CN108963330B

CN108963330B - Gellable system containing inorganic nanoparticles and preparation method and application thereof

Info

Publication number: CN108963330B
Application number: CN201710386734.1A
Authority: CN
Inventors: 李林; 刘凤泉; 周建军; 方芳
Original assignee: Beijing Normal University
Current assignee: Beijing Normal University
Priority date: 2017-05-26
Filing date: 2017-05-26
Publication date: 2020-11-13
Anticipated expiration: 2037-05-26
Also published as: CN108963330A

Abstract

The invention discloses a gellable system containing inorganic nanoparticles, a gel and/or solid electrolyte prepared from the gellable system, and a preparation method and application of the gel and/or solid electrolyte. The system comprises the following components: (a) a lithium salt, (b) an ether compound selected from cyclic ether compounds, and (c) inorganic nanoparticles; by adjusting the content and the type of the components of the lithium salt, the cyclic ether compound and the inorganic nano-particles in the system, the gel and/or the solid electrolyte with adjustable strength, adjustable formation time and adjustable transition temperature and reversibility can be prepared; the preparation method is simple, mild in reaction condition, short in reaction period, high in product yield, low in preparation cost and easy to realize industrial production. The gel and/or the solid electrolyte may be applied to the fields of lithium-based batteries, building materials, and the like, and the solid electrolyte may be applied to the fields of lithium-based batteries, and the like.

Description

Gellable system containing inorganic nanoparticles and preparation method and application thereof

Technical Field

The invention belongs to the technical field of gel, and particularly relates to a gellable system containing inorganic nanoparticles, and a preparation method and application thereof.

Background

The lithium ion battery becomes a hot point of novel energy technology research by virtue of high specific energy, high working voltage, wide working temperature range, long cycle life, no memory effect, rapid charge and discharge and the like, is not only widely applied to mobile phones, notebook computers and digital electronic products, but also is applied in the fields of aerospace, artificial satellites, small medical treatment and the like. However, lithium ion batteries also have safety problems, such as potential safety hazards, such as combustion, caused by volatile electrolyte.

Gel is a semi-solid system between liquid and solid, and has the advantages and characteristics of both liquid and solid, thereby making it a hot spot in research field and production life, and many researchers try to design various materials into a gel state to meet the application of people. Therefore, the gel electrolyte and the solid electrolyte are used to replace the liquid electrolyte in the lithium ion battery, which is also the most common method for the researchers to solve the safety of the electrolyte at present, generally, the gel electrolyte or the solid electrolyte of the lithium ion battery is composed of a polymer matrix, electrolyte lithium salt and a plasticizer according to a certain proportion, and is equivalent to an aggregate of a diaphragm and the electrolyte, polyethylene oxide (PEO) is a polymer matrix applied to the solid polymer electrolyte earlier, and the solid electrolyte prepared from the PEO has low ionic conductivity at room temperature because the PEO has good structural regularity and is easy to crystallize, but the high crystallinity can reduce the migration of lithium ions, and in addition, the gel electrolyte prepared from the PEO is poor in mechanical strength because the PEO can be partially dissolved in the ester electrolyte.

At present, there are two main types of common gel system building: one is that one or more high molecules are directly introduced into a solvent to form a network structure or an interpenetrating network structure, and the strength of the gel is high; the other is to introduce small molecule organogelators into it to make it soluble in a solvent at high temperature and form a gel at room temperature or low temperature, which is generally low in strength. For the gel systems formed by the two methods, macromolecules are inevitably introduced from raw materials or micromolecule organic gel factors with complex synthesis steps are inevitably introduced into the gel systems, a complicated and tedious experimental method is usually used, the preparation is time-consuming, labor-consuming and raw materials are wasted, the high molecular weight is easy to be different, the obtained gel systems are different, and products prepared from the gels have differences. And the gel systems reported at present are all irreversible, namely, after the gel is damaged, the original appearance and advantages are difficult to restore, so that the use and popularization of the gel are limited. The gel system is introduced into the design of the electrolyte of the lithium battery, so that how to make the prepared lithium battery have high safety and good charge-discharge efficiency is urgently needed to be solved. Or the gel system is introduced into the preparation of the building material, and if the prepared novel building material has the properties of light weight, high strength, capability of reaching A-level fire-proof standards and the like, the novel building material also has special commercial value.

Disclosure of Invention

In order to solve the disadvantages of the prior art, it is an object of the present invention to provide a gellable system comprising the following components: lithium salt, ether compound and inorganic nano-particles, wherein the ether compound is selected from cyclic ether compound.

The invention also aims to provide a gel or solid electrolyte prepared by the gelable system through gelation, and a preparation method and application of the gel or solid electrolyte.

The invention also aims to provide a gel electrolyte, a preparation method and application thereof, wherein the gel electrolyte comprises the gel.

In the research, the applicant finds that a gel system or a solid system can be formed by the interaction between the lithium salt and the small molecular cyclic ether compound (such as the generation of a new complex or the self-assembly) and the ring-opening polymerization or polycondensation of the small molecular cyclic ether compound; if inorganic nanoparticles are added in the process of forming the system, the prepared gel system or solid system not only has use safety superior to that of a common gel system or solid system, but also can effectively control the strength of the gel system or solid system by adjusting the content and the type of each component in the gel system, and the change of the strength can expand the gel system into the solid system, so that the application range of the system is further expanded; in addition, the addition of the inorganic nanoparticles can not only improve the mechanical strength of the gel system or the solid system, but also hinder the regular arrangement of polymer chain segments, reduce the crystallinity of the polymer, and simultaneously improve the porosity of the electrolyte membrane, so that the electrolyte membrane can adsorb more liquid electrolyte, and the mobility and the conductivity of lithium ions in the gel system or the solid system are improved. In addition, the gel system or the solid system has reversibility, namely the gel system or the solid system can be prepared at room temperature, and after high-temperature treatment (the temperature is higher than the transition temperature), the gel system or the solid system can become flowable, but can be restored to the original gel system or the original solid system after being rested and cooled again (the temperature is lower than the transition temperature), and the properties of the gel system or the solid system can not be changed. The present invention has been completed based on such a concept.

In a first aspect the present invention provides a gellable system comprising the following components: (a) a lithium salt, (b) an ether compound and (c) inorganic nanoparticles; the ether compound is selected from cyclic ether compounds; the mass percentage of the gellable polymer and/or the gellable prepolymer in the system is not more than 1 wt%.

In the gellable system, the sum of the weight percentages of the components is 100 wt%.

According to the invention, in the gellable system, the lithium salt is present in an amount of greater than 5wt% and not greater than 60 wt%; the mass percentage of the cyclic ether compound is more than or equal to 20wt% and less than or equal to 95 wt%; the mass percentage of the inorganic nano-particles is more than 0 and less than or equal to 30 wt%.

Preferably, in the gellable system, the lithium salt is present in an amount of 10wt% or more and 40wt% or less; the mass percentage of the cyclic ether compound is more than or equal to 20wt% and less than or equal to 60 wt%; the mass percentage of the inorganic nano-particles is more than 0wt% and less than or equal to 15 wt%.

Preferably, in the gellable system, the lithium salt is present in an amount greater than 10% and equal to or less than 40% by weight; the mass percentage of the cyclic ether compound is more than 60wt% and less than or equal to 90 wt%; the mass percentage of the inorganic nano-particles is more than 0wt% and less than or equal to 20 wt%.

According to the present invention, the lithium salt may be selected from one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium perfluorobutylsulfonate, lithium bistrifluoromethanesulfonylimide, lithium difluorosulfonylimide, lithium aluminate, lithium chloroaluminate, lithium fluorosulfonylimide, lithium chloride and lithium iodide; preferably, the lithium salt is selected from one or two of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate and the like.

According to the present invention, the cyclic ether compound is selected from cyclic ether compounds containing one oxygen, two oxygen, three oxygen or more.

According to the present invention, the cyclic ether compound may be a monocyclic ring, a fused ring (e.g., bicyclic ring), a spiro ring or a bridged ring.

According to the present invention, the inorganic nanoparticles are selected from one or more of silicon dioxide, aluminum oxide, silicon nitride, zinc oxide, titanium dioxide, silicon carbide, silicate, calcium carbonate, barium sulfate, clay, ferroferric oxide, cerium oxide, nanocarbon materials, iron oxide, etc.; preferably, the inorganic nanoparticles are selected from one or more of silica, alumina, titania, zinc oxide.

According to the invention, the gelable system further comprises (d) a further solvent and/or electrolyte comprising at least one of an electrolyte for a lithium sulphur battery, a solvent for an electrolyte for a lithium sulphur battery, an electrolyte for a lithium ion battery, a solvent for an electrolyte for a lithium ion battery.

According to the present invention, the gellable system may further comprise (d) another solvent and/or an electrolyte in an amount of 0wt% or more and 75wt% or less.

Preferably, in the gellable system, the content of the (d) other solvent and/or electrolyte is 5wt% or more and 60wt% or less.

A second aspect of the present invention provides a gel obtained by gelling the gellable system described above; wherein, in the gelable system, the mass percentage of the lithium salt is more than 5wt% and less than or equal to 60 wt%; the mass percentage of the cyclic ether compound is more than or equal to 20wt% and less than or equal to 60 wt%; the mass percentage of the inorganic nano particles is more than 0 and less than or equal to 30 wt%; and the mass percentage of the other solvent and/or the electrolyte is more than or equal to 0wt% and less than or equal to 75 wt%.

Preferably, in the gellable system, the lithium salt is present in an amount of 10wt% or more and 40wt% or less; the mass percentage of the cyclic ether compound is more than or equal to 20wt% and less than or equal to 60 wt%; the mass percentage of the inorganic nano particles is more than 0wt% and less than or equal to 15 wt%; and the mass percentage of the other solvent and/or the electrolyte is more than or equal to 5wt% and less than or equal to 60 wt%.

According to the invention, the transition temperature of the gel is 40-170 ℃, preferably 45-105 ℃.

According to the invention, the gel has a conductivity of 10^-5～10^-1S/cm, preferably 10^-5～8×10^-2S/cm。

The third aspect of the present invention provides a method for preparing the above gel, which comprises the following steps:

mixing inorganic nano-particles, lithium salt and cyclic ether compound, stirring to obtain a cyclic ether compound solution containing the lithium salt of the inorganic nano-particles, namely the gellable system, continuing to stir the solution, and gelling to obtain the gel.

Preferably, the preparation method of the gel specifically comprises the following steps:

1) adding inorganic nano particles into a cyclic ether compound to prepare a uniformly dispersed mixed solution;

2) adding the mixed solution prepared above into lithium salt, stirring to obtain a cyclic ether compound solution containing inorganic nanoparticle lithium salt, namely the gellable system, continuing to stir the solution, and gelling to obtain the gel.

Still preferably, the preparation method of the gel specifically comprises the following steps:

mixing inorganic nano-particles, lithium salt, a cyclic ether compound and other solvents and/or electrolyte, stirring to obtain a cyclic ether compound solution containing the lithium salt of the inorganic nano-particles, namely the gellable system, continuing to stir the solution, and gelling to obtain the gel.

Further preferably, the preparation method of the gel specifically comprises the following steps:

1') adding inorganic nano particles into a cyclic ether compound to prepare a uniformly dispersed mixed solution;

2') dissolving lithium salt in other solvents and/or electrolytes to prepare a lithium salt solution;

3 ') adding the mixed solution prepared in the step 1 ') into the lithium salt solution prepared in the step 2 '), stirring to obtain a cyclic ether compound solution containing inorganic nano-particles and lithium salt dissolved with other solvents and/or electrolytes, namely the gelable system, continuously stirring the solution, and gelling to obtain the gel.

According to the invention, the lithium salt, the cyclic ether compound, the inorganic nano-particles and other solvents and/or electrolyte are subjected to water removal treatment in advance; preferably, the lithium salt, the cyclic ether compound, the inorganic nanoparticles and other solvents and/or electrolytes are subjected to preliminary water removal treatment by using a molecular sieve and/or vacuum drying method.

According to the present invention, the gelation process needs to be completed under a static condition.

According to the invention, the temperature at which the gel is formed is lower than the transition temperature of the gel, and the time for gel formation is between 30 seconds and 300 hours.

A fourth aspect of the present invention is to provide a solid electrolyte obtained by gelling the above gellable system; wherein, in the gelable system, the mass percentage of the lithium salt is more than 5wt% and less than or equal to 60 wt%; the mass percentage of the cyclic ether compound is more than 60wt% and less than or equal to 95 wt%; the mass percentage of the inorganic nano particles is more than 0wt% and less than or equal to 30 wt%; and the mass percentage of the other solvent and/or the electrolyte is more than or equal to 0wt% and less than or equal to 75 wt%.

Preferably, in the gellable system, the lithium salt is present in an amount greater than 10% and equal to or less than 40% by weight; the mass percentage of the cyclic ether compound is more than 60wt% and less than or equal to 90 wt%; the mass percentage of the inorganic nano particles is more than 0wt% and less than or equal to 20 wt%; and the mass percentage of the other solvent and/or the electrolyte is more than or equal to 5wt% and less than or equal to 60 wt%.

According to the invention, the transition temperature of the solid electrolyte is 70-180 ℃, preferably 72-145 ℃.

According to the invention, the solid electrolyte has a conductivity of 10^-7～10^-2S/cm, preferably 10^-6～2×10^-3S/cm。

A fifth aspect of the present invention provides a method for preparing the above solid electrolyte, comprising the steps of:

mixing inorganic nano-particles, lithium salt and cyclic ether compound, stirring to obtain a cyclic ether compound solution containing the lithium salt of the inorganic nano-particles, namely the gellable system, continuing to stir the solution, and gelling to obtain the solid electrolyte.

Preferably, the preparation method of the solid electrolyte specifically comprises the following steps:

a) adding inorganic nano particles into a cyclic ether compound to prepare a uniformly dispersed mixed solution;

b) adding the mixed solution prepared above into lithium salt, stirring to obtain a cyclic ether compound solution containing inorganic nanoparticle lithium salt, namely the gellable system, continuing to stir the solution, and gelling to obtain the solid electrolyte.

Still preferably, the method for preparing the solid electrolyte specifically comprises the following steps:

mixing inorganic nano-particles, lithium salt, a cyclic ether compound and other solvents and/or electrolyte, stirring to obtain a cyclic ether compound solution containing the lithium salt of the inorganic nano-particles, namely the gellable system, continuing to stir the solution, and gelling to obtain the solid electrolyte.

Further preferably, the preparation method of the solid electrolyte specifically comprises the following steps:

a') adding inorganic nano particles into a cyclic ether compound to prepare a uniformly dispersed mixed solution;

b') dissolving lithium salt in other solvents and/or electrolytes to prepare a lithium salt solution;

c ') adding the mixed solution prepared in the step a ') into the lithium salt solution prepared in the step b '), stirring to obtain a cyclic ether compound solution containing inorganic nano-particles and lithium salt dissolved with other solvents and/or electrolyte, namely the gelable system, continuously stirring the solution, and gelling to obtain the solid electrolyte.

According to the present invention, the solid electrolyte is formed at a temperature lower than the transition temperature of the gel solid electrolyte, and the time for forming the solid electrolyte is 30 minutes to 150 hours.

A sixth aspect of the invention provides a gel electrolyte comprising the gel described above.

A seventh aspect of the invention is to provide a lithium-based battery including the above gel electrolyte and/or solid electrolyte.

An eighth aspect of the present invention is to provide a use of the above gel, which can be used in the fields of lithium-based batteries, building materials, and the like.

A ninth aspect of the present invention is to provide a use of the above solid electrolyte, which can be used in the fields of lithium-based batteries, building materials, and the like.

A tenth aspect of the present invention is to provide a use of the above gel electrolyte, which can be used in the field of lithium batteries and the like.

Preferably, the lithium-based battery includes at least one of a lithium ion battery, a lithium sulfur battery, and a lithium air battery.

The invention has the beneficial effects that:

1. the invention provides a gellable system containing inorganic nanoparticles, a gel and/or solid electrolyte prepared from the gellable system, and a preparation method and application of the gel and/or solid electrolyte. The system comprises the following components: (a) a lithium salt, (b) an ether compound and (c) inorganic nanoparticles; the ether compound is selected from cyclic ether compounds; the mass percentage of the gellable polymer and/or the gellable prepolymer in the system is not more than 1 wt%. The gel and/or solid electrolyte can be prepared by adjusting the content and the type of the components of the lithium salt, the cyclic ether compound and the inorganic nanoparticles in the system, and the gel or solid electrolyte can be applied to the field of lithium batteries (such as lithium ion batteries, lithium sulfur batteries, lithium air batteries and the like).

2. The strength of the gel and/or solid electrolyte prepared by the inorganic nanoparticle-containing gellable system is adjustable, the forming time (namely, the state of the gel or the solid electrolyte is converted from a free-flowing liquid state into a non-flowable state) is adjustable, the conversion temperature (namely, the lowest temperature when the gel or the solid electrolyte is converted from the non-flowable state into the free-flowing liquid state) is adjustable, and the gel and the solid electrolyte with different strengths can be prepared according to specific needs so as to meet different needs. The gel and the solid electrolyte have stronger impact resistance, when the gel and the solid electrolyte are applied to the fields of lithium batteries and the like, the leakage of a liquid electrolyte solution can be effectively solved, the problems of battery short circuit and the like caused by the fact that a diaphragm or the solid electrolyte is punctured by the growth of lithium dendrites can be better prevented, the lithium batteries can have higher charge-discharge efficiency and better impact resistance, the lithium batteries have higher use safety, and particularly the gel and the solid electrolyte are applied to the lithium sulfur batteries, so that the shuttle flying effect can be effectively slowed down or even stopped. When the material is applied to the fields of building materials and the like, the building material with adjustable strength can be prepared, and the material has the characteristics of light weight, environmental protection, fire prevention and the like.

3. The gel and/or solid electrolyte prepared by the inorganic nanoparticle-containing gellable system has higher transition temperature, the mechanical strength of the gel system and the solid system is enhanced by adding the inorganic nanoparticles, the porosity of the electrolyte membrane can be improved, and the electrolyte membrane can adsorb more liquid electrolyte, so that the mobility and the conductivity of lithium ions in the gel or solid electrolyte are improved; and also has reversibility. The gelled or solid electrolyte may become flowable when the use temperature of the gelled or solid electrolyte is above its transition temperature; but after cooling below the transition temperature, it has reversible ability and can be reused by reforming gel or solid electrolyte; because the gel material has higher transition temperature and reversibility, the service life of the gel material can be prolonged, and the cost is saved, so that the gel material becomes a novel green and environment-friendly gel material.

4. The preparation method of the gel or solid electrolyte is simple, mild in reaction condition, short in reaction period, high in product yield, low in preparation cost and easy to realize industrial production.

5. The gel and the solid electrolyte prepared by the inorganic nanoparticle-containing gellable system can show a better gel state or solid electrolyte state at low temperature, namely, the gel state or the solid electrolyte state can be kept well below the transition temperature of the gel or the solid electrolyte, and the strength of the gel and the solid electrolyte is better at low temperature.

6. The gel and/or solid electrolyte prepared by the inorganic nanoparticle-containing gellable system can be applied to the fields of lithium batteries (such as lithium ion batteries, lithium sulfur batteries, lithium air batteries and the like), and can be used particularly under high and low temperature conditions.

Drawings

Fig. 1 is a diagram showing the first charge and discharge of a battery assembled by using the gel electrolyte obtained in example 1 as an electrolyte of a lithium ion battery.

Fig. 2 is a graph showing the cycle performance of a battery assembled by using the gel electrolyte obtained in example 1 as an electrolyte of a lithium ion battery.

Fig. 3 is a diagram illustrating the first charge and discharge of a battery assembled by using the gel electrolyte obtained in example 5 as an electrolyte of a lithium sulfur battery.

Fig. 4 is a graph showing the cycle performance of the gel electrolyte obtained in example 5 assembled into a battery as an electrolyte for a lithium sulfur battery.

Detailed Description

[ other solvents and/or electrolytes ]

In a preferred embodiment, the gellable system further comprises (d) other solvents and/or electrolytes including at least one of an electrolyte for a lithium sulfur battery, a solvent for an electrolyte for a lithium sulfur battery, an electrolyte for a lithium ion battery, a solvent for an electrolyte for a lithium ion battery.

In the present invention, the electrolyte for a lithium ion battery is selected from an ester mixture containing a lithium salt for a lithium ion battery, for example, lithium hexafluorophosphate (LiPF) containing 1M₆) Wherein the volume ratio of the Ethylene Carbonate (EC) to the dimethyl carbonate (DMC) is 1: 1.

In the present invention, the solvent for the electrolyte of the lithium ion battery is selected from at least one of a cyclic nonaqueous organic solvent for the electrolyte of the lithium ion battery and a chain-like nonaqueous organic solvent for the electrolyte of the lithium ion battery.

In a preferred embodiment, the cyclic non-aqueous organic solvent of the electrolyte for a lithium ion battery is selected from at least one of Ethylene Carbonate (EC), Propylene Carbonate (PC), fluoroethylene carbonate (FEC), γ -butyrolactone (GBL), Ethylene Sulfite (ES), Propylene Sulfite (PS), Sulfolane (SL), Glycerol Carbonate (GC).

In a preferred embodiment, the chain non-aqueous organic solvent of the electrolyte for a lithium ion battery is selected from at least one of diethyl carbonate (DEC), dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), Methyl Propyl Carbonate (MPC), dipropyl carbonate (DPC), Ethyl Propyl Carbonate (EPC), Ethyl Acetate (EA), Propyl Acetate (PA), Ethyl Propionate (EP), Ethyl Butyrate (EB), Methyl Butyrate (MB), dimethyl sulfite (DMS), diethyl sulfite (DES), Ethyl Methyl Sulfite (EMS), dimethyl sulfone (MSM), dimethyl sulfoxide (DMSO).

In the present invention, the electrolyte for a lithium-sulfur battery is selected from an ether-based mixed solution containing a lithium salt, for example: the liquid mixture contains 1M lithium bistrifluoromethanesulfonimide (LiTFSI) and 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME), wherein the volume ratio of the 1, 3-Dioxolane (DOL) to the ethylene glycol dimethyl ether (DME) is 1: 1.

In the present invention, the solvent of the electrolyte for a lithium sulfur battery is selected from one or more of 1, 3-dioxolane, 1, 2-dimethoxyethane, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, fluoroethylene carbonate, polyethylene glycol borate, and 1,1 ', 2, 2' -tetrafluoroethyl-2, 2 ', 3, 3' -tetrafluoropropenyl ether.

[ Cyclic ether Compound ]

The gellable system of the present invention comprises an ether compound selected from cyclic ether compounds. The cyclic ether compound is selected from C containing at least 1 oxygen atom₂～C₂₀Cycloalkanes (i.e. having 2 to 20 carbon atoms in the ring structure) or C containing at least 1 oxygen atom₃～C₂₀Cyclic olefins (i.e., cyclic structures having 3 to 20 carbon atoms) which contain at least one carbon-carbon double bond.

In the present invention, the cycloalkane or cycloalkene is a monocyclic ring, a fused ring (e.g., bicyclic ring), a spiro ring or a bridged ring; when the cycloalkane or cycloalkene is a spiro ring or bridged ring and contains two or more oxygen atoms, the oxygen atoms may be in one ring or in a plurality of rings.

In the present invention, the cyclic ether compound is selected from C containing at least 1 oxygen atom₂～C₂₀Preferably selected from C containing at least 1 oxygen atom₃～C₂₀Such as one of the following first compounds:

in the present invention, the cyclic ether compound is selected from C containing at least 1 oxygen atom₄～C₂₀The fused cycloalkane of (a) is, for example, one of the following second classes of compounds:

in the present invention, the cyclic ether compound is selected from C containing at least 1 oxygen atom₄～C₂₀For example, one of the following compounds of the third class:

in the present invention, the cyclic ether compound is selected from C containing at least 1 oxygen atom₄～C₂₀The spirocycloalkane of (a) is, for example, one of the following fourth classes of compounds:

in the present invention, the compound in which at least one of the C — C bonds in the ring structure in the above-mentioned four groups is replaced with C ═ C and which is stably present is the above-mentioned C having at least 1 oxygen atom₃～C₂₀Cyclic olefins, which are one of the preferred cyclic ether compounds of the present invention.

In the present invention, when the cycloalkane or cycloalkene is monocyclic or fused, carbon atoms on the ring may be substituted with 1 or more R1 groups; where the cycloalkane or cycloalkene is a bridged ring, its unbridged ring carbon atoms may be substituted with 1 or more R1 groups; when the cycloalkane or cycloalkene is a spiro ring, the carbon atoms on the ring may be substituted with 1 or more R1 groups; the R1 group is selected from one of the following groups: alkyl, alkenyl, alkynyl, alkoxy, alkylthio, haloalkyl, cycloalkyl, cycloalkyloxy, cycloalkylthio, heterocyclyl, heterocyclyloxy, heterocyclylthio, aryl, aryloxy, heteroaryl, heteroaryloxy, hydroxy, mercapto, nitro, carboxy, amino, ester, halogen, acyl, aldehyde.

In a preferred embodiment of the present invention, the cyclic ether compound containing one oxygen is selected from the group consisting of substituted or unsubstituted oxetane, substituted or unsubstituted tetrahydrofuran, substituted or unsubstituted tetrahydropyran; the number of the substituents may be one or more; the substituent is the R1 group described above.

In a preferred embodiment of the present invention, the cyclic ether compound containing one oxygen is selected from the group consisting of 3, 3-dichloromethyloxetane, 2-chloromethyloxetane, 2-chloromethylepoxypropane, 1, 4-epoxycyclohexane, 1, 3-epoxycyclohexane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, tetrahydropyran, 2-methyltetrahydropyran, oxepane, oxooctane, oxononane and oxodecane.

In a preferred embodiment of the present invention, the cyclic ether compound having two oxygens is selected from substituted or unsubstituted 1, 3-Dioxolane (DOL), substituted or unsubstituted 1, 4-dioxane; the number of the substituents may be one or more; the substituent is the R1 group described above.

In a preferred embodiment of the present invention, the cyclic ether-based compound containing three oxygens is selected from substituted or unsubstituted trioxymethylenes; the number of the substituents may be one or more; the substituent is the R1 group described above.

In a preferred embodiment of the present invention, the ether compound containing more oxygen 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 R1 group described above.

[ terms and definitions ]

Unless otherwise specified, the definitions of groups and terms described in the specification of the present application, including definitions thereof as examples, exemplary definitions, preferred definitions, definitions described in tables, definitions of specific compounds in examples, and the like, may be arbitrarily combined and combined with each other. Such combinations and definitions of groups and structures of compounds after combination are intended to fall within the scope of the present application.

The term "gel" in the present invention has a meaning well known in the art, and the term "gelation" also has a meaning well known in the art.

The gellable polymer and/or gellable prepolymer in the present invention means a polymer and/or prepolymer which can form a gel or can be gelled under certain conditions. Without limitation, the gellable polymer and/or gellable prepolymer of the present invention may be selected from one or more of polyethylene oxide (PEO), polyethylene glycol (PEG), polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC), Polystyrene (PS), Polyacrylonitrile (PAN), polyvinyl acetate (PVAC), polyvinylpyrrolidone (PVP), polydivinyl sulfide (PVS), polytrimethylene carbonate (PTMC), polymethyl methacrylate (PMMA), polyethylene glycol dimethacrylate (PEGDM), polypropylene oxide (PPO), Polydimethylsiloxane (PDMSO) or prepolymers thereof, or copolymers thereof, or blends thereof.

Where a range of numerical values is recited in the specification of the present application, and where the range of numerical values is defined as an "integer", it is understood that the two endpoints of the range and each integer within the range are recited. For example, "an integer of 0 to 10" should be understood to describe each integer of 0, 1,2, 3,4, 5, 6, 7, 8, 9, and 10. When a range of values is defined as "a number," it is understood that the two endpoints of the range, each integer within the range, and each decimal within the range are recited. For example, "a number of 0 to 10" should be understood to not only recite each integer of 0, 1,2, 3,4, 5, 6, 7, 8, 9, and 10, but also to recite at least the sum of each integer and 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, respectively.

"halogen" as used herein refers to fluorine, chlorine, bromine and iodine.

"alkyl" used herein alone or as a suffix or prefix, is intended to include both branched and straight chain saturated aliphatic hydrocarbon groups having from 1 to 20, preferably 1-6, carbon atoms (or the particular number of carbon atoms if provided). For example, "C_1-6Alkyl "denotes straight-chain and branched alkyl groups having 1,2, 3,4, 5 or 6 carbon atoms. Examples of 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" used herein alone or as a suffix or prefix, is intended to include both branched and straight chain saturated aliphatic hydrocarbon groups having at least one halogen substituent and having from 1 to 20, preferably from 1 to 6, carbon atoms (or the particular number of carbon atoms if provided). For example, "C_1-10Haloalkyl "denotes haloalkyl having 0, 1,2, 3,4, 5, 6, 7, 8, 9, 10 carbon atoms. Examples of haloalkyl groups include, but are not limited to, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, 1-fluoroethyl, 3-fluoropropyl, 2-chloropropyl, 3, 4-difluorobutyl, and the like.

"alkenyl" used alone or as suffix or prefix in the present invention is intended to include groups having 2 to 20, preferably 2 to 6 carbon atoms (or the specific number of carbon atoms if provided)Branched and straight chain aliphatic hydrocarbon groups comprising alkenyl or alkene groups. For example, "C_2-6Alkenyl "denotes alkenyl having 2,3, 4, 5 or 6 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl, allyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, 3-methylbut-1-enyl, 1-pentenyl, 3-pentenyl, and 4-hexenyl.

"alkynyl" used herein alone or as a suffix or prefix is intended to include both branched and straight chain aliphatic hydrocarbon radicals containing alkynyl groups or alkynes having 2 to 20, preferably 2-6 carbon atoms (or the particular number of carbon atoms if provided). For example ethynyl, propynyl (e.g., l-propynyl, 2-propynyl), 3-butynyl, pentynyl, hexynyl and 1-methylpent-2-ynyl.

The term "aryl" as used herein refers to an aromatic ring structure made up of 5 to 20 carbon atoms. For example: the aromatic ring structure containing 5, 6, 7 and 8 carbon atoms may be a monocyclic aromatic group such as phenyl; the ring structure containing 8, 9, 10, 11, 12, 13 or 14 carbon atoms may be polycyclic, for example naphthyl. The aromatic ring may be substituted at one or more ring positions with those substituents described above. The term "aryl" also includes polycyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings (the rings are "fused rings"), wherein at least one of the rings is aromatic and the other cyclic rings can be, for example, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, and/or heterocyclyl. Examples of polycyclic rings include, but are not limited to, 2, 3-dihydro-1, 4-benzodioxine and 2, 3-dihydro-1-benzofuran.

The term "cycloalkyl" as used herein is intended to include saturated cyclic groups having the specified number of carbon atoms. These terms may include fused or bridged polycyclic ring systems. Cycloalkyl groups have 3 to 40 carbon atoms in their ring structure. In one embodiment, the cycloalkyl group has 3,4, 5, or 6 carbon atoms in its ring structure. For example, "C_3-6Cycloalkyl "denotes a group such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

As used herein, "heteroaryl" refers to a heteroaromatic heterocycle having at least one ring heteroatom (e.g., sulfur, oxygen, or nitrogen). Heteroaryl groups include monocyclic ring systems and polycyclic ring systems (e.g., having 2,3, or 4 fused rings). Examples of heteroaryl groups include, but are not limited to, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furyl, quinolinyl, isoquinolinyl, thienyl, imidazolyl, thiazolyl, indolyl, pyrrolyl, oxazolyl, benzofuryl, benzothienyl, benzothiazolyl, isoxazolyl, pyrazolyl, triazolyl, tetrazolyl, indazolyl, 1,2, 4-thiadiazolyl, isothiazolyl, benzothienyl, purinyl, carbazolyl, benzimidazolyl, benzoxazolyl, azabenzoxazolyl, imidazothiazolyl, benzo [1,4] dioxanyl, benzo [1,3] dioxolyl, and the like. In some embodiments, heteroaryl groups have from 3 to 40 carbon atoms and in other embodiments from 3 to 20 carbon atoms. In some embodiments, heteroaryl groups contain 3 to 14, 4 to 14, 3 to 7, or 5 to 6 ring-forming atoms. In some embodiments, heteroaryl has 1 to 4, 1 to 3, or 1 to 2 heteroatoms. In some embodiments, the heteroaryl group has 1 heteroatom.

The term "heterocyclyl", as used herein, unless otherwise specified, 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, which may be attached through carbon or nitrogen, unless otherwise specified, wherein-CH is₂-the group is optionally replaced by-c (o) -; and wherein unless otherwise stated to the contrary, the ring nitrogen atom or the ring sulfur atom is optionally oxidized to form an N-oxide or S-oxide or the ring nitrogen atom is optionally quaternized; wherein-NH in the ring is optionally substituted with acetyl, formyl, methyl or methanesulfonyl; and the ring is optionally substituted with one or more halogens. It is understood that when the total number of S and O atoms in the heterocyclic group exceeds 1, these heteroatoms are not adjacent to each other. If the heterocyclyl is bicyclic or tricyclic, at least one ring may optionally be a heteroaromatic ring or an aromatic ring, provided that at least one ring is non-heteroaromatic. If the heterocyclic group is monocyclic, it is not necessarily aromatic. Examples of heterocyclyl groups include, but are not limited to, piperidinyl, N-acetylpiperidinyl, N-methylpiperidinylN-formylpiperazinyl, N-methylsulfonylpiperazinyl, homopiperazinyl, piperazinyl, azetidinyl, oxetanyl, morpholinyl, tetrahydroisoquinolinyl, tetrahydroquinolinyl, indolinyl, tetrahydropyranyl, dihydro-2H-pyranyl, tetrahydrofuranyl, tetrahydrothiopyranyl-1-oxide, tetrahydrothiopyranyl-1, 1-dioxide, 1H-pyridin-2-one, and 2, 5-dioxoimidazolidinyl.

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the description of the present invention, and such equivalents also fall within the scope of the invention.

The test method comprises the following steps:

the conductivity of the sample is measured by using an electrochemical workstation model Interface 1000 of Gamry corporation, and the scanning frequency of the measurement is 1.0 Hz-100 kHz.

Raw materials and reagents:

the conventional electrolyte for lithium ion batteries used in this example was selected from the group consisting of lithium hexafluorophosphate (LiPF) containing 1M₆) Wherein the volume ratio of the Ethylene Carbonate (EC) to the dimethyl carbonate (DMC) is 1: 1.

The conventional electrolyte of the lithium-sulfur battery selected in this embodiment is selected from an ether mixture containing lithium salts, such as: the liquid mixture contains 1M lithium bistrifluoromethanesulfonimide (LiTFSI) and 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME), wherein the volume ratio of the 1, 3-Dioxolane (DOL) to the ethylene glycol dimethyl ether (DME) is 1: 1.

In this example, the lithium salt was subjected to dehydration treatment at 40 ℃ under vacuum for 10 hours or more before use.

In this example, the cyclic ether compound was subjected to water removal treatment with a molecular sieve before use.

In this embodiment, the inorganic nanoparticles are subjected to a water removal treatment by vacuum drying at 60 ℃ for 10 hours or more before use.

In this embodiment, the other solvents and/or electrolytes are subjected to a water removal treatment by a molecular sieve before use.

The composition of the cells in the following examples is as follows:

the positive electrode material of the lithium ion battery: uniformly mixing lithium cobaltate with conductive graphite, conductive agent acetylene black (super p) and adhesive polyvinylidene fluoride (PVDF) according to a mass ratio of 85:5:5:5, preparing the mixture into slurry by using N-methyl-pyrrolidone (NMP), uniformly coating the slurry on an aluminum foil, and drying the slurry in a vacuum oven at 120 ℃ for 24 hours for later use;

positive electrode material for lithium-sulfur battery: uniformly mixing a carbon-sulfur composite material, a conductive agent acetylene black (super p) and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 8:1:1, preparing the mixture into slurry by using N-methyl-pyrrolidone (NMP), uniformly coating the slurry on an aluminum foil, and drying the slurry in a vacuum oven at 60 ℃ for 24 hours for later use;

electrolyte solution: the gel electrolyte or solid electrolyte prepared in each example;

negative electrode: a lithium sheet;

a diaphragm: polypropylene (PP) porous films.

Example 1

(1) Gelable systems and preparation of gels (useful as gel electrolytes for batteries)

0.06g of silica was weighed in a reagent bottle, 2.6mL of tetrahydrofuran was added thereto, and the mixture was sufficiently and uniformly mixed under magnetic stirring to obtain a mixed solution A.

0.8g of lithium tetrafluoroborate was put into a reagent bottle, and 2.6mL of dimethyl carbonate was added thereto, followed by stirring until the lithium salt was completely dissolved, to obtain a mixed solution B.

Fully mixing the solution A and the solution B to obtain a mixed solution, and obtaining a gellable system; standing for a period of time to form a gel.

In the gel system, the mass percentage of lithium salt is 13 wt%; the mass percentage of the cyclic ether compound is 43 wt%; the mass percentage of the inorganic nano particles is 1 wt%; the mass percentage of other solvents and/or electrolyte is 43 wt%.

The test shows that the formation time of the gel is 20h, the formation temperature of the gel is room temperature, the transition temperature of the gel is 55 ℃, and the conductivity of the gel is 1.78 multiplied by 10^-2S/cm。

When the prepared gel is heated to a temperature 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 downwards, which indicates that the temperature reaches the transition temperature of the gel, and when the temperature drops below the transition temperature of the gel, the gel is reformed, which indicates that the prepared gel has good reversibility.

(2) Preparation of the Battery

The prepared gel is applied to a button cell as a gel electrolyte, and the electrochemical performance of the button cell is tested by using a blue battery (the test results are listed in table 2). The preparation method of the button battery comprises the following steps: and (2) placing the diaphragm between the positive electrode and the negative electrode, filling the gellable system prepared in the step (1) between the positive electrode and the negative electrode, packaging and compacting, assembling into the CR-2032 type button battery, and standing until the gellable system becomes gel electrolyte.

Examples 2 to 7 and comparative example 1

The preparation method of the gel is the same as that of the gel in example 1, and only the selection and the use amount of each component in the gel system are different; the specific components and amounts are listed in table 1.

(2) Preparation of the Battery

Example 8

(1) Gelable systems and preparation of solid electrolytes

0.05g of alumina was weighed into a reagent bottle, 4.5mL of 1, 3-dioxolane was added thereto, and the mixture was thoroughly and uniformly mixed under magnetic stirring to obtain a mixed solution A.

And adding 0.4g of lithium fluorosulfonyl imide and 0.6g of lithium perchlorate into a reagent bottle, adding 1.2mL of conventional electrolyte of the lithium-sulfur battery, and stirring until the lithium salt is completely dissolved to obtain a mixed solution B.

Fully mixing the solution A and the solution B to obtain a mixed solution, and obtaining a gellable system; standing for a period of time to form a solid electrolyte.

In the gel system, the mass percentage of lithium salt is 15 wt%; the mass percentage of the cyclic ether compound is 66.3 wt%; the mass percentage of the inorganic nano particles is 0.7 wt%; the mass percentage of other solvents and/or electrolyte is 18 wt%.

The test proves that the forming time of the solid electrolyte is 12h, the forming temperature of the solid electrolyte is room temperature, the transition temperature of the solid electrolyte is 96 ℃, and the conductivity of the solid electrolyte is 2.38 multiplied by 10^-5S/cm。

When the prepared solid electrolyte is heated to the temperature above the gel transition temperature of the solid electrolyte gel, the solid electrolyte begins to become sticky, the solid electrolyte is observed to flow downwards when the reagent bottle is inverted, the temperature is indicated to reach the transition temperature of the solid electrolyte, and when the temperature is reduced to the temperature below the gel transition temperature, the solid electrolyte is formed again, and the prepared solid electrolyte has good reversibility.

(2) Preparation of the Battery

The solid electrolyte prepared above was applied to a button cell, and the electrochemical performance of the button cell was tested using a blue cell battery (test results are listed in table 3). The preparation method of the button battery comprises the following steps: and (2) placing the diaphragm between the positive electrode and the negative electrode, filling the gellable system prepared in the step (1) between the positive electrode and the negative electrode, packaging and compacting, assembling into the CR-2032 type button battery, and standing until the gellable system becomes a solid electrolyte.

Examples 9 to 14 and comparative example 2

(1) Gelable systems and preparation of solid electrolytes

The preparation method of the solid electrolyte is the same as that of the embodiment 8, and only the difference is that the selection and the dosage of each component in the solid electrolyte system are different; the specific components and amounts are listed in table 1.

(2) Preparation of the Battery

TABLE 1 compositions and contents of respective components of gel electrolytes or solid electrolytes in examples 1 to 14 and comparative examples 1 to 2

TABLE 2 gels and performance parameters of the batteries prepared in examples 1-7 and comparative example 1

TABLE 3 solid electrolyte and performance parameters of the battery prepared in examples 8 to 14 and comparative example 2

Fig. 1 is a diagram showing the first charge and discharge of a battery assembled by using the gel electrolyte obtained in example 1 as an electrolyte of a lithium ion battery. As can be seen from the figure, the gel electrolyte can be used as an electrolyte of a lithium ion battery, so that the lithium ion battery can be normally charged and discharged, active substances in the lithium ion battery can be fully exerted, and a high specific capacity can be obtained.

Fig. 2 is a graph showing the cycle performance of a battery assembled by using the gel electrolyte obtained in example 1 as an electrolyte of a lithium ion battery. As can be seen from the figure, the gel can show stable cycle performance as an electrolyte of a lithium ion battery, and the specific capacity is basically kept unchanged.

Fig. 3 is a diagram illustrating the first charge and discharge of a battery assembled by using the gel electrolyte obtained in example 5 as an electrolyte of a lithium sulfur battery. As can be seen from the figure, the gel electrolyte, as an electrolyte of a lithium-sulfur battery, can enable normal charge and discharge of the lithium-ion battery, and sufficiently exert active substances therein, thereby obtaining a high specific capacity.

Fig. 4 is a graph showing the cycle performance of the gel electrolyte obtained in example 5 assembled into a battery as an electrolyte for a lithium sulfur battery. As can be seen from the figure, the gel electrolyte can effectively reduce the "shuttle flying effect" as an electrolyte of a flow battery, thereby improving the utilization rate of an active material, improving the specific capacity of the battery, and showing excellent cycle performance.

Compared with comparative examples 1 and 2, the addition of the inorganic nanoparticles can effectively improve the conductivity of the gel or solid electrolyte, and show more excellent electrochemical properties.

The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A gellable system, comprising: lithium salt, ether compound, inorganic nano-particles and solvent of electrolyte; the ether compound is selected from cyclic ether compounds;

in the gelable system, the mass percentage of the lithium salt is more than or equal to 10wt% and less than or equal to 40 wt%; the mass percentage of the cyclic ether compound is more than or equal to 20wt% and less than or equal to 60 wt%; the mass percentage of the inorganic nano particles is more than 0wt% and less than or equal to 15 wt%; the mass percentage of the solvent of the electrolyte is more than or equal to 0wt% and less than or equal to 75 wt%; alternatively, the first and second electrodes may be,

in the gelable system, the mass percentage of the lithium salt is more than 10wt% and less than or equal to 40 wt%; the mass percentage of the cyclic ether compound is more than 60wt% and less than or equal to 90 wt%; the mass percentage of the inorganic nano particles is more than 0wt% and less than or equal to 20 wt%; the mass percentage of the solvent of the electrolyte is more than or equal to 0wt% and less than or equal to 75 wt%;

the lithium salt is selected from one or more of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium perfluorobutylsulfonate, lithium bistrifluoromethanesulfonylimide, lithium difluorosulfonylimide, lithium aluminate, lithium chloroaluminate, lithium fluorosulfonylimide, lithium chloride and lithium iodide;

the cyclic ether compound is selected from C containing one oxygen, two oxygen, three oxygen or more oxygen₂~C₂₀One or more of a cycloalkane, which cycloalkane is a monocyclic, fused, spiro or bridged ring.

2. A gellable system, comprising: lithium salt, ether compound, inorganic nano-particles and electrolyte; the ether compound is selected from cyclic ether compounds;

in the gelable system, the mass percentage of the lithium salt is more than or equal to 10wt% and less than or equal to 40 wt%; the mass percentage of the cyclic ether compound is more than or equal to 20wt% and less than or equal to 60 wt%; the mass percentage of the inorganic nano particles is more than 0wt% and less than or equal to 15 wt%; the mass percentage of the electrolyte is more than or equal to 0wt% and less than or equal to 75 wt%; alternatively, the first and second electrodes may be,

in the gelable system, the mass percentage of the lithium salt is more than 10wt% and less than or equal to 40 wt%; the mass percentage of the cyclic ether compound is more than 60wt% and less than or equal to 90 wt%; the mass percentage of the inorganic nano particles is more than 0wt% and less than or equal to 20 wt%; the mass percentage of the electrolyte is more than or equal to 0wt% and less than or equal to 75 wt%;

3. The gellable system of claim 1 further comprising a gellable polymer and/or a gellable prepolymer, wherein the mass percent of the gellable polymer and/or the gellable prepolymer is less than or equal to 1 wt%.

4. The gellable system of claim 2 further comprising a gellable polymer and/or a gellable prepolymer, wherein the mass percent of the gellable polymer and/or the gellable prepolymer is less than or equal to 1 wt%.

5. Gelable system according to any of claims 1-4, wherein the lithium salt is selected from one or both of lithium hexafluorophosphate, lithium perchlorate.

6. The gellable system of any one of claims 1-4, wherein the inorganic nanoparticles are selected from one or more of silica, alumina, silicon nitride, zinc oxide, titanium dioxide, silicon carbide, silicates, calcium carbonate, barium sulfate, clay, ferroferric oxide, cerium oxide, nanocarbon materials, iron oxide.

7. Gelable system according to any of claims 1-4, characterized in that when the cycloalkane is a spiro or bridged ring and contains more than two oxygen atoms, the oxygen atoms are on one ring or on more than one ring.

8. Gelable system according to any of claims 1 to 4, wherein the cyclic ether compound is selected from at least one of the following first class of compounds:

。

9. gellable system according to any one of claims 1 to 4, wherein the cyclic ether compound is selected from C comprising one oxygen, two oxygen, three oxygen or more₄~C₂₀Fused cycloalkane of (2).

10. Gelable system according to claim 9, characterized in that said cyclic ether compound is selected from at least one of the following second classes of compounds:

。

11. gellable system according to any one of claims 1 to 4, wherein the cyclic ether compound is selected from C comprising one oxygen, two oxygen, three oxygen or more₄~C₂₀Bridged cycloalkanes of (a).

12. Gelable system according to claim 11, characterized in that said cyclic ether compound is selected from at least one of the following third classes of compounds:

。

13. gellable system according to any one of claims 1 to 4, wherein the cyclic ether compound is selected from C comprising one oxygen, two oxygen, three oxygen or more₄~C₂₀Is used as the spiro cycloalkane.

14. Gelable system according to claim 13, characterized in that said cyclic ether compound is selected from at least one of the following fourth classes of compounds:

。

15. gelable system according to any of claims 1-4, characterized in that when the cycloalkane is a single or fused ring, the hydrogen on the carbon atoms of the ring is substituted by 1 or more R1 groups; when the cycloalkane is a bridged ring, the hydrogen on the carbon atom on the unbridged ring is substituted with 1 or more R1 groups; when the cycloalkane is a spiro ring, the hydrogen on the carbon atom on the ring is substituted with 1 or more R1 groups; the R1 group is selected from one of the following groups: alkyl, alkenyl, alkynyl, alkoxy, alkylthio, haloalkyl, cycloalkyl, cycloalkyloxy, cycloalkylthio, heterocyclyl, heterocyclyloxy, heterocyclylthio, aryl, aryloxy, heteroaryl, heteroaryloxy, hydroxy, mercapto, nitro, carboxy, amino, ester, halogen, acyl, aldehyde.

16. The gellable system of any one of claims 1 to 4 wherein the cyclic ether-based compound containing one oxygen is selected from the group consisting of substituted or unsubstituted oxetanes, substituted or unsubstituted tetrahydrofurans, substituted or unsubstituted tetrahydropyrans; the number of the substituents is one or more; the substituent is a group R1 as described in claim 15.

17. The gellable system of claim 16 wherein the cyclic ether compound containing an oxygen is selected from the group consisting of 3, 3-dichloromethyloxetane, 2-chloromethyloxetane, 2-chloromethylpropylene oxide, 1, 3-epoxycyclohexane, 1, 4-epoxycyclohexane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, tetrahydropyran, 2-methyltetrahydropyran, oxepane, oxooctane, oxononane and oxodecane.

18. The gellable system of any one of claims 1 to 4 wherein the cyclic ether compound containing two oxygens is selected from the group consisting of substituted or unsubstituted 1, 3-dioxolanes, substituted or unsubstituted 1, 4-dioxanes; the number of the substituents is one or more; the substituent is a group R1 as described in claim 15.

19. Gelatable system according to any one of claims 1 to 4, characterised in that the cyclic ether-based compound containing three oxygens is selected from substituted or unsubstituted trioxymethylenes; the number of the substituents is one or more; the substituent is a group R1 as described in claim 15.

20. The gellable system of any one of claims 1 to 4, wherein the oxygen-rich 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 is one or more; the substituent is a group R1 as described in claim 15.

21. The gellable system of claim 1 or 3, wherein the solvent of the electrolyte comprises at least one of a solvent of an electrolyte for a lithium sulfur battery, a solvent of an electrolyte for a lithium ion battery; in the gelable system, the mass percentage of the solvent of the electrolyte is more than or equal to 5wt% and less than or equal to 60 wt%.

22. The gellable system of claim 2 or 4, wherein the electrolyte comprises at least one of an electrolyte for a lithium sulfur battery, an electrolyte for a lithium ion battery; in the gelable system, the mass percentage of the electrolyte is more than or equal to 5wt% and less than or equal to 60 wt%.

23. A gel obtainable by gelling a gellable system according to any one of claims 1,3 and 21; wherein, in the gelable system, the mass percentage of the lithium salt is more than 10wt% and less than or equal to 40 wt%; the mass percentage of the cyclic ether compound is more than or equal to 20wt% and less than or equal to 60 wt%; the mass percentage of the inorganic nano particles is more than 0wt% and less than or equal to 15 wt%; the mass percentage of the solvent of the electrolyte is more than or equal to 0wt% and less than or equal to 75 wt%.

24. The gel of claim 23, wherein said gellable system comprises, in mass percent, 10wt% or more and 40wt% or less of said lithium salt; the mass percentage of the cyclic ether compound is more than or equal to 20wt% and less than or equal to 60 wt%; the mass percentage of the inorganic nano particles is more than 0wt% and less than or equal to 15 wt%; the mass percentage of the solvent of the electrolyte is more than or equal to 5wt% and less than or equal to 60 wt%.

25. The gel of claim 23 or 24, wherein the gel has a transition temperature of 40 ℃ to 170 ℃ and a conductivity of 10^-5~10^-1S/cm。

26. The gel of claim 25, wherein said gel has a conductivity of 10^-5~8×10^-2S/cm; the transition temperature of the gel is 45-105 ℃.

27. The gel of claim 23 or 24, wherein said lithium salt is as defined in claim 5.

28. The gel of claim 23 or 24, wherein the inorganic nanoparticles are as defined in claim 6.

29. The gel according to claim 23 or 24, wherein the cyclic ether-based compound is defined as in claims 7 to 20.

30. A gel obtainable by gelling a gellable system according to any one of claims 2,4 and 22; wherein, in the gelable system, the mass percentage of the lithium salt is more than 10wt% and less than or equal to 40 wt%; the mass percentage of the cyclic ether compound is more than or equal to 20wt% and less than or equal to 60 wt%; the mass percentage of the inorganic nano particles is more than 0wt% and less than or equal to 15 wt%; the mass percentage of the electrolyte is more than or equal to 0wt% and less than or equal to 75 wt%.

31. The gel of claim 30, wherein said gellable system comprises, in mass percent, 10wt% or more and 40wt% or less of said lithium salt; the mass percentage of the cyclic ether compound is more than or equal to 20wt% and less than or equal to 60 wt%; the mass percentage of the inorganic nano particles is more than 0wt% and less than or equal to 15 wt%; the mass percentage of the electrolyte is more than or equal to 5wt% and less than or equal to 60 wt%.

32. The gel of claim 30 or 31, wherein the gel has a transition temperature of 40 ℃ to 170 ℃ and a conductivity of 10^-5~10^-1S/cm。

33. The gel of claim 32, wherein said gel has a conductivity of 10^-5~8×10^-2S/cm; the transition temperature of the gel is 45-105 ℃.

34. The gel of claim 30 or 31, wherein said lithium salt is as defined in claim 5.

35. The gel of claim 30 or 31, wherein the inorganic nanoparticles are as defined in claim 6.

36. The gel according to claim 30 or 31, wherein the cyclic ether compound is as defined in claims 7 to 20.

37. A method of preparing a gel according to any one of claims 23 to 36, comprising the steps of:

38. The method for preparing a gel according to claim 37, wherein the method for preparing a gel specifically comprises the steps of:

39. The method for preparing a gel according to claim 37, wherein the method for preparing a gel specifically comprises the steps of:

mixing inorganic nano-particles, lithium salt, a cyclic ether compound and a solvent of an electrolyte, stirring to obtain a cyclic ether compound solution containing the lithium salt of the inorganic nano-particles, namely the gellable system, continuing to stir the solution, and gelling to obtain the gel; alternatively, the first and second electrodes may be,

mixing inorganic nano-particles, lithium salt, a cyclic ether compound and an electrolyte, stirring to obtain a cyclic ether compound solution containing the lithium salt of the inorganic nano-particles, namely the gellable system, continuing to stir the solution, and gelling to obtain the gel.

40. The method for preparing a gel according to claim 37, wherein the method for preparing a gel specifically comprises the steps of:

2') dissolving lithium salt in a solvent of the electrolyte to prepare a lithium salt solution;

3 ') adding the mixed solution prepared in the step 1 ') into the lithium salt solution prepared in the step 2 '), stirring to obtain a cyclic ether compound solution of lithium salt containing inorganic nano-particles and a solvent of an electrolyte, namely the gelable system, continuously stirring the solution, and obtaining the gel through gelation; alternatively, the first and second electrodes may be,

2') dissolving lithium salt in the electrolyte to prepare a lithium salt solution;

3 ') adding the mixed solution prepared in the step 1 ') into the lithium salt solution prepared in the step 2 '), stirring to obtain a cyclic ether compound solution containing inorganic nano-particles and lithium salt dissolved with electrolyte, namely the gellable system, continuing to stir the solution, and gelling to obtain the gel.

41. A solid electrolyte obtained by gelling the gellable system of any one of claims 1,3 and 21; wherein, in the gelable system, the mass percentage of the lithium salt is more than 10wt% and less than or equal to 40 wt%; the mass percentage of the cyclic ether compound is more than 60wt% and less than or equal to 90 wt%; the mass percentage of the inorganic nano particles is more than 0 and less than or equal to 20 wt%; the mass percentage of the solvent of the electrolyte is more than or equal to 0wt% and less than or equal to 75 wt%.

42. The solid electrolyte of claim 41, wherein the gellable system comprises the lithium salt in an amount greater than 10% and equal to or less than 40% by weight; the mass percentage of the cyclic ether compound is more than 60wt% and less than or equal to 90 wt%; the mass percentage of the inorganic nano particles is more than 0wt% and less than or equal to 20 wt%; the mass percentage of the solvent of the electrolyte is more than or equal to 5wt% and less than or equal to 60 wt%.

43. The solid electrolyte of claim 41 or 42, wherein the solid electrolyte has a transition temperature of 70-180 ℃ and a conductivity of 10^-7~10^-2S/cm。

44. The solid state electrolyte of claim 43, wherein the solid state electrolyte is in a solid stateThe transition temperature of the electrolyte is 72-145 ℃, and the conductivity of the solid electrolyte is 10^-6~2×10^-3S/cm。

45. A solid-state electrolyte according to claim 41 or 42, wherein said lithium salt is as defined in claim 5.

46. A solid-state electrolyte according to claim 41 or 42, wherein the inorganic nanoparticles are as defined in claim 6.

47. The solid electrolyte according to claim 41 or 42, wherein the cyclic ether-based compound is defined as in claims 7 to 20.

48. A solid electrolyte obtained by gelling the gellable system of any one of claims 2,4 and 22; wherein, in the gelable system, the mass percentage of the lithium salt is more than 10wt% and less than or equal to 40 wt%; the mass percentage of the cyclic ether compound is more than 60wt% and less than or equal to 90 wt%; the mass percentage of the inorganic nano particles is more than 0 and less than or equal to 20 wt%; the mass percentage of the electrolyte is more than or equal to 0wt% and less than or equal to 75 wt%.

49. The solid electrolyte of claim 48, wherein the gellable system comprises the lithium salt in an amount greater than 10wt% and equal to or less than 40 wt%; the mass percentage of the cyclic ether compound is more than 60wt% and less than or equal to 90 wt%; the mass percentage of the inorganic nano particles is more than 0wt% and less than or equal to 20 wt%; the mass percentage of the electrolyte is more than or equal to 5wt% and less than or equal to 60 wt%.

50. The solid electrolyte of claim 48 or 49, wherein the solid electrolyte has a transition temperature of 70-180 ℃ and a conductivity of 10^-7~10^-2S/cm。

51. The solid electrolyte of claim 50, wherein the solid electrolyte has a transition temperature of 72-145 ℃ and a conductivity of 10^-6~2×10^-3S/cm。

52. A solid-state electrolyte according to claim 48 or 49, wherein said lithium salt is as defined in claim 5.

53. A solid-state electrolyte according to claim 48 or 49, wherein the inorganic nanoparticles are as defined in claim 6.

54. The solid electrolyte according to claim 48 or 49, wherein the cyclic ether-based compound is defined as in any one of claims 7 to 20.

55. A method of preparing a solid state electrolyte as claimed in any one of claims 41 to 54, wherein the method comprises the steps of:

56. The method of preparing a solid electrolyte of claim 55, wherein the method of preparing a solid electrolyte comprises the steps of:

57. The method of preparing a solid electrolyte of claim 55, wherein the method of preparing a solid electrolyte comprises the steps of:

mixing inorganic nanoparticles, lithium salt, a cyclic ether compound and a solvent of an electrolyte, stirring to obtain a cyclic ether compound solution containing the lithium salt of the inorganic nanoparticles, namely the gellable system, continuing to stir the solution, and gelling to obtain the solid electrolyte; alternatively, the first and second electrodes may be,

mixing inorganic nano-particles, lithium salt, a cyclic ether compound and an electrolyte, stirring to obtain a cyclic ether compound solution containing the lithium salt of the inorganic nano-particles, namely the gellable system, continuing to stir the solution, and gelling to obtain the solid electrolyte.

58. The method of preparing a solid electrolyte of claim 55, wherein the method of preparing a solid electrolyte comprises the steps of:

b') dissolving lithium salt in a solvent of the electrolyte to prepare a lithium salt solution;

c ') adding the mixed solution prepared in the step a ') into the lithium salt solution prepared in the step b '), stirring to obtain a cyclic ether compound solution of lithium salt containing inorganic nano-particles and dissolved with a solvent of an electrolyte, namely the gelable system, continuously stirring the solution, and gelling to obtain the solid electrolyte; alternatively, the first and second electrodes may be,

b') dissolving a lithium salt in the electrolyte to prepare a lithium salt solution;

c ') adding the mixed solution prepared in the step a ') into the lithium salt solution prepared in the step b '), stirring to obtain a cyclic ether compound solution containing inorganic nano-particles and lithium salt dissolved with electrolyte, namely the gellable system, continuously stirring the solution, and gelling to obtain the solid electrolyte.

59. A gel electrolyte, characterized in that it comprises a gel according to any one of claims 23 to 36.

60. A lithium-based battery comprising the gel electrolyte of claim 59 and/or the solid-state electrolyte of any one of claims 41 to 54.

61. Use of a gel according to any one of claims 23 to 36, wherein said gel is used in the field of lithium batteries, building materials.

62. Use of the solid-state electrolyte according to any one of claims 41 to 54, wherein the solid-state electrolyte is used in the field of lithium-based batteries, building materials.

63. Use of the gel electrolyte of claim 59, wherein the gel electrolyte is used in the field of lithium-based batteries.

64. The use of any one of claims 61-63, wherein the lithium-based battery comprises at least one of a lithium-ion battery, a lithium-sulfur battery, and a lithium-air battery.