CN107645013A - Compound quasi-solid electrolyte, its preparation method and the lithium battery or lithium ion battery containing it - Google Patents
Compound quasi-solid electrolyte, its preparation method and the lithium battery or lithium ion battery containing it Download PDFInfo
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- CN107645013A CN107645013A CN201610585885.5A CN201610585885A CN107645013A CN 107645013 A CN107645013 A CN 107645013A CN 201610585885 A CN201610585885 A CN 201610585885A CN 107645013 A CN107645013 A CN 107645013A
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Abstract
The present invention provides a kind of compound quasi-solid electrolyte, compound quasi-solid electrolyte film and preparation method thereof and includes the lithium battery or lithium ion battery of the compound quasi-solid electrolyte film.Wherein, compound quasi-solid electrolyte of the invention includes solid electrolyte, the liquid electrolyte containing lithium salts, inorganic nanoparticles and binding agent.Electrolyte can be adsorbed in the electrostatic on inorganic nanoparticles surface or functional group, compound quasi-solid electrolyte is had very strong adsorption capacity and liquid-maintaining capacity.Meanwhile inorganic nanoparticles can adsorb lithium salts, change lithium ion conduction mechanism, reduce the interface resistance between liquid electrolyte and solid electrolyte, change the deposition morphology of lithium, hinder Li dendrite to be formed, reduce the efflorescence of lithium.In addition, the addition of solid electrolyte can make the compound quasi-solid electrolyte of the present invention keep high conductance, the content of liquid electrolyte can be effectively reduced, so as to improve the security of battery.
Description
Technical field
The present invention relates to electrochemistry and novel energy resource material technology field, more particularly to a kind of compound quasi-solid electrolyte and its
Preparation method, and lithium battery or lithium ion battery including the compound quasi-solid electrolyte.
Background technology
At present, lithium ion battery is energy density highest battery in commercial batteries, is widely used in various small electricals
Sub- product and electric automobile etc..In recent years, electric automobile and the fast-developing energy to lithium ion battery of energy storage industry are close
Degree, cost and security propose higher requirement.
Lithium metal is considered as forth generation negative pole, the deposition of peak capacity and relatively low -3.04V with 3860mAh/g
Current potential；300Wh/kg can be improved significantly to by the energy density of existing lithium ion battery by being used as negative pole using lithium metal, be had
Effect alleviates the mileage anxiety of electric automobile.Meanwhile for lithium battery, it can also use without lithium positive pole, so as to expand the choosing of positive pole
Select scope.Existing subject matter is the unlimited volumetric expansion of lithium anode when lithium metal is as negative pole.Further, since fill
Lithium deposition is uneven in electric process, and local substantial amounts of lithium deposition can cause solid electrolyte interface film (Solid Electrolyte
Interphase, SEI) rupture, Li dendrite is formed, and Li dendrite penetrates readily through barrier film, causes short circuit.In addition, Li dendrite has
Higher chemical reactivity, easily reacts with electrolyte.The dissolving abjection of the lithium of Li dendrite root causes Li dendrite to break
Split, form dead lithium, cause storehouse can efficiency reduce and the problem of potential safety hazard.
The method for solving lithium anode at present mainly has adding liquid film for additive, and organosol polymeric battery is made,
Using dry polymeric solid electrolyte, solid oxide electrolyte, sulfide solid electrolyte, and lithium metal is carried out various
Structural modification, to reduce effective current density and reduce volumetric expansion.Although film for additive can effectively improve battery
Storehouse energy efficiency, suppresses lithium dendrite growth, but still can not fully suppress the growth of Li dendrite.Although copolymer solid electrolyte has
There is certain pliability, Li dendrite can be stopped, but electrical conductivity is relatively low, the internal resistance of cell being prepared is larger.
Solid electrolyte has wider electrochemical window, and chemical environment is stable, non-volatile, nonflammable；Solid electrolyte
Presence prevented that side reaction occurs between lithium anode and solution；Solid electrolyte has stronger mechanical performance, can
Hinder the growth of Li dendrite.
Solid oxide electrolyte film is frangible, and mechanical flexibility is poor, and the interracial contact of electrolyte and positive electrode is difficult to solve
Certainly, it is not easy to make the battery of high power capacity.
There is sulfide solid electrolyte the problem of higher electrical conductivity and pliability, interracial contact to be easier to solve, and lead to
Cross to be cold-pressed and just solve the problems, such as the interracial contact of positive pole and electrolyte, but sulfide solid electrolyte positive pole chemically unstable,
And sulfide electrolyte preparation condition requires high, and air stability is poor.
Therefore, in order to be protected to lithium metal, it is necessary to prepare a kind of flexibility with polymer, solid electrolyte
The composite electrolyte membrane of hardness, the electrical conductivity of liquid electrolyte and wellability.
The content of the invention
In view of the above-mentioned problems, it is an aspect of the present invention to provide a kind of compound quasi-solid electrolyte, the compound quasi- solid-state electricity
Solution matter includes solid electrolyte, the liquid electrolyte containing lithium salts, inorganic nanoparticles and binding agent.
Preferably, compound quasi-solid electrolyte of the present invention also includes surfactant；The surfactant is excellent
Elect as selected from neopelex, sodium alkyl sulfate, pareth sulfate, Alkyl ethoxy carboxylate acid
One or more in sodium, sodium alkyl sulfonate.
Preferably, in compound quasi-solid electrolyte of the present invention, the inorganic nanoparticles are selected from Al2O3、
SiO2、MgO、CaO、TiO2、ZnO、ZrO2、Y2O3、BaTiO3, 3A molecular sieves, 4A molecular sieves, 5A molecular sieves, 10X molecular sieves, 13A
One or more in molecular sieve, 13X-AGP molecular sieves, ZSM-5 molecular sieve, lithium magnesium silicate, aluminium-magnesium silicate, montmorillonite.It is more excellent
Selection of land, in compound quasi-solid electrolyte of the present invention, the particle diameter of the inorganic nanoparticles is 0.1nm~1000nm；
More preferably 0.1nm~100nm.Inorganic nanoparticles are smaller, and specific surface area is bigger, and the liquid electrolyte of absorption is more,
Increase simultaneously with the area of solid electrolyte or positive contact.But particle is too small, production cost can increase.Further preferably
Ground, inorganic nanoparticles mass fraction shared in compound quasi-solid electrolyte are 10%~60%；More preferably 10%~
50%.Inorganic nanoparticles have the function that strong adsorptive liquid electrolyte, and particle is smaller, and liquid electrolyte is fewer, then electric
Pond is safer.
It is highly preferred that the present invention compound quasi-solid electrolyte in, the solid electrolyte be sulfide electrolyte or
Oxide electrolyte；It is highly preferred that the sulfide electrolyte is selected from Li10GeP2S12、Li3.25Ge0.25P0.75S4、Li3PS4、
Li3Zn0.5GeS4、Li3.4Si0.4P0.6S4、Li7P3S11In one or more；The oxide electrolyte is selected from Li1+ xAlxGe2-x(PO4)3、Li3yLa2/3-yTiO3、LiZr2-zTiz(PO4)3、Li1+mAlmTi2-m(PO4)3、Li7-2n-jAnLa3Zr2- jBjO12、Li7-2n-2jAnLa3Zr2-jCjO12In one or more；Wherein, 0≤x≤2,0≤y≤2/3,0≤z≤2,0≤m≤
2,0≤n≤3,0≤j≤2, A is Ge and/or Al, B are Nb and/or Ta, C are Te and/or W.
It is further preferred that in the compound quasi-solid electrolyte of the present invention, the solid electrolyte is particle form, and it is average
Particle diameter is 10~10000nm.It is further preferred that the mass fraction that the solid electrolyte accounts for compound quasi-solid electrolyte is
10%~80%, more preferably 20%~70%.In the range of this mass fraction, obtained compound quasi-solid electrolyte film causes
It is close, while electrical conductivity is also higher.
More preferably, in the compound quasi-solid electrolyte of the present invention, the liquid electrolyte containing lithium salts includes solvent,
The solvent is selected from methyl ethyl carbonate (EMC), gamma-valerolactone (γ-VL), γ-fourth lactones (γ-BL), dimethyl carbonate
(DMC), propene carbonate (PC), diethyl carbonate (DEC), ethylene carbonate (EC), glycol dimethyl ether (DME), diethyl two
Diethylene glycol dimethyl ether, TRIGLYME, tetraethyleneglycol dimethyl ether, 1,3- dioxolanes (DOL), tetrahydrofuran (THF),
P13(trimethyl fluoride sulfonyl) inferior amine salt (PP of TFSI, N- methyI-oropvD piperidines-two13TFSI), N- methyl-butvls piperidines-two (three
Methyl fluoride sulphonyl) inferior amine salt (PP14TFSI), (trimethyl fluoride sulfonyl) inferior amine salt of N- methyl-butvls pyrroles-two (PYR14TFSI)、
(trimethyl fluoride sulfonyl) inferior amine salt of N- methyI-oropvDs pyrroles-two (PYR13TFSI the one or more in).
Again preferably, in the compound quasi-solid electrolyte of the present invention, the liquid electrolyte containing lithium salts also includes boundary
Face wetting agent, flame-retardant additive, film for additive or its combination；It is highly preferred that the boundary moisture agent is fluoro-ether, the resistance
Combustion additive is phosphate, and the film for additive is sub- selected from ethylene sulfite (ES), propylene sulfite (PS), carbonic acid
Vinyl acetate (VC), dimethyl sulfite (DMS), diethyl sulfite (DES), 1,2- trifluoroacetic acid base ethane (BTE), carbon
One or more in sour ethene vinylene (VEC), fluorinated ethylene carbonate (FEC).Boundary moisture agent can be carried effectively
High interface wellability, flame-retardant additive can improve battery security, and film for additive can then improve the interface stability of battery.
It is further preferred that in the compound quasi-solid electrolyte of the present invention, the liquid electrolyte containing lithium salts includes
Lithium salts, the lithium salts are selected from lithium hexafluoro phosphate, LiBF4, lithium perchlorate, hexafluoroarsenate lithium, trifluoromethyl sulfonic acid lithium, double
One or more in (trimethyl fluoride sulfonyl is sub-) amine lithium, double fluorine sulfimide lithiums, di-oxalate lithium borate, lithium nitrate.Further
Preferably, the concentration of the lithium salts in the liquid electrolyte containing lithium salts by the liquid electrolyte containing lithium salts be calculated as 0.1mol/L~
5mol/L；More preferably 0.5mol/L~1.5mol/L.The concentration of lithium salts in the liquid electrolyte containing lithium salts is above-mentioned
During scope, the electrical conductivity and cost of the liquid electrolyte containing lithium salts are more reasonable.
Still further preferably, in the compound quasi-solid electrolyte of the present invention, the liquid electrolyte containing lithium salts accounts for
The mass fraction of compound quasi-solid electrolyte is 5%~60%；More preferably 15%~50%.
Further preferably, in the compound quasi-solid electrolyte of the present invention, the binding agent is selected from poly- inclined chloroethene
Alkene (PVDF), Vingon-hexafluoropropene (PVDF-HFP), polytetrafluoroethylene (PTFE) (PTFE), polyethylene glycol oxide, polyester, polyamides
One in amine, polymethyl methacrylate, makrolon, carboxymethyl cellulose, SB, polyacrylonitrile
Kind is a variety of.It is highly preferred that the quality summation of the inorganic nanoparticles and solid electrolyte and the mass ratio of the binding agent
For 60: 40 to 99.5: 0.5.In the range of above-mentioned mass ratio, compound quasi-solid electrolyte film of the invention can obtain well
Mechanical performance and compared with high ionic conductivity.In the present invention, due to not requiring that binding agent can turn on lithium ion, binding agent
Content can be very low.
The electrostatic on inorganic nanoparticles surface or functional group can adsorptive liquid electrolyte, have than organosol polymeric electrolyte
There are stronger adsorption capacity and stronger liquid-maintaining capacity, can be liquid curing.Meanwhile inorganic nanoparticles can adsorb
The anion or cation of lithium salts, surface conduction of the lithium ion along inorganic nanoparticles, so as to change the conduction of lithium ion
Mechanism, reduce the interface resistance between liquid electrolyte to solid electrolyte.Inorganic nanoparticles have inertia and height simultaneously
Dielectric constant, the deposition morphology of lithium can be changed, hinder Li dendrite to be formed, reduce the efflorescence of lithium, improve compound quasi- solid state electrolysis
The pliability of plasma membrane.It was found by the inventors of the present invention that when inorganic nanoparticles are less, its contact with solid electrolyte can become
Difference, electrical conductivity is caused to reduce.Because inorganic nanoparticles can absorb the liquid electrolyte containing lithium salts, therefore, pass through regulation
The content of liquid electrolyte, the electrical conductivity of the compound quasi-solid electrolyte of the present invention can be adjusted.If only consideration electrical conductivity
Just, then without adding inorganic nanoparticles in compound quasi-solid electrolyte, and liquid electrolyte need to only be adjusted.But
Bridge of the present invention using the liquid electrolyte containing lithium salts that inorganic nanoparticles absorb as connection solid electrolyte, required nothing
The content of machine nano particle can be than relatively low.
The addition of solid electrolyte can make the compound quasi-solid electrolyte of the present invention keep higher electrical conductivity, can be effective
The content of the liquid electrolyte containing lithium salts is reduced, improves the security of battery.
The compound quasi-solid electrolyte of the present invention has good mechanical performance, can effectively suppress Li dendrite, prevent
The volumetric expansion of lithium battery or lithium ion battery plus-negative plate.
Lithium ion conduction between electrolyte and electrolyte and between electrolyte and positive pole is that the core of solid state battery is asked
Inscribe, the liquid electrolyte containing lithium salts in compound quasi-solid electrolyte of the invention provides good interface wellability.
Another aspect of the present invention is to provide a kind of method for preparing compound quasi-solid electrolyte.
In first embodiment of the method that the present invention prepares compound quasi-solid electrolyte, of the invention is compound accurate solid
State electrolyte is prepared according to following steps：
(1) inorganic nanoparticles, solid electrolyte particle, optional surfactant are added in dispersant, divided
Granular media system；
(2) binding agent is added in the dispersion that step (1) obtains, is well mixed, obtains mixed slurry；To what is obtained
Mixed slurry carries out deaeration processing, and the mixed slurry after optionally deaeration is handled with scraper is scraped in release liners, prepared
Negative or positive electrode surface；It is subsequently placed in vacuum desiccator (such as vacuum drying oven) and dries, obtains compound quasi- solid state electrolysis
Matter butt；
(3) in anhydrous atmosphere or vacuum, add and contain in the compound quasi-solid electrolyte butt obtained to step (2)
The liquid electrolyte of lithium salts, produce compound quasi-solid electrolyte.
Preferably, in the step of preparing first embodiment of compound quasi-solid electrolyte method (1) of the invention, institute
Dispersant is stated as in water, 1-METHYLPYRROLIDONE, acetonitrile, acetone, N,N-dimethylformamide, methanol, ethanol, dimethyl sulfoxide (DMSO)
One or more；Preferably, the gross mass of the inorganic nanoparticles and solid electrolyte particle accounts for dispersant quality
25%~100%.
It is highly preferred that in the step of preparing first embodiment of compound quasi-solid electrolyte method (1) of the invention,
The dispersion obtains under conditions of rotating speed is more than 200rpm, mixing time is 30~60min；Further preferably
Ground, the dispersion obtain under conditions of rotating speed is more than 1000rpm, mixing time is 60~120min.
More preferably, in the step of preparing first embodiment of compound quasi-solid electrolyte method (1) of the invention,
The surfactant is selected from neopelex, sodium alkyl sulfate, pareth sulfate, alkyl polyoxy
One or more in vinethene carboxylic acid sodium, sodium alkyl sulfonate.
Again preferably, in the step of preparing first embodiment of compound quasi-solid electrolyte method (2) of the invention,
The deaeration processing is vacuum defoamation and/or sieving defoaming.
It is further preferred that in the step of preparing first embodiment of compound quasi-solid electrolyte method (2) of the invention,
The drying is carried out at a temperature of less than 90 DEG C.
It is further preferred that in the step of preparing first embodiment of compound quasi-solid electrolyte method of the invention
(3) in, the condition of anhydrous atmosphere is 20 DEG C of temperature, dew point is 30 DEG C~50 DEG C.
In the present invention prepares second embodiment of compound quasi-solid electrolyte method, the compound quasi- solid state electrolysis
Matter is prepared according to following steps：
(1) in anhydrous atmosphere, take inorganic nanoparticles, solid electrolyte particle, the liquid electrolyte containing lithium salts and
Optional surfactant is added in non-aqueous dispersion agent, obtains dispersion；
(2) binding agent is added in the dispersion that step (1) obtains, is well mixed, obtains mixed slurry；To what is obtained
Mixed slurry carries out deaeration processing；It is subsequently placed at the temperature in vacuum desiccator below 50 DEG C and dries to remove non-aqueous point
Powder, obtain compound quasi-solid electrolyte.
Preferably, in the step of preparing second embodiment of compound quasi-solid electrolyte method (1) of the invention, institute
Non-aqueous dispersion agent is stated as the one or more in acetonitrile, acetone, methanol, ethanol, glycol dimethyl ether；It is it is highly preferred that described
The gross mass of inorganic nanoparticles and solid electrolyte particle accounts for the 25%~100% of dispersant quality.
It is highly preferred that in the step of preparing second embodiment of compound quasi-solid electrolyte method (1) of the invention,
The dispersion obtains under conditions of rotating speed is more than 200rpm, mixing time is 30~60min；Further preferably
Ground, the dispersion obtain under conditions of rotating speed is more than 1000rpm, mixing time is 60~120min.
It is further preferred that in the step of preparing second embodiment of compound quasi-solid electrolyte method (1) of the invention,
The surfactant is selected from neopelex, sodium alkyl sulfate, pareth sulfate, alkyl polyoxy
One or more in vinethene carboxylic acid sodium, sodium alkyl sulfonate.
More preferably, in the step of preparing second embodiment of compound quasi-solid electrolyte method (2) of the invention,
The deaeration processing is vacuum defoamation and/or sieving defoaming.
Still further preferably, in the present invention prepares second embodiment of compound quasi-solid electrolyte method, institute
Stating scheme also includes repeatedly rolling the compound quasi-solid electrolyte obtained in step (2) to prepare with certain mechanical performance
Compound quasi-solid electrolyte film the step of.Relative to no mechanical performance, unyielding solid electrolyte powder, the present invention
Compound quasi-solid electrolyte film it is flexible, there is pliability, and there is good ionic conductivity.
The present invention also provides the compound quasi-solid electrolyte film that a kind of the method according to the invention is prepared, wherein described
The thickness of compound quasi-solid electrolyte film is 10~80 μm, preferably 20~50 μm.Consider from battery energy density, it is compound accurate solid
State dielectric film is relatively more reasonable in above-mentioned thickness range.
The compound quasi-solid electrolyte film of the present invention has polymer flexibility (flexible), solid electrolyte hardness, liquid
The electrical conductivity and wellability of electrolyte.The compound quasi-solid electrolyte film of the present invention can effectively suppress the growth of Li dendrite with
And prevent Li dendrite from piercing through barrier film, reduce and further chemically reacted between lithium metal and liquid electrolyte, effectively protection gold
Belong to lithium electrode, while reduce the content of the liquid electrolyte containing lithium salts, effectively improve the security of battery.
It is a further aspect of the present invention to provide a kind of lithium battery or lithium ion battery, lithium battery or the lithium ion battery bag
Include positive pole, negative pole, barrier film；Wherein described barrier film is compound quasi-solid electrolyte film of the invention.
Preferably, in the lithium battery or lithium ion battery of the present invention, the just extremely lithium positive pole；It is it is highly preferred that described
The material of positive pole is selected from LiFePO4, lithium manganese phosphate, lithium ferric manganese phosphate, cobalt phosphate lithium, cobalt acid lithium, lithium nickelate, LiMn2O4, nickel
One or more in cobalt manganic acid lithium, nickel cobalt aluminium lithium, lithium-rich oxide, nickel ion doped.
Preferably, in the lithium battery of the present invention or an embodiment of lithium ion battery, the material of the positive pole is
Manganese oxide, manganous oxide, vanadium oxide, chromium oxide, iron oxide, manganous fluoride, ferric flouride, iron sulfide, fluorographite, graphite oxide,
One or more in sulphur, ferric phosphate.It is highly preferred that in the lithium battery or lithium ion battery of the present invention, the positive pole also wraps
Include binding agent, electronic conductive additive and compound quasi-solid electrolyte of the present invention；Or the present invention's is compound accurate solid
State electrolyte preparation process oxide-free solid electrolyte or sulfide solid electrolyte.In view of energy density and power
Density, it is highly preferred that the mass percent of the lithium storage materials in positive pole is calculated as 60%~95% by positive pole gross mass；It is compound accurate solid
The mass percent of state electrolyte is 5%~40%, and the mass percent of electronic conductive additive is 0.5%~10%, is bonded
The mass percent of agent is 1%~10%.
More preferably, in the lithium battery or lithium ion battery of the present invention, the negative pole is for cathode of lithium or without cathode of lithium.
Preferably, the cathode of lithium is lithium metal active film, lithium alloy active film and formed by the compound containing lithium metal
Active film.It is highly preferred that the lithium alloy is in lithium-aluminium alloy, lithium magnesium alloy, lithium boron alloy, Li-Si alloy, lithium-tin alloy
One or more.Or it is highly preferred that the compound containing lithium metal be metallic lithium powder or lithium piece with carbon, silicon, aluminium, copper,
Tin formed physical mixture, or the compound containing lithium metal be lithium copper nitrogen, lithium iron nitrogen, lithium manganese nitrogen, lithium cobalt nitrogen,
Li7MP3(M=Ti, V or Mn).The lithium metal active film can directly using or be compressed on the paper tinsel, net, porous thin of conduction
On film, wherein the material of the conductive paper tinsel, net, porous membrane includes carbon, copper, titanium, stainless steel, nickel etc..
It is further preferred that the cathode of lithium that is free of is native graphite, Delanium, soft carbon, hard carbon, silicon, germanium, lithium titanate
In one or more.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM) of the quasi-solid electrolyte film of the Plays group 1 of the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of the quasi-solid electrolyte film of the Plays group 2 of the embodiment of the present invention 1；
Fig. 3 is the scanning electron microscope (SEM) photograph (SEM) of the quasi-solid electrolyte film of the Plays group 3 of the embodiment of the present invention 1；
Fig. 4 is the picture of the quasi-solid electrolyte film of the Plays group 2 of the embodiment of the present invention 1；
Fig. 5 is the scanning electron microscope (SEM) photograph (SEM) of the compound quasi-solid electrolyte film of control group 1 in the embodiment of the present invention 2；
Fig. 6 is the scanning electron microscope (SEM) photograph (SEM) of the compound quasi-solid electrolyte film of control group 2 in the embodiment of the present invention 2；
Fig. 7 is the scanning electron microscope (SEM) photograph (SEM) of the compound quasi-solid electrolyte film of control group 3 in the embodiment of the present invention 2；
Fig. 8 is the picture of the compound quasi-solid electrolyte film of control group 2 in the embodiment of the present invention 2；
Fig. 9 is Li in the embodiment of the present invention 21.5Al0.5Ge1.5(PO4)3The picture of solid electrolyte powder；
Figure 10 shows the electrical conductivity of the quasi-solid electrolyte film of embodiment 1 and the compound quasi-solid electrolyte film of embodiment 2
Variation with temperature situation；
Figure 11 is the room temperature discharge and recharge of the LiMn2O4 of the composite membrane quasi-solid electrolyte film of the control group 1 of the embodiment of the present invention 2
Curve map；
Figure 12 shows the electrical conductivity of the quasi-solid electrolyte film of embodiment 1 and the compound quasi-solid electrolyte film of embodiment 3
Variation with temperature situation；
Below by accompanying drawing and specific embodiment, technical scheme is further described.
Embodiment
In the examples below, used material is as follows：
Solid electrolyte particle 1：Li1.5Al0.5Ge1.5(PO4)3；Solid electrolyte particle 2：Li0.5La0.5TiO3；Solid electricity
Solve matter particle 3：LiZr0.5Ti1.5(PO4)3；Solid electrolyte particle 4：Li1.4Al0.4Ti1.6(PO4)3；Solid electrolyte particle 5：
Li3.5Ge0.5P0.5S4；Solid electrolyte particle 6：Li6.75La3Zr1.75Ta0.25O12；Solid electrolyte particle 7：
Li6.75La3Zr1.75Nb0.25O12；Solid electrolyte particle 8：Li6.85Al0.05La3Zr2O12。
Inorganic nanoparticles 1：Aluminum oxide；Inorganic nanoparticles 2：Nano silicon；Inorganic nanoparticles 3：10A molecules
Sieve；Inorganic nanoparticles 4：Lithium magnesium silicate；Inorganic nanoparticles 5：Aluminium-magnesium silicate；Inorganic nanoparticles 6：Titanium dioxide；It is inorganic
Nano particle 7：Zinc oxide.
Lithium salts 1：LiPF6；Lithium salts 2：LiN(CF3SO2)2；Lithium salts 3：LiBF4；Lithium salts 4：LiClO4；Lithium salts 5：LiCF3SO3；
Lithium salts 6：Li(CF3SO2)3；Lithium salts 7：LiNO3；Lithium salts 8：LiAsF6；Lithium salts 9：LiBOB.
Binding agent 1：Vingon (PVDF)；Binding agent 2：Vingon-hexafluoropropene (PVDF-HFP)；Binding agent
3：Polytetrafluoroethylene (PTFE) (PTFE)；Binding agent 4：Polyethylene glycol oxide；Binding agent 5：Polyester；Binding agent 6：Polyamide；Binding agent 7：It is poly-
Methyl methacrylate；Binding agent 8：Makrolon；Binding agent 9：Carboxymethyl cellulose；Binding agent 10：Styrene-butadiene is total to
Polymers；Binding agent 11：Polyacrylonitrile；Binding agent 12：Sodium carboxymethylcellulose；Binding agent 13：Sodium carboxymethylcellulose: benzene second
Alkene-butadiene rubber=1: 1.
Solvent 1：EC；Solvent 2：PC；Solvent 3：DEC；Solvent 4：DMC；Solvent 5：PP13TFSI；Solvent 6：PYR13TFSI；
Solvent 7：TEGDME (TRIGLYME)；Solvent 8：EC: DEC=1: 1；Solvent 9：EC: DMC=1: 1；Solvent 10：EC∶
DEC=1: 1.
Positive electrode 1：Cobalt acid lithium；Positive electrode 2：LiFePO4；Positive electrode 3：LiMn2O4；Positive electrode 4：Nickel cobalt manganese
Sour lithium；Positive electrode 5：Nickel cobalt lithium aluminate；Positive electrode 6：Lithium-rich oxide；Positive electrode 7：Nickel ion doped；Positive pole material
Material 8：MnO2；Positive electrode 9：FeS2；Positive electrode 10：FeF3；Positive electrode 11：S；Positive electrode 12：Ferric phosphate；Positive pole material
Material 13：Manganese phosphate；Positive electrode 14：O2；Positive electrode 15：O2+CO2。
Negative pole 1：Lithium metal；Negative pole 2：Lithium-aluminium alloy；Negative pole 3：Lithium magnesium alloy；Negative pole 4：Lithium boron alloy；Negative pole 5：Lithium/stone
Black compound；Negative pole 6：Lithium/oxidation Asia silicon compound；Negative pole 7：Lithium/nano-silicon is compound.
In following each embodiment, the G3 in LiG3TFSI represents TEGDME (TRIGLYME).LiG3TFSI
It is to pass through the material ratio of LiTFSI: G3=1: 1 (mol ratio) to prepare.
For the ease of distinguishing, the quasi-solid electrolyte in example 1 below -3 refers to by inorganic nanoparticles (such as nanometer
Aerosil), the quasi-solid electrolyte that is prepared of the liquid electrolyte containing lithium salts and binding agent, the quasi-solid electrolyte
Without solid electrolyte；And compound quasi-solid electrolyte is then by solid electrolyte, inorganic nanoparticles (such as nano-gas-phase dioxy
SiClx), the liquid electrolyte containing lithium salts and binding agent be prepared.
Embodiment 1
It is added without the comparative example of solid electrolyte
In the present embodiment, quasi-solid electrolyte film is prepared using second embodiment of the inventive method, still
In this comparative example, solid electrolyte is not added.Specially in 20 DEG C of temperature, dew point is to be made under 30 DEG C~50 DEG C of anhydrous atmosphere
Standby quasi-solid electrolyte film.In this comparative example, using the composition and content listed in standard group 1, standard group 2 and standard group 3,
Prepare three kinds of quasi-solid electrolyte films for being free of solid electrolyte.
Standard group 1：3.3g nano fumed silicas (particle diameter 7nm), 4.48g LiG3TFSI and binding agent PTFE powder
Body (0.324g)；Wherein, based on the gross mass of quasi-solid electrolyte composition, LiG3TFSI mass fraction is (corresponding for 55.28%
Volume fraction be 70%；The volume fraction is counted using the volume sum of each composition before mixing as 100%, similarly hereinafter)；
Standard group 2：4.4g nano fumed silicas (particle diameter 7nm), 3.84g LiG3TFSI and binding agent PTFE powder
Body (0.34g)；Wherein, based on the gross mass of quasi-solid electrolyte composition, LiG3TFSI mass fraction is (corresponding for 44.7%
60%) volume fraction is；
Standard group 3：5.5g nano fumed silicas (particle diameter 7nm), 3.2g LiG3TFSI and binding agent PTFE powders
(0.36g)；Wherein, based on the gross mass of quasi-solid electrolyte composition, LiG3TFSI mass fraction is (corresponding for 35.32%
50%) volume fraction is.
The composition of standard group 1, standard group 2, standard group 3 is added in methanol (15g) respectively, the mixture that then will be obtained
90min is stirred with 400rpm rotating speed by magneton.After stirring the mixture for uniformly, mixture is defoamed with screen filtration, then
It is placed in vacuum drying oven and is incubated 3 hours at a temperature of 50 DEG C, is volatilized methanol solvate, and three kinds of quasi- solid state electrolysises are prepared through rolling
Plasma membrane.
Electron-microscope scanning is carried out to the obtained quasi-solid electrolyte film for not adding solid electrolyte, obtains respective scanning electricity
Mirror figure.
Wherein, Fig. 1 shows the scanning electron microscope (SEM) photograph (SEM) of the quasi-solid electrolyte film in standard group 1.
Fig. 2 shows the scanning electron microscope (SEM) photograph (SEM) of the quasi-solid electrolyte film in standard group 2.
Fig. 3 shows the scanning electron microscope (SEM) photograph (SEM) of the quasi-solid electrolyte film in standard group 3.
Schemed from the SEM in Fig. 1-3, with the increase of solids content, the contact between nano fumed silica becomes
Difference, the electrical conductivity for the quasi-solid electrolyte film for causing to obtain reduce.
Fig. 4 shows the quasi-solid electrolyte film of standard group 2.From fig. 4, it can be seen that the standard being prepared according to embodiment is consolidated
State dielectric film has mechanical flexibility.
Embodiment 2
In the present embodiment, compound quasi-solid electrolyte film is prepared using second embodiment of the inventive method,
In the present embodiment, solid electrolyte is added in compound quasi-solid electrolyte.Specially in 20 DEG C of temperature, dew point is 30 DEG C
Compound quasi-solid electrolyte film is prepared under~50 DEG C of anhydrous atmosphere.In the present embodiment, using control group 1, control group 2 and right
According to the composition and content listed in group 3, three kinds of compound quasi-solid electrolyte films for including solid electrolyte are prepared.
Control group 1 (standard group 1 corresponded in embodiment 1)：2.2g nano fumed silicas (particle diameter 7nm),
5.12g LiG3TFSI, 2.5g Li1.5Al0.5Ge1.5(PO4)3, binding agent PTFE powders (0.41g).By compound quasi- solid state electrolysis
The gross mass meter of matter composition, the mass fraction that the mass fraction of nano fumed silica is 21%, LiG3TFSI is 50% (right
The volume fraction answered is 70%) Li1.5Al0.5Ge1.5(PO4)3Mass fraction be 25%, the quality of binding agent PTFE powders point
Number is 4%.
Control group 2 (standard group 2 corresponded in embodiment 1)：2.2g nano fumed silicas (particle diameter 7nm),
5.12g LiG3TFSI, 5.8g Li1.5Al0.5Ge1.5(PO4)3, binding agent PTFE powders (0.55g).By compound quasi- solid state electrolysis
The gross mass meter of matter composition, the mass fraction that the mass fraction of nano fumed silica is 16%, LiG3TFSI is 37.5%
(corresponding volume fraction is 60%), Li1.5Al0.5Ge1.5(PO4)3Mass fraction be 42.5%, the matter of binding agent PTFE powders
It is 4% to measure fraction.
Control group 3 (standard group 3 corresponded in embodiment 1)：2.2g nano fumed silicas (particle diameter 7nm),
5.12g LiG3TFSI, 10.5g Li1.5Al0.5Ge1.5(PO4)3, binding agent PTFE powders (0.74g).By compound quasi- solid state electrolysis
The gross mass meter of matter composition, the mass fraction that the mass fraction of nano fumed silica is 12%, LiG3TFSI is 28% (right
The volume fraction answered is 50%) Li1.5Al0.5Ge1.5(PO4)3Mass fraction be 56%, the quality of binding agent PTFE powders point
Number is 4%.
The composition of control group 1, control group 2, control group 3 is added in methanol (30g) respectively, by magneton with 400rpm's
Rotating speed stirs 90min.After stirring the mixture for uniformly, screen filtration defoaming, it is subsequently placed in vacuum drying oven in 50 DEG C of temperature
Lower insulation 3 hours, volatilized methanol solvate, and three kinds of compound quasi-solid electrolyte films are prepared through rolling.
Electron-microscope scanning is carried out to obtained compound quasi-solid electrolyte film, obtains respective scanning electron microscope (SEM) photograph.
Wherein, Fig. 5 shows the scanning electron microscope (SEM) photograph (SEM) of the compound quasi-solid electrolyte film of control group 1.
Fig. 6 shows the scanning electron microscope (SEM) photograph (SEM) of the compound quasi-solid electrolyte film of control group 2.
Fig. 7 shows the scanning electron microscope (SEM) photograph (SEM) of the compound quasi-solid electrolyte film of control group 3.
Fig. 8 shows the compound quasi-solid electrolyte film of control group 2.As can be seen from Figure 8, solid electricity is added in preparation process
After solving matter, the compound quasi-solid electrolyte film of control group 2 also has mechanical flexibility.
Fig. 9 shows Li1.5Al0.5Ge1.5(PO4)3Solid electrolyte powder.
Simple solid electrolyte powder is can be seen that by Fig. 8 and Fig. 9 comparison without mechanical performance (not have
Have pliability), such solid electrolyte powder can not directly make solid state battery；And the compound quasi- solid state electrolysis of control group 2
Plasma membrane has good mechanical flexibility, can stop Li dendrite.
Although the content that the liquid electrolyte containing lithium salts is can be seen that by two groups of SEM in example 1 and embodiment 2 drops
It is low, but the contact between inorganic nanoparticles is not deteriorated.Inorganic nanoparticles are filled in Li1.5Al0.5Ge1.5(PO4)3It
Between, serve connection Li1.5Al0.5Ge1.5(PO4)3Effect and serve as Li1.5Al0.5Ge1.5(PO4)3Between bridge.
Figure 10 shows the electrical conductivity of the quasi-solid electrolyte film of embodiment 1 and the compound quasi-solid electrolyte film of embodiment 2
Situation about varying with temperature.
Found by testing, although the volume fraction of the liquid electrolyte LiG3TFSI containing lithium salts is constant (that is, in embodiment
In 1 quasi-solid electrolyte and the compound quasi-solid electrolyte film of embodiment 2, respectively 70%, 60%, 50%), but add
The electrical conductivity of the compound quasi-solid electrolyte (embodiment 2) of solid electrolyte is not apparently higher than to add the standard of solid electrolyte
Solid electrolyte (embodiment 1).When the liquid electrolytic liquid hold-up containing lithium salts in compound quasi-solid electrolyte film be reduced to according to
Mass fraction meter 29% when (volume fraction keeps constant, still for 50%), the electricity of compound quasi-solid electrolyte film at room temperature
Conductance is up to 10-4S/cm.The contribution of electrical conductivity comes from inorganic nanoparticles, the liquid electrolyte containing lithium salts and solid electrolytic
Matter.And the electrical conductivity of the quasi-solid electrolyte film in the standard group of embodiment 1 only has 10-5S/cm, reason are the standard group of embodiment 1
In quasi-solid electrolyte film be free of solid electrolyte, the contribution of its electrical conductivity is only from inorganic nanoparticles and containing lithium salts
Liquid electrolyte；When the content of the liquid electrolyte containing lithium salts is reduced, electrical conductivity will reduce.By contrast, it is of the invention
Compound quasi-solid electrolyte in the electrical conductivity of solid electrolyte do not influenceed by the liquid electrolytic liquid hold-up of saliferous lithium, therefore
The total conductivity of the compound quasi-solid electrolyte of the embodiment of the present invention 2 is higher than in the standard group of embodiment 1 without solid electrolyte
Quasi-solid electrolyte.
Being assemblied in the glove box filled with argon gas for simulated battery is carried out, and the numbering of compound quasi-solid electrolyte film is table 1
In composite membrane 1, just extremely lithium manganate cathode is lithium metal to electrode.
Constant current charge-discharge pattern test, charge cutoff voltage 4.2V are carried out using discharge and recharge instrument, discharge cut-off voltage is
3.0V, test and carried out under C/10 current densities, test temperature is 25 DEG C.
Tested with tester, obtain discharge and recharge 1 week, 15 weeks, 30 weeks, 45 weeks Posterior circle curve maps, as shown in figure 11.
Embodiment 3
The preparation method of the compound quasi-solid electrolyte film of the present embodiment is same as Example 2.
Control group 4：2.2g nano fumed silicas (particle diameter 7nm), 5.12g LiG3TFSI, 3.5g
Li6.75La3Zr1.75Ta0.25O12, binding agent PTFE powders (0.45g).Based on the gross mass of compound quasi-solid electrolyte composition, receive
The mass fraction that the mass fraction of rice aerosil is 19.5%, LiG3TFSI is 45%, and (corresponding volume fraction is
70%), Li6.75La3Zr1.75Ta0.25O12Mass fraction be 31.5%, the mass fractions of binding agent PTFE powders is 4%.
Control group 5：2.2g nano fumed silicas (particle diameter 7nm), 5.12g LiG3TFSI, 8.2g
Li6.75La3Zr1.75Ta0.25O12, binding agent PTFE powders (0.646g).Based on the gross mass of compound quasi-solid electrolyte composition,
The mass fraction that the mass fraction of nano fumed silica is 13.6%, LiG3TFSI is 31.7% (corresponding volume fraction
For 60%), Li6.75La3Zr1.75Ta0.25O12Mass fraction be 50.7%, the mass fractions of binding agent PTFE powders is 4%.
Control group 6：2.2g nano fumed silicas (particle diameter 7nm) 5.12g LiG3TFSI, 15g
Li6.75La3Zr1.75Ta0.25O12, binding agent PTFE powders (0.74g).Based on the gross mass of compound quasi-solid electrolyte composition, receive
The mass fraction that the mass fraction of rice aerosil is 9.5%, LiG3TFSI is 22%, and (corresponding volume fraction is
50%), Li6.75La3Zr1.75Ta0.25O12Mass fraction be 64.5%, the mass fractions of binding agent PTFE powders is 4%.
The composition of control group 4 to 6 is added in methanol (30g) respectively, stirred by magneton with 400rpm rotating speed
90min.After stirring the mixture for uniformly, screen filtration defoaming, it is small that the insulation 3 at a temperature of 50 DEG C is subsequently placed in vacuum drying oven
When, volatilized methanol solvate, and compound quasi-solid electrolyte film is prepared through rolling.
Figure 12 shows the electricity of the quasi-solid electrolyte film of above-described embodiment 1 and the compound quasi- solid state electrolysis film of embodiment 3
The situation that conductance varies with temperature.
By test it was found that although the volume fraction of the liquid electrolyte containing lithium salts is constant, compound quasi- solid-state
The electrical conductivity of electrolyte (embodiment 3) is apparently higher than quasi-solid electrolyte (standard group of embodiment 1).According to mass fraction meter, when
When the content of the liquid electrolyte containing lithium salts in compound quasi-solid electrolyte film is reduced to 22%, compound quasi- solid-state is electric at room temperature
The electrical conductivity for solving matter is still up to 10-4S/cm；And the electrical conductivity of the quasi-solid electrolyte of the standard group of embodiment 1 only has 10-5S/
cm.The contribution of quasi-solid electrolyte electrical conductivity receives particle and liquid electrolyte containing lithium salts only from inorganic, when containing lithium salts
When liquid electrolyte is reduced, electrical conductivity will be reduced.And the electricity of the solid electrolyte in the compound quasi-solid electrolyte of the present invention
Conductance is not influenceed by the liquid electrolytic liquid hold-up of saliferous lithium, therefore the total conductivity of compound quasi-solid electrolyte is higher than embodiment
Quasi-solid electrolyte in 1 standard group.
Embodiment 4 is to embodiment 43
The compound quasi-solid electrolyte film that table 1 below provides the embodiment of the present invention 4 to embodiment 43 (referred to as " is answered in table 1
Close film ") composition and electrical conductivity.
Table 1
The compound quasi-solid electrolyte into embodiment 43 of embodiment 4 is respectively provided with high conductance, reaches practical level.
Embodiment 44 to embodiment 92 in table 2 below provides the battery for including the compound quasi-solid electrolyte film of the present invention
Composition and its running parameter.
Table 2
Above example has carried out further details of explanation to the purpose of the present invention, technical scheme and beneficial effect.Should
When understanding, embodiments of the invention are the foregoing is only, the protection domain being not intended to limit the present invention.It is all in the present invention
Spirit and principle within any modification, equivalent substitution and improvements done etc., should be included in protection scope of the present invention it
It is interior.
Claims (10)
1. a kind of compound quasi-solid electrolyte, it is characterised in that the compound quasi-solid electrolyte includes solid electrolyte, containing lithium salts
Liquid electrolyte, inorganic nanoparticles and binding agent；
Preferably, the compound quasi-solid electrolyte also includes surfactant；The surfactant is preferably selected from 12
Sodium alkyl benzene sulfonate, sodium alkyl sulfate, pareth sulfate, Alkyl ethoxy carboxylate acid sodium, sodium alkyl sulfonate
In one or more.
2. compound quasi-solid electrolyte according to claim 1, it is characterised in that the inorganic nanoparticles be selected from
Al2O3、SiO2、MgO、CaO、TiO2、ZnO、ZrO2、Y2O3、BaTiO3, 3A molecular sieves, 4A molecular sieves, 5A molecular sieves, 10X molecules
Sieve, 13A molecular sieves, 13X-AGP molecular sieves, ZSM-5 molecular sieve, lithium magnesium silicate, aluminium-magnesium silicate, one kind in montmorillonite or more
Kind；
Preferably, the particle diameter of the inorganic nanoparticles is 0.1nm~1000nm；More preferably 0.1nm~100nm；Further preferably
Ground, inorganic nanoparticles mass fraction shared in compound quasi-solid electrolyte are 10%~60%, further preferably
For 10%~50%.
3. compound quasi-solid electrolyte according to claim 1, it is characterised in that the solid electrolyte is sulfide electricity
Solve matter or oxide electrolyte；
Preferably, the sulfide electrolyte is selected from Li10GeP2S12、Li3.25Ge0.25P0.75S4、Li3PS4、Li3Zn0.5GeS4、
Li3.4Si0.4P0.6S4、Li7P3S11In one or more, the oxide electrolyte be selected from Li1+xAlxGe2-x(PO4)3、
Li3yLa2/3-yTiO3、LiZr2-zTiz(PO4)3、Li1+mAlmTi2-m(PO4)3、Li7-2n-jAnLa3Zr2-jBjO12、Li7-2n- 2jAnLa3Zr2-jCjO12In one or more；Wherein, 0≤x≤2,0≤y≤2/3,0≤z≤2,0≤m≤2,0≤n≤3,0
≤ j≤2, A are Ge and/or Al, B are Nb and/or Ta, C are Te and/or W；
It is highly preferred that the solid electrolyte is particle form, its average grain diameter is 10~10000nm；
More preferably, the mass fraction that the solid electrolyte accounts for compound quasi-solid electrolyte is 10%~80%, more preferably
20%~70%.
4. compound quasi-solid electrolyte according to claim 1, it is characterised in that the liquid electrolyte bag containing lithium salts
Containing solvent, the solvent is selected from methyl ethyl carbonate, gamma-valerolactone, γ-fourth lactones, dimethyl carbonate, propene carbonate, carbonic acid
Diethylester, ethylene carbonate, glycol dimethyl ether, diethylene glycol dimethyl ether, TRIGLYME, tetraethyleneglycol dimethyl ether,
1,3- dioxolanes, tetrahydrofuran, P13TFSI, N- methyI-oropvD piperidines-two (trimethyl fluoride sulfonyl) inferior amine salt, N- methyl-
Butyl piperidine-two (trimethyl fluoride sulfonyl) inferior amine salt, N- methyl-butvls pyrroles-two (trimethyl fluoride sulfonyl) inferior amine salt, N- first
One or more in base-propyl pyrrole-two (trimethyl fluoride sulfonyl) inferior amine salt；
Preferably, the liquid electrolyte containing lithium salts also includes boundary moisture agent, flame-retardant additive, film for additive or its group
Close；It is further preferred that the boundary moisture agent is fluoro-ether, the flame-retardant additive is phosphate, the film for additive
For selected from ethylene sulfite, propylene sulfite, vinylene carbonate, dimethyl sulfite, diethyl sulfite, 1,
One or more in 2- trifluoroacetic acid bases ethane, ethylene carbonate vinylene, fluorinated ethylene carbonate；
It is highly preferred that the liquid electrolyte containing lithium salts includes lithium salts, the lithium salts is selected from lithium hexafluoro phosphate, tetrafluoro boric acid
Lithium, lithium perchlorate, hexafluoroarsenate lithium, trifluoromethyl sulfonic acid lithium, double (trimethyl fluoride sulfonyl sub-) amine lithiums, double fluorine sulfimide lithiums,
One or more in di-oxalate lithium borate, lithium nitrate；
More preferably, the concentration of the lithium salts in the liquid electrolyte containing lithium salts is calculated as by the liquid electrolyte containing lithium salts
0.1mol/L~5mol/L, more preferably 0.5mol/L~1.5mol/L；
It is further preferred that the liquid electrolyte containing lithium salts account for the mass fraction of compound quasi-solid electrolyte for 5%~
60%, more preferably 15%~50%.
5. compound quasi-solid electrolyte according to claim 1, it is characterised in that the binding agent is selected from poly- inclined chloroethene
It is alkene, Vingon-hexafluoropropene, polytetrafluoroethylene (PTFE), polyethylene glycol oxide, polyester, polyamide, polymethyl methacrylate, poly-
One or more in carbonic ester, carboxymethyl cellulose, SB, polyacrylonitrile；It is it is highly preferred that described
The quality summation of inorganic nanoparticles and solid electrolyte is 60: 40 to 99.5: 0.5 with the binding agent mass ratio.
A kind of 6. method for preparing the compound quasi-solid electrolyte any one of claim 1 to 5, it is characterised in that institute
The method of stating comprises the following steps：
(1) inorganic nanoparticles, solid electrolyte particle and optional surfactant are added in dispersant, divided
Granular media system；
(2) binding agent is added in the dispersion that step (1) obtains, is well mixed, obtains mixed slurry；Mixing to obtaining
Slurry carries out deaeration processing, and the mixed slurry after optionally deaeration is handled with scraper is scraped in release liners, prepared just
Pole or the surface of negative pole；It is subsequently placed in vacuum desiccator and dries, obtains compound quasi-solid electrolyte butt；
(3) in anhydrous atmosphere, the liquid electrolytic containing lithium salts is added in the compound quasi-solid electrolyte butt obtained to step (2)
Liquid, produce compound quasi-solid electrolyte；
Preferably, in step (1), the dispersant is water, 1-METHYLPYRROLIDONE, acetonitrile, acetone, N, N- dimethyl formyls
One or more in amine, methanol, ethanol, dimethyl sulfoxide (DMSO)；It is highly preferred that the inorganic nanoparticles and solid electrolyte
The gross mass of grain accounts for the 25%~100% of dispersant quality；
It is highly preferred that in step (1), the dispersion be rotating speed be more than 200rpm, mixing time be 30~60min
Under conditions of obtain；It is highly preferred that the dispersion be rotating speed be more than 1000rpm, mixing time be 60~
Obtained under conditions of 120min；
Again preferably, in step (1), the surfactant is selected from neopelex, sodium alkyl sulfate, alkyl
One or more in polyethenoxy ether sodium sulfate, Alkyl ethoxy carboxylate acid sodium, sodium alkyl sulfonate；
More preferably, in step (2), the deaeration processing is vacuum defoamation and/or sieving defoaming；
It is further preferred that in step (2), the drying is carried out at a temperature of less than 90 DEG C；
It is further preferred that in step (3), the condition of the anhydrous atmosphere is 20 DEG C of temperature, dew point is 30 DEG C to 50 DEG C.
A kind of 7. method for preparing the compound quasi-solid electrolyte any one of claim 1 to 5, it is characterised in that institute
The method of stating comprises the following steps：
(1) in anhydrous atmosphere, take inorganic nanoparticles, solid electrolyte particle, the liquid electrolyte containing lithium salts and optionally
Surfactant be added in non-aqueous dispersion agent, obtain dispersion；
(2) binding agent is added in the dispersion that step (1) obtains, after being well mixed, obtained mixed slurry is taken off
Bubble processing, it is subsequently placed at the temperature in vacuum desiccator below 50 DEG C and dries, obtain compound quasi-solid electrolyte；
Preferably, in step (1), the condition of the anhydrous atmosphere is 20 DEG C of temperature, dew point is 30 DEG C to 50 DEG C；
It is highly preferred that in step (1), the non-aqueous dispersion agent is in acetonitrile, acetone, methanol, ethanol, glycol dimethyl ether
One or more；Preferably, the gross mass of the inorganic nanoparticles and solid electrolyte particle accounts for dispersant quality
25%~100%；
More preferably, in step (1), the dispersion be rotating speed be more than 200rpm, mixing time be 30~60min
Under conditions of obtain；It is highly preferred that it is described it is scattered be rotating speed be more than 1000rpm, mixing time be 60~120min
Under the conditions of obtain；
Again preferably, in step (1), the surfactant is selected from neopelex, sodium alkyl sulfate, alkyl
One or more in polyethenoxy ether sodium sulfate, Alkyl ethoxy carboxylate acid sodium, sodium alkyl sulfonate；
It is further preferred that in step (2), the deaeration processing is vacuum defoamation and/or sieving defoaming；
It is further preferred that in step (2), the dry progress 3 hours；
Still further preferably, methods described also includes multiple by the compound quasi-solid electrolyte that will be obtained in step (2)
The step of rolling is to prepare compound quasi-solid electrolyte film.
8. compound quasi-solid electrolyte film prepared by a kind of method according to claim 6 or 7, it is characterised in that described
The thickness of compound quasi-solid electrolyte film is 10~80 μm, preferably 20~50 μm.
9. a kind of lithium battery or lithium ion battery, the lithium battery or lithium ion battery include positive pole, negative pole and barrier film, its feature
It is, the compound quasi-solid electrolyte film that the barrier film is prepared for the method according to claim 6 or 7；Or the barrier film
For the compound quasi-solid electrolyte film described in claim 8；
Preferably, the just extremely lithium positive pole；It is highly preferred that the material of the positive pole is selected from LiFePO4, lithium manganese phosphate, phosphorus
Sour ferrimanganic lithium, cobalt phosphate lithium, cobalt acid lithium, lithium nickelate, LiMn2O4, nickle cobalt lithium manganate, nickel cobalt aluminium lithium, lithium-rich oxide, nickel
One or more in LiMn2O4；
It is highly preferred that the material of the positive pole be selected from manganese oxide, manganous oxide, vanadium oxide, chromium oxide, iron oxide, manganous fluoride,
One or more in ferric flouride, iron sulfide, fluorographite, graphite oxide, sulphur, ferric phosphate；
More preferably, the positive pole also includes the compound standard described in binding agent, electronic conductive additive and claim 1 or 2
One or more in solid electrolyte；It is highly preferred that the mass percent of the lithium storage materials in positive pole is based on positive pole gross mass
For 60%~95%；The mass percent of compound quasi-solid electrolyte is 5%~40%, the quality percentage of electronic conductive additive
Than being 1%~10% for the mass percent of 0.5%~10%, binding agent；
It is further preferred that the negative pole is for cathode of lithium or without cathode of lithium；It is highly preferred that the cathode of lithium is that lithium metal activity is thin
Film, lithium alloy active film and the active film formed by the compound containing lithium metal；More preferably, the lithium alloy is
One or more in lithium-aluminium alloy, lithium magnesium alloy, lithium boron alloy, Li-Si alloy, lithium-tin alloy；It is it is further preferred that described
Compound containing lithium metal is the physical mixture that metallic lithium powder or lithium piece are formed with carbon, silicon, aluminium, copper, tin；It is or described containing gold
The compound for belonging to lithium is lithium copper nitrogen, lithium iron nitrogen, lithium manganese nitrogen, lithium cobalt nitrogen, Li7MP3, wherein M=Ti, V or Mn；Still further preferably
Ground, the lithium metal active film are compressed on the paper tinsel of conduction, net, on porous membrane, wherein the conductive paper tinsel, net, porous thin
One or more of the material of film in carbon, copper, titanium, stainless steel, nickel；
It is further preferred that the cathode of lithium that is free of is in native graphite, Delanium, soft carbon, hard carbon, silicon, germanium, lithium titanate
It is one or more kinds of.
10. the answering in lithium battery or lithium ion battery of the compound quasi-solid electrolyte any one of claim 1 to 5
With.
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