CN108963330A

CN108963330A - It is a kind of containing inorganic nanoparticles can gelling system and its preparation method and application

Info

Publication number: CN108963330A
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: 2018-12-07
Anticipated expiration: 2037-05-26
Also published as: CN108963330B

Abstract

The invention discloses a kind of containing inorganic nanoparticles can gelling system and its be prepared gel and/or solid electrolyte, and its preparation method and application.It include following components: (a) lithium salts in the system, (b) ether compound and (c) inorganic nanoparticles, the ether compound are selected from ring-type ethers compound；It by adjusting the constituent content and type of lithium salts, ring-type ethers compound and inorganic nanoparticles in the system, can be prepared that intensity is adjustable, forms that the time is adjustable, transition temperature is adjustable, while also there is reversible gel and/or solid electrolyte；The preparation method is simple, reaction condition is mild, reaction time is short, product yield high, preparation cost is low, is easily industrialized production.The gel and/or solid electrolyte can be applied in the fields such as lithium system battery, construction material, and the solid electrolyte can be applied in the fields such as lithium system battery.

Description

It is a kind of containing inorganic nanoparticles can gelling system and its preparation method and application

Technical field

The invention belongs to gel technique fields, and in particular to it is a kind of containing inorganic nanoparticles can gelling system and its Preparation method and application.

Background technique

Lithium ion battery is with its high-energy-density, high working voltage, wide operating temperature range, long circulation life, memoryless effect It answers and hot spot the advantages that fast charging and discharging as new energy source technology research, is not only widely used in mobile phone, notebook electricity Brain, digital electronic product, and also applied in the fields such as aerospace, artificial satellite, small medical.But lithium Ion battery is also faced with the problem of safety, as electrolyte it is volatile caused by burning etc. security risks.

The advantages of gel is a kind of semisolid system between liquid and solid, it has both both liquid and solid and Feature, as a result, its become research field and production and living in hot spot, also have many researchers by every means will be each Kind design of material meets the application of people at the state of gel.So being replaced using gel electrolyte and solid electrolyte Liquid electrolyte in lithium ion battery is also the method that numerous researchers' solution electrolyte safety is the most commonly used at present, is led to Often, lithium ion battery gel electrolyte or solid electrolyte are all by polymeric matrix, electrolyte lithium salt, plasticizer according to certain Ratio composition, is equivalent to the aggregate of diaphragm and electrolyte, and polyethylene glycol oxide (PEO) is relatively early applies in solid polymer electrolyte One of matter polymeric matrix is easy to crystallize since itself structural regularity is good, but crystallinity height can reduce lithium ion Migration, so the ionic conductivity of the solid electrolyte being prepared by it at room temperature is lower, in addition, since PEO can portion Divide and be dissolved in esters electrolyte, so its gel electrolyte mechanical strength obtained is poor.

At present, there are mainly two types of universal gel rubber system is built: one is one or more kinds of macromolecules are direct It is introduced into solvent, forms it into network structure or inierpeneirating network structure, the intensity of this gel is higher；Another be by The organogel factor of small molecule introduces wherein, is dissolved in it at high temperature in certain solvent, and the shape under room temperature or low temperature At gel, the intensity of this gel is generally all relatively low.For the gel rubber system that above two mode is formed, all inevitably Macromolecule or the more complicated Low-molecular weight organogel factor of synthesis step are introduced from raw material in wherein, it will usually use than Cumbersome interminable experimental method prepares time-consuming and laborious expense raw material, and is easy to appear the difference of molecular weight polymeric, obtains Gel rubber system is just not quite similar, and the product being prepared by the gel can also have differences.And the gel rubber system reported at present All be it is irreversible, i.e., after gel is destroyed, be difficult to restore again original pattern and advantage, which also limits the uses of gel With popularization.And gel rubber system is introduced into the electrolyte design of lithium battery, have the lithium battery being prepared can There is higher safety, and can have preferable efficiency for charge-discharge and people in the urgent need to address.Again either by gel System is introduced into the preparation of construction material, if the New Building Materials being prepared is made to have lightweight, intensity high, again reachable To performances such as A grades of fire-protection standards, also compare with its special commercial value.

Summary of the invention

In order to solve the deficiencies in the prior art, it is an object of the present invention to provide one kind can gelling system, the system In include following components: lithium salts, ether compound and inorganic nanoparticles, the ether compound be selected from ring-type ethers chemical combination Object.

The second object of the present invention be to provide it is a kind of it is above-mentioned can the gel that is prepared through gelation of gelling system or The preparation method and application of solid electrolyte and the gel or solid electrolyte.

The third object of the present invention is to provide a kind of gel electrolyte and its preparation method and application, the gel electrolyte Liquid includes above-mentioned gel.

Applicant has found under study for action, and lithium salts and small molecule ring-type ethers compound are mixed, the phase interaction of the two is passed through With (such as generating new complex compound or self assembly effect etc.) and ring-opening polymerisation or polycondensation of small molecule ring-type ethers compound etc. Mode can form gel rubber system or solid-state system；If being added with inorganic nanoparticles during forming above-mentioned system, then The gel rubber system or solid-state system being prepared, not only have the safety in utilization better than ordinary gel system or solid-state system, And by adjust can in gel rubber system each component content and type, can effectively control the gel rubber system or solid-state system Intensity, the change of the intensity may make the gel rubber system to expand in the solid-state system, to more expand institute State the application range of system；In addition, the gel rubber system or solid-state system not only can be improved in the addition of inorganic nanoparticles Mechanical strength, but also the regular arrangement of polymer segment can be hindered, the crystallinity of polymer is reduced, while improving electrolyte The porosity of film enables dielectric film to adsorb more liquid electrolytes, to improve lithium ion in gel rubber system or solid-state Mobility and conductivity in system.In addition, the gel rubber system or solid-state system also have invertibity, i.e., the described gel rubber system Or solid bodies are tied up to and can be prepared at room temperature, and after high-temperature process (temperature is higher than its transition temperature), the gelinite System or solid-state system can become flow, but after it is stood cooling (temperature is lower than its transition temperature) again, and can be extensive Again at original gel rubber system or solid-state system, and property will not change.Based on such thinking, this hair is completed It is bright.

The first aspect of the invention be to provide one kind can gelling system, include following components: (a) lithium in the system Salt, (b) ether compound and (c) inorganic nanoparticles；The ether compound is selected from ring-type ethers compound；In addition, system In can gelation polymer and/or can gelation prepolymer mass percentage be less than or equal to 1wt%.

It is described can be in gelling system, the sum of weight percent of each component is 100wt%.

According to the present invention, described can be in gelling system, the mass percentage of the lithium salts is greater than 5wt% and is less than etc. In 60wt%；The mass percentage of the ring-type ethers compound is more than or equal to 20wt% and is less than or equal to 95wt%；It is described The mass percentage of inorganic nanoparticles is greater than 0 and is less than or equal to 30wt%.

Preferably, described can be in gelling system, the mass percentage of the lithium salts is more than or equal to 10wt% and is less than Equal to 40wt%；The mass percentage of the ring-type ethers compound is more than or equal to 20wt% and is less than or equal to 60wt%；Institute The mass percentage for stating inorganic nanoparticles is greater than 0wt% and is less than or equal to 15wt%.

Preferably, described can be in gelling system, the mass percentage of the lithium salts is greater than 10% and is less than or equal to 40wt%；The mass percentage of the ring-type ethers compound is greater than 60wt% and is less than or equal to 90wt%；It is described inorganic to receive The mass percentage of rice grain is greater than 0wt% and is less than or equal to 20wt%.

According to the present invention, the lithium salts can be selected from lithium hexafluoro phosphate, LiBF4, hexafluoroarsenate lithium, lithium perchlorate, three Methyl fluoride Sulfonic Lithium, perfluoro butyl Sulfonic Lithium, double trifluoromethanesulfonimide lithiums, double fluorine sulfimide lithiums, lithium aluminate, chlorine aluminic acid One of lithium, fluoro sulfimide lithium, lithium chloride and lithium iodide are a variety of；Preferably, the lithium salts be selected from lithium hexafluoro phosphate, One or both of lithium perchlorate, LiBF4 etc..

According to the present invention, the ring-type ethers compound is selected from the ring containing an oxygen, two oxygen, three oxygen or more Shape ether compound.

According to the present invention, the ring-type ethers compound can be monocycle, fused rings (such as bicyclic), loop coil or bridged ring.

According to the present invention, the inorganic nanoparticles are selected from silica, aluminium oxide, silicon nitride, zinc oxide, titanium dioxide In titanium, silicon carbide, silicate, calcium carbonate, barium sulfate, clay, ferroso-ferric oxide, cerium oxide, nano-carbon material, iron oxide etc. It is one or more；Preferably, the inorganic nanoparticles are selected from one of silica, aluminium oxide, titanium dioxide, zinc oxide Or it is a variety of.

According to the present invention, it is described can gelling system further include (d) other solvents and/or electrolyte, (d) other are molten Agent and/or electrolyte include the electrolyte for lithium-sulfur cell, the solvent of the electrolyte for lithium-sulfur cell, for lithium-ion electric The electrolyte in pond, at least one of solvent of electrolyte of lithium ion battery.

According to the present invention, described can be in gelling system, the quality percentage of (d) other solvents and/or electrolyte contains Amount is more than or equal to 0wt% and is less than or equal to 75wt%.

Preferably, described can be in gelling system, the mass percentage of (d) other solvents and/or electrolyte is big In equal to 5wt% and less than or equal to 60wt%.

The second aspect of the invention is to provide a kind of gel, by it is above-mentioned can gelling system obtain through gelation； Wherein, described can be in gelling system, the mass percentage of the lithium salts is greater than 5wt% and is less than or equal to 60wt%；It is described The mass percentage of ring-type ethers compound is more than or equal to 20wt% and is less than or equal to 60wt%；The inorganic nanoparticles Mass percentage is greater than 0 and is less than or equal to 30wt%；The mass percentage of (d) other solvents and/or electrolyte is big In equal to 0wt% and less than or equal to 75wt%.

Preferably, described can be in gelling system, the mass percentage of the lithium salts is more than or equal to 10wt% and is less than Equal to 40wt%；The mass percentage of the ring-type ethers compound is more than or equal to 20wt% and is less than or equal to 60wt%；Institute The mass percentage for stating inorganic nanoparticles is greater than 0wt% and is less than or equal to 15wt%；(d) other solvents and/or electricity The mass percentage for solving liquid is more than or equal to 5wt% and is less than or equal to 60wt%.

According to the present invention, the transition temperature of the gel is 40~170 DEG C, preferably 45~105 DEG C.

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

The third aspect of the invention is to provide a kind of preparation method of above-mentioned gel comprising following steps:

Inorganic nanoparticles, lithium salts and ring-type ethers compound are mixed, obtained under stirring containing inorganic nanoparticles The ring-type ethers compound solution of lithium salts, i.e., it is described can gelling system, continue to stir the solution, be obtained through gelation described Gel.

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

1) inorganic nanoparticles are added in ring-type ethers compound, finely dispersed mixed solution is prepared；

2) the above-mentioned mixed solution being prepared is added in lithium salts, the lithium containing inorganic nanoparticles is obtained under stirring The ring-type ethers compound solution of salt, i.e., it is described can gelling system, continue to stir the solution, be obtained through gelation described solidifying Glue.

It is further preferred that the preparation method of the gel specifically comprises the following steps:

Inorganic nanoparticles, lithium salts, ring-type ethers compound and other solvents and/or electrolyte are mixed, under stirring To the ring-type ethers compound solution of the lithium salts containing inorganic nanoparticles, i.e., it is described can gelling system, continue described in stirring Solution obtains the gel through gelation.

1 ') inorganic nanoparticles are added in ring-type ethers compound, finely dispersed mixed solution is prepared；

2 ') lithium salts is dissolved in other solvents and/or electrolyte, lithium salt solution is prepared；

3 ') by step 1 ') in the mixed solution that is prepared be added to step 2 ') in the lithium salt solution that is prepared, stir Mix down obtain the lithium salts dissolved with other solvents and/or electrolyte containing inorganic nanoparticles ring-type ethers compound it is molten Liquid, i.e., it is described can gelling system, continue to stir the solution, obtain the gel through gelation.

According to the present invention, to the lithium salts, ring-type ethers compound, inorganic nanoparticles and other solvents and/or electrolysis Liquid carries out removing water process in advance；Preferably, using molecular sieve and/or vacuum drying method to the lithium salts, ring-type ethers It closes object, inorganic nanoparticles and other solvents and/or electrolyte carries out removing water process in advance.

According to the present invention, the gelation process needs are completed under static conditions.

According to the present invention, the temperature of the gel-forming be lower than the gel transition temperature, the gel-forming when Between be 30 seconds~300 hours.

The fourth aspect of the invention is to provide a kind of solid electrolyte, by it is above-mentioned can gelling system through gelation It obtains；Wherein, described can be in gelling system, the mass percentage of the lithium salts is greater than 5wt% and is less than or equal to 60wt%； The mass percentage of the ring-type ethers compound is greater than 60wt% and is less than or equal to 95wt%；The inorganic nanoparticles Mass percentage is greater than 0wt% and is less than or equal to 30wt%；The quality percentage of (d) other solvents and/or electrolyte contains Amount is more than or equal to 0wt% and is less than or equal to 75wt%.

Preferably, described can be in gelling system, the mass percentage of the lithium salts is greater than 10% and is less than or equal to 40wt%；The mass percentage of the ring-type ethers compound is greater than 60wt% and is less than or equal to 90wt%；It is described inorganic to receive The mass percentage of rice grain is greater than 0wt% and is less than or equal to 20wt%；The matter of (d) other solvents and/or electrolyte Percentage composition is measured to be more than or equal to 5wt% and be less than or equal to 60wt%.

According to the present invention, the transition temperature of the solid electrolyte is 70~180 DEG C, preferably 72~145 DEG C.

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

The fifth aspect of the invention is to provide a kind of preparation method of above-mentioned solid electrolyte comprising following steps:

Inorganic nanoparticles, lithium salts and ring-type ethers compound are mixed, obtained under stirring containing inorganic nanoparticles The ring-type ethers compound solution of lithium salts, i.e., it is described can gelling system, continue to stir the solution, be obtained through gelation described Solid electrolyte.

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

A) inorganic nanoparticles are added in ring-type ethers compound, finely dispersed mixed solution is prepared；

B) the above-mentioned mixed solution being prepared is added in lithium salts, the lithium containing inorganic nanoparticles is obtained under stirring The ring-type ethers compound solution of salt, i.e., it is described can gelling system, continue to stir the solution, be obtained through gelation described solid State electrolyte.

It is further preferred that the preparation method of the solid electrolyte specifically comprises the following steps:

Inorganic nanoparticles, lithium salts, ring-type ethers compound and other solvents and/or electrolyte are mixed, under stirring To the ring-type ethers compound solution of the lithium salts containing inorganic nanoparticles, i.e., it is described can gelling system, continue described in stirring Solution obtains the solid electrolyte through gelation.

A ') inorganic nanoparticles are added in ring-type ethers compound, finely dispersed mixed solution is prepared；

B ') lithium salts is dissolved in other solvents and/or electrolyte, lithium salt solution is prepared；

C ') mixed solution being prepared in step a ') is added to step b ') in the lithium salt solution that is prepared, stir Mix down obtain the lithium salts dissolved with other solvents and/or electrolyte containing inorganic nanoparticles ring-type ethers compound it is molten Liquid, i.e., it is described can gelling system, continue to stir the solution, obtain the solid electrolyte through gelation.

According to the present invention, the temperature that the solid electrolyte is formed is lower than the transition temperature of the gel solid state electrolyte, The time of the formation of the solid electrolyte is 30 minutes~150 hours.

The sixth aspect of the invention is to provide a kind of gel electrolyte, and the gel electrolyte includes above-mentioned gel.

The seventh aspect of the invention is to provide a kind of lithium system battery comprising above-mentioned gel electrolyte and/or solid-state Electrolyte.

The eighth aspect of the invention is to provide the application of above-mentioned gel, can be used for lithium system battery, construction material etc. In field.

The ninth aspect of the invention is to provide the application of above-mentioned solid electrolyte, can be used for lithium system battery, building In the fields such as material.

The tengh aspect of the invention is to provide a kind of application of above-mentioned gel electrolyte, can be used for the neck such as lithium system battery In domain.

Preferably, lithium system battery includes at least one of lithium ion battery, lithium-sulfur cell, lithium-air battery.

Beneficial effects of the present invention:

1. the present invention provides a kind of containing inorganic nanoparticles can gelling system and its gel that is prepared and/ Or solid electrolyte, and its preparation method and application.In the system include following components: (a) lithium salts, (b) ether compound and (c) inorganic nanoparticles；The ether compound is selected from ring-type ethers compound；In addition, in system can gelation polymer And/or can gelation prepolymer mass percentage be less than or equal to 1wt%.By adjusting lithium salts, ring-type in the system The constituent content and type of ether compound and inorganic nanoparticles, can be prepared the gel and/or solid electrolyte, The gel or solid electrolyte can be applied to lithium system battery (such as lithium ion battery, lithium-sulfur cell, lithium-air battery etc.) In field.

2. it is of the present invention containing inorganic nanoparticles can the gel that is prepared of gelling system and/or solid-state electricity The intensity of solution matter is adjustable, forms the time (is transformed into not flowable gel state by free flowable liquid condition or consolidates State electrolyte conditions) (being transformed by not flowable gel state or solid electrolyte state can be free for adjustable, transition temperature The minimum temperature when liquid condition of flowing) it is adjustable, it can the gel and solid-state electricity of varying strength are prepared according to specific needs Xie Zhi, to meet different needs.The gel and solid electrolyte have stronger impact resistance, are being applied to lithium system electricity When in the fields such as pond, the leakage of liquid electrolytic liquor not only can be effectively solved, can also be better protected from due to Li dendrite The problems such as growth punctures diaphragm or solid electrolyte and causes battery short circuit, it is also possible that lithium system battery has higher fill Discharging efficiency, better impact resistance make lithium system battery have higher safety in utilization, especially apply in lithium sulphur electricity Chi Zhong effectively can slow down or even prevent " shuttle effect ".When being applied in the fields such as construction material, can not only be prepared into To intensity adjustable building material, the features such as also having both lightweight, environmental protection, prevent fires.

3. it is of the present invention containing inorganic nanoparticles can the gel that is prepared of gelling system and/or solid-state electricity Matter transition temperature with higher is solved, addition inorganic nanoparticles more enhance gel rubber system and the machinery of solid-state system is strong Degree, can be improved the porosity of dielectric film, dielectric film is enable to adsorb more liquid electrolytes, to improve lithium ion Mobility and conductivity in gel or solid electrolyte；Also there is invertibity simultaneously.When the gel or solid electrolyte Use temperature be higher than its transition temperature after, gel or solid electrolyte can become flow；But it is cooled to low After transition temperature, with reversible capacity, and gel or solid electrolyte can be re-formed and be reused；Due to its tool Have higher transition temperature and invertibity, can delay its service life, save the cost, become one it is environmentally protective new Type gel rubber material.

4. the preparation method of gel of the present invention or solid-state electrolytic solution is simple, reaction condition is mild, reaction time is short, Product yield high, preparation cost are low, are easily industrialized production.

5. it is of the present invention containing inorganic nanoparticles can the gelling system gel and solid state electrolysis that are prepared Matter can show better gel state or solid electrolyte state in low temperature, i.e., in the gel or turn of solid electrolyte Good gel state or solid electrolyte state, and the gel and solid state electrolysis under low temperature can be kept below temperature The intensity of matter is more preferably.

6. it is of the present invention containing inorganic nanoparticles can the gel that is prepared of gelling system and/or solid-state electricity Solution matter can be applied in the fields such as lithium system battery (such as lithium ion battery, lithium-sulfur cell, lithium-air battery etc.), especially in height Still be able under cryogenic conditions using.

Detailed description of the invention

Fig. 1 is gel electrolyte obtained in embodiment 1 as the electrolyte of lithium ion battery and is assembled into battery for the first time Charge and discharge electrograph.

Fig. 2 is the circulation that gel electrolyte obtained in embodiment 1 is assembled into battery as the electrolyte of lithium ion battery Performance map.

Fig. 3 is gel electrolyte obtained in embodiment 5 as the electrolyte of lithium-sulfur cell and is assembled into filling for the first time for battery Electric discharge figure.

Fig. 4 is the cyclicity that gel electrolyte obtained in embodiment 5 is assembled into battery as the electrolyte of lithium-sulfur cell It can figure.

Specific embodiment

[other solvents and/or electrolyte]

In one preferred embodiment, it is described can gelling system further include (d) other solvents and/or electrolyte, (d) other solvents and/or electrolyte include the electrolyte for lithium-sulfur cell, the electrolyte for lithium-sulfur cell it is molten At least one of agent, the electrolyte for lithium ion battery, the solvent of electrolyte for lithium ion battery.

In the present invention, the electrolyte for lithium ion battery is selected from the esters containing the lithium salts for lithium ion battery Mixed liquor, such as (LiPF of lithium hexafluoro phosphate containing 1M₆) ethylene carbonate (EC) and dimethyl carbonate (DMC) mixed liquor, In, the volume ratio of the ethylene carbonate (EC) and dimethyl carbonate (DMC) is 1:1.

In the present invention, the solvent of the electrolyte for lithium ion battery is selected from the electrolyte for lithium ion battery At least one of cyclic annular non-aqueous organic solvent and the chain non-aqueous organic solvent of electrolyte for lithium ion battery.

In one preferred embodiment, the cyclic annular non-aqueous organic solvent choosing of the electrolyte for lithium ion battery From ethylene carbonate (EC), propene carbonate (PC), fluorinated ethylene carbonate (FEC), gamma-butyrolacton (GBL), sulfurous acid ethylene At least one of ester (ES), propylene sulfite (PS), sulfolane (SL), carbonic acid glyceride (GC).

In one preferred embodiment, the chain non-aqueous organic solvent choosing of the electrolyte for lithium ion battery From diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), methyl propyl carbonate (MPC), dipropyl carbonate (DPC), ethyl propyl carbonic acid ester (EPC), ethyl acetate (EA), propyl acetate (PA), ethyl propionate (EP), ethyl butyrate (EB), fourth Sour methyl esters (MB), dimethyl sulfite (DMS), sulfurous acid diethyl ester (DES), sulfurous acid methyl ethyl ester (EMS), dimethyl sulfone (MSM), at least one of dimethyl sulfoxide (DMSO).

In the present invention, the electrolyte for lithium-sulfur cell is selected from the ethers mixed liquor containing lithium salts, such as: contain 1M The 1,3-dioxolane (DOL) of double trifluoromethanesulfonimide lithiums (LiTFSI) and the mixed liquor of glycol dimethyl ether (DME), In, the volume ratio of the 1,3-dioxolane (DOL) and glycol dimethyl ether (DME) is 1:1.

In the present invention, the solvent of the electrolyte for lithium-sulfur cell is selected from 1,3-dioxolane, 1,2- dimethoxy Ethane, triethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, fluorinated ethylene carbonate, polyethylene glycol borate, 1,1 ', 2,2 '-four Fluoro ethyl -2,2 ', one of 3,3 '-tetrafluoropropene ethers or a variety of.

[ring-type ethers compound]

Of the invention can contain ether compound in gelling system, and the ether compound is selected from ring-type ethers chemical combination Object.The ring-type ethers compound is selected from the C at least containing 1 oxygen atom₂~C₂₀Cycloalkane (the carbon atom i.e. in cyclic structure Number is 2-20) or C at least containing 1 oxygen atom₃~C₂₀Cycloolefin (carbon atom number i.e. in cyclic structure is 3-20), Wherein at least contain a carbon-carbon double bond.

In the present invention, the cycloalkane or cycloolefin are monocycle, fused rings (such as bicyclic), loop coil or bridged ring；When the ring Alkane or cycloolefin are loop coil or bridged ring and when containing more than two oxygen atoms, and oxygen atom can be on a ring, can also be On multiple rings.

In the present invention, the ring-type ethers compound is selected from the C at least containing 1 oxygen atom₂~C₂₀Monocycle alkane, it is excellent Choosing is selected from the C at least containing 1 oxygen atom₃~C₂₀Monocycle alkane, one of for example, following first kind compounds:

In the present invention, the ring-type ethers compound is selected from the C at least containing 1 oxygen atom₄~C₂₀Fused naphthene, One of for example, following dioxins:

In the present invention, the ring-type ethers compound is selected from the C at least containing 1 oxygen atom₄~C₂₀Bridged ring alkane, example One of for example following third class compounds:

In the present invention, the ring-type ethers compound is selected from the C at least containing 1 oxygen atom₄~C₂₀Loop coil alkane, example One of for example following 4th class compounds:

In the present invention, the C-C key on ring structure in above-mentioned four classes compound at least one substituted by C=C and be steady Fixed existing compound, then be the above-mentioned C at least containing 1 oxygen atom₃~C₂₀Cycloolefin is currently preferred cyclic ether One kind of class compound.

In the present invention, when the cycloalkane or cycloolefin are monocycle or fused rings, the carbon atom on the ring can be by 1 A or multiple R1 groups replace；When the cycloalkane or cycloolefin are bridged ring, non-bridged ring carbon atom can be by one or more R1 group replaces；When the cycloalkane or cycloolefin are loop coil, it can be taken by one or more R1 groups on carbon atom on ring Generation；The R1 group be selected from following radicals one kind: alkyl, alkenyl, alkynyl, alkoxy, alkylthio group, halogenated alkyl, naphthenic base, Cycloalkyl oxy, cycloalkylsulfanyl, heterocycle, heterocycle oxygroup, heterocyclic thio, aryl, aryloxy, heteroaryl, heteroaryl Base oxygroup, hydroxyl, sulfydryl, nitro, carboxyl, amino, ester group, halogen, acyl group, aldehyde radical.

In a preferred embodiment of the present invention, the ring-type ethers compound containing an oxygen be selected from replace or Unsubstituted oxetanes, substituted or unsubstituted tetrahydrofuran, substituted or unsubstituted oxinane；The substituent group Number can be one or more；The substituent group is above-mentioned R1 group.

In a preferred embodiment of the present invention, the ring-type ethers compound containing an oxygen is selected from 3,3- bis- Chloromethyl oxetanes, 2- chloromethyl oxetanes, 2- chloromethyl propylene oxide, 1,4- 7-oxa-bicyclo[4.1.0,1,3- epoxy Hexamethylene, tetrahydrofuran, 2- methyltetrahydrofuran, 3- methyltetrahydrofuran, oxinane, 2- methyl oxinane, oxa- ring Heptane, oxocane, oxonane or oxecane.

In a preferred embodiment of the present invention, it is described containing there are two oxygen ring-type ethers compound be selected from replace or Unsubstituted 1,3- dioxolanes (DOL), substituted or unsubstituted 1,4- dioxane；The number of the substituent group can be one It is a or multiple；The substituent group is above-mentioned R1 group.

In a preferred embodiment of the present invention, it is described containing there are three oxygen ring-type ethers compound be selected from replace or Unsubstituted metaformaldehyde；The number of the substituent group can be one or more；The substituent group is above-mentioned R1 group.

In a preferred embodiment of the present invention, the ether compound containing more polyoxy, which is selected from, replaces or does not take 18- crown- 6, substituted or unsubstituted 12-crown-4, the substituted or unsubstituted 24- crown- 8 in generation；The number of the substituent group can be with It is one or more；The substituent group is above-mentioned R1 group.

[term and definition]

Unless otherwise indicated, recorded in present specification group and term definition, including its as example definition, The definition etc. of particular compound in the illustrative definition for defining, preferably defining, recording in table, embodiment, can be each other Between any combination and combination.Group definition and compound structure after such combination and combination, should belong to the application guarantor In the range of shield.

Term " gel " in the present invention has meaning well known in the art, and term " gelation " also has known in this field Meaning.

In the present invention can gelation polymer and/or can the prepolymer of gelation refer under certain condition can be with shape At gel or can be with the polymer and/or prepolymer of gelation.Do not limit, it is of the present invention can gelation polymer and/ Or can the prepolymer of gelation can be selected from polyethylene glycol oxide (PEO), polyethylene glycol (PEG), Kynoar (PVDF), polychlorostyrene second Alkene (PVC), polyacrylonitrile (PAN), poly- ethyl acetate (PVAC), polyvinylpyrrolidone (PVP), gathers polystyrene (PS) Divinyl sulfide (PVS), polytrimethylene carbonate (PTMC), polymethyl methacrylate (PMMA), polyethylene glycol dimethyl Acrylate (PEGDM), polypropylene oxide (PPO), dimethyl silicone polymer (PDMSO) or its prepolymer or its copolymer, or One of its blend is a variety of.

The numberical range recorded in present specification, when the numberical range is defined as " integer ", it should be understood that Two endpoints and each integer within the scope of this for describing the range.For example, " 0~10 integer " should be understood as remembering 0,1,2,3,4,5,6,7,8,9 and 10 each integer is carried.When the numberical range is defined as " counting ", it should be understood that Describe two endpoints, each integer within the scope of this and each decimal within the scope of this of the range.For example, " 0~ 10 number " should be understood as not only describing 0,1,2,3,4,5,6,7,8,9 and 10 each integer, also at least describe it In each integer respectively with 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9 and.

" halogen " that the present invention uses refers to fluorine, chlorine, bromine and iodine.

The present invention is used alone or " alkyl " as suffix or prefix is intended to include having 1 to 20, preferably 1-6 carbon The branch and linear saturation aliphatic hydrocarbyl of atom (if or provide the specific number of carbon atom, refer to the specific number).For example, “C_1-6Alkyl " indicates the straight chain and branched alkyl with 1,2,3,4,5 or 6 carbon atom.The example of alkyl includes but is not limited to Methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, amyl and hexyl.

The present invention is used alone or " halogenated alkyl " or " alkyl halide " as suffix or prefix is intended to include having At least one halogenic substituent and there is 1-20, preferably 1-6 carbon atom (if or provide the specific number of carbon atom, Refer to the specific number) branch and linear saturation aliphatic hydrocarbyl.For example, " C_1-10Halogenated alkyl " indicate have 0,1,2,3,4,5, 6, the halogenated alkyl of 7,8,9,10 carbon atoms.The example of halogenated alkyl includes but is not limited to methyl fluoride, difluoromethyl, fluoroform Base, chlorine methyl fluoride, 1- fluoro ethyl, 3- fluoropropyl, 2- chloropropyl, 3,4- difluorobutyl groups etc..

The present invention is used alone or " alkenyl " as suffix or prefix is intended to include having 2 to 20, preferably 2-6 carbon The branch and straight chain rouge comprising alkenyl or alkene of atom (if or provide the specific number of carbon atom, refer to the specific number) Race's alkyl.For example, " C_2-6Alkenyl " indicates the alkenyl with 2,3,4,5 or 6 carbon atoms.The example of alkenyl includes but is not limited to Vinyl, allyl, 1- acrylic, 1- cyclobutenyl, 2- cyclobutenyl, 3- cyclobutenyl, 2- methyl but-2-ene base, 3- methyl butyl- 1- Alkenyl, 1- pentenyl, 3- pentenyl and 4- hexenyl.

The present invention is used alone or " alkynyl " as suffix or prefix is intended to include having 2 to 20, preferably 2-6 carbon The branch and straight chain rouge comprising alkynyl or alkynes of atom (if or provide the specific number of carbon atom, refer to the specific number) Race's alkyl.Such as acetenyl, propinyl (such as l- propinyl, 2-propynyl), 3- butynyl, pentynyl, hexin base and 1- first The amyl- 2- alkynyl of base.

Terminology used in the present invention " aryl " refers to the aromatic ring structure being made of 5 to 20 carbon atoms.Such as: comprising 5,6, The aromatic ring structure of 7 and 8 carbon atoms can be mono-cyclic aromatic group such as phenyl；Include 8,9,10,11,12,13 or 14 The ring structure of carbon atom can be polycyclic such as naphthalene.Aromatic ring can replace in one or more ring positions those described above substitution Base.Term " aryl " further includes the polycyclic ring system with two or more rings, and two of them or more carbon is two adjacent (ring is " condensed ring ") common to ring, wherein at least one ring is aromatics and other rings for example can be naphthenic base, cyclenes Base, cycloalkynyl radical, aryl and/or heterocycle.Polycyclic example includes but is not limited to 2,3- dihydro -1,4- benzo dioxa hexamethylene two Alkene and 2,3- dihydro -1- benzofuran.

Terminology used in the present invention " naphthenic base " is intended to include the saturation ring group with carbon atom is specified number.These terms It may include condensed or bridge joint multi-loop system.Naphthenic base has 3 to 40 carbon atoms in its ring structure.In an embodiment In, naphthenic base has 3,4,5 or 6 carbon atoms in its ring structure.For example, " C_3-6Naphthenic base " indicates such as cyclopropyl, ring fourth The group of base, cyclopenta or cyclohexyl.

" heteroaryl " that the present invention uses refers to the heteroaromatic miscellaneous of at least one ring hetero atom (such as sulphur, oxygen or nitrogen) Ring.Heteroaryl includes single loop system and multi-loop system (such as with 2,3 or 4 condensed ring).The example of heteroaryl includes but unlimited In pyridyl group, pyrimidine radicals, pyrazinyl, pyridazinyl, triazine radical, furyl, quinolyl, isoquinolyl, thienyl, imidazole radicals, thiophene Oxazolyl, indyl, pyrrole radicals, oxazolyl, benzofuranyl, benzothienyl, benzothiazolyl, isoxazolyl, pyrazolyl, three Oxazolyl, tetrazole radical, indazolyl, 1,2,4- thiadiazolyl group, isothiazolyl, benzothienyl, purine radicals, carbazyl, benzimidazole Base, benzoxazolyl, azepine benzoxazolyl, Imidazothiazole base, benzo [1,4] dioxine base, benzo [1,3] two Oxole base etc..In some embodiments, heteroaryl has 3 to 40 carbon atoms and has in other embodiments 3 to 20 carbon atoms.In some embodiments, heteroaryl includes that 3 to 14,4 to 14,3 to 7 or 5 to 6 cyclization are former Son.In some embodiments, heteroaryl has 1 to 4,1 to 3 or 1 to 2 hetero atom.In some embodiments, miscellaneous Aryl has 1 hetero atom.

Unless otherwise indicated, terminology used in the present invention " heterocycle " refer to the saturation comprising 3 to 20 atoms, insatiable hunger and/or The monocyclic, bicyclic or tricyclic of fractional saturation, wherein 1,2,3,4 or 5 annular atom is selected from nitrogen, sulphur or oxygen, unless otherwise indicated, It can be connected by carbon or nitrogen, wherein-CH₂Group is optionally replaced by-C (O)-；And wherein unless otherwise indicated, ring nitrogen Atom or ring sulfur atom are optionally oxidized to form N- oxide or S- oxide or theheterocyclic nitrogen atom and optionally be quaternized；Its middle ring In-NH optionally replaced by acetyl group, formoxyl, methyl or mesyl；And ring is optionally replaced by one or more halogens.It answers It should be appreciated that these hetero atoms are not adjacent to each other when the sum of S atom in heterocycle and O atom is more than 1.If described miscellaneous Ring group is two rings or tricyclic, then at least one ring may optionally be heteroaromatic rings or aromatic ring, and condition is that at least one ring is non-miscellaneous Aromatics.It is not centainly aromatics if the heterocycle is monocycle.The example of heterocycle include but is not limited to piperidyl, N- acetylpiperidinyl, N- methyl piperidine base, N- formyl piperazine base, N- mesylpiperazinyl, high piperazine base, piperazinyl, Azetidinyl, oxetanyl, morpholinyl, tetrahydro isoquinolyl, tetrahydric quinoline group, indolinyl, oxinane Base, dihydro -2H- pyranose, tetrahydrofuran base, tetrahydro thiapyran base, tetrahydric thiapyran -1- oxide, tetrahydric thiapyran -1,1- titanium dioxide Object, 1H- pyridin-2-ones and 2,5- dioxoimidazolidin alkyl.

Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.Furthermore, it is to be understood that after having read documented content of the invention, this field skill Art personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within limited range of the present invention.

Test method:

Conductivity described in the present embodiment is the electrochemical workstation using 1000 model of Interface of Gamry company What test obtained, the test scan frequency is 1.0Hz~100kHz.

Raw materials and reagents:

Lithium ion battery conventional electrolysis liquid used in the present embodiment is selected from the (LiPF of lithium hexafluoro phosphate containing 1M₆) carbonic acid second The mixed liquor of enester (EC) and dimethyl carbonate (DMC), wherein the ethylene carbonate (EC) and dimethyl carbonate (DMC) Volume ratio is 1:1.

The lithium-sulfur cell conventional electrolysis liquid selected in the present embodiment is selected from the ethers mixed liquor containing lithium salts, such as: contain The 1,3-dioxolane (DOL) of the bis- trifluoromethanesulfonimide lithiums (LiTFSI) of 1M and the mixed liquor of glycol dimethyl ether (DME), Wherein, the volume ratio of the 1,3-dioxolane (DOL) and glycol dimethyl ether (DME) is 1:1.

In the present embodiment, the lithium salts through 40 DEG C of vacuum drying 10h or more before use, carry out except water process.

In the present embodiment, the ring-type ethers compound through molecular sieve before use, carry out except water process.

In the present embodiment, the inorganic nanoparticles through 60 DEG C of vacuum drying 10h or more before use, carry out at water removal Reason.

In the present embodiment, other described solvents and/or electrolyte through molecular sieve before use, carry out except water process.

The composition of battery in following embodiments is as follows:

The positive electrode of lithium ion battery: by cobalt acid lithium and electrically conductive graphite, conductive agent acetylene black (super p), binder Polyvinylidene fluoride (PVDF) is uniformly mixed according to mass ratio 85:5:5:5, with N- methyl-pyrrolidon (NMP) by this mixture It is modulated into slurry, even application is 24 hours dry in 120 DEG C of vacuum drying ovens on aluminium foil, spare；

The positive electrode of lithium-sulfur cell: carbon sulphur composite material and conductive agent acetylene black (super p), binder are gathered inclined two Vinyl fluoride (PVDF) is uniformly mixed according to mass ratio 8:1:1, and the modulation of this mixture is slurried with N- methyl-pyrrolidon (NMP) Material, even application is 24 hours dry in 60 DEG C of vacuum drying ovens on aluminium foil, spare；

Electrolyte: the gel electrolyte or solid electrolyte prepared in each embodiment；

Cathode: lithium piece；

Diaphragm: polypropylene (PP) perforated membrane.

Embodiment 1

(1) can gelling system and gel (gel electrolyte that can be used as battery) preparation

The silica of 0.06g is weighed in reagent bottle, the tetrahydrofuran of 2.6mL is added thereto, under magnetic stirring It mixes them thoroughly uniformly, obtains mixed liquor A.

It separately takes 0.8g LiBF4 in reagent bottle, the dimethyl carbonate of 2.6mL is added thereto, stir until lithium salts It is completely dissolved, obtains mixed liquid B.

A obtained above and B solution are sufficiently mixed, obtained mixed liquor, obtaining can gelling system；Stand one The section time forms gel.

In the gel rubber system, the mass percentage of lithium salts is 13wt%；The quality percentage of ring-type ethers compound contains Amount is 43wt%；The mass percentage of inorganic nanoparticles is 1wt%；The quality percentage of other solvents and/or electrolyte contains Amount is 43wt%.

After tested, the formation time of the gel is 20h, and the formation temperature of the gel is room temperature, and the gel turns Temperature is 55 DEG C, and the conductivity of the gel is 1.78 × 10^-2S/cm。

When the gel being prepared to be heated to the transition temperature of the gel or more, gel starts to become sticky, and is inverted reagent It can observe that gel flows downward when bottle, illustrate that temperature has reached the transition temperature of the gel, and when temperature drops to gel When below transition temperature, gel is formed again, illustrates that the gel being prepared has good invertibity.

(2) preparation of battery

The above-mentioned gel being prepared is applied in button cell as gel electrolyte, is tested using blue electric battery pack The chemical property of button cell (test result is listed in Table 2 below).Wherein, the preparation method of the button cell: diaphragm is put Be placed in anode and cathode between, between three full of step (1) preparation can gelling system, encapsulation compacting, be assembled into CR- 2032 type button cells, stand to it is described can gelling system become gel electrolyte.

Embodiment 2-7 and comparative example 1

The preparation method is the same as that of Example 1 for the gel, and difference is only that, the selection of each component in the gel rubber system and Dosage is different；Concrete component and dosage are listed in Table 1 below.

(2) preparation of battery

Embodiment 8

(1) can gelling system and solid electrolyte preparation

The aluminium oxide of 0.05g is weighed in reagent bottle, the 1,3-dioxolane of 4.5mL is added thereto, in magnetic agitation Under mix them thoroughly uniformly, obtain mixed liquor A.

It separately takes 0.4g fluoro sulfimide lithium and 0.6g lithium perchlorate in reagent bottle, the lithium sulphur of 1.2mL is added thereto Battery conventional electrolysis liquid, stirring are completely dissolved until lithium salts, obtain mixed liquid B.

A obtained above and B solution are sufficiently mixed, obtained mixed liquor, obtaining can gelling system；Stand one The section time forms solid electrolyte.

In the gel rubber system, the mass percentage of lithium salts is 15wt%；The quality percentage of ring-type ethers compound contains Amount is 66.3wt%；The mass percentage of inorganic nanoparticles is 0.7wt%；The quality hundred of other solvents and/or electrolyte Dividing content is 18wt%.

After tested, the formation time of the solid electrolyte is 12h, and the formation temperature of the solid electrolyte is room temperature, The transition temperature of the solid electrolyte is 96 DEG C, and the conductivity of the solid electrolyte is 2.38 × 10^-5S/cm。

When the solid electrolyte being prepared to be heated to the gel transition temperature of the solid electrolyte glue or more, solid-state Electrolyte starts to become sticky, and can observe that solid electrolyte flows downward when being inverted reagent bottle, illustrate that temperature has reached the solid-state The transition temperature of electrolyte, and when temperature drops to gel transition temperature or less, solid electrolyte is formed again, illustrates to prepare Obtained solid electrolyte has good invertibity.

(2) preparation of battery

The above-mentioned solid electrolyte being prepared is applied in button cell, tests button cell using blue electric battery pack Chemical property (test result is listed in Table 3 below).Wherein, diaphragm the preparation method of the button cell: is placed in anode Between cathode, between three full of step (1) preparation can gelling system, encapsulation compacting, be assembled into CR-2032 type button Battery, stand to it is described can gelling system become solid electrolyte.

Embodiment 9-14 and comparative example 2

(1) can gelling system and solid electrolyte preparation

With embodiment 8, difference is only that the preparation method of the solid electrolyte, each in the solid state electrolysis plastidome The selection of component and dosage difference；Concrete component and dosage are listed in Table 1 below.

(2) preparation of battery

The composition and content of each component of gel electrolyte or solid electrolyte in table 1 embodiment 1-14 and comparative example 1-2

The performance parameter of 2 embodiment 1-7 of table and gel and the battery being prepared in comparative example 1

The performance parameter of 3 embodiment 8-14 of table and solid electrolyte and the battery being prepared in comparative example 2

Fig. 1 is gel electrolyte obtained in embodiment 1 as the electrolyte of lithium ion battery and is assembled into battery for the first time Charge and discharge electrograph.As seen from the figure, electrolyte of the gel electrolyte as lithium ion battery can make lithium ion battery normal Charge and discharge, and active material therein is given full play of, obtain higher specific capacity.

Fig. 2 is the circulation that gel electrolyte obtained in embodiment 1 is assembled into battery as the electrolyte of lithium ion battery Performance map.As seen from the figure, electrolyte of the gel as lithium ion battery can show stable cycle performance, specific capacity It is held essentially constant.

Fig. 3 is gel electrolyte obtained in embodiment 5 as the electrolyte of lithium-sulfur cell and is assembled into filling for the first time for battery Electric discharge figure.As seen from the figure, electrolyte of the gel electrolyte as lithium-sulfur cell can make the normal charge and discharge of lithium ion battery Electricity, and active material therein is given full play of, obtain higher specific capacity.

Fig. 4 is the cyclicity that gel electrolyte obtained in embodiment 5 is assembled into battery as the electrolyte of lithium-sulfur cell It can figure.As seen from the figure, electrolyte of the gel electrolyte as galvanic battery can effectively slow down " shuttle effect ", Jin Erti The utilization rate of high active substance improves the specific capacity of battery, shows excellent cycle performance.

Compared with comparative example 1 and 2, the addition of inorganic nanoparticles can effectively improve the electricity of gel or solid electrolyte Conductance shows superior chemical property.

More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention Within the scope of shield.

Claims

1. one kind can gelling system, which is characterized in that include following components: (a) lithium salts, (b) ether compound in the system (c) inorganic nanoparticles；The ether compound is selected from ring-type ethers compound；In addition, in system can gelation polymerization Object and/or can gelation prepolymer mass percentage be less than or equal to 1wt%.

2. according to claim 1 can gelling system, which is characterized in that it is described can be in gelling system, the lithium salts Mass percentage be greater than 5wt% and be less than or equal to 60wt%；The mass percentage of the ring-type ethers compound is greater than Equal to 20wt% and it is less than or equal to 95wt%；The mass percentage of the inorganic nanoparticles is greater than 0 and is less than or equal to 30wt%.

Preferably, described can be in gelling system, the mass percentage of the lithium salts is more than or equal to 10wt% and is less than or equal to 40wt%；The mass percentage of the ring-type ethers compound is more than or equal to 20wt% and is less than or equal to 60wt%；The nothing The mass percentage of machine nano particle is greater than 0wt% and is less than or equal to 15wt%.

Preferably, described can be in gelling system, the mass percentage of the lithium salts is greater than 10% and is less than or equal to 40wt%； The mass percentage of the ring-type ethers compound is greater than 60wt% and is less than or equal to 90wt%；The inorganic nanoparticles Mass percentage is greater than 0wt% and is less than or equal to 20wt%.

Preferably, the lithium salts can be selected from lithium hexafluoro phosphate, LiBF4, hexafluoroarsenate lithium, lithium perchlorate, trifluoromethyl sulphur Sour lithium, perfluoro butyl Sulfonic Lithium, double trifluoromethanesulfonimide lithiums, double fluorine sulfimide lithiums, lithium aluminate, chlorine lithium aluminate, fluoro One of sulfimide lithium, lithium chloride and lithium iodide are a variety of；Preferably, the lithium salts is selected from lithium hexafluoro phosphate, perchloric acid One or both of lithium, LiBF4 etc..

3. according to claim 1 or 2 can gelling system, which is characterized in that the ring-type ethers compound, which is selected from, to be contained There is the ring-type ethers compound an of oxygen, two oxygen, three oxygen or more.

Preferably, the ring-type ethers compound can be monocycle, fused rings (such as bicyclic), loop coil or bridged ring.

Preferably, the ring-type ethers compound is selected from the C at least containing 1 oxygen atom₂~C₂₀Cycloalkane, i.e., in cyclic structure Carbon atom number be 2-20；Or the C at least containing 1 oxygen atom₃~C₂₀Cycloolefin, i.e. carbon atom number in cyclic structure are 3-20, wherein at least contain a carbon-carbon double bond.

Preferably, the cycloalkane or cycloolefin are monocycle, fused rings (such as bicyclic), loop coil or bridged ring；When the cycloalkane or When cycloolefin is loop coil or bridged ring and contains more than two oxygen atoms, oxygen atom can be on a ring, can also be in multiple rings On.

Preferably, the ring-type ethers compound is selected from the C at least containing 1 oxygen atom₂~C₂₀Monocycle alkane, be preferably selected from C at least containing 1 oxygen atom₃~C₂₀Monocycle alkane, one of for example, following first kind compounds:

Preferably, the ring-type ethers compound is selected from the C at least containing 1 oxygen atom₄~C₂₀Fused naphthene, for example, One of following dioxins:

Preferably, the ring-type ethers compound is selected from the C at least containing 1 oxygen atom₄~C₂₀Bridged ring alkane, for example, under State one of third class compound:

Preferably, the ring-type ethers compound is selected from the C at least containing 1 oxygen atom₄~C₂₀Loop coil alkane, for example, under State one of the 4th class compound:

Preferably, the C-C key on the ring structure in above-mentioned four classes compound at least one substituted by C=C and to be stabilized Compound, then be the above-mentioned C at least containing 1 oxygen atom₃~C₂₀Cycloolefin is currently preferred ring-type ethers chemical combination One kind of object.

Preferably, when the cycloalkane or cycloolefin are monocycle or fused rings, on the carbon atom on the ring can by 1 or Multiple R1 groups replace；When the cycloalkane or cycloolefin are bridged ring, non-bridged ring carbon atom can be by one or more R1 bases Group replaces；When the cycloalkane or cycloolefin are loop coil, it can be replaced by one or more R1 groups on carbon atom on ring；Institute State one kind that R1 group is selected from following radicals: alkyl, alkenyl, alkynyl, alkoxy, alkylthio group, halogenated alkyl, naphthenic base, cycloalkanes Base oxygroup, cycloalkylsulfanyl, heterocycle, heterocycle oxygroup, heterocyclic thio, aryl, aryloxy, heteroaryl, heteroaryl oxygen Base, hydroxyl, sulfydryl, nitro, carboxyl, amino, ester group, halogen, acyl group, aldehyde radical.

Preferably, the ring-type ethers compound containing an oxygen be selected from substituted or unsubstituted oxetanes, substitution or Unsubstituted tetrahydrofuran, substituted or unsubstituted oxinane；The number of the substituent group can be one or more；It is described Substituent group is above-mentioned R1 group.

Preferably, the ring-type ethers compound containing an oxygen is selected from 3,3- dichloromethyl oxetanes, 2- chloromethyl Oxetanes, 2- chloromethyl propylene oxide, 1,4- 7-oxa-bicyclo[4.1.0,1,3- 7-oxa-bicyclo[4.1.0, tetrahydrofuran, 2- methyl tetrahydro Furans, 3- methyltetrahydrofuran, oxinane, 2- methyl oxinane, oxepane, oxocane, oxonane Or oxecane.

Preferably, it is described containing there are two oxygen ring-type ethers compound be selected from substituted or unsubstituted 1,3-dioxolane (DOL), Substituted or unsubstituted 1,4- dioxane；The number of the substituent group can be one or more；The substituent group is above-mentioned R1 group.

Preferably, described containing there are three the ring-type ethers compounds of oxygen to be selected from substituted or unsubstituted metaformaldehyde；The substitution The number of base can be one or more；The substituent group is above-mentioned R1 group.

Preferably, the ether compound containing more polyoxy is selected from substituted or unsubstituted 18- crown- 6, substituted or unsubstituted 12-crown-4, substituted or unsubstituted 24- crown- 8；The number of the substituent group can be one or more；The substituent group is upper The R1 group stated.

Preferably, the inorganic nanoparticles be selected from silica, aluminium oxide, silicon nitride, zinc oxide, titanium dioxide, silicon carbide, One of silicate, calcium carbonate, barium sulfate, clay, ferroso-ferric oxide, cerium oxide, nano-carbon material, iron oxide etc. are more Kind；Preferably, the inorganic nanoparticles are selected from one of silica, aluminium oxide, titanium dioxide, zinc oxide or a variety of.

Preferably, it is described can gelling system further include (d) other solvents and/or electrolyte, (d) other solvents and/or Electrolyte includes the electrolyte for lithium-sulfur cell, the solvent of the electrolyte for lithium-sulfur cell, the electricity for lithium ion battery Solve liquid, at least one of solvent of electrolyte of lithium ion battery.

Preferably, described can be in gelling system, the mass percentage of (d) other solvents and/or electrolyte is greater than etc. In 0wt% and it is less than or equal to 75wt%.

Preferably, described can be in gelling system, the mass percentage of (d) other solvents and/or electrolyte is greater than etc. In 5wt% and it is less than or equal to 60wt%.

4. a kind of gel, which is characterized in that the gel by claim 1-3 it is described in any item can gelling system through gel Change obtains；Wherein, described can be in gelling system, the mass percentage of the lithium salts is greater than 5wt% and is less than or equal to 60wt%；The mass percentage of the ring-type ethers compound is more than or equal to 20wt% and is less than or equal to 60wt%；The nothing The mass percentage of machine nano particle is greater than 0wt% and is less than or equal to 30wt%；(d) other solvents and/or electrolyte Mass percentage be more than or equal to 0wt% and be less than or equal to 75wt%.

Preferably, described can be in gelling system, the mass percentage of the lithium salts is more than or equal to 10wt% and is less than or equal to 40wt%；The mass percentage of the ring-type ethers compound is more than or equal to 20wt% and is less than or equal to 60wt%；The nothing The mass percentage of machine nano particle is greater than 0wt% and is less than or equal to 15wt%；(d) other solvents and/or electrolyte Mass percentage be more than or equal to 5wt% and be less than or equal to 60wt%.

Preferably, the transition temperature of the gel is 40~170 DEG C, preferably 45~105 DEG C.

Preferably, the conductivity of the gel is 10^-5~10^-1S/cm, preferably 10^-5~8 × 10^-2S/cm。

5. the preparation method of gel described in claim 4, which is characterized in that the described method comprises the following steps:

Inorganic nanoparticles, lithium salts and ring-type ethers compound are mixed, the lithium salts containing inorganic nanoparticles is obtained under stirring Ring-type ethers compound solution, i.e., it is described can gelling system, continue to stir the solution, be obtained through gelation described solidifying Glue.

2) the above-mentioned mixed solution being prepared is added in lithium salts, the lithium salts containing inorganic nanoparticles is obtained under stirring Ring-type ethers compound solution, i.e., it is described can gelling system, continue to stir the solution, obtain the gel through gelation.

Inorganic nanoparticles, lithium salts, ring-type ethers compound and other solvents and/or electrolyte are mixed, are contained under stirring The ring-type ethers compound solution of the lithium salts of organic/inorganic nano particle, i.e., it is described can gelling system, continue to stir the solution, The gel is obtained through gelation.

3 ') by step 1 ') in the mixed solution that is prepared be added to step 2 ') in the lithium salt solution that is prepared, under stirring The ring-type ethers compound solution of the lithium salts dissolved with other solvents and/or electrolyte containing inorganic nanoparticles is obtained, i.e., It is described can gelling system, continue to stir the solution, obtain the gel through gelation.

6. a kind of solid electrolyte, which is characterized in that the solid electrolyte by claim 1-3 is described in any item can gel Change system is obtained through gelation；Wherein, it is described can in gelling system, the mass percentage of the lithium salts be greater than 5wt% and Less than or equal to 60wt%；The mass percentage of the ring-type ethers compound is greater than 60wt% and is less than or equal to 95wt%；Institute The mass percentage for stating inorganic nanoparticles is greater than 0 and is less than or equal to 30wt%；(d) other solvents and/or electrolyte Mass percentage be more than or equal to 0wt% and be less than or equal to 75wt%.

Preferably, described can be in gelling system, the mass percentage of the lithium salts is greater than 10% and is less than or equal to 40wt%； The mass percentage of the ring-type ethers compound is greater than 60wt% and is less than or equal to 90wt%；The inorganic nanoparticles Mass percentage is greater than 0wt% and is less than or equal to 20wt%；The quality percentage of (d) other solvents and/or electrolyte contains Amount is more than or equal to 5wt% and is less than or equal to 60wt%.

Preferably, the transition temperature of the solid electrolyte is 70~180 DEG C, preferably 72~145 DEG C.

Preferably, the conductivity of the solid electrolyte is 10^-7~10^-2S/cm, preferably 10^-6~2 × 10^-3S/cm。

7. the preparation method of solid electrolyte as claimed in claim 6, which is characterized in that the described method comprises the following steps:

Inorganic nanoparticles, lithium salts and ring-type ethers compound are mixed, the lithium salts containing inorganic nanoparticles is obtained under stirring Ring-type ethers compound solution, i.e., it is described can gelling system, continue to stir the solution, obtain the solid-state through gelation Electrolyte.

B) the above-mentioned mixed solution being prepared is added in lithium salts, the lithium salts containing inorganic nanoparticles is obtained under stirring Ring-type ethers compound solution, i.e., it is described can gelling system, continue to stir the solution, obtain the solid-state electricity through gelation Xie Zhi.

Inorganic nanoparticles, lithium salts, ring-type ethers compound and other solvents and/or electrolyte are mixed, are contained under stirring The ring-type ethers compound solution of the lithium salts of organic/inorganic nano particle, i.e., it is described can gelling system, continue to stir the solution, The solid electrolyte is obtained through gelation.

C ') mixed solution being prepared in step a ') is added to step b ') in the lithium salt solution that is prepared, under stirring The ring-type ethers compound solution of the lithium salts dissolved with other solvents and/or electrolyte containing inorganic nanoparticles is obtained, i.e., It is described can gelling system, continue to stir the solution, obtain the solid electrolyte through gelation.

8. a kind of gel electrolyte, which is characterized in that the gel electrolyte includes gel as claimed in claim 4.

9. a kind of lithium system battery, which is characterized in that lithium system battery include gel electrolyte according to any one of claims 8 and/or Solid electrolyte as claimed in claim 6.

10. gel as claimed in claim 4, solid electrolyte as claimed in claim 6 or gel electrolyte according to any one of claims 8 The application of liquid, which is characterized in that the gel or solid electrolyte can be used for lithium system battery, in the field of building materials；It is described Gel electrolyte can be used in lithium system field of batteries.