CN108962627A - A kind of supercapacitor or capacitor batteries of organic system - Google Patents

Abstract

The invention discloses a kind of supercapacitor of organic system or capacitor batteries, it includes gel electrolyte and/or solid electrolyte, the gel electrolyte and/or solid electrolyte by can gelling system be prepared, it is described can gelling system include following component, (a) lithium salts, (b) ether compound；In system can gelation polymer and/or can gelation prepolymer mass percentage be less than or equal to 1wt%；It by adjusting lithium salts, the constituent content of ether compound and type 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.

Description

A kind of supercapacitor or capacitor batteries of organic system

Technical field

The invention belongs to gel electrolyte technical fields, and in particular to a kind of supercapacitor or capacitor electricity of organic system Pond.

Background technique

In recent years, consuming excessively for fossil energy causes energy crisis and environmental problem, a large amount of motor vehicle exhaust emission Global warming and the increasingly exacerbation of haze weather are caused, these problems have all seriously affected the production and living of the mankind.Electric energy is one It plants clean energy resource and can be realized by rechargeable battery and is recycled, lithium battery is due to high voltage platform, high-energy Density has extended cycle life and the advantages such as low self-discharge, can not only be applied to portable electronic device, such as: digital phase In the equipment such as machine and portable computer, and electric tool, in terms of also have a wide range of applications, wherein the most Typically lithium ion battery, lithium-sulfur cell and lithium-air battery etc., however these lithium batteries in fast charging and discharging performance and make With on the service life far away from supercapacitor.Supercapacitor (Supercapacitor, Ultracapacitor) is called electrochemistry Capacitor (Electrochemical Capacitor, EC), is a kind of electrochemical element, by polarized electrolytic matter come energy storage, and The process of energy storage does not chemically react, and is physical process always, therefore performance is stablized；This thermal energy storage process is reversible, Also just because of this supercapacitor can be hundreds of thousands of times with repeated charge, service life has obtained greatly extending；Not only such as This, when applied voltage is added on two pole plates of supercapacitor, the positive electrode of pole plate stores positive charge, and negative plate storage is negative Charge is formed on electrolyte and interelectrode interface on the two-plate of supercapacitor under the electric field action of charge generation Opposite charge, with the internal electric field of balanced electrolyte, this positive charge and negative electrical charge be on the contact surface between two different phases, With gap arrangement extremely short between positive and negative charge on opposite position, therefore the capacitance stored is very big.However, simple is super Although grade capacitor has very high power density, energy density still needs to be further increased.By the study found that in battery Parallel connection large value capacitor in both ends can buffer impact of the high current to battery, to extend the cycle life of battery, thus capacitor Type lithium ion battery just comes into being.Later period, people by the way of interior connection, make each battery material particle all in electricity again Among the protection of container, this electronic device of capacitor batteries is thus generated, with battery high energy metric density and super electricity The characteristics of holding high power density.

Classify by electrolyte type, supercapacitor can be divided into water-based system supercapacitor and the super electricity of organic system Container；The supercapacitor of water-based system mostly uses highly acid or strong basicity makees electrolyte, but its decomposition voltage is lower, generally exists 1.2V, high degree affect the energy density of device；The supercapacitor of organic system then mostly uses volatile organic molten Electrolyte is made in agent；Equally, the electrolyte of capacitor batteries is also mostly organic system.However, organic system electrolyte bring is such as The safety problems such as burning, explosion also restrict its further development, the supercapacitor of organic system and the safety of capacitor batteries The problems such as problem is mainly concerned with the volatilization, leakage and heat Fire explosion of liquid state organic electrolyte, electrolyte decomposition.Cause This, the leakage of volatility electrolyte, battery is flammable and overpotential decompose the problems such as seriously restrict the safety of supercapacitor.

In order to overcome liquid electrolyte leakage and it is flammable the problems such as, inorganic solid electrolyte, solid polyelectrolyte And polymer gel electrolyte etc. has been widely studied, wherein inorganic solid electrolyte is that one kind contains inorganic super-ionic The lithium salts of electric conductivity；Solid polyelectrolyte is that the conductive solid that polymer and lithium salts are constituted still is reported at present The electric conductivity of the solid electrolyte in road is bad, this has seriously affected the service life for the supercapacitor being prepared.

Although polymer gel electrolyte has preferable electric conductivity, and its porous structure can effectively inhibit to be electrolysed The volatilization and leakage of liquid, however, the preparation for the polymeric gel electrolyte reported at present be all from raw material introduce macromolecule or The more complicated Low-molecular weight organogel factor of synthesis step is in conventional electrolysis liquid, and obtained polymer gel electrolyte It requires that flow regime could be presented at relatively high temperatures, is at low temperature gel state, high temperature is used when this allows for fluid injection Fluid injection, increases the complexity of experimental implementation, in addition, the transition temperature for the polymer gel electrolyte being prepared is also all opposite Relatively low, gel state is easier to be destroyed, and after gel is destroyed, can not utilize again, considerably increase cost.

Summary of the invention

In order to solve the deficiencies in the prior art, one of the objects of the present invention is to provide a kind of super capacitors of organic system Device comprising gel electrolyte and/or solid electrolyte, the gel electrolyte and/or solid electrolyte are by can gelation body System is prepared, it is described can gelling system include following component, (a) lithium salts, (b) ether compound；It can gel in system The polymer of change and/or can gelation prepolymer mass percentage be less than or equal to 1wt%.

The second object of the present invention is to provide a kind of capacitor batteries of organic system comprising gel electrolyte and/or Solid electrolyte, the gel electrolyte and/or solid electrolyte by can gelling system be prepared, it is described can gelation System includes following component, (a) lithium salts, (b) ether compound；In system can gelation polymer and/or can gelation The mass percentage of prepolymer is less than or equal to 1wt%.

Based on the polymer gel electrolyte for applying supercapacitor or capacitor batteries in organic system reported at present Deficiency existing for liquid and solid electrolyte, applicant have found under study for action, by lithium salts and small molecule ether compound (ring-type ethers One of compound or straight chain ether compound) mixing, by the interaction of the two (such as generate new complex compound or from Assembling effect etc.) and the modes such as ring-opening polymerisation or polycondensation of small molecule ether compound can form gel rubber system or solid-state system； The gel rubber system or solid-state system not only have the safety in utilization better than ordinary gel system or solid-state system, but also pass through Described in adjusting can in gelling system each component content and type, can effectively control the gel rubber system or solid-state system The formation time of intensity, the gel rubber system or solid-state system, the transition temperature of the gel rubber system or solid-state system are described strong The change of degree may make gel rubber system to expand in solid-state system, to more expand the application range of gel rubber system.In addition, institute Stating gel rubber system or solid-state system also has invertibity, i.e., can prepare when gel rubber system or solid bodies are tied up to lower than transition temperature It obtains, and after high-temperature process (being heated to transition temperature or more), the gel rubber system or solid-state system can become flow It is dynamic, but after it is stood again cooling down (being down to transition temperature or less), and original gel rubber system or solid bodies can be reverted to System, and property will not change.The gel rubber system or solid-state system not only can satisfy the super capacitor of organic system The safety of device or capacitor batteries and the normal use of battery, and prepare that raw material is universal, and preparation process is simple, it is not related to cumbersome Interminable experimental procedure.Based on such thinking, the present invention is completed.

A kind of supercapacitor of organic system comprising gel electrolyte and/or solid electrolyte, the gel electrolyte Liquid and/or solid electrolyte by can gelling system be prepared；It is described can gelling system include following component: (a) lithium Salt and (b) ether compound, the ether compound are selected from one of ring-type ethers compound and straight chain ether compound；Body In system can gelation polymer and/or can gelation prepolymer mass percentage be less than or equal to 1wt%.

A kind of capacitor batteries of organic system comprising gel electrolyte and/or solid electrolyte, the gel electrolyte And/or solid electrolyte by can gelling system be prepared；It is described can gelling system include following component: (a) lithium salts (b) ether compound, the ether compound are selected from one of ring-type ethers compound and straight chain ether compound；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, the mass percentage of the lithium salts is more than or equal to 2wt% and is less than or equal to 50wt%；The ether The mass percentage of class compound is more than or equal to 50wt% and is less than or equal to 98wt%.

Preferably, the mass percentage of the lithium salts is more than or equal to 5wt% and is less than 20wt%；Alternatively, the lithium salts Mass percentage be more than or equal to 20wt% and be less than or equal to 30wt%.

According to the present invention, described can further include supercapacitor or the capacitor electricity of (c) for organic system in gel rubber system The electrolyte in pond or its solvent.

According to the present invention, described can be in gelling system, the supercapacitor or capacitor batteries for organic system Electrolyte or its solvent mass percentage be more than or equal to 0wt% and be less than or equal to 48wt%.

Preferably, described can be described for the supercapacitor of organic system or the electricity of capacitor batteries in gelling system The mass percentage for solving liquid or its solvent is greater than 0wt% and is less than or equal to 40wt%.

According to the present invention, it is described can gelling system further comprise (d) inorganic nanoparticles.

According to the present invention, described can be in gelling system, the mass percentage of the inorganic nanoparticles is more than or equal to 0wt% and be less than or equal to 30wt%.

Preferably, described can be in gelling system, the mass percentage of the inorganic nanoparticles is greater than 0wt% and small In equal to 20wt%.

According to the present invention, described to still further comprise (e) additive in gelling system, the additive is selected from polyester Or one or more of its blend；Wherein, the polyester is obtained by polyacid or acid anhydrides and polyhydric alcohol；It is described polynary For acid selected from binary acid, ternary acid or more member acid, the polyalcohol is selected from the first alcohol of dihydric alcohol, trihydroxylic alcohol or more.

According to the present invention, it is described can in gelling system, the mass percentage of the additive be more than or equal to 0wt% and Less than or equal to 30wt%.

Preferably, described can be in gelling system, the mass percentage of the additive is greater than 0wt% and is less than or equal to 20wt%.

According to the present invention, the gel electrolyte by can gelling system be prepared, it is described can in gelling system, The mass percentage of the lithium salts is more than or equal to 2wt% and is less than 20wt%；The mass percentage of the ether compound Greater than 50wt% and it is less than or equal to 98wt%；It is described for the supercapacitor of organic system or the electrolyte of capacitor batteries or its The mass percentage of solvent is more than or equal to 0wt% and is less than or equal to 48wt%；The quality percentage of the inorganic nanoparticles contains Amount is more than or equal to 0wt% and is less than or equal to 30wt%；The mass percentage of the additive be more than or equal to 0wt% and be less than etc. In 30wt%.

Preferably, the mass percentage of the lithium salts is more than or equal to 5wt% and is less than 20wt%；The ether compound Mass percentage be greater than 55wt% and be less than or equal to 95wt%；Supercapacitor or the capacitor electricity for organic system The mass percentage of the electrolyte in pond or its solvent is greater than 0wt% and is less than or equal to 40wt%；The inorganic nanoparticles Mass percentage is greater than 0wt% and is less than or equal to 20wt%；The mass percentage of the additive is greater than 0wt% and is less than Equal to 20wt%.

According to the present invention, the transition temperature of the gel electrolyte is 40~95 DEG C, preferably 45~85 DEG C.

According to the present invention, the conductivity of the gel electrolyte is 10^-5~10^-1S/cm, preferably 10^-4~10^-2S/cm。

According to the present invention, the solid electrolyte by can gelling system be prepared, it is described can in gelling system, The mass percentage of the lithium salts is more than or equal to 20wt% and is less than or equal to 50wt%；The quality percentage of the ether compound Content is more than or equal to 50wt% and is less than or equal to 80wt%；It is described for the supercapacitor of organic system or the electricity of capacitor batteries The mass percentage for solving liquid or its solvent is more than or equal to 0wt% and is less than or equal to 30wt%；The matter of the inorganic nanoparticles Percentage composition is measured to be more than or equal to 0wt% and be less than or equal to 30wt%；The mass percentage of the additive is more than or equal to 0wt% And it is less than or equal to 30wt%.

Preferably, the mass percentage of the lithium salts is more than or equal to 20wt% and is less than or equal to 30wt%；The ethers The mass percentage of compound is more than or equal to 55wt% and is less than or equal to 80wt%；The super capacitor for organic system The mass percentage of the electrolyte or its solvent of device or capacitor batteries is greater than 0wt% and is less than or equal to 25wt%；It is described inorganic The mass percentage of nano particle is greater than 0wt% and is less than or equal to 20wt%；The mass percentage of the additive is greater than 0wt% and be less than or equal to 20wt%.

According to the present invention, the transition temperature of the solid electrolyte is 60~130 DEG C, preferably 80~110 DEG C.

According to the present invention, the conductivity of the solid electrolyte is 10^-7~10^-3S/cm, preferably 10^-6~10^-4S/cm。

Beneficial effects of the present invention:

1. the present invention provides a kind of supercapacitor of organic system or capacitor batteries comprising gel electrolyte and/ Or solid electrolyte, the gel electrolyte and/or solid electrolyte by can gelling system be prepared；It is described can gel Change system includes following component: (a) lithium salts and (b) ether compound, the ether compound be selected from ring-type ethers compound and One kind of straight chain ether compound；In system can gelation polymer and/or can the quality percentage of prepolymer of gelation contain Amount is less than or equal to 1wt%.

2. the supercapacitor of organic system of the present invention or gel electrolyte and solid state electrolysis in capacitor batteries The intensity of matter is adjustable, forms the time (is transformed into not flowable gel state by free flowable liquid condition and/or consolidates State electrolyte conditions) (being transformed by not flowable gel state and/or solid electrolyte state can for adjustable, transition temperature The minimum temperature when liquid condition of free-flowing) it is adjustable, it can the gel of varying strength is prepared according to specific needs and is consolidated State electrolyte, to meet different needs.The gel electrolyte and solid electrolyte have stronger impact resistance, are answering When in the fields such as the supercapacitor of organic system or capacitor batteries, it not only can effectively solve liquid electrolytic liquor and let out The problems such as dew, it is also possible that the supercapacitor of organic system or capacitor batteries have higher efficiency for charge-discharge, preferably Impact resistance makes the supercapacitor of the organic system or capacitor batteries have higher safety in utilization.

3. the supercapacitor of organic system of the present invention or gel electrolyte and solid electrolyte in capacitor batteries Transition temperature with higher, while also there is invertibity.When the use temperature of the gel electrolyte or solid electrolyte is high After its transition temperature, gel electrolyte and solid electrolyte become to flow, but are cooled to lower than transition temperature Afterwards, with invertibity, and gel electrolyte or solid electrolyte can be re-formed and be reused；Since it is with higher Transition temperature and invertibity, service life can be delayed, save the cost becomes an environmentally protective new type gel material Material.

4. the supercapacitor of organic system of the present invention or gel electrolyte and solid state electrolysis in capacitor batteries The preparation method of matter is simple, reaction condition is mild, reaction time is short, product yield high, preparation cost is low, is easily industrialized Production.

5. the supercapacitor of organic system of the present invention or gel electrolyte and solid state electrolysis in capacitor batteries Matter can show better gel state or solid electrolyte state in low temperature, i.e., in the gel or solid state electrolysis fundamental change Good gel state or solid electrolyte state, and the gel and solid electrolyte under low temperature can be kept below temperature Intensity more preferably.

Detailed description of the invention

Fig. 1 is assembled into for gel electrolyte obtained in embodiment 1 as the electrolytic solution for super capacitor of organic system super The preceding charge and discharge datagram three times of grade capacitor.

Fig. 2 is solid electrolyte obtained in embodiment 6 as the capacitor batteries electrolyte of organic system and is assembled into capacitor The cycle performance figure of battery.

Specific embodiment

[lithium salts]

In the present invention, the lithium salts can be selected from lithium hexafluoro phosphate, LiBF4, hexafluoroarsenate lithium, lithium perchlorate, trifluoro Methane sulfonic acid 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 etc..

[ether compound]

In the present invention, the ether compound is selected from one of ring-type ethers compound or straight chain ether compound.

[straight chain ether compound]

Ether compound of the invention can be selected from straight chain ether compound, the general formula such as formula of the straight chain ether compound (1) shown in:

R₁—O—(R₂—O)_n—R₃Formula (1)

Wherein, n is the integer greater than 0；

R₂C selected from linear chain or branched chain₁-C₆Alkylidene, linear chain or branched chain C₂-C₆Alkenylene；The R₂On carbon H on atom can be replaced by least one of following radicals: alkenyl, alkynyl, alkoxy, alkylthio group, naphthenic base, naphthenic base Oxygroup, cycloalkylsulfanyl, heterocycle, heterocycle oxygroup, heterocyclic thio, aryl, aryloxy, heteroaryl, heteroaryl oxygroup, Hydroxyl, sulfydryl, nitro, carboxyl, amino, ester group, halogen, acyl group, aldehyde radical；

R₁And R₃It is identical or different, be independently from each other hydrogen atom, alkyl, naphthenic base, heterocycle, alkenyl, in alkynyl It is one or more；The R₁And R₃Carbon atom on H can be replaced by least one of following radicals: alkenyl, alkynyl, alkane Oxygroup, alkylthio group, naphthenic base, cycloalkyl oxy, cycloalkylsulfanyl, heterocycle, heterocycle oxygroup, heterocyclic thio, aryl, virtue Base oxygroup, hydroxyl, sulfydryl, nitro, carboxyl, amino, ester group, halogen, acyl group, aldehyde radical.

Preferably, n is the integer between 1~6；

R₂C selected from linear chain or branched chain₁-C₄Alkylidene, linear chain or branched chain C₂-C₆Alkenylene；

R₁And R₃It is identical or different, it is independently from each other the C of linear chain or branched chain₁-C₆Alkyl.

It is highly preferred that R₂Selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, vinyl；

R₁And R₃It is identical or different, it is independently from each other methyl, ethyl, propyl.

It is further preferred that the straight chain ether compound is selected from glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol first and second Ether, 1,4-butanediol dimethyl ether, 1,4-butanediol diethyl ether, one of 1,4-butanediol ethyl methyl ether etc. or a variety of.

In the present invention, the straight chain ether compound is, for example, one of following compounds:

[ring-type ethers compound]

Ether compound of the invention can be selected from ring-type ethers compound, and the ring-type ethers compound, which is selected from, at least to be contained The C of 1 oxygen atom₂~C₂₀Cycloalkane (carbon atom number i.e. in cyclic structure is 2-20) or at least containing 1 oxygen atom C₃~C₂₀Cycloolefin (carbon atom number i.e. in cyclic structure is 3-20), wherein at least contains 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.

[additive]

In the present invention, the additive is selected from one or more of polyester or its blend.

Wherein, the polyester is obtained by polyacid or acid anhydrides and polyhydric alcohol.

Wherein, the polyacid is selected from binary acid, ternary acid or more member acid, and the polyalcohol is selected from dihydric alcohol, ternary Alcohol or more member alcohol.

In one preferred embodiment, the polyacid is selected from one of substituted or unsubstituted following polyacids Two or three or be more than three kinds: ethanedioic acid, malonic acid, succinic acid, butene dioic acid, glutaric acid, adipic acid, pimelic acid are pungent Diacid, decanedioic acid, azelaic acid, the third three acid；The number of the substituent group can be one or more；When the substituent group is multiple When, it can cyclization；The substituent group be alkyl, naphthenic base, aryl, hydroxyl, amino, ester group, halogen, acyl group, aldehyde radical, sulfydryl, One of alkoxy etc. is a variety of.

In one preferred embodiment, the acid anhydrides is selected from one of substituted or unsubstituted following acid anhydrides or two Kind or three kinds or be more than three kinds: ethanedioic acid acid anhydride, malonic anhydride, succinic anhydride, anhydride maleique, glutaric anhydride, adipic anhydride, heptan Dicarboxylic anhydride, suberic anhydride, sebacic anhydride, azelaic acid acid anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride；The number of the substituent group can be one It is a or multiple；It, can cyclization when the substituent group is multiple；The substituent group is alkyl, naphthenic base, aryl, hydroxyl, ammonia One of base, ester group, halogen, acyl group, aldehyde radical, sulfydryl, alkoxy etc. are a variety of.

In one preferred embodiment, the polyalcohol is selected from one of substituted or unsubstituted following polyalcohols Or it is several: propylene glycol, butanediol, pentanediol, hexylene glycol, heptandiol, ethohexadiol, nonanediol, decanediol, polyethylene glycol, the third three Alcohol；The number of the substituent group can be one or more；It, can cyclization when the substituent group is multiple；The substituent group For one of alkyl, naphthenic base, aryl, hydroxyl, amino, ester group, halogen, acyl group, aldehyde radical, sulfydryl, alkoxy etc. or a variety of.

In one preferred embodiment, the polyalcohol be selected from polyethylene glycol or polyethylene glycol with it is following polynary The combination of one or more of alcohol: propylene glycol, butanediol, pentanediol, hexylene glycol, heptandiol, ethohexadiol, nonanediol, the last of the ten Heavenly stems two Alcohol.

In one preferred embodiment, the degree of polymerization of the polyethylene glycol be 100-1000, preferably 150-800, Also preferably 200-600.Wherein, the weight ratio of the polyethylene glycol and other polyalcohols is 1:(0~1), preferably 1:(0~ 0.9), also preferably 1:(0~0.8).

[for the supercapacitor of organic system or the electrolyte of capacitor batteries or its solvent]

In the present invention, described for the supercapacitor of organic system or the electrolyte of capacitor batteries or its solvent includes ether Class electrolyte and its solvent, esters electrolyte and its solvent, amides electrolyte and its solvent, nitrile electrolyte and its solvent with And sulfone class electrolyte and its solvent.

In the present invention, the esters electrolyte is selected from the esters mixed liquor containing lithium salts, such as lithium hexafluoro phosphate containing 1M (LiPF₆) ethylene carbonate (EC) and dimethyl carbonate (DMC) mixed liquor, wherein the ethylene carbonate (EC) and carbon The volume ratio of dimethyl phthalate (DMC) is 1:1.

In the present invention, the solvent of the esters electrolyte is selected from esters ring-type non-aqueous organic solvent and esters chain is non-aqueous has At least one of solvent.

In the present invention, the esters ring-type non-aqueous organic solvent is selected from ethylene carbonate (EC), propene carbonate (PC), fluorine For ethylene carbonate (FEC), gamma-butyrolacton (GBL), ethylene sulfite (ES), propylene sulfite (PS), carbonic acid glyceride At least one of (GC).

In the present invention, the chain non-aqueous organic solvent is selected from diethyl carbonate (DEC), dimethyl carbonate (DMC), carbonic acid Methyl ethyl ester (EMC), methyl propyl carbonate (MPC), dipropyl carbonate (DPC), ethyl propyl carbonic acid ester (EPC), ethyl acetate (EA), acetic acid Propyl ester (PA), ethyl propionate (EP), ethyl butyrate (EB), methyl butyrate (MB), dimethyl sulfite (DMS), sulfurous acid diethyl At least one of ester (DES), sulfurous acid methyl ethyl ester (EMS).

In the present invention, the ethers electrolyte is selected from the ethers mixed liquor containing lithium salts, such as: contain the bis- fluoroforms of 1M The 1,3-dioxolane (DOL) of sulfimide lithium (LiTFSI) and the mixed liquor of glycol dimethyl ether (DME), wherein described 1, The volume ratio of 3- dioxolanes (DOL) and glycol dimethyl ether (DME) is 1:1.

In the present invention, the solvent of the ethers electrolyte is selected from 1,3-dioxolane, 1,2- dimethoxy-ethane, three second two Diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, fluorinated ethylene carbonate, polyethylene glycol borate, 1,1 ', 2,2 '-four fluoro ethyl -2, One of 2 ', 3,3 '-tetrafluoropropene ethers are a variety of.

In the present invention, the amides electrolyte is selected from the amides mixed liquor containing lithium salts, such as: trifluoromethyl containing 1M The DMAC N,N' dimethyl acetamide solution of Sulfonic Lithium.

In the present invention, the solvent of the amides electrolyte is selected from the compound containing amide group；

Preferably, the solvent of the amides electrolyte is selected from C₁~C₂₀Alkylamide, C₁~C₂₀Acrylamide nitrile, C₁ ~C₂₀Ynylamide, C₁~C₂₀Halogenated alkyl amide, C₁~C₂₀Halogenated alkenyl amide, C₁~C₂₀Halo alkynyl acyl Amine, C₇~C₂₀Aryl amide, C₁~C₂₀At least one of epoxy group amide.

Preferably, the solvent of the amides electrolyte is selected from n,N-Dimethylformamide, n,N-dimethylacetamide, benzene Formamide, formamide, acetamide, succimide, phthalimide, N- methyl para toluene sulfonamide, N- methyl vinyl Amine, 3- amino -6- methyl benzenesulfonamide, 2,2,2- trichloroacetamide, benzyl ester N- ethyl para toluene sulfonamide, 3- amino -2,2- Dimethylpropionamide, erucyl amide, N- ethyl -5- methyl -2- (1- Methylethyl) hexamethylene formamide, 4- methoxybenzoyl Amine, 2,4- dihydroxy benzoyl amine, N, N- diethyl -2- chloroacetamide, N-butylbenzenesulfonamide, N- ethyl acetamide, chloroethene Amide, hydrochloride N- (2- chlorphenyl) acetamide, N, N'- ethylene bis stearamide, pentanamide, 2- hydroxy-isobutyric amide, ethoxy Amide, benzene methyl cinnamamide, sulfonamide, malonamide, sulfonamide, cyclopropyl-sulfonylamide, 2- ethylsulfonyl in L- (+)-camphor Imidazo [1,2-a] pyridine -3- sulfonamide, N, N- diethyl acetamide, 4- chlorine thiobenzamide, N, N'- dimethyl oxalyl Amine, N- methoxy N-methylacetamide, benzamide, N- methyl caprolactam, (S)-(-)-t-butyl sulfonamide, 3- ammonia Base-N-methyl-benzamide, N, N'- methylene-bisacrylamide, the bromo- 3- nitrilo- propionamide of 2,2- bis-, N, N- diethyl ten Diamides, hydrazine carboximidamide, monochlor(in)ate hydrogen thioacetamide, cyanoacetamide, propionamide, benzamide, 2- nitrobenzene sulphur Amide, Para Amino Benzamide, isobutyramide, caprolactam, o-methyl formate benzene sulfonamide, DMAC N,N' dimethyl acetamide, N- Methylformamide, N tert butyl acrylamide, 6- methylnicotinamide, N, N- dimethyl sulfonamide, 2,3- dibromo propionamide, 2- ammonia Base -5- methyl benzamide, levo-camphor sultam, DL- aminocaproic lactam stearmide, 1,1- cyclohexanediacetic acid list Amide, cyclopropyl amide, p-nitrophenyl formamide, 4- (2- aminoethyl) benzsulfamide, 2- methyl-5-nitro benzsulfamide, 3,5- Dihydroxy benzoyl amine, 2- acrylamide-2-methylpro panesulfonic acid-N- methyl succinamide, N, 2,3- trimethyl -2- isopropyl Butyramide, N, N- dimethylpropionamide, N- caprolactam, 2- iodoacetamide, orthanilamide, 2,4- bis- are chloro- The chloro- 2,4- disulfonyl amido aniline of 5- sulfamoylbenzoic acid-N-phenylmaleimide, n-ethylmaleimide, 5- is adjacent Chlorobenzene sulfonamide, N, N- dimethylglycylamide, Ortho-Aminophenol -5- (N, N- dimethyl) sulfonamide, 4- amino -3,5- dinitro Yl-benzamide, 4- Amino-N-methyl benzamide, 2- phenyl acetamide, N- (tertbutyloxycarbonyl) para toluene sulfonamide, 4- fluorobenzene Formamide, oxime 2- amino malonamide, bis- (tetramethylene) Fluoro-formamides, N- hydroxyl-isobutyramide, thiopropionamide, second Ester 1- ((cyano -1- Methylethyl) azo) formamide, cinnamamide, 4- aminophenyl-N- methylmethane sulfonamide, 4- are bromo- 3- fluorobenzenesulfonamide, 2,6- difluorobenzenesulfonamide, 2- bromophenylsulfonyl amine, 4- fluorobenzenesulfonamide, 4- trifluoro-metoxybenzene sulfamide, 4- chlorobenzene sulfonamide, 2,5- difluorobenzenesulfonamide, trifluoro Methanesulfomide, N- [bis- (methyl mercapto) methylene] para toluene sulfonamide, The chloro- 3- nitro -5- sulfamoylbenzoic acid of 4-, N- methyl diacetayl amide N- benzylidene benzsulfamide, 2- methoxyl group -5- sulphonyl Amine, 3,5- dichloro benzsulfamide, 2- fluorobenzenesulfonamide, the bromo- 2- chlorobenzene sulfanilamide (SN) of 4-, the chloro- 2- fluorobenzene sulphonyl of 5-, amine are to methoxybenzene Sulfonamide, 4- chloro-salicylic acid -5- sulfonamide, 2- amino-N- ethyl, N-phenyl benzsulfamide, the bromo- 4- fluorobenzenesulfonamide of 2-, 4- Fluoro-2-methylbenzene sulfonamide, 2- cvanobenzenesulfonamide, 4- [2- (the chloro- 2- Methoxybenzamido of 5-) ethyl] benzsulfamide, 3,4- difluorobenzenesulfonamide, DL- aminocaproic lactam, 2,4,6- trichlorine benzsulfamide, cyclopropanesulfonamide, the bromo- 3- (trifluoro of 4- Methyl) benzene sulfanilamide (SN), N- (4- aminobutyl)-acetamide ceramide, N- [(1R) -2- (3- amino-sulfonyl -4- methoxyl group) - 1- methyl] acetamide, N- benzyl-N- nitroso-para toluene sulfonamide, N- (2- amino-ethyl) -4- methyl benzenesulfonamide, (1R) -10- camphor sulfonamide, 4- amino -6- (trifluoromethyl) benzene -1,3- disulfonic acid amide, 2- bromo- 4- (trifluoromethyl) benzene sulfonyl The fluoro- 4- methyl toluene sulfonamide of amine, 3-, 2- bromo- 5- (trifluoromethyl) benzsulfamide, naphthalene -2- sulfonamide, (1S) -10- camphor sulphur Amide, (S)-(+)-are to methylbenzene sulfenamide, (1R)-trans- N, bis- (the 1,1,1- trifluoro methylsulfonyls of N ' -1,2- hexamethylene diyl Amine), N- (2- fluorophenyl) Methanesulfomide, (S)-N- (-)-p-methylphenyl sulfinyl tryptamines, N- acetoxyl group-N- acetyl group- 4- chlorobenzene sulfonamide, 2- (trimethyl silicon substrate) ethyl sulfonamide, N- (4- aminobenzene)-sulfonamide -4- methylbenzene (R)-(-) -4- first Base phenylsulfinyl amine, N- ethyl para toluene sulfonamide, bis- (Α-methylbenzyl) sulfonamide of (R, R)-(+)-N, N '-, (S)-(-)- N- [1- (methylol) -2- phenylethyl] -4- methyl benzenesulfonamide, cyclopropyl amide, the fluoro- 5- sulfamoylbenzoic acid of the chloro- 4- of 2- At least one of N- benzal-P, P- diphenyl phosphonic acid amide, N- (4- chlorobenzene methylene) -4- toluenesulfonamide.

In the present invention, the nitrile electrolyte is selected from the nitrile mixed liquor containing lithium salts, such as: the second of the lithium perchlorate containing 1M Nitrile solution.

In the present invention, the solvent of the nitrile electrolyte is selected from the compound containing itrile group；

Preferably, the solvent of the nitrile electrolyte is selected from C₁~C₂₀Alkyl nitrile, C₁~C₂₀Alkenyl nitrile, C₁~C₂₀'s Alkynyl nitrile, C₁~C₂₀Halogenated alkyl nitrile, C₁~C₂₀Halogenated alkenyl nitrile, C₁~C₂₀Halo alkynyl nitrile, C₇~C₂₀Aryl Nitrile, C₁~C₂₀At least one of epoxy group nitrile.

Preferably, the solvent of the nitrile electrolyte is selected from acetonitrile, butyronitrile.

In the present invention, sulfone class electrolyte is selected from the sulfone class mixed liquor containing lithium salts, such as: the diformazan of the lithium perchlorate containing 1M is sub- Sulfone (DMSO) solution.

In the present invention, the solvent of sulfone class electrolyte is selected from the compound containing sulfuryl；

Preferably, the solvent of the nitrile electrolyte is selected from C₁~C₂₀Alkyl sulfone, C₁~C₂₀Alkenyl sulfone, C₁~C₂₀'s Alkynyl sulfone, C₁~C₂₀Haloalkylsulfone, C₁~C₂₀Halogenated alkenyl sulfone, C₁~C₂₀Halo alkynyl sulfone, C₇~C₂₀Aryl Sulfone, C₁~C₂₀At least one of epoxy group sulfone.

Preferably, the solvent of the sulfone class electrolyte is selected from sulfolane (SL), dimethyl sulfoxide.

[inorganic nanoparticles]

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

[preparation method of gel electrolyte]

The present invention also provides a kind of preparation methods of above-mentioned gel electrolyte comprising following steps:

By ether compound, lithium salts and optionally for the supercapacitor of organic system or the electrolyte of capacitor batteries Or its solvent and optionally inorganic nanoparticles and optionally additive mixes, the ether compound that lithium salts is obtained under stirring is molten Liquid, i.e., it is described can gelling system, continue to stir the solution, obtain the gel electrolyte through gelation.

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

Ether compound is added in lithium salts, the ether compound solution of lithium salts is obtained under stirring, will be optionally used for The supercapacitor of body system or the electrolyte of capacitor batteries or its solvent and/or inorganic nanoparticles and/or additive are added To the ether compound solution of lithium salts, i.e., it is described can gelling system, continue to stir the solution, be obtained through gelation described solidifying Glue electrolyte.

According to the present invention, to the lithium salts, ether compound, will optionally be used for the supercapacitor or electricity of organic system The electrolyte or its solvent and inorganic nanoparticles and additive of appearance battery carry out removing water process in advance；Preferably, using molecule Sieve and/or vacuum drying method to the lithium salts, ether compound, optionally by be used for organic system supercapacitor or The electrolyte of capacitor batteries or its solvent and inorganic nanoparticles and additive carry 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 that the gel electrolyte is formed is lower than the transition temperature of the gel electrolyte, described The time that gel electrolyte is formed is 5 seconds~300 hours.

[preparation method of solid electrolyte]

The present invention also provides a kind of preparation methods of above-mentioned solid electrolyte comprising following steps:

By ether compound, lithium salts and optionally for the supercapacitor of organic system or the electrolyte of capacitor batteries Or its solvent and optionally inorganic nanoparticles and optionally additive mixes, the ether compound that lithium salts is obtained under stirring is molten Liquid, i.e., it is described can gelling system, continue to stir the solution, obtain the solid electrolyte through gelation.

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

Ether compound is added in lithium salts, the ether compound solution of lithium salts is obtained under stirring, will be optionally used for The supercapacitor of body system or the electrolyte of capacitor batteries or its solvent and/or inorganic nanoparticles and/or additive are added To the ether compound solution of lithium salts, i.e., it is described can gelling system, continue to stir the solution, be obtained through gelation described solid State electrolyte.

According to the present invention, to the lithium salts, ether compound, will optionally be used for the supercapacitor or electricity of organic system The electrolyte or its solvent and inorganic nanoparticles and additive of appearance battery carry out removing water process in advance；Preferably, using molecule Sieve and/or vacuum drying method to the lithium salts, ether compound, optionally by be used for organic system supercapacitor or The electrolyte of capacitor batteries or its solvent and inorganic nanoparticles and additive carry 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 formation of the solid electrolyte is lower than the transition temperature of the solid electrolyte, institute The time for stating the formation of solid electrolyte is 30 minutes~100 hours.

According to the present invention, to the lithium salts, ether compound, will optionally be used for the supercapacitor or electricity of organic system The electrolyte or its solvent and inorganic nanoparticles and additive of appearance battery carry out removing water process in advance；Preferably, using molecule Sieve and/or vacuum drying method to the lithium salts, ether compound, optionally by be used for organic system supercapacitor or The electrolyte of capacitor batteries or its solvent and inorganic nanoparticles and additive carry out removing water process in advance.

[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.

The test of supercapacitor described in the present embodiment or capacitor batteries is in blue electric tester.

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 ether compound through molecular sieve before use, carry out except water process.

It is described to make for the supercapacitor of organic system or the electrolyte of capacitor batteries or its solvent in the present embodiment With preceding, drying is removed water through molecular sieve.

In the present embodiment, the additive is before use, through more than 45 DEG C of vacuum drying for 24 hours removing water process.

In the present embodiment, the inorganic nanoparticles are before use, through more than 60 DEG C of vacuum drying for 24 hours removing water process.

Embodiment 1

(1) preparation of the gel electrolyte as supercapacitor

The lithium hexafluoro phosphate solid of 0.8g is weighed in reagent bottle, the oxinane of 9.2mL is added, fills under magnetic stirring Divide mixing, obtaining can gelling system；A period of time is stood, gel electrolyte is formed.

In the gel rubber system, the mass percentage of lithium salts is 8wt%；The mass percentage of ether compound is 92wt%；It is 48wt% for the mass percentage of the electrolyte of lithium ion battery or its solvent.

After tested, the performance parameter of the gel is listed in Table 1 below.

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 gel, and when temperature drops to turning for gel When below temperature, gel is formed again, illustrates that the gel being prepared has good invertibity.

(2) preparation of supercapacitor

The preparation of supercapacitor positive electrode: by active carbon material, conductive agent Ketjen black, binder polyvinylidene fluoride (PVDF) it is uniformly mixed according to mass ratio 8:1:1, this mixture is modulated into slurry with N- methyl-pyrrolidon (NMP), uniformly Coated on aluminium foil, drying 24 hours, spare in 120 DEG C of vacuum drying ovens；

Super capacitor anode: lithium foil.

The above-mentioned gel electrolyte being prepared is applied in supercapacitor, with above-mentioned supercapacitor positive electrode and Super capacitor anode is assembled into supercapacitor, uses the chemical property (test of blue electric tester test supercapacitor The results are shown in Table 1).Wherein, the preparation method of the supercapacitor: diaphragm is placed between anode and cathode, three Between full of step (1) preparation can gelling system, encapsulation compacting, be assembled into the button-shaped supercapacitor of CR2032 type, it is quiet Set to it is described can gelling system become gel electrolyte.

Embodiment 2

(1) preparation of the gel electrolyte as capacitor batteries

The lithium perchlorate of 1.0g and the trifluoromethyl sulfonic acid lithium solid of 0.5g are weighed in reagent bottle, the second of 8.5mL is added Glycol ethyl methyl ether is in above-mentioned mixed liquor, and after being sufficiently mixed, obtaining can gelling system；A period of time is stood, gel electricity is formed Solve liquid.

In the gel rubber system, the mass percentage of lithium salts is 15wt%；The mass percentage of ether compound is 85wt%.

After tested, the performance parameter of the gel is listed in Table 1 below.

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 gel, and when temperature drops to turning for gel When below temperature, gel is formed again, illustrates that the gel being prepared has good invertibity.

(2) preparation of capacitor batteries

Capacitor batteries anode: manganic acid lithium electrode material and electrically conductive graphite, conductive agent Ketjen black, binder are gathered into inclined difluoro second Alkene (PVDF) is uniformly mixed according to mass ratio 85:5:5:5, and the modulation of this mixture is slurried with N- methyl-pyrrolidon (NMP) Material, even application is 24 hours dry in 120 DEG C of vacuum drying ovens on aluminium foil, spare；

Capacitance cell negative electrode: by lithium titanate electrode material and conductive agent Ketjen black, binder polyvinylidene fluoride (PVDF) It is uniformly mixed according to mass ratio 85:8:7, this mixture is modulated into slurry, even application with N- methyl-pyrrolidon (NMP) It is 24 hours dry in 120 DEG C of vacuum drying ovens on aluminium foil, it is spare；

The above-mentioned gel electrolyte being prepared is applied in capacitor batteries, with above-mentioned capacitor batteries anode and capacitor Battery cathode is assembled into capacitor batteries, and using the chemical property of blue electric tester testing capacitor battery, (test result is listed in table 1 In).Wherein, the preparation method of the capacitor batteries: diaphragm is placed between anode and cathode, and step is full of between three (1) preparation can gelling system, encapsulation compacting is assembled into the button-shaped capacitor batteries of CR2032 type, stand to it is described can gel Change system becomes gel electrolyte.

Embodiment 3

(1) preparation of the solid electrolyte as supercapacitor

The LiBF4 solid of 2.5g is weighed in reagent bottle, Isosorbide-5-Nitrae-dioxane of 7.5mL is added in above-mentioned mixing In solution, after being sufficiently mixed, obtaining can gelling system；A period of time is stood, solid electrolyte is formed.

In the solid state electrolysis plastidome, the mass percentage of lithium salts is 25wt%；The quality percentage of ether compound Content is 75wt%.

After tested, the performance parameter of the solid electrolyte is listed in Table 1 below.

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

(2) preparation of supercapacitor

Supercapacitor positive electrode: preparation process is the same as 1 supercapacitor positive electrode preparation process of embodiment.

Super capacitor anode: iron-cobalt-nickel compound super capacitance material, conductive agent Ketjen black, binder are gathered into inclined difluoro second Alkene (PVDF) is uniformly mixed according to mass ratio 8:1:1, this mixture is modulated into slurry with N- methyl-pyrrolidon (NMP), It is even to be coated on aluminium foil, it is 24 hours dry in 60 DEG C of vacuum drying ovens, it is spare；

The above-mentioned gel electrolyte being prepared is applied in supercapacitor, with above-mentioned supercapacitor positive electrode and Super capacitor anode is assembled into supercapacitor, uses the chemical property (test of blue electric tester test supercapacitor The results are shown in Table 1).Wherein, the preparation method of the supercapacitor: diaphragm is placed between anode and cathode, three Between full of step (1) preparation can gelling system, encapsulation compacting, be assembled into the button-shaped supercapacitor of CR2032 type, it is quiet Set to it is described can gelling system become gel electrolyte.

Embodiment 4

(1) preparation of the solid electrolyte as capacitor batteries

1.7g lithium hexafluoro phosphate and 0.5g fluoro sulfimide lithium solid are weighed in reagent bottle, the tetrahydro of 3.0mL is added The metaformaldehyde of furans and 4.8mL, after being sufficiently mixed, obtaining can gelling system；A period of time is stood, solid state electrolysis is formed Matter.

In the solid state electrolysis plastidome, the mass percentage of lithium salts is 22wt%；The quality percentage of ether compound Content is 78wt%.

After tested, the performance parameter of the solid electrolyte is listed in Table 1 below.

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

(2) preparation of capacitor batteries

Capacitor batteries anode: preparation process is the same as 2 capacitor batteries anode preparation process of embodiment.

Capacitance cell negative electrode: preparation process is the same as 2 capacitance cell negative electrode preparation process of embodiment.

The above-mentioned solid electrolyte being prepared is applied in capacitor batteries, with above-mentioned capacitor batteries anode and capacitor Battery cathode is assembled into capacitor batteries, and using the chemical property of blue electric tester testing capacitor battery, (test result is listed in table 1 In).Wherein, the preparation method of the capacitor batteries: diaphragm is placed between anode and cathode, and step is full of between three (1) preparation can gelling system, encapsulation compacting is assembled into the button-shaped capacitor batteries of CR2032 type, stand to it is described can gel Change system becomes solid electrolyte.

Embodiment 5

(1) preparation of the gel electrolyte as capacitor batteries

The LiBF4 solid of 0.8g is weighed in reagent bottle, the ester of the lithium salts of 2.5mL lithium-ion capacitor battery is added Class the mixed liquor ((LiPF of lithium hexafluoro phosphate containing 1M₆) ethylene carbonate (EC) and dimethyl carbonate (DMC) mixed liquor, wherein The volume ratio of the ethylene carbonate (EC) and dimethyl carbonate (DMC) is 1:1).It is sufficiently mixed under magnetic stirring until lithium Salt all dissolves, and 6.7mL3 is added, 3- dichloromethyl oxetanes, after being sufficiently mixed, obtaining can gelling system；Static one The section time forms gel electrolyte.

In the gel electrolyte liquid system, the mass percentage of lithium salts is 15wt%；The quality percentage of ether compound Content is 40wt%；It is 45wt% for the mass percentage of the electrolyte of lithium ion battery or its solvent.

After tested, the performance parameter of the gel electrolyte is listed in Table 1 below.

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

(2) preparation of capacitor batteries

(2) preparation of capacitor batteries

Capacitor batteries anode: preparation process is the same as 2 capacitor batteries anode preparation process of embodiment.

Capacitance cell negative electrode: preparation process is the same as 2 capacitance cell negative electrode preparation process of embodiment.

The above-mentioned gel electrolyte being prepared is applied in capacitor batteries, with above-mentioned capacitor batteries anode and capacitor Battery cathode is assembled into capacitor batteries, and using the chemical property of blue electric tester testing capacitor battery, (test result is listed in table 1 In).Wherein, the preparation method of the capacitor batteries: diaphragm is placed between anode and cathode, and step is full of between three (1) preparation can gelling system, encapsulation compacting is assembled into the button-shaped capacitor batteries of CR2032 type, stand to it is described can gel Change system becomes gel electrolyte.

Embodiment 6

(1) preparation of the solid electrolyte as capacitor batteries

2.5g lithium iodide is weighed in reagent bottle, 6.5mL1 is added thereto, 4- dioxane is added 1g aluminium oxide, stirs It mixes after being sufficiently mixed, obtaining can gelling system；Static a period of time forms solid electrolyte.

In the gel rubber system, the mass percentage of lithium salts is 25wt%；The mass percentage of ether compound is 65wt%；The percentage composition of inorganic nanoparticles is 30wt%.

After tested, the performance parameter of the solid electrolyte is listed in Table 1 below.

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

(2) preparation of capacitor batteries

Capacitor batteries anode: preparation process is the same as 2 capacitor batteries anode preparation process of embodiment.

Capacitance cell negative electrode: preparation process is the same as 2 capacitance cell negative electrode preparation process of embodiment.

The above-mentioned solid electrolyte being prepared is applied in capacitor batteries, with above-mentioned capacitor batteries anode and capacitor Battery cathode is assembled into capacitor batteries, and using the chemical property of blue electric tester testing capacitor battery, (test result is listed in table 1 In).Wherein, the preparation method of the capacitor batteries: diaphragm is placed between anode and cathode, and step is full of between three (1) preparation can gelling system, encapsulation compacting is assembled into the button-shaped capacitor batteries of CR2032 type, stand to it is described can gel Change system becomes solid electrolyte.

Embodiment 7

(1) preparation of the gel electrolyte as supercapacitor

1.2g perfluoro butyl Sulfonic Lithium is weighed in reagent bottle, 4mL1,4- 7-oxa-bicyclo[4.1.0 and 4mL2- chlorine are added thereto Additive 0.8g is added in methyl oxygen cyclobutane, stirs so that being sufficiently mixed, obtaining can gelling system；Static a period of time, shape At gel electrolyte.

In the gel electrolyte liquid system, the mass percentage of lithium salts is 12wt%；The quality percentage of ether compound Content is 80wt%；The mass percentage of additive is 8wt%.

After tested, the performance parameter of the gel electrolyte is listed in Table 1 below.

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

(2) preparation of supercapacitor

Supercapacitor positive electrode: preparation process is the same as 1 supercapacitor positive electrode preparation process of embodiment.

Super capacitor anode: preparation process is the same as 1 super capacitor anode preparation process of embodiment；

The above-mentioned gel electrolyte being prepared is applied in supercapacitor, with above-mentioned supercapacitor positive electrode and Super capacitor anode is assembled into supercapacitor, uses the chemical property (test of blue electric tester test supercapacitor The results are shown in Table 1).Wherein, the preparation method of the supercapacitor: diaphragm is placed between anode and cathode, three Between full of step (1) preparation can gelling system, encapsulation compacting, be assembled into the button-shaped supercapacitor of CR2032 type, it is quiet Set to it is described can gelling system become gel electrolyte.

Embodiment 8

(1) preparation of the gel electrolyte as supercapacitor

The lithium perchlorate solid of 0.5g is weighed in reagent bottle, the propene carbonate (PC) of 0.5mL is added, 8.8mL is added 2- chloromethyl propylene oxide, be added 0.2g nano SiO 2 particle, be sufficiently mixed under magnetic stirring, obtaining can gelation System；A period of time is stood, gel electrolyte is formed.

In the gel rubber system, the mass percentage of lithium salts is 5wt%；The mass percentage of ether compound is 88wt%；It is 5wt%, inorganic nanoparticles for the electrolyte of organic system super capacitor or the mass percentage of its solvent Mass percentage be 2wt%.

After tested, the performance parameter of the gel is listed in Table 1 below.

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 gel, and when temperature drops to turning for gel When below temperature, gel is formed again, illustrates that the gel being prepared has good invertibity.

(2) preparation of supercapacitor

Supercapacitor positive electrode: preparation process is the same as 1 supercapacitor positive electrode preparation process of embodiment.

Super capacitor anode: preparation process is the same as 1 super capacitor anode preparation process of embodiment；

The above-mentioned gel electrolyte being prepared is applied in supercapacitor, with above-mentioned supercapacitor positive electrode and Super capacitor anode is assembled into supercapacitor, uses the chemical property (test of blue electric tester test supercapacitor The results are shown in Table 1).Wherein, the preparation method of the supercapacitor: diaphragm is placed between anode and cathode, three Between full of step (1) preparation can gelling system, encapsulation compacting, be assembled into the button-shaped supercapacitor of CR2032 type, it is quiet Set to it is described can gelling system become gel electrolyte.

Embodiment 9

(1) preparation of the solid electrolyte as supercapacitor

The lithium hexafluoro phosphate solid of 2.1g is weighed in reagent bottle, 0.3mL acetonitrile is added, Isosorbide-5-Nitrae-dioxy of 7.4mL is added 0.2g polyethylene glycol borate is added in six rings, and after being sufficiently mixed, obtaining can gelling system；A period of time is stood, solid-state is formed Electrolyte.

In the solid state electrolysis plastidome, the mass percentage of lithium salts is 21wt%；The quality percentage of ether compound Content is 74wt%；It is 3wt%, the quality of additive for the mass percentage of the electrolyte of supercapacitor or its solvent Percentage composition is 2wt%.

After tested, the performance parameter of the solid electrolyte is listed in Table 1 below.

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

(2) preparation of supercapacitor

Supercapacitor positive electrode: preparation process is the same as 1 supercapacitor positive electrode preparation process of embodiment.

Super capacitor anode: preparation process is the same as 2 super capacitor anode preparation process of embodiment.

The above-mentioned gel electrolyte being prepared is applied in supercapacitor, with above-mentioned supercapacitor positive electrode and Super capacitor anode is assembled into supercapacitor, uses the chemical property (test of blue electric tester test supercapacitor The results are shown in Table 1).Wherein, the preparation method of the supercapacitor: diaphragm is placed between anode and cathode, three Between full of step (1) preparation can gelling system, encapsulation compacting, be assembled into the button-shaped supercapacitor of CR2032 type, it is quiet Set to it is described can gelling system become gel electrolyte.

Comparative example 1

The bis- trifluoromethanesulfonimide lithiums of 1.0g and 1.0g lithium hexafluoro phosphate are weighed in reagent bottle, it is organic that 4.0mL is added Supercapacitor conventional electrolysis the liquid ((LiClO of lithium perchlorate containing 1M of system₄) acetonitrile solution be sufficiently stirred so that lithium salts is complete Fully dissolved, it is static.

In above-mentioned system, the mass percentage of lithium salts is 33wt%；The mass percentage of ether compound is 0wt%；The electrolyte of supercapacitor for organic system or the mass percentage of its solvent are 67wt%.

It was found that the static some time, the mobility of solution is all fine, can not form stable gel.

Illustrate in the presence of no cyclo other compounds, only lithium salts and solvent mixing, is that can not form stable coagulate Glue.

The gel electrolyte and/or solid electrolyte of 1 embodiment 1-9 of table and comparative example 1 and the organic system being prepared Supercapacitor or capacitor batteries performance parameter

Fig. 1 is assembled into for gel electrolyte obtained in embodiment 1 as the electrolytic solution for super capacitor of organic system super The preceding charge and discharge figure three times of grade capacitor.As seen from the figure, which, can as organic system electrolytic solution for super capacitor So that the normal charge and discharge of supercapacitor, while the active material in electrolyte can play one's part to the full, supercapacitor Specific capacity with higher.

Fig. 2 is the circulation that solid electrolyte obtained in embodiment 6 is assembled into capacitor batteries as capacitor batteries electrolyte Performance map.As seen from the figure, electrolyte of the solid electrolyte as capacitor batteries can make the normal charge and discharge of capacitor batteries, together When electrolyte in active material can play one's part to the full, capacitor batteries specific capacity with higher.

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 (10)

1. a kind of supercapacitor of organic system, which is characterized in that the supercapacitor includes gel electrolyte and/or consolidates State electrolyte, the gel electrolyte and/or solid electrolyte by can gelling system be prepared；It is described can gelation body System includes following component: (a) lithium salts and (b) ether compound, and the ether compound is selected from ring-type ethers compound and straight chain One of ether compound；In system can gelation polymer and/or can gelation prepolymer mass percentage Less than or equal to 1wt%.

2. a kind of capacitor batteries of organic system, which is characterized in that the capacitor batteries include gel electrolyte and/or solid-state electricity Xie Zhi, the gel electrolyte and/or solid electrolyte by can gelling system be prepared；It is described can gelling system packet Include following component: (a) lithium salts and (b) ether compound, the ether compound are selected from ring-type ethers compound and straight chain ethers One of compound；In system can gelation polymer and/or can the mass percentage of prepolymer of gelation be less than Equal to 1wt%.

3. supercapacitor according to claim 1 or capacitor batteries as claimed in claim 2, which is characterized in that described The mass percentage of lithium salts is more than or equal to 2wt% and is less than or equal to 50wt%；The mass percentage of the ether compound More than or equal to 50wt% and it is less than or equal to 98wt%.

Preferably, the mass percentage of the lithium salts is more than or equal to 5wt% and is less than 20wt%；Alternatively, the matter of the lithium salts Percentage composition is measured to be more than or equal to 20wt% and be less than or equal to 30wt%.

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 etc..

4. supercapacitor according to claim 1 or capacitor batteries as claimed in claim 2, which is characterized in that described Shown in the general formula of straight chain ether compound such as formula (1):

R₁—O—(R₂—O)_n—R₃Formula (1)

Wherein, n is the integer greater than 0；

R₂C selected from linear chain or branched chain₁-C₆Alkylidene, linear chain or branched chain C₂-C₆Alkenylene；The R₂On carbon atom On H can be replaced by least one of following radicals: alkenyl, alkynyl, alkoxy, alkylthio group, naphthenic base, cycloalkyloxy group Base, cycloalkylsulfanyl, heterocycle, heterocycle oxygroup, heterocyclic thio, aryl, aryloxy, heteroaryl, heteroaryl oxygroup, hydroxyl Base, sulfydryl, nitro, carboxyl, amino, ester group, halogen, acyl group, aldehyde radical；

R₁And R₃It is identical or different, it is independently from each other one of hydrogen atom, alkyl, naphthenic base, heterocycle, alkenyl, alkynyl Or it is a variety of；The R₁And R₃Carbon atom on H can be replaced by least one of following radicals: alkenyl, alkynyl, alkoxy, Alkylthio group, naphthenic base, cycloalkyl oxy, cycloalkylsulfanyl, heterocycle, heterocycle oxygroup, heterocyclic thio, aryl, aryl oxide Base, hydroxyl, sulfydryl, nitro, carboxyl, amino, ester group, halogen, acyl group, aldehyde radical.

Preferably, n is the integer between 1~6；

R₂C selected from linear chain or branched chain₁-C₄Alkylidene, linear chain or branched chain C₂-C₆Alkenylene；

R₁And R₃It is identical or different, it is independently from each other the C of linear chain or branched chain₁-C₆Alkyl.

Preferably, R₂Selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, vinyl；

R₁And R₃It is identical or different, it is independently from each other methyl, ethyl, propyl.

Preferably, the straight chain ether compound is selected from glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ether, Isosorbide-5-Nitrae- Butanediol dimethyl ether, 1,4-butanediol diethyl ether, one of 1,4-butanediol ethyl methyl ether etc. or a variety of.

5. supercapacitor according to claim 1 or capacitor batteries as claimed in claim 2, which is characterized in that described Ring-type ethers compound is selected from the ring-type ethers compound containing an 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.

6. supercapacitor according to claim 1 or capacitor batteries as claimed in claim 2, which is characterized in that described It can further include (c) for the supercapacitor of organic system or the electrolyte or its solvent of capacitor batteries in gel rubber system.

Preferably, described can be described for the supercapacitor of organic system or the electrolyte of capacitor batteries in gelling system Or the mass percentage of its solvent is more than or equal to 0wt% and is less than or equal to 48wt%.

Preferably, described can be described for the supercapacitor of organic system or the electrolyte of capacitor batteries in gelling system Or the mass percentage of its solvent is greater than 0wt% and is less than or equal to 40wt%.

Preferably, it is described can gelling system further comprise (d) inorganic nanoparticles.

Preferably, described can be in gelling system, the mass percentage of the inorganic nanoparticles is more than or equal to 0wt% and small In equal to 30wt%.

Preferably, described can be in gelling system, the mass percentage of the inorganic nanoparticles is greater than 0wt% and is less than etc. In 20wt%.

7. supercapacitor according to claim 1 or capacitor batteries as claimed in claim 2, which is characterized in that described (e) additive can be still further comprised in gelling system, the additive is selected from one of polyester or its blend or several Kind；Wherein, the polyester is obtained by polyacid or acid anhydrides and polyhydric alcohol；The polyacid be selected from binary acid, ternary acid or More polyacid, the polyalcohol are selected from the first alcohol of dihydric alcohol, trihydroxylic alcohol or more.

Preferably, described can be in gelling system, the mass percentage of the additive is more than or equal to 0wt% and is less than or equal to 30wt%.

Preferably, described can be in gelling system, the mass percentage of the additive is greater than 0wt% and is less than or equal to 20wt%.

8. supercapacitor according to claim 1 or capacitor batteries as claimed in claim 2, which is characterized in that described Gel electrolyte by can gelling system be prepared, it is described can be in gelling system, the gel electrolyte is by can gel Change system is prepared, it is described can be in gelling system, the mass percentage of the lithium salts is more than or equal to 2wt% and is less than 20wt%；The mass percentage of the ether compound is greater than 50wt% and is less than or equal to 98wt%；It is described to be used for organism The mass percentage of the supercapacitor of system or the electrolyte of capacitor batteries or its solvent is more than or equal to 0wt% and is less than or equal to 48wt%；The mass percentage of the inorganic nanoparticles is more than or equal to 0wt% and is less than or equal to 30wt%；The additive Mass percentage be more than or equal to 0wt% and be less than or equal to 30wt%.

Preferably, the mass percentage of the lithium salts is more than or equal to 5wt% and is less than 20wt%；The matter of the ether compound Percentage composition is measured to be greater than 55wt% and be less than or equal to 95wt%；The supercapacitor or capacitor batteries for organic system The mass percentage of electrolyte or its solvent is greater than 0wt% and is less than or equal to 40wt%；The quality of the inorganic nanoparticles Percentage composition is greater than 0wt% and is less than or equal to 20wt%；The mass percentage of the additive is greater than 0wt% and is less than or equal to 20wt%.

9. supercapacitor according to claim 1 or capacitor batteries as claimed in claim 2, which is characterized in that described Solid electrolyte by can gelling system be prepared, it is described can be in gelling system, the solid electrolyte is by can gel Change system is prepared, it is described can be in gelling system, the mass percentage of the lithium salts is more than or equal to 20wt% and small In equal to 50wt%；The mass percentage of the ether compound is more than or equal to 50wt% and is less than or equal to 80wt%；It is described It is more than or equal to 0wt% for the mass percentage of the supercapacitor of organic system or the electrolyte of capacitor batteries or its solvent And it is less than or equal to 30wt%；The mass percentage of the inorganic nanoparticles is more than or equal to 0wt% and is less than or equal to 30wt%； The mass percentage of the additive is more than or equal to 0wt% and is less than or equal to 30wt%.

Preferably, the mass percentage of the lithium salts is more than or equal to 20wt% and is less than or equal to 30wt%；The ethers chemical combination The mass percentage of object is more than or equal to 55wt% and is less than or equal to 80wt%；The supercapacitor for organic system or The mass percentage of the electrolyte of capacitor batteries or its solvent is greater than 0wt% and is less than or equal to 25wt%；The inorganic nano The mass percentage of particle is greater than 0wt% and is less than or equal to 20wt%；The mass percentage of the additive is greater than 0wt% And it is less than or equal to 20wt%.

10. supercapacitor according to claim 7 or capacitor batteries, which is characterized in that the polyacid, which is selected from, to be replaced Or one or both of unsubstituted following polyacids or three kinds or it is more than three kinds: ethanedioic acid, malonic acid, succinic acid, butylene Diacid, glutaric acid, adipic acid, pimelic acid, suberic acid, decanedioic acid, azelaic acid, the third three acid；The number of the substituent group can be It is one or more；It, can cyclization when the substituent group is multiple；The substituent group is alkyl, naphthenic base, aryl, hydroxyl, ammonia One of base, ester group, halogen, acyl group, aldehyde radical, sulfydryl, alkoxy etc. are a variety of.

Preferably, the acid anhydrides is selected from one or both of substituted or unsubstituted following acid anhydrides or three kinds or is more than three kinds: Ethanedioic acid acid anhydride, malonic anhydride, succinic anhydride, anhydride maleique, glutaric anhydride, adipic anhydride, pimelic acid acid anhydride, suberic anhydride, the last of the ten Heavenly stems Dicarboxylic anhydride, azelaic acid acid anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride；The number of the substituent group can be one or more；When the substitution It, can cyclization when base is multiple；The substituent group is alkyl, naphthenic base, aryl, hydroxyl, amino, ester group, halogen, acyl group, aldehyde One of base, sulfydryl, alkoxy etc. are a variety of.

Preferably, the polyalcohol is selected from one or more of substituted or unsubstituted following polyalcohols: propylene glycol, fourth two Alcohol, pentanediol, hexylene glycol, heptandiol, ethohexadiol, nonanediol, decanediol, polyethylene glycol, glycerine；The number of the substituent group It can be one or more；It, can cyclization when the substituent group is multiple；The substituent group be alkyl, naphthenic base, aryl, One of hydroxyl, amino, ester group, halogen, acyl group, aldehyde radical, sulfydryl, alkoxy etc. are a variety of.

Preferably, the polyalcohol is selected from the group of one or more of polyethylene glycol or polyethylene glycol and following polyalcohols It closes: propylene glycol, butanediol, pentanediol, hexylene glycol, heptandiol, ethohexadiol, nonanediol, decanediol.

Preferably, the degree of polymerization of the polyethylene glycol is 100-1000, preferably 150-800, also preferably 200-600.Wherein, The weight ratio of the polyethylene glycol and other polyalcohols is 1:(0~1), preferably 1:(0~0.9), also preferably 1:(0~ 0.8)。