CN108963329A - A kind of solid electrolyte and solid electrolyte composition for lithium rechargeable battery - Google Patents

Abstract

The invention discloses a kind of solid electrolytes for lithium rechargeable battery, it includes lithium-ion-conducting polymer substrate or adhesive and the lithium-ion-conducting inorganic substances for being dispersed in polymer substrate or adhesive or being chemically bonded therewith, wherein the lithium-ion-conducting inorganic substances are selected from sodium conductive materials or sodium salt and are selected from 2 CO 3 of Li, 2 O of Li, 2 C of Li, 2 O 4, LiOH, LiX, 2 Li of ROCO, HCOLi, ROLi, (2 Li of ROCO) 2, (2 OCO of CH, 2 Li) 2, 2 S of Li, LixSOy or combinations thereof, wherein X=F, Cl, I or Br, R=alkyl, x=0-1, y=1-4, and the wherein polymeric matrix or bonding The amount of agent is the 1% to 99% of the volume of the electrolyte composition, and feature is high-energy density, high power density, long circulation life and due to using safer, nonflammable solid electrolyte without the danger of explosion.The present invention also provides a kind of solid electrolyte compositions for lithium rechargeable battery.

Description

A kind of solid electrolyte and solid electrolyte composition for lithium rechargeable battery

Technical field

The present invention relates to a kind of solid electrolyte for lithium rechargeable battery and solid electrolyte compositions.

Background technique

Chargeable lithium ion, lithium metal, lithium sulphur and lithium metal air cell are considered as electric car (EV), hybrid power The promising power supply of automobile (HEV) and portable electronic device (such as laptop computer and mobile phone).As metal member The lithium of element has highest lithium storage volume (3861 milliampere/gram) compared with any other metal or metal inlaid scheme, makees For active material of positive electrode (in addition to LI4.4Si, the specific capacity with 4200 Mach/gram).Therefore, it is however generally that, Lee's metal electricity Pond (with lithium anodes) is with higher energy density more significant than lithium ion battery (having graphite anode).In history, Use the non-lithiated compounds (such as TiS2, MoS2, MnO2, COO2 and V2O5) with relatively high specific capacity as chargeable lithium Metal battery is coupled as active material of cathode with lithium anodes.When the cell is discharged, lithium ion passes through electrolyte from lithium Metal anode is transferred to cathode, and cathode becomes lithiumation.Unfortunately, in recharge and electric discharge, lithium metal causes in anode Upper formation dendrite, eventually leads to internal short-circuit, thermal runaway and explosion.Due to a series of accidents relevant to this problem, these classes The production of the secondary cell of type stops in early stage generation nineteen ninety, provides approach to lithium ion battery.Even if now, stable circulation Property and safety issue be still lithium metal battery (such as lithium sulphur and the lithium transition gold for preventing EV, HEV and microelectronic component from applying Belong to oxide cell) further commercialized principal element.Equally, the cyclical stability of lithium metal rechargeable battery and safety are asked It is related that topic mainly forms the high trend of pine-tree structure with Lee's metal during repeated charge-discharge cycles or overcharge, causes internal electric Short circuit and thermal runaway.It is (such as the carbonic acid of solvent of the organic liquid solvent as used in electrolyte that this thermal runaway, which is even exploded, Salt and ether race) caused by, unfortunately, they have high volatility and inflammability.Many trials have been done to solve branch Brilliant and thermal runaway problem.However, having succeeded on the market although the effort of these early stages without chargeable lithium metal battery. This may be since these art methods still have the concept of significant deficiency.For example, in some cases, being designed for Prevent anode or the electrolyte structure of dendrite too complicated.In other materials, material cost is too high, or manufactures these materials Process is too laborious or difficult.In most of lithium metal batteries and lithium ion battery, electrolyte solvent is inflammable.There is an urgent need to It is a kind of it is simpler, it is more cost effective and be easier realize method come prevent internal short-circuit caused by Lee's metallic dendrite and heat lose Control problem is in lithium metal battery and other lithium rechargeable batteries.It is consistent with above-mentioned effort, and due to above-mentioned to lithium metal The worry of safety of secondary battery promotes the development of lithium ion secondary battery, wherein pure lithium metal piece or film are replaced by carbonaceous material (such as natural graphite part).As active material of positive electrode.Carbonaceous material absorbs lithium (for example, by between graphene planes It is embedded in lithium ion or atom), and recharged and discharge regime desorption lithium ion respectively in lithium ion battery operating process.Carbon Material can mainly include can be expressed as LIXC6 with the graphite of lithium intercalation, obtained graphite intercalation compound, wherein X is usually less than 1.Although lithium ion battery is the energy storage device of promising electro-motive vehicle, state-of-the-art Lee's ion battery There are no meet cost, safety and performance objective.Lee's ion battery is usually using lithium transition-metal oxide or phosphate conduct Positive (cathode), relative to Carbon anode (anode) with high potential go/be embedded in again Lee+.Lithium transition-metal oxide or phosphate The specific capacity of base positive active material is usually in the range of 140~170 milliampere/gram.Therefore, the ratio of commercially available Lee's ion battery Can be usually in the range of 120~220WH/kg, most typically 150~180WH/kg.These specific energy values compare battery Energy needed for the electric car of power supply is three to 2 times low.In addition, being previously used for the identical flammable solvent of lithium metal secondary cell For most of lithium ion batteries.Although the tendency for forming dendron in lithium ion battery (relative to lithium metal battery) obviously subtracts It is few, but lithium ion battery has the essential safety problem of its own.For example, the transition metal element in lithium metal oxide cathode is High activated catalyst can promote and accelerate the decomposition of organic solvent, cause in relatively low electrolyte temperature (such as < 200 DEG C) issue heat it is out of control or explosion cause.With normal 400 DEG C on the contrary, without catalytic action.

Ionic liquid (ILS) is a new class of pure ion salt type material, is liquid in very low temperatures.The official of ILS Fang Dingyi is as a reference point using the boiling point of water: " ionic compound that ionic liquid is less than 100 DEG C of liquid ".One especially The useful and interested class ILS of science is ionic liquid at room temperature (RTIL), it is referred in room temperature or liquid below.RTILS Also referred to as organic liquid salt or organic molten salt.The generally acknowledged definition of RITL is with any of the fusion temperature lower than environment temperature Salt.Although ILs is proposed as the potential electrolyte of rechargeable lithium battery, due to its incombustibility, traditional ionic liquid Composition may show satisfactory performance when being used as electrolyte, this may be due to several inherent shortcomings: (a) ILS With opposite H.Viscosity under room temperature or lower temperature；Therefore it is considered being not suitable for lithium ion transport；(b) for Li-S battery Purposes, ILS can dissolving lithium polysulfide on cathode and allow dissolve material transport to anode (i.e. shuttle effect holding not Become).(c) for lithium metal secondary cell, most of ILS on anode with lithium metal kickback, in recharge and electric discharge Period continues to consume Lee and depleted of electrolyte itself.These factors cause relatively poor specific capacity (especially in high current or Under high charge-discharge rate conditions, therefore power density is lower), low specific energy density, fast capacity decaying and the poor circulation longevity Life.In addition, ILs is still very expensive.Therefore, up to the present, not commercially available lithium battery is made using ionic liquid For main electrolyte components.With hybrid vehicle (HEV), plug-in hybrid electric automobile (HEV) and all batteries The fast development of electric car (EV) is provided with higher ratio energy, more there is an urgent need to anode and cathode material and electrolyte The rechargeable battery of high energy density.High-speed, long-life and safety.Lithium ion battery (Li-S) is most promising One of energy storage device, the theoretical capacity of lithium are 3861 milliamperes/gram, and the capacity of S is 1675 milliamperes/gram.Simplest form be with Elementary sulfur is anode, and lithium is the lithium ion battery of cathode.The redox coupling of lithium-sulfur cell work, the reaction S8+ of description 16Li 8LI2S, the Li+/Li near 2.2V.This electrochemical potential is about electrochemical potential shown in conventional cathode.So And this disadvantage is offset by the very high theoretical capacity of Lee and S, therefore, with traditional lithium ion battery based on intercalation It compares, Li-S battery has an opportunity to provide significant higher energy density (product of capacity and voltage).According to the weight of Lee and S or Volume (is not based on total cell weight or volume), and value can be close to 2500WH/kg or 2800WH/L, assumes respectively complete to LI2S Reaction.Under cell design appropriate, cellular level specific energy is 1200WH/kg (cell weight) and cellular level.Gy density It should can be achieved on for 1400W/L (cell volume).However, testing electricity in the Li sulphur of sulphur cathode technique industry-leading at present Pond has the largest battery specific energy of 250400WH/kg (be based on total battery weight), much smaller than can be obtained in practical operation.

In order to cope with these challenges, new electrolyte, lithium anode protective film and solid electrolyte have been developed.It is some to have The cathode development of interest is recently it has been reported that contain lithium polysulfide, still, their performance still is below required for practical application 's.The each of the high density rechargeable battery containing elementary sulfur, organic sulfur and carbon sulphur cathode material is used to prepare although proposing Kind method, but they still need material and battery design (a) delays O--.Anion reduzate is diffused into from cathode chamber In other components in these batteries, the safety of battery (b) is improved, and (c) is provided in a large amount of circulations with high capacity Rechargeable battery.

Technical solution

A kind of solid electrolyte for lithium rechargeable battery, it includes lithium-ion-conducting polymer substrate or bondings Agent and the lithium-ion-conducting inorganic substances for being dispersed in polymer substrate or adhesive or being chemically bonded therewith, wherein described Lithium-ion-conducting inorganic substances are selected from sodium conductive materials or sodium salt and are selected from 2 CO 3 of Li, 2 C of Li 2 O, Li, 2 O 4, LiOH, LiX, ROCO 2 Li, HCOLi, ROLi, (2 Li of ROCO) 2, (2 OCO of CH, 2 Li) 2, Li 2 S, LixSOy or its Combination, wherein X=F, Cl, I or Br, R=alkyl, x=0-1, y=1-4, and the wherein polymeric matrix or adhesive Amount is the 1% to 99% of the volume of the electrolyte composition.

Optionally, wherein the sodium conduction species or sodium salt be selected from Na2CO3, Na2O, Na2C2O4, NaOH, NaX, RoCO2Na、HCONa、RONa、(RoCO2NA)2、(CH2OCO2NA)2、Na2S、NaxCeO、NaCl 4、NaFF6、NaF4、 NaASF6, NaCf3SO3, nanmu (CF3SO2) 2, bis- (oxalic acid) sodium borates, NaBOB, NABF2C2O4, NABF2C2O4, NaNO3, NAPF3 (CF2CF3) 3, fluorine second sulfimide sodium of enjoying a double blessing, NaBETI, bis- (trifyl) acid imide sodium, bis- (fluorine sulphonyl Base) acid imide sodium, trifluoromethanesulp-onyl -onyl imide sodium, NaTFSI, ionic liquid base sodium salt or their combination；Wherein X=F, Cl, I or Br, R=alkyl, x=0-1, y=1-4.

Optionally, wherein the polymer substrate or adhesive include sulfonated polymer, sulfonated polymer and electronic conduction The mixture or electronics mixture of the mixture of polymer, sulfonated polymer and the non-conductive polymer of electronics.

A kind of solid electrolyte composition for lithium rechargeable battery, the electrolyte composition include that (A) is selected from Sulfonated polymer, (B) lithium ion conductive inorganic substance or lithium salts and (C) lithium ion conducting polymeric matrix or adhesive) sodium from Sub- transmitter or sodium salt, wherein the inorganic substances or lithium salts of the conducting lithium ions and the sodium ion-conductive substance or sodium salt It is scattered in the polymeric matrix or adhesive or is chemically bonded therewith, (LiBF 4), hexafluoro lithium arsenide, LiAsF 6, trifluoro Methanesulfonic acid lithium, 3 SO 3 of LiCF, bis trifluoromethyl sulfimide lithium, LiN (3 SO 2 of CF) 2, bis- (oxalates) close lithium, boric acid Lithium, LiBOB, ethanedioic acid difluoro lithium borate, 2 C of LiBF, 2 O 4, ethanedioic acid difluoro lithium borate, 2 C of LiBF, 2 O 4, nitric acid Lithium, LiNO 3, Li- fluoro-alkyl-phosphate, LiPF 3 (2 CF 3 of CF) 3, fluorine second sulfimide lithium of enjoying a double blessing, LiBETI are double (trifluoromethane sulfonyl group) imide li, bis- (fluorosulfonyl) imide lis, fluoroform sulfimide lithium, LiTFSI, ionic liquid Body base lithium salts or combinations thereof, and wherein the amount of polymer substrate or adhesive is the 1% to 99% of electrolyte composition weight, And the weight ratio between the lithium-ion-conducting inorganic substances or lithium salts and the sodium ion-conductive substance or sodium salt is 1/ 99 to 99/1

The invention mainly solves the technical problem of providing a kind of solid electrolyte for lithium rechargeable battery and admittedly State electrolyte composition, show high-energy density, high power density, long circulation life and due to use it is safer, be not easy Danger of the solid electrolyte of combustion without explosion.

Embodiment

The preferred embodiments of the present invention will be described in detail below so that advantages and features of the invention can be easier to by It will be appreciated by those skilled in the art that so as to make a clearer definition of the protection scope of the present invention.

For illustrative purposes, the discussion of preferred embodiment below is based primarily upon Li-S battery (as an example), but It is that the same or similar principle and program are suitable for every other rechargeable lithium metal battery and (are closed using lithium metal or metal Gold is as anode activity).Material).Active material of cathode can be, for example, transition metal oxide (such as V2O5) or vulcanization Object (such as MoS2), sulphur or polysulfide (such as more lithium sulfides), or only outside air (being used for lithium air).Solid-state electricity Solution matter can also be used for lithium ion battery.The hybrid solid-state electrolyte composition includes (a) lithium ion conducting polymer substrate or viscous Mixture, (b) lithium ion conducting inorganic species or lithium salts (also referred to as inorganic species containing lithium), and (c) sodium ion-conductive species or sodium Salt, wherein (b) being dispersed or being chemically combined by polymer substrate or adhesive with (c).Lithium ion conducting inorganic species are selected from Li 2CO3、Li 2O、Li 2C2O4、LIOH、LIX、RoCO2Li、HCOLi、ROLi、(RoCO2Li)2、(CH2OCO2Li)2、LI2S、 LIX soybean or their combination, wherein X=F, Cl, I or Br, R=alkyl, X=0-1, Y=1-4.Polymer substrate or bonding The volume of agent by electrolyte composition volume 1% to 99%.In the hybrid solid electrolyte composition, sodium conductive materials Or sodium salt be selected from Na2CO3, Na2O, Na2C2O4, NaOH, NaX, ROCO2NA, HCONa, RONa, (R2CO2NO2, CH2OCO2NO2, Na2S, NaCeO4, NaPF6, NaF4, NaFS6, NaCf3SO3, nanmu (CF3SO2) 2, bis- (sodium oxalate) boric acid Salt, NaBOB, NaBF.2C2O4, NaBF2C2O4, NaNO3, NaPF3 (CF2CF3) 3, fluorine second sulfimide sodium of enjoying a double blessing, NaBETI, Bis- (trifluoromethyl sulfonyl) acid imide sodium, bis- (fluorosulfonyl) acid imide sodium, trifluoromethanesulfonic acid sulfimide sodium, NaTFSI, Ionic liquid base sodium salt or combinations thereof；Wherein X=F, Cl, I or Br, R=alkyl, x=0-1, y=1-4.

Sodium conduction species or sodium salt and coexisting for lithium ion conduction species or lithium salts seem to show significant synergistic effect, As the surprising high-lithium ion electric conductivity by the hybrid solid-state electrolyte containing lithium ion is shown.It polymerize in ionic conduction The sodium ion Conductive inorganic species or salt dispersed in object (such as sulfonated polymer).We are surprisingly observed that various sulfonation are poly- Closing object has very high electric conductivity, especially when being used in combination with above-mentioned lithium ion conducting inorganic compound, shape to lithium ion At composite solid electrolyte.Polymer substrate or adhesive can be from sulfonated polymer itself, sulfonated polymer and electronic conductions The mixture or EL mixture of the mixture of polymer (being mainly used for cathode side), sulfonated polymer and the non-conductive polymer of electronics Middle selection.EcCon conducting polymer and lithium ion conducting polymer.

In one embodiment, polymer substrate or adhesive are selected from sulfonated polyaniline, sulfonated polypyrroles, the poly- thiophene of sulfonation Pheno, the poly- furans of sulfonation or their combination.Such polymer is not only lithium ion conduction, and is that electronics conducts, therefore, It cannot act as unique electrolyte of no another layer of non-electrical conductive electrolyte or porous insulating layer.However, in Li-S or Li Se Realize that this polymer dielectric is very advantageously, to reduce the molten of sulphur, more lithium sulfides, selenium or lithium selenide in the cathode of battery It solves (for reducing or eliminating shuttle effect), and increases electric conductivity.Cathode layer (is imitated for enhancing utilizing for active material of cathode Rate).The optional autohemagglutination of sulfonated polymer (perfluorinated sulfonic acid), sulfonated tetrafluorethylene, polytetrafluoroethylene (PTFE) sulfonated perfluorocarbon alkoxy are derivative Object, sulfonated polysulfone, sulfonated polyether-ether-ketone, sulfonated polyether-ether-ketone, sulfonated polyether sulfone etc..Polystyrene, sulfonated polyimide, sulfonation Styrene-butadiene copolymer, sulfonation polychlorotrifluoroethylene, sulfonated perfluorocarbon ethylene propylene copolymer, sulfonated ethylene trifluoro-ethylene Copolymer, sulfonation Kynoar, sulfonated polyethylene alcohol copolymer fluorinated acrylamide and hexafluoropropene and tetrafluoroethene, ethylene and four Vinyl fluoride sulfonated copolymer, polybenzimidazoles and chemical derivative, copolymer and its blend.

These sulfonated polymers can be easily with above-mentioned lithium ion conducting inorganic matter (for example, Li 2CO3, Li 2O, Li 2C2O4, LIOH, LIX, RoCO2Li, HCOLi, ROLi, (RoCO2Li) 2, (CH2OCO2Li) 2, LI2S, LIXYAG and its mixing Object) and sodium ion-conductive species or sodium salt mixed by any solution.Mixing or melting mixing method are many institutes in the art Known.These inorganic matters are commercially available in the lab or are readily synthesized.However, later, we will introduce a kind of new Method, these lithium ions and/or sodium are formed in situ in situ or in the matrix of various sulfonated polymers and its blend Ionic conduction inorganic species (also referred to as lithium or inorganic species containing sodium).In certain embodiments, polymer substrate or adhesive Mixture including electronic conductive polymer and lithium ion conducting polymer, wherein lithium ion conducting polymer is selected from poly- (perfluor Sulfonic acid), sulfonated tetrafluorethylene, SUL.Polytetrafluoroethylene (PTFE), sulfonated polysulfone, sulfonated polyether-ether-ketone, sulfonated polyether-ether-ketone, sulfonation are poly- Styrene, sulfonated polyimide, sulfonated styrene-butadiene copolymer, sulfonation polychlorotrifluoroethylene sulfonation P perfluoro alkoxy Derivative difluoroethylene propylene copolymer, sulfonated ethylene-trifluoro-ethylene copolymer, sulfonation polyvinylidene fluoride, Kynoar With hexafluoropropene and tetrafluoroethene sulfonated copolymer, ethylene and tetrafluoroethene sulfonated copolymer, polybenzimidazoles E and chemical derivatization Object, copolymer and its blend, wherein the weight ratio of electronic conductive polymer and lithium ion conducting polymer is 1/99 to 99/1. Electronic conductive polymer be selected from polyaniline, polypyrrole, polythiophene, poly- furans, bicyclic polymer, their derivative and they Combination.This mixture can be good lithium ion conductor, but the electronic conduction of the mixture of poor electronic conductor offer is poly- Polymer component is by volume less than 30%.If the electronic conductive polymer component of mixture is more than 70%, mixture will be very Good electronic conductor.In certain ideal embodiments, polymer substrate or adhesive include from poly- (ethylene oxide) (PEO), polypropylene oxide, poly- (acrylonitrile) (PAN), poly- (methyl methacrylate) (PMMA), polyvinylidene fluoride (PVDF), the lithium ion conducting polymer selected in poly bis methoxy ethoxy thiophosphate.PaseNEX, polyvinyl chloride, gather Dimethyl siloxane and Kynoar-hexafluoropropene (PVDF-HFP), its derivative or their combination.

Of the invention is preferably a kind of hybrid solid-state electrolyte composition with desired embodiment, and it includes lithium ion conductings Polymer substrate or the adhesive and sodium ion-conductive object selected from sulfonated polymer, lithium ion conducting inorganic species or lithium salts Matter.S or sodium salt, wherein lithium ion conducting inorganic species or lithium salts and sodium ion-conductive species or sodium salt by polymer substrate or glue Mixture dispersion or chemical bonding.From lithium perchlorate, lithium chloride, lithium hexafluoro phosphate, LiPF6, lithium fluoride, LiPF4, hexafluoro arsenic The lithium ions such as lithium, LaASF6, trifluoro lithium metaphosphate, LiPF3SO3, bis trifluoromethyl sulfimide lithium, woods (CF3SO2) 2, lithium are led Selection bis- (oxalic acid) borates of lithium ion conducting inorganic matter in electric inorganic species, LiBOB, LiODFB, LiPF2C2O4, LiODFB, LiPF2C2O4, lithium nitrate, LaNO3, Li Fluoroalkyl Phosphates, LiPF3 (CF2CF3) 3, fluorine second sulfimide of enjoying a double blessing, LiBETI, double lithium (trifluoromethyl sulfonyl) acid imides, bis- (fluorine sulphonyl Base) lithium IMIDE, trifluoromethanesulfonimide lithium, LiTFSI, ionic liquid base lithium salts or their combination.Polymer substrate or The weight of adhesive be 1%~99% weight electrolyte composition (preferably 5% to 95%, more preferably 20% to 80%), the weight ratio between lithium ion conducting inorganic matter or lithium salts and sodium ion-conductive species or SODIU is from 1/99 to 99/1. In the hybrid solid electrolyte composition, sodium ion-conductive substance or sodium salt be selected from Na2CO3, Na2O, Na2C2O4, NaOH, NaX、RoCO2Na、HCONa、RONa、(RoCO2NA)2、(CH2OCO2NA)2、Na2S、NaxCeO、NaCl 4、NaFF6、NaF4、 NaASF6, NaCf3SO3, nanmu (CF3SO2) 2, bis- (sodium oxalate) borates, NaBOB.NABF2C2O4,NaBF2C2O4,NaNO3, NaPF3 (CF2CF3) 3, fluorine second sulfimide sodium of enjoying a double blessing, NaBETI, bis- (trifluoromethyl sulfonyl) acid imide sodium, bis- (fluorine sulphonyl Base) acid imide sodium, trifluoromethanesulp-onyl -onyl imide sodium, NaTFSI, ionic liquid base sodium salt or their combination；Wherein X=F, Cl, I, or Br, R=alkyl, x=0-1, y=1-4.

In preferred embodiments, containing lithium species can be selected from Li 2CO3, Li 2O, Li 2C2O4, LIOH, LIX, RoCO2Li, HCOLi, ROLi, (RoCO2Li) 2, (CH2OCO2Li) 2, LI2S, LIX soybean, their combination, or with sodium salt Mixture (such as Na2CO3, Na2O, Na2C2O4, NaOH, NaiX, ROCO2NA, HCONa, RONa, (ROCO2).Na) 2, (CH2OCO2NA) 2, Na2S, NAXEAGEY, wherein X=F, Cl, I or Br, R=alkyl is (for example, R CH, CH2, CH3CH2 Deng), x=0-1, Y=1-4.These species, when be dispersed in lithium ion conduction matrix polymer or by it is this polymer-bonded when, It is surprisingly capable of forming solid-state electrolyte layer firm in structure, it is sufficiently strong to intercept or dendrite is prevented to penetrate, but keep High lithium ion excitability.

The sequencing of above embodiments is not only for ease of description, represent the advantages or disadvantages of the embodiments.

Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features； And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and Range.

Claims (4)

1. a kind of solid electrolyte for lithium rechargeable battery, it includes lithium-ion-conducting polymer substrate or adhesives And the lithium-ion-conducting inorganic substances for being dispersed in polymer substrate or adhesive or being chemically bonded therewith, feature exist In: wherein the lithium-ion-conducting inorganic substances are selected from sodium conductive materials or sodium salt and are selected from Li 2CO 3, Li 2O, Li 2C 2O 4, LiOH, LiX, ROCO 2Li, HCOLi, ROLi, (ROCO 2Li) 2, (CH 2OCO 2Li) 2, Li 2S, LixSOy or its Combination, wherein X=F, Cl, I or Br, R=alkyl, x=0-1, y=1-4, and the wherein polymeric matrix or adhesive Amount is the 1% to 99% of the volume of the electrolyte composition.

2. a kind of solid electrolyte for lithium rechargeable battery according to claim 1, it is characterised in that: wherein institute State sodium conduction species or sodium salt be selected from Na2CO3, Na2O, Na2C2O4, NaOH, NaX, RoCO2Na, HCONa, RONa, (RoCO2NA) 2, (CH2OCO2NA) 2, Na2S, NaxCeO, NaCl 4, NaFF6, NaF4, NaASF6, NaCf3SO3, nanmu (CF3SO2) 2, bis- (oxalic acid) sodium borates, NaBOB, NABF2C2O4, NABF2C2O4, NaNO3, NAPF3 (CF2CF3) 3 are double Perfluoroethyl sulfonyl imines sodium, NaBETI, bis- (trifyl) acid imide sodium, bis- (fluorosulfonyl) acid imide sodium, fluoroform Base sulfimide sodium, NaTFSI, ionic liquid base sodium salt or their combination；Wherein X=F, Cl, I or Br, R=alkyl, x =0-1, y=1-4.

3. a kind of solid electrolyte for lithium rechargeable battery according to claim 1, it is characterised in that: wherein institute It states polymer substrate or adhesive includes that the mixture of sulfonated polymer, sulfonated polymer and electronic conductive polymer, sulfonation are poly- Close the mixture or electronics mixture of object and the non-conductive polymer of electronics.

4. a kind of solid electrolyte composition for lithium rechargeable battery, the electrolyte composition includes that (A) is selected from sulphur Fluidized polymer, (B) lithium ion conductive inorganic substance or lithium salts and (C) lithium ion conducting polymeric matrix or adhesive) sodium ion Transmitter or sodium salt, wherein the inorganic substances or lithium salts of the conducting lithium ions and the sodium ion-conductive substance or sodium salt point It dissipates in the polymeric matrix or adhesive or is chemically bonded therewith, (LiBF 4), hexafluoro lithium arsenide, LiAsF 6, fluoroform Sulfonic Lithium, 3 SO 3 of LiCF, bis trifluoromethyl sulfimide lithium, LiN (3 SO 2 of CF) 2, bis- (oxalates) close lithium, boric acid Lithium, LiBOB, ethanedioic acid difluoro lithium borate, LiBF 2C 2O 4, ethanedioic acid difluoro lithium borate, LiBF 2C 2O 4, lithium nitrate, LiNO 3, Li- fluoro-alkyl-phosphate, LiPF 3 (2 CF 3 of CF) 3, fluorine second sulfimide lithium of enjoying a double blessing, LiBETI, bis- (three Fluoromethane sulfonyl) imide li, bis- (fluorosulfonyl) imide lis, fluoroform sulfimide lithium, LiTFSI, ionic liquid base Lithium salts or combinations thereof, and wherein the amount of polymer substrate or adhesive is the 1% to 99% of electrolyte composition weight, and Weight ratio between the lithium-ion-conducting inorganic substances or lithium salts and the sodium ion-conductive substance or sodium salt be 1/99 to 99/1。