中，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％；所述用于锂空气电池的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％。
其中，所述用于锂空气电池的可凝胶化体系中，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等于20wt％且小于等于60wt％；所述用于锂空气电池的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％。
本发明中，所述凝胶的转变温度为40～90℃，优选为60～75℃。
本发明中，所述凝胶的导电率为10 -6～10 -1S/cm，优选为10 -5～5×10 -2S/cm。
本发明的第三个方面是提供一种上述凝胶的制备方法，其包括以下步骤：
1)将锂盐加入到用于锂空气电池的电解液或其溶剂中，搅拌均匀后，得到含有锂盐的混合溶液；
2)将醚类化合物，任选地无机纳米颗粒和/或添加剂加入到上述混合溶液中，搅拌下得到混合体系，即所述用于锂空气电池的可凝胶化体系，继续搅拌所述溶液，经凝胶化得到所述凝胶。
本发明中，在步骤2)中，所述凝胶化过程需要在静置条件下完成。所述凝胶形成的温度低于所述凝胶的转变温度，所述凝胶形成的时间为30秒～300小时。
本发明中，对用于锂空气电池的电解液或其溶剂、锂盐和醚类化合物进行预先除水处理；优选地，采用分子筛和/或真空干燥的方法对用于锂空气电池的电解液或其溶剂、锂盐和醚类化合物进行预先除水处理。
本发明的第四个方面是提供一种固态电解质，其由上述的用于锂空气电池的可凝胶化体系经凝胶化得到；其中，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％；所述用于锂空气电池的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％。其中，所述用于锂空气电池的可凝胶化体系中，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％；所述用于锂空气电池的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％。
本发明中，所述固态电解质的转变温度为65～130℃，优选为75～120℃。
本发明中，所述固态电解质的导电率为10 -7～10 -3S/cm，优选为10 -6～10 -3S/cm。
本发明的第五个方面是提供一种上述固态电解质的制备方法，其包括以下步骤：
1)将锂盐加入到用于锂空气电池的电解液或其溶剂中，搅拌均匀后，得到含有锂盐的混合溶液；
2)将醚类化合物，任选地无机纳米颗粒和/或添加剂加入到上述混合溶液中，搅拌下得到混合体系，即所述用于锂空气电池的可凝胶化体系，继续搅拌所述溶液，经凝胶化得到所述固态电解质。
本发明中，在步骤2)中，所述凝胶化过程需要在静置条件下完成。所述固态电解质的形成的温度低于所述固态电解质的转变温度，所述固态电解质的形成的时间为30分钟～150小时。
本发明中，对用于锂空气电池的电解液或其溶剂、锂盐和醚类化合物进行预先除水处理；优选地，采用分子筛和/或真空干燥的方法对用于锂空气电池的电解液或其溶剂、锂盐和醚类化合物进行预先除水处理。
本发明的第六个方面是提供一种凝胶电解质，所述凝胶电解质包括上述的凝胶。
本发明的第七个方面是提供上述凝胶、上述固态电解质、上述凝胶电解质的应用，其用于锂空气电池等领域中。
本发明的第八个方面是提供一种锂空气电池，其包括凝胶电解质和/或固态电解质，所述凝胶电解质和/或固态电解质由可凝胶化体系制备得到的；所述可凝胶化体系包括如下组分：(a)锂盐，(b)醚类化合物和(c)用于锂空气电池的电解液或其溶剂；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；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％。
[有机体系的超级电容器和有机体系的电容电池]
本发明的第九个方面是提供一种有机体系的超级电容器，其包括凝胶电解质和/或固态电解质，所述凝胶电解质和/或固态电解质由可凝胶化体系制备得到的；所述可凝胶化体系包括如下组分：(a)锂盐和(b)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；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％。
本发明的第十个方面是提供一种有机体系的电容电池，其包括凝胶电解质和/或固态电解质，所述凝胶电解质和/或固态电解质由可凝胶化体系制备得到的；所述可凝胶化体系包括如下组分：(a)锂盐和(b)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；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％。
所述可凝胶化体系中，各组分的重量百分比之和为100wt％。
本发明中，所述锂盐的质量百分含量大于等于2wt％且小于等于50wt％；所述醚类化合物的质量百分含量大于等于50wt％且小于等于98wt％。其中，所述锂盐的质量百分含量大于等于5wt％且小于20wt％；或者，所述锂盐的质量百分含量大于等于20wt％且小于等于30wt％。
本发明中，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。
本发明中，所述可凝胶体系中还包括(c)用于有机体系的超级电容器或电容电池的电解液或其溶剂。所述可凝胶化体系中，所述用于有机体系的超级电容器或电容电池的电解液或其溶剂的质量百分含量大于等于0wt％且小于等于48wt％。优选地，所述可凝胶化体系中，所述用于有机体系的超级电容器或电容电池的电解液或其溶剂的质量百分含量大于0wt％且小于等于40wt％。
本发明中，所述可凝胶化体系中进一步包括(d)无机纳米颗粒。所述可凝胶化体系中，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％。优选地，所述可凝胶化体系中，所述无机纳米颗粒的质量百分含量大于0wt％且小于等于20wt％。
本发明中，所述可凝胶化体系中还进一步包括(e)添加剂，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。所述可凝胶化体系中，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，所述可凝胶化体系中，所述添加剂的质量百分含量大于0wt％且小于等于20wt％。
本发明中，所述凝胶电解质由可凝胶化体系制备得到的，所述可凝胶化体系中，所述锂盐的质量百分含量大于等于2wt％且小于20wt％；所述醚类化合物的质量百分含量大于50wt％且小于等于98wt％；所述用于有机体系的超级电容器或电容电池的电解液或其溶剂的质量百分含量大于等于0wt％且小于等于48wt％；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％。其中，所述锂盐的质量百分含量大于等于5wt％且小于20wt％；所述醚类化合物的质量百分含量大于55wt％且小于等于95wt％；所述用于有机体系的超级电容器或电容电池的电解液或其溶剂的质量百分含量大于0wt％且小于等于40wt％；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％。
本发明中，所述凝胶电解质的转变温度为40～95℃，优选为45～85℃。
本发明中，所述凝胶电解质的导电率为10 -5～10 -1S/cm，优选为10 -4～10 -2S/cm。
本发明中，所述固态电解质由可凝胶化体系制备得到的，所述可凝胶化体系中，所述锂盐的质量百分含量大于等于20wt％且小于等于50wt％；所述醚类化合物的质量百分含量大于等于50wt％且小于等于80wt％；所述用于有机体系的超级电容器或电容电池的电解液或其溶剂的质量百分含量大于等于0wt％且小于等于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％。其中，所述锂盐的质量百分含量大于等于20wt％且小于等于30wt％；所述醚类化合物的质量百分含量大于等于55wt％且小于等于80wt％；所述用于有机体系的超级电容器或电容电池的电解液或其溶剂的质量百分含量大于0wt％且小于等于25wt％；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％。
本发明中，所述固态电解质的转变温度为60～130℃，优选为80～110℃。
本发明中，所述固态电解质的导电率为10 -7～10 -3S/cm，优选为10 -6～10 -4S/cm。
本发明的第十一个方面是提供一种上述凝胶电解质的制备方法，其包括以下步骤：
将醚类化合物、锂盐以及任选地用于有机体系的超级电容器或电容电池的电解液或其溶剂和任选地无机纳米颗粒和任选地添加剂混合，搅拌下得到锂盐的醚类化合物溶液，即所述可凝胶化体系，继续搅拌所述溶液，经凝胶化得到所述凝胶电解质。
优选地，所述凝胶电解质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，任选地将用于有机体系的超级电容器或电容电池的电解液或其溶剂和/或无机纳米颗粒和/或添加剂加入到锂盐的醚类化合物溶液，即所述可凝胶化体系，继续搅拌所述溶液，经凝胶化得到所述凝胶电解质。
本发明中，对所述锂盐、醚类化合物、任选地将用于有机体系的超级电容器或电容电池的电解液或其溶剂和无机纳米颗粒和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锂盐、醚类化合物、任选地将用于有机体系的超级电容器或电容电池的电解液或其溶剂和无机纳米颗粒和添加剂进行预先除水处理。
本发明中，所述凝胶化过程需要在静置条件下完成。所述凝胶电解质形成的温度低于所述凝胶电解质的转变温度，所述凝胶电解质形成的时间为5秒～300小时。
本发明的第十二个方面是提供一种上述的固态电解质的制备方法，其包括以下步骤：
将醚类化合物、锂盐以及任选地用于有机体系的超级电容器或电容电池的电解液或其溶剂和任选地无机纳米颗粒和任选地添加剂混合，搅拌下得到锂盐的醚类化合物溶液，即所述可凝胶化体系，继续搅拌所述溶液，经凝胶化得到所述固态电解质。
优选地，所述固态电解质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，任选地将用于有机体系的超级电容器或电容电池的电解液或其溶剂和/或无机纳米颗粒和/或添加剂加入到锂盐的醚类化合物溶液，即所述可凝胶化体系，继续搅拌所述溶液，经凝胶化得到所述固态电解质。
本发明中，对所述锂盐、醚类化合物、任选地将用于有机体系的超级电容器或电容电池的电解液或其溶剂和无机纳米颗粒和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锂盐、醚类化合物、任选地将用于有机体系的超级电容器或电容电池的电解液或其溶剂和无机纳米颗粒和添加剂进行预先除水处理。
本发明中，所述凝胶化过程需要在静置条件下完成。所述固态电解质的形成的温度低于所述固态电解质的转变温度，所述固态电解质的形成的时间为30分钟～100小时。
本发明中，对所述锂盐、醚类化合物、任选地将用于有机体系的超级电容器或电容电池的电解液或其溶剂和无机纳米颗粒和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锂盐、醚类化合物、任选地将用于有机体系的超级电容器或电容电池的电解液或其溶剂和无机纳米颗粒和添加剂进行预先除水处理。
[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 PCTCN2018088496-appb-000001
[环状醚类化合物]
本发明中，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可以是单环、稠合环(如双环)、螺环或桥环。
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 PCTCN2018088496-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的稠合环烷烃，例如为下述第二类化合物中的一种：
Figure PCTCN2018088496-appb-000003
Figure PCTCN2018088496-appb-000004
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 PCTCN2018088496-appb-000005
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 PCTCN2018088496-appb-000006
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。
[用于锂空气电池、用于有机体系的超级电容器或电容电池的电解液或其溶剂]
本发明中，所述用于锂空气电池、用于有机体系的超级电容器或电容电池的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。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。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。其中，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)。
[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。
[术语和定义]
除非另有说明，本申请说明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。
本申请说明书中记载的数值范围，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，这些杂原子不彼此相邻。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用于限制本发明的范围。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于本发明所限定的范围。
[测试方法]
本实施例所述的导电率是使用Gamry公司的Interface 1000型号的电化学工作站测试得到的，所述测试扫描频率为1.0Hz～100kHz。本实施例所述的电池的测试是蓝电电池组。所述的有机体系的超级电容器或电容电池的测试是在蓝电测试仪。
本实施例中，所述锂盐在使用前，经40℃真空干燥10h以上进行除水处理。所述添加剂在使用前，经45℃真空干燥24h以上除水处理。所述无机纳米颗粒在使用前，经60℃真空干燥24h以上除水处理。
本实施例中，所述醚类化合物在使用前，经分子筛进行除水处理。所述用于锂空气电池的电解液或其溶剂在使用前，经分子筛除水干燥。所述用于有机体系的超级电容器或电容电池的电解液或其溶剂在使用前，经分子筛除水干燥。
[下述实施例中的锂空气电池的组成]
石墨烯空气电极的制备：称取质量比为9:1的石墨烯和聚偏氟乙烯(PVDF)，向PVDF中滴加一定量的N-甲基吡咯烷酮(NMP)，超声波振荡混合1小时，向此溶液倒入研钵中，加入石墨烯，研磨1小时左右，再把混合后的浆料在一定面积的碳纸上均匀涂覆，100℃下真空干燥48小时后，用切片机裁成所需大小；
负极为锂片；电解液：各实施例中制备的凝胶电解质或固态电解质；隔膜：Whatman隔膜。
实施例1-1
(1)可凝胶化体系和凝胶(可用作电池的凝胶电解质)的制备
称取0.8g六氟磷酸锂于试剂瓶中，向其中加入2.0mL碳酸二甲酯和碳酸乙烯酯的混合液(其中碳酸二甲酯：碳酸乙烯酯＝1:1(v/v))，搅拌使得锂盐完全溶解，将2.0mL1,4-二氧六环和2.0mL1,3-二氧戊环混合液加入上述锂盐溶液中，搅拌充分混合后，得到可凝胶化体系；静止一段时间，形成凝胶。所述凝胶体系中，锂盐的质量百分含量为12wt％；醚类化合物的质量百分含量为58wt％；用于锂空气电池的电解液或其溶剂的质量百分含量为30wt％。经测试，所述凝胶的性能参数列于表1中。
将制备得到的凝胶加热到所述凝胶的转变温度以上时，凝胶开始变粘，倒置试剂瓶时会观察到凝胶向下流动，说明温度已经达到凝胶的转变温度，而当温度降到凝胶的转变温度以下时，凝胶又重新形成，说明制备得到的凝胶具有很好的可逆性。
将此凝胶电解质用溶剂(如去离子水)全部溶解，然后在乙醇中沉降出，得到的聚合物用氘代氯仿溶解，进行核磁共振氢谱的测试，测试结果如图5所示，从结果可以看出：化学位移为3.54ppm归属于聚合物链段-O-CH 2-CH 2-O-，化学位移为4.50ppm归属于聚合物链段-O-CH 2-O-，两者的积分面积为3:1，与1,4-二氧六环和1,3-二氧戊环的投料比相符，表明在电解质体系中，成功得到目标聚合物。
(2)电池的制备
将上述制备得到的凝胶作为凝胶电解质应用到锂空气电池中，使用蓝电电池组测试纽扣电池的电化学性能(测试结果列于表1中)。锂空气电池的组装过程在手套箱中进行，使用Swagelok可拆洗型电池模具，模具、隔膜、空气电极等工具在使用之前都需要在真空烘箱中100℃真空干燥24小时，电池组装时先取光泽度好的锂片置于模具底座中央，再依次加入适量的电解液、隔膜、石墨烯空气电极，组装成锂空气电池，静置待所述可凝胶化体系变成凝胶电解质。
实施例1-2
(1)可凝胶化体系和固态电解质的制备
称取0.5g的高氯酸锂、1.0g六氟磷酸锂和0.2g双三氟甲烷磺酰亚胺锂于试剂瓶中，向其中加入3.0mL四乙二醇二甲醚，在磁力搅拌下，使锂盐完全溶解，加入8.0mL的四氢吡喃，充分混合后，得到可凝胶化体系；静置一段时间，形成固态电解质。所述固态电解质体系中，锂盐的质量百分含量为15wt％；醚类化合物的质量百分含量为68wt％；用于锂空气电池的电解液或其溶剂的质量百分含量为17wt％。经测试，所述固态电解质的性能参数列于表1中。
将制备得到的固态电解质加热到所述固态电解质的转变温度以上时，固态电解质开始变粘，倒置试剂瓶时会观察到固态电解质向下流动，说明温度已经达到固态电解质的转变温度，而当温度降低到固态电解质的转变温度以下时，固态电解质又重新形成，说明制备得到的固态电解质具有很好的可逆性。
(2)电池的制备
将上述制备得到的固态电解质应用到锂空气电池中，使用蓝电电池组测试纽扣电池的电化学性能(测试结果列于表1中)。锂空气电池的组装过程在手套箱中进行，使用Swagelok可拆洗型电池模具，模具、隔膜、空气电极等工具在使用之前都需要在真空烘箱中100℃真空干燥24小时，电池组装时先取光泽度好的锂片置于模具底座中央，再依次加入适量的电解液、隔膜、石墨烯空气电极，组装成锂空气电池，静置待所述可凝胶化体系变成固态电解质。
实施例1-3
(1)可凝胶化体系和凝胶(可用作电池的凝胶电解质)的制备
称取0.1g的氧化铝于试剂瓶中，向其中加入4.5mL的1,3-二氧戊环，在磁力搅拌下使其充分混合均匀，得到混合液A。另取0.4g三氟甲基磺酸锂和0.6g高氯酸锂于试剂瓶中，向其中加入1.2mL的二甲亚砜(DMSO)，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；静置一段时间，形成固态电解质。所述凝胶体系中，锂盐的质量百分含量为15wt％；醚类化合物的质量百分含量为65.5wt％；无机纳米颗粒的质量百分含量为1.5wt％；锂空气电池溶剂和/或电解液的质量百分含量为18wt％。经测试，所述固态电解质的性能参数列于表1中。
将制备得到的固态电解质加热到所述固态电解质胶的凝胶转变温度以上时，固态电解质开始变粘，倒置试剂瓶时会观察到固态电解质向下流动，说明温度已经达到该固态电解质的转变温度，而当温度降到凝胶转变温度以下时，固态电解质又重新形成，说明制备得到的固态电解质具有很好的可逆性。
(2)电池的制备
将上述制备得到的固态电解质应用到锂空气电池中，使用蓝电电池组测试纽扣电池的电化学性能(测试结果列于表1中)。锂空气电池的组装过程在手套箱中进行，使用Swagelok可拆洗型电池模具，模具、隔膜、空气电极等工具在使用之前都需要在真空烘箱中100℃真空干燥24小时，电池组装时先取光泽度好的锂片置于模具底座中央，再依次加入适量的电解液、隔膜、石墨烯空气电极，组装成锂空气电池，静置待所述可凝胶化体系变成固态电解质。
实施例1-4
(1)聚酯的合成
称取20.0g丙二酸，20.0g丁二酸，94.0g聚乙二醇-400于三口烧瓶中，于油浴中加热至温度升至120℃，恒温0.5h，每隔25min升温30℃，直到温度升至210℃，恒温3h，后加入0.32g催化剂(钛酸四丁酯)，反应0.5h，之后抽真空2h，停止加热，并且降温，得到相关产物，加入三氯甲烷40.0mL，45℃回流加热6h，滴加到甲醇中沉降，产物于60℃真空烘箱中干燥12h，得聚酯C，于手套箱中保存。
(2)可凝胶化体系和凝胶(可用作凝胶电解质)的制备
量取0.83mL聚酯C，1.8mL 1,4-环氧环己烷，0.07g氧化铝，0.44mL N,N-二甲基乙酰胺(DMA)搅拌使四者混合，得澄清透明液体，之后加入0.87g六氟磷酸锂，搅拌2h，使六氟磷酸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8h，得无色凝胶。所述凝胶体系中，锂盐的质量百分含量为22wt％；醚类化合物的质量百分含量为45wt％；聚酯添加剂的质量百分含量为21wt％；锂空气电池溶剂和/或电解液的质量百分含量为11wt％；二氧化硅的质量百分含量1wt％。经测试，所述凝胶电解质的性能参数列于表1中。
将制备得到的凝胶加热到60℃以上时，凝胶变得可以流动，倒置试剂瓶时会发现凝胶向下流动，说明此时已经达到凝胶的转变温度，而当温度降到60℃以下时，凝胶又重新形成，说明制备得到的凝胶具有很好的可逆性。
(3)电池的制备
将上述制备得到的凝胶作为凝胶电解质应用到锂空气电池中，使用蓝电电池组测试纽扣电池的电化学性能(测试结果列于表1中)。锂空气电池的组装过程在手套箱中进行，使用Swagelok可拆洗型电池模具，模具、隔膜、空气电极等工具在使用之前都需要在真空烘箱中100℃真空干燥24小时，电池组装时先取光泽度好的锂片置于模具底座中央，再依次加入适量的电解液、隔膜、石墨烯空气电极，组装成锂空气电池，静置待所述可凝胶化体系变成凝胶电解质。
实施例1-5
(1)可凝胶化体系和固态电解质的制备
称取0.7g三聚甲醛、0.8g氯化锂和0.8g高氯酸锂于试剂瓶中，向其中加入1.1mL乙腈，在磁力搅拌下，使得锂盐和三聚甲醛完全溶解，向其中加入3.5mL1,4-二氧六环，搅拌使得充分混合，得到可凝胶化体系；静止一段时间，形成固态电解质。所述固态电解质体系中，用于锂盐的质量百分含量为23wt％；醚类化合物的质量百分含量为61wt％；用于锂空气电池的电解液或其溶剂的质量百分含量为16wt％。经测试，所述固态电解质的性能参数列于表1中。
将制备得到的固态电解质加热到所述固态电解质的转变温度以上时，固态电解质开始变粘，倒置试剂瓶时会观察到固态电解质向下流动，说明温度已经达到固态电解质的转变温度，而当温度降到固态电解质的转变温度以下时，固态电解质又重新形成，说明制备得到的固态电解质具有很好的可逆性。
(2)电池的制备
将上述制备得到的固态电解质应用到锂空气电池中，使用蓝电电池组测试纽扣电池的电化学性能(测试结果列于表1中)。锂空气电池的组装过程在手套箱中进行，使用Swagelok可拆洗型电池模具，模具、隔膜、空气电极等工具在使用之前都需要在真空烘箱中100℃真空干燥24小时，电池组装时先取光泽度好的锂片置于模具底座中央，再依次加入适量的电解液、隔膜、石墨烯空气电极，组装成锂空气电池，静置待所述可凝胶化体系变成固态电解质。
实施例1-6
(1)可凝胶化体系和凝胶(可用作凝胶电解质)的制备
称取1.60g四氟硼酸锂和0.6g双三氟甲烷磺酰亚胺锂固体于试剂瓶中，加入四乙二醇二甲醚3mL和乙二醇二甲醚1.0mL，在磁力搅拌下使四氟硼酸锂和双三氟甲烷磺酰亚胺锂全部溶解，向其中加入6.0mL 3-甲基四氢呋喃，充分混合后，得到可凝胶化体系；静置一段时间，形成凝胶。所述凝胶体系中，锂盐的质量百分含量为17wt％；醚类化合物的质量百分含量为50wt％；用于锂空气电池的电解液或其溶剂的质量百分含量为33wt％。经测试，所述凝胶电解质的性能参数列于表1中。
将制备得到的凝胶加热到所述凝胶的转变温度以上时，凝胶开始变粘，倒置试剂瓶时会观察到凝胶向下流动，说明温度已经达到凝胶的转变温度，而当温度降低到所述凝胶的转变温度以下时，凝胶又重新形成，说明制备得到的凝胶具有很好的可逆性。
(2)电池的制备
将上述制备得到的凝胶作为凝胶电解质应用到锂空气电池中，使用蓝电电池组测试纽扣电池的电化学性能(测试结果列于表1中)。锂空气电池的组装过程在手套箱中进行，使用Swagelok可拆洗型电池模具，模具、隔膜、空气电极等工具在使用之前都需要在真空烘箱中100℃真空干燥24小时，电池组装时先取光泽度好的锂片置于模具底座中央，再依次加入适量的电解液、隔膜、石墨烯空气电极，组装成锂空气电池，静置待所述可凝胶化体系变成凝胶电解质。
实施例1-7
(1)可凝胶化体系和凝胶(可用作电池的凝胶电解质)的制备
称取0.05g的二氧化硅于试剂瓶中，向其中加入3.0mL的四氢呋喃，在磁力搅拌下使其充分混合均匀，得到混合液A。另取1.0g四氟硼酸锂于试剂瓶中，向其中加入3.0mL的二甲亚砜(DMSO)，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；静置一段时间，形成凝胶。所述凝胶体系中，锂盐的质量百分含量为14wt％；醚类化合物的质量百分含量为42.6wt％；无机纳米颗粒的质量百分含量为0.8wt％；锂空气电池溶 剂和/或电解液的质量百分含量为42.6wt％。经测试，所述凝胶电解质的性能参数列于表1中。
将制备得到的凝胶加热到所述凝胶的转变温度以上时，凝胶开始变粘，倒置试剂瓶时会观察到凝胶向下流动，说明温度已经达到该凝胶的转变温度，而当温度降到凝胶的转变温度以下时，凝胶又重新形成，说明制备得到的凝胶具有很好的可逆性。
(2)电池的制备
将上述制备得到的凝胶作为凝胶电解质应用到锂空气电池中，使用蓝电电池组测试纽扣电池的电化学性能(测试结果列于表1中)。锂空气电池的组装过程在手套箱中进行，使用Swagelok可拆洗型电池模具，模具、隔膜、空气电极等工具在使用之前都需要在真空烘箱中100℃真空干燥24小时，电池组装时先取光泽度好的锂片置于模具底座中央，再依次加入适量的电解液、隔膜、石墨烯空气电极，组装成锂空气电池，静置待所述可凝胶化体系变成凝胶电解质。
实施例1-8
(1)可凝胶化体系和固态电解质的制备
称取0.9g三聚甲醛、0.5g三氟甲磺酸锂和1.0g双草酸硼酸锂于试剂瓶中，向其中加入1.0mL碳酸二甲酯，在磁力搅拌下，使得锂盐和三聚甲醛完全溶解，得到溶液A。称取0.1g氮化碳，并向其中加入3.8mL四氢呋喃，搅拌使得充分混合，得到溶液B。将溶液A和溶液B混合均匀，得到可凝胶化体系；静止一段时间，形成固态电解质。所述固态电解质体系中，用于锂盐的质量百分含量为20.5wt％；醚类化合物的质量百分含量为64.3wt％；无机纳米颗粒的质量百分含量为1.4wt％；用于锂空气电池的电解液或其溶剂的质量百分含量为13.8wt％。经测试，所述固态电解质的性能参数列于表1中。
将制备得到的固态电解质加热到所述固态电解质的转变温度以上时，固态电解质开始变粘，倒置试剂瓶时会观察到固态电解质向下流动，说明温度已经达到固态电解质的转变温度，而当温度降到固态电解质的转变温度以下时，固态电解质又重新形成，说明制备得到的固态电解质具有很好的可逆性。
(2)电池的制备
将上述制备得到的固态电解质应用到锂空气电池中，使用蓝电电池组测试纽扣电池的电化学性能(测试结果列于表1中)。锂空气电池的组装过程在手套箱中进行，使用Swagelok可拆洗型电池模具，模具、隔膜、空气电极等工具在使用之前都需要在真空烘箱中100℃真空干燥24小时，电池组装时先取光泽度好的锂片置于模具底座中央，再依次加入适量的电解液、隔膜、石墨烯空气电极，组装成锂空气电池，静置待所述可凝胶化体系变成固态电解质。
对比例1-1
称取1.0g双三氟甲烷磺酰亚胺锂和1.0g六氟磷酸锂于试剂瓶中，加入4.0mL锂空气电池常规电解液(含1M LiPF 6的碳酸二甲酯(DMC)和碳酸乙烯酯(EC)体积比＝1/1)充分搅拌，使得锂盐完全溶解，静止。上述体系中，锂盐的质量百分含量为33wt％；醚类化合物的质量百分含量为0wt％；用于锂空气电池的电解液或其溶剂的质量百分含量为67wt％。
发现静止很长时间，溶液的流动性都很好，并不能形成稳定的凝胶。说明在没有环醚类化合物的存在下，只是锂盐和溶剂混合，是无法形成稳定的凝胶的。
表1 实施例1-1至1-8和对比例1-1的凝胶电解质和/或固态电解质及制备得到的电池的性能参数
Figure PCTCN2018088496-appb-000007
Figure PCTCN2018088496-appb-000008
图1为实施例1-1中得到的凝胶电解质作为锂空气电池电解液组装成电池的循环性能图。由图可知，该凝胶电解质在锂空气电池中表现出优异的循环性能，放电比容量衰减的很慢，到后期基本上保持不变，表现出稳定的循环性能。
图2为实施例1-3中得到的固态电解质作为锂空气电池电解质组装成电池的循环性能图。由图可知，该固态电解质在锂空气电池中表现出优异的循环性能，放电比容量衰减的很慢，到后期基本上保持不变，表现出稳定的循环性能。
实施例2-1
(1)用作超级电容器的凝胶电解质的制备
称取0.8g的六氟磷酸锂固体于试剂瓶中，加入9.2mL的四氢吡喃，在磁力搅拌下充分混合，得到可凝胶化体系；静置一段时间，形成凝胶电解质。所述凝胶体系中，锂盐的质量百分含量为8wt％；醚类化合物的质量百分含量为92wt％。经测试，所述凝胶的性能参数列于表2中。
将制备得到的凝胶加热到所述凝胶的转变温度以上时，凝胶开始变粘，倒置试剂瓶时会观察到凝胶向下流动，说明温度已经达到凝胶的转变温度，而当温度降到凝胶的转变温度以下时，凝胶又重新形成，说明制备得到的凝胶具有很好的可逆性。
(2)超级电容器的制备
超级电容器正极的制备：将活性碳材料、导电剂科琴黑、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120℃真空烘箱中干燥24小时，备用；超级电容器负极：锂箔。
将上述制备得到的凝胶电解质应用到超级电容器中，与上述的超级电容器正极和超级电容器负极组装成超级电容器，使用蓝电测试仪测试超级电容器的电化学性能(测试结果列于表2中)。 其中，所述超级电容器的制备方法：将隔膜放置于正极和负极之间，三者之间充满步骤(1)制备的可凝胶化体系，封装压实，组装成CR2032型纽扣式超级电容器，静置待所述可凝胶化体系变成凝胶电解质。
实施例2-2
(1)用作电容电池的凝胶电解质的制备
称取1.0g的高氯酸锂和0.5g的三氟甲基磺酸锂固体于试剂瓶中，加入8.5mL的乙二醇甲乙醚于上述混合液中，充分混合后，得到可凝胶化体系；静置一段时间，形成凝胶电解质。所述凝胶体系中，锂盐的质量百分含量为15wt％；醚类化合物的质量百分含量为85wt％。经测试，所述凝胶的性能参数列于表2中。
将制备得到的凝胶加热到所述凝胶的转变温度以上时，凝胶开始变粘，倒置试剂瓶时会观察到凝胶向下流动，说明温度已经达到凝胶的转变温度，而当温度降到凝胶的转变温度以下时，凝胶又重新形成，说明制备得到的凝胶具有很好的可逆性。
(2)电容电池的制备
电容电池正极：将锰酸锂电极材料与导电石墨、导电剂科琴黑、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；
电容电池负极：将钛酸锂电极材料与导电剂科琴黑、粘结剂聚偏二氟乙烯(PVDF)按照质量比85:8:7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；
将上述制备得到的凝胶电解质应用到电容电池中，与上述的电容电池正极和电容电池负极组装成电容电池，使用蓝电测试仪测试电容电池的电化学性能(测试结果列于表2中)。其中，所述电容电池的制备方法：将隔膜放置于正极和负极之间，三者之间充满步骤(1)制备的可凝胶化体系，封装压实，组装成CR2032型纽扣式电容电池，静置待所述可凝胶化体系变成凝胶电解质。
实施例2-3
(1)用作超级电容器的固态电解质的制备
称取2.5g的四氟硼酸锂固体于试剂瓶中，加入7.5mL的1,4-二氧六环于上述混合溶液中，充分混合后，得到可凝胶化体系；静置一段时间，形成固态电解质。所述固态电解质体系中，锂盐的质量百分含量为25wt％；醚类化合物的质量百分含量为75wt％。经测试，所述固态电解质的性能参数列于表2中。
将制备得到的固态电解质加热到所述固态电解质的转变温度以上时，固态电解质开始变粘，倒置试剂瓶时会观察到固态电解质向下流动，说明温度已经达到固态电解质的转变温度，而当温度降到固态电解质的转变温度以下时，固态电解质又重新形成，说明制备得到的固态电解质具有很好的可逆性。
(2)超级电容器的制备
超级电容器正极：制备过程同实施例2-1超级电容器正极制备过程。
超级电容器负极：将铁钴镍复合超级电容材料、导电剂科琴黑、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；
将上述制备得到的固态电解质应用到超级电容器中，与上述的超级电容器正极和超级电容器负极组装成超级电容器，使用蓝电测试仪测试超级电容器的电化学性能(测试结果列于表2中)。其中，所述超级电容器的制备方法：将隔膜放置于正极和负极之间，三者之间充满步骤(1)制 备的可凝胶化体系，封装压实，组装成CR2032型纽扣式超级电容器，静置待所述可凝胶化体系变成固态电解质。
实施例2-4
(1)用作电容电池的固态电解质的制备
称取4.8g三聚甲醛、1.7g六氟磷酸锂和0.5g氟代磺酰亚胺锂固体于试剂瓶中，加入3.0mL的四氢呋喃，充分混合后，得到可凝胶化体系；静置一段时间，形成固态电解质。所述固态电解质体系中，锂盐的质量百分含量为22wt％；醚类化合物的质量百分含量为78wt％。经测试，所述固态电解质的性能参数列于表2中。
将制备得到的固态电解质加热到所述固态电解质的转变温度以上时，固态电解质开始变粘，倒置试剂瓶时会观察到固态电解质向下流动，说明温度已经达到固态电解质的转变温度，而当温度降到固态电解质的转变温度以下时，固态电解质又重新形成，说明制备得到的固态电解质具有很好的可逆性。
(2)电容电池的制备
电容电池正极：制备过程同实施例2-2电容电池正极制备过程。
电容电池负极：制备过程同实施例2-2电容电池负极制备过程。
将上述制备得到的固态电解质应用到电容电池中，与上述的电容电池正极和电容电池负极组装成电容电池，使用蓝电测试仪测试电容电池的电化学性能(测试结果列于表2中)。其中，所述电容电池的制备方法：将隔膜放置于正极和负极之间，三者之间充满步骤(1)制备的可凝胶化体系，封装压实，组装成CR2032型纽扣式电容电池，静置待所述可凝胶化体系变成固态电解质。
实施例2-5
(1)用作电容电池的凝胶电解质的制备
称取0.8g的四氟硼酸锂固体于试剂瓶中，加入2.5mL锂离子电容电池的锂盐的酯类混合液(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)。在磁力搅拌下充分混合直到锂盐全部溶解，加入6.7mL3,3-二氯甲基氧杂环丁烷，充分混合后，得到可凝胶化体系；静止一段时间，形成凝胶电解质。所述凝胶电解质体系中，锂盐的质量百分含量为15wt％；醚类化合物的质量百分含量为40wt％；用于锂离子电池的电解液或其溶剂的质量百分含量为45wt％。经测试，所述凝胶电解质的性能参数列于表2中。
将制备得到的凝胶电解质加热到所述凝胶电解质的转变温度以上时，凝胶电解质开始变粘，倒置试剂瓶时会观察到凝胶电解质向下流动，说明温度已经达到凝胶电解质的转变温度，而当温度降到凝胶电解质的转变温度以下时，凝胶电解质又重新形成，说明制备得到的凝胶电解质具有很好的可逆性。
(2)电容电池的制备
电容电池正极：制备过程同实施例2-2电容电池正极制备过程。
电容电池负极：制备过程同实施例2-2电容电池负极制备过程。
将上述制备得到的凝胶电解质应用到电容电池中，与上述的电容电池正极和电容电池负极组装成电容电池，使用蓝电测试仪测试电容电池的电化学性能(测试结果列于表2中)。其中，所述电容电池的制备方法：将隔膜放置于正极和负极之间，三者之间充满步骤(1)制备的可凝胶化体系，封装压实，组装成CR2032型纽扣式电容电池，静置待所述可凝胶化体系变成凝胶电解质。
实施例2-6
(1)用作电容电池的固态电解质的制备
称取2.5g碘化锂于试剂瓶中，向其中加入6.5mL1,4-二氧六环，加入1g氧化铝，搅拌充分混合后，得到可凝胶化体系；静止一段时间，形成固态电解质。所述凝胶体系中，锂盐的质量百分含量为25wt％；醚类化合物的质量百分含量为65wt％；无机纳米颗粒的百分含量为30wt％。经测试，所述固态电解质的性能参数列于表2中。
将制备得到的固态电解质加热到所述固态电解质的转变温度以上时，固态电解质开始变粘，倒置试剂瓶时会观察到固态电解质向下流动，说明温度已经达到固态电解质的转变温度，而当温度降到固态电解质的转变温度以下时，固态电解质又重新形成，说明制备得到的固态电解质具有很好的可逆性。
(2)电容电池的制备
电容电池正极：制备过程同实施例2-2电容电池正极制备过程。
电容电池负极：制备过程同实施例2-2电容电池负极制备过程。
将上述制备得到的固态电解质应用到电容电池中，与上述的电容电池正极和电容电池负极组装成电容电池，使用蓝电测试仪测试电容电池的电化学性能(测试结果列于表2中)。其中，所述电容电池的制备方法：将隔膜放置于正极和负极之间，三者之间充满步骤(1)制备的可凝胶化体系，封装压实，组装成CR2032型纽扣式电容电池，静置待所述可凝胶化体系变成固态电解质。
实施例2-7
(1)用作超级电容器的凝胶电解质的制备
称取1.2g全氟丁基磺酸锂于试剂瓶中，向其中加入4mL1,4-环氧环己烷和4mL2-氯甲基氧环丁烷，加入添加剂0.8g，搅拌使得充分混合，得到可凝胶化体系；静止一段时间，形成凝胶电解质。
所述凝胶电解质体系中，锂盐的质量百分含量为12wt％；醚类化合物的质量百分含量为80wt％；添加剂的质量百分含量为8wt％。经测试，所述凝胶电解质的性能参数列于表2中。
将制备得到的凝胶电解质加热到所述凝胶电解质的转变温度以上时，凝胶电解质开始变粘，倒置试剂瓶时会观察到凝胶电解质向下流动，说明温度已经达到凝胶电解质的转变温度，而当温度降到凝胶电解质的转变温度以下时，凝胶电解质又重新形成，说明制备得到的凝胶电解质具有很好的可逆性。
(2)超级电容器的制备
超级电容器正极：制备过程同实施例2-1超级电容器正极制备过程。
超级电容器负极：制备过程同实施例2-1超级电容器负极制备过程；
将上述制备得到的凝胶电解质应用到超级电容器中，与上述的超级电容器正极和超级电容器负极组装成超级电容器，使用蓝电测试仪测试超级电容器的电化学性能(测试结果列于表2中)。其中，所述超级电容器的制备方法：将隔膜放置于正极和负极之间，三者之间充满步骤(1)制备的可凝胶化体系，封装压实，组装成CR2032型纽扣式超级电容器，静置待所述可凝胶化体系变成凝胶电解质。
实施例2-8
(1)用作超级电容器的凝胶电解质的制备
称取0.5g的高氯酸锂固体于试剂瓶中，加入0.5mL的碳酸丙烯酯(PC)，加入8.8mL的2-氯甲基环氧丙烷，加入0.2g二氧化硅纳米颗粒，在磁力搅拌下充分混合，得到可凝胶化体系；静置一段时间，形成凝胶电解质。所述凝胶体系中，锂盐的质量百分含量为5wt％；醚类化合物的质量百分含量为88wt％；用于有机体系超级电容的电解液或其溶剂的质量百分含量为5wt％，无机纳米颗粒的质量百分含量为2wt％。经测试，所述凝胶的性能参数列于表2中。
将制备得到的凝胶加热到所述凝胶的转变温度以上时，凝胶开始变粘，倒置试剂瓶时会观察 到凝胶向下流动，说明温度已经达到凝胶的转变温度，而当温度降到凝胶的转变温度以下时，凝胶又重新形成，说明制备得到的凝胶具有很好的可逆性。
(2)超级电容器的制备
超级电容器正极：制备过程同实施例2-1超级电容器正极制备过程。
超级电容器负极：制备过程同实施例2-1超级电容器负极制备过程；
将上述制备得到的凝胶电解质应用到超级电容器中，与上述的超级电容器正极和超级电容器负极组装成超级电容器，使用蓝电测试仪测试超级电容器的电化学性能(测试结果列于表2中)。其中，所述超级电容器的制备方法：将隔膜放置于正极和负极之间，三者之间充满步骤(1)制备的可凝胶化体系，封装压实，组装成CR2032型纽扣式超级电容器，静置待所述可凝胶化体系变成凝胶电解质。
实施例2-9
(1)用作超级电容器的固态电解质的制备
称取2.1g的六氟磷酸锂固体于试剂瓶中，加入0.3mL乙腈，加入7.4mL的1,4-二氧六环，加入0.2g聚乙二醇硼酸酯，充分混合后，得到可凝胶化体系；静置一段时间，形成固态电解质。
所述固态电解质体系中，锂盐的质量百分含量为21wt％；醚类化合物的质量百分含量为74wt％；用于超级电容器的电解液或其溶剂的质量百分含量为3wt％，添加剂的质量百分含量为2wt％。经测试，所述固态电解质的性能参数列于表2中。
将制备得到的固态电解质加热到所述固态电解质的转变温度以上时，固态电解质开始变粘，倒置试剂瓶时会观察到固态电解质向下流动，说明温度已经达到固态电解质的转变温度，而当温度降到固态电解质的转变温度以下时，固态电解质又重新形成，说明制备得到的固态电解质具有很好的可逆性。
(2)超级电容器的制备
超级电容器正极：制备过程同实施例2-1超级电容器正极制备过程，将得到的极片浸润在上述固态电解质的前驱体溶液中。
超级电容器负极：制备过程同实施例2-2超级电容器负极制备过程，将得到的极片浸润在上述固态电解质的前驱体溶液中。
将上述固态电解质前驱体刮涂在玻璃板上，待其固化后，用刀片轻轻揭下，得到固态电解质薄膜。将上述制备得到的固态电解质薄膜放置在上述的超级电容器正极和超级电容器负极之间，组装成超级电容器，使用蓝电测试仪测试超级电容器的电化学性能(测试结果列于表2中)。其中，所述超级电容器的制备方法：将隔膜放置于正极和负极之间，三者之间充满步骤(1)制备的可凝胶化体系，封装压实，组装成CR2032型纽扣式超级电容器，静置待所述可凝胶化体系变成固态电解质。
实施例2-10
(1)聚酯的合成
称取5.0g丙二酸，5.0g丁二酸，5.0g1,2-丙二醇，12.5g聚乙二醇-200于三口烧瓶中，油浴加热至温度升至110℃，恒温1h，每隔半个小时升温25℃，直到温度升至240℃，恒温4h，后加入0.08g催化剂钛酸四丁酯反应1h，停止加热，并降温，得到相关产物，加入二氯甲烷25.0mL，室温搅拌溶解12h，置于石油醚中沉降，产物于60℃真空烘箱中干燥12h，得聚酯B，于手套箱中保存。
(2)用作电容电池的凝胶电解质的制备
量取1.5mL上述聚酯，加入1.5mL碳酸二甲酯、1.5mL碳酸丙烯酯和3.5mL1,2-环氧环己烷，在磁力搅拌下，使其混合均匀，得到澄清的溶液，称取1.8g的四氟硼酸锂固体加入上述混合液中， 充分溶解后，得到可凝胶化体系；静止一段时间，形成凝胶电解质。所述凝胶电解质体系中，锂盐的质量百分含量为18wt％；醚类化合物的质量百分含量为35.7wt％；聚酯添加剂的质量百分含量为15.3％；用于锂离子电池的电解液或其溶剂的质量百分含量为31wt％。
经测试，所述凝胶电解质的性能参数列于表2中。将制备得到的凝胶电解质加热到所述凝胶电解质的转变温度以上时，凝胶电解质开始变粘，倒置试剂瓶时会观察到凝胶电解质向下流动，说明温度已经达到凝胶电解质的转变温度，而当温度降到凝胶电解质的转变温度以下时，凝胶电解质又重新形成，说明制备得到的凝胶电解质具有很好的可逆性。
(2)电容电池的制备
电容电池正极：将锰酸锂电极材料与导电石墨、导电剂科琴黑、上述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；电容电池负极：将钛酸锂电极材料与导电剂科琴黑、上述可凝胶化体系按照质量比85:8:7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。
将上述制备得到的凝胶电解质应用到电容电池中，与上述的电容电池正极和电容电池负极组装成电容电池，使用蓝电测试仪测试电容电池的电化学性能(测试结果列于表2中)。其中，所述电容电池的制备方法：将隔膜放置于正极和负极之间，三者之间充满步骤(1)制备的可凝胶化体系，封装压实，组装成CR2032型纽扣式电容电池，静置待所述可凝胶化体系变成凝胶电解质。
对比例2-1
称取1.0g双三氟甲烷磺酰亚胺锂和1.0g六氟磷酸锂于试剂瓶中，加入4.0mL有机体系的超级电容器常规电解液(含1M高氯酸锂(LiClO 4)的乙腈溶液充分搅拌，使得锂盐完全溶解，静止。
上述体系中，锂盐的质量百分含量为33wt％；醚类化合物的质量百分含量为0wt％；用于有机体系的超级电容器的电解液或其溶剂的质量百分含量为67wt％。
发现静止很长时间，溶液的流动性都很好，并不能形成稳定的凝胶。
说明在没有环醚类化合物的存在下，只是锂盐和溶剂混合，是无法形成稳定的凝胶的。
表2 实施例2-1至2-10和对比例2-1的凝胶电解质和/或固态电解质及制备得到的有机体系的超级电容器或电容电池的性能参数
Figure PCTCN2018088496-appb-000009
Figure PCTCN2018088496-appb-000010
图3为实施例2-1中得到的凝胶电解质作为有机体系的超级电容器电解液组装成超级电容器的前三次充放电图。由图可知，该凝胶电解质作为有机体系超级电容器电解液，可以使得超级电容器正常充放电，同时电解液中的活性物质可以充分发挥作用，超级电容器具有较高的比容量。
图4为实施例2-6中得到的固态电解质作为电容电池电解质组装成电容电池的循环性能图。由图可知，该固态电解质作为电容电池的电解质，可以使电容电池正常充放电，同时电解质中的活性物质可以充分发挥作用，电容电池具有较高的比容量。
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. 一种用于锂空气电池的可凝胶化体系，该体系中包括以下组分：(a)锂盐，(b)醚类化合物和(c)用于锂空气电池的电解液或其溶剂；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；所述用于锂空气电池的电解液或其溶剂选自酯类电解液及其溶剂、醚类电解液及其溶剂、酰胺类电解液及其溶剂、腈类电解液及其溶剂、砜类电解液及其溶剂；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. 根据权利要求1所述的可凝胶化体系，其特征在于，所述用于锂空气电池的可凝胶化体系中，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90wt％；所述用于锂空气电池的电解液或其溶剂的质量百分含量大于等于5wt％小于等于75wt％。
    优选地，所述用于锂空气电池的可凝胶化体系中，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等于20wt％且小于等于60wt％；所述用于锂空气电池的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％。
    优选地，所述用于锂空气电池的可凝胶化体系中，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％；所述用于锂空气电池的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％。
  3. 根据权利要求1或2所述的可凝胶化体系，其特征在于，所述可凝胶化体系中还包括(d)无机纳米颗粒。
    优选地，所述可凝胶化体系中，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％，例如大于0wt％且小于等于20wt％。
    优选地，所述可凝胶化体系中进一步包括(e)添加剂，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，所述可凝胶化体系中，所述添加剂的质量百分含量大于等于0wt％且小于等于30wt％，例如大于0wt％且小于等于20wt％。
  4. 一种凝胶，其特征在于，所述凝胶由权利要求1-3任一项所述的用于锂离子电池的可凝胶化体系经凝胶化得到；其中，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％；所述用于锂空气电池的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，所述用于锂空气电池的可凝胶化体系中，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等于20wt％且小于等于60wt％；所述用于锂空气电池的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％。
  5. 一种固态电解质，其特征在于，所述固态电解质由权利要求1-3任一项所述的用于锂离子电池的可凝胶化体系经凝胶化得到；其中，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％；所述用于锂空气电池的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，所述用于锂空气电池的可凝胶化体系中，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％；所述用于锂空气电池的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％。
  6. 一种凝胶电解质，其特征在于，所述凝胶电解质包括权利要求4所述的凝胶。
  7. 一种锂空气电池，其特征在于，所述锂空气电池包括凝胶电解质和/或固态电解质，所述凝胶电解质和/或固态电解质由可凝胶化体系制备得到的；所述可凝胶化体系包括如下组分：(a)锂盐，(b)醚类化合物和(c)用于锂空气电池的电解液或其溶剂；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；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％。
  8. 一种有机体系的超级电容器或有机体系的电容电池，其特征在于，所述有机体系的超级电容器或电容电池包括凝胶电解质和/或固态电解质，所述凝胶电解质和/或固态电解质由可凝胶化体系制备得到的；所述可凝胶化体系包括如下组分：(a)锂盐和(b)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；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％。
  9. 根据权利要求8所述的有机体系的超级电容器或有机体系的电容电池，其特征在于，所述锂盐的质量百分含量大于等于2wt％且小于等于50wt％；所述醚类化合物的质量百分含量大于等于50wt％且小于等于98wt％。
    优选地，所述锂盐的质量百分含量大于等于5wt％且小于20wt％；或者，所述锂盐的质量百分含量大于等于20wt％且小于等于30wt％。
    优选地，所述可凝胶体系中还包括(c)用于有机体系的超级电容器或电容电池的电解液或其溶剂；所述用于有机体系的超级电容器或电容电池的电解液或其溶剂的质量百分含量大于等于0wt％且小于等于48wt％，例如大于0wt％且小于等于40wt％。
    优选地，所述可凝胶化体系中进一步包括(d)无机纳米颗粒；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％，例如大于0wt％且小于等于20wt％。
    优选地，所述可凝胶化体系中还进一步包括(e)添加剂，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；所述添加剂的质量百分含量大于等于0wt％且小于等于30wt％，例如大于0wt％且小于等于20wt％。
    优选地，所述凝胶电解质由可凝胶化体系制备得到的，所述可凝胶化体系中，所述凝胶电解质由可凝胶化体系制备得到的，所述可凝胶化体系中，所述锂盐的质量百分含量大于等于2wt％且小于20wt％；所述醚类化合物的质量百分含量大于50wt％且小于等于98wt％；所述用于有机体系的超级电容器或电容电池的电解液或其溶剂的质量百分含量大于等于0wt％且小于等于48wt％；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，所述锂盐的质量百分含量大于等于5wt％且小于20wt％；所述醚类化合物的质量百分含量大于55wt％且小于等于95wt％；所述用于有机体系的超级电容器或电容电池的电解液或其溶剂的质量百分含量大于0wt％且小于等于40wt％；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，所述固态电解质由可凝胶化体系制备得到的，所述可凝胶化体系中，所述固态电解质由可凝胶化体系制备得到的，所述可凝胶化体系中，所述锂盐的质量百分含量大于等于20wt％且小于等于50wt％；所述醚类化合物的质量百分含量大于等于50wt％且小于等于80wt％；所述用于有机体系的超级电容器或电容电池的电解液或其溶剂的质量百分含量大于等于0wt％且小于等于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，所述锂盐的质量百分含量大于等于20wt％且小于等于30wt％；所述醚类化合物的质量百分含量大于等于55wt％且小于等于80wt％；所述用于有机体系的超级电容器或电容电池的电解液或其溶剂的质量百 分含量大于0wt％且小于等于25wt％；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％。
  10. 根据权利要求1-3任一项所述的可凝胶化体系、权利要求4所述的凝胶、权利要求5所述的固态电解质、权利要求6所述的凝胶电解质、权利要求8所述的有机体系的超级电容器或有机体系的电容电池，其特征在于，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，例如选自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(A-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双三氟甲烷磺酰亚胺锂的乙腈溶液。
    优选地，所述腈类电解液的溶剂选自含有腈基的化合物，例如选自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，例如选自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 PCTCN2018088496-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 PCTCN2018088496-appb-100002
    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 PCTCN2018088496-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的螺环烷烃，例如为下述第四类化合物中的一种：
    Figure PCTCN2018088496-appb-100004
    Figure PCTCN2018088496-appb-100005
    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。
    优选地，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)。
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