CN107346834A - Without lithium salts addition composite solid electrolyte material, dielectric film and preparation method thereof - Google Patents
Without lithium salts addition composite solid electrolyte material, dielectric film and preparation method thereof Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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Abstract
The present invention relates to without lithium salts addition composite solid electrolyte material, dielectric film and preparation method thereof, including polymeric matrix material and fast-ionic conductor powder body material, the chemical formula of the fast ion conducting material is Li7‑xLa3Zr2‑xMxO12, wherein M is at least one of Al, Ta, Nb, W, Ga, Y, Te, and 0≤x≤1, the composite solid electrolyte material does not include lithium salts.The present invention is not both no any type of lithium salts of addition in polymer compared with other composite solid electrolytes maximum, and its conductivity at room temperature can reach 10 on this condition‑4 S cm‑1.Composite solid electrolyte film in the present invention is when applied to lithium secondary battery, in room temperature（25℃）With 60 DEG C at have good cycle performance and high rate performance.
Description
Technical field
The present invention relates to a kind of macroion conductance composite solid electricity without lithium salts addition that can be applied to all solid lithium secondary battery
Material, dielectric film and preparation method thereof are solved, belongs to cell art.
Background technology
As the green high-capacity battery of a new generation, lithium secondary battery has that weight is small, energy density is high, have extended cycle life,
The advantages such as operating voltage height, memory-less effect, non-environmental-pollution, are widely used to mobile phone, notebook computer, video camera etc.
In portable electric appts, and following electric automobile and the preferable electrical source of power of mixed type electric automobile, there is wide answer
With prospect and huge economic benefit.
Electrolyte is the carrier of lithium ion transmission in lithium secondary battery system, is that can system crucial group of normal operation
Into part.Widely used lithium secondary battery mainly uses organic liquid electrolytes in the market, has inflammable and explosive, electrochemical
Learn that window is relatively low, the problems such as operating temperature range is small, the not only use to lithium secondary battery brings potential safety hazard, while also without
Method meets the following requirement for stablizing energy storage to the high-energy-density of lithium secondary battery, in wider operating temperature range.
The use of the composite solid electrolyte of the high ionic conductivity of tool is the excellent approach to solve the above problems.With organic liquor
State electrolyte phase ratio, composite solid electrolyte can effectively slow down the growth of Li dendrite due to the presence of polymeric matrix, have more preferable
Security and machining property.The addition of inorganic powder material makes composite solid electrolyte have higher electrochemical window simultaneously
And heat endurance, the working environment that high-voltage anode material and adaptive temperature can be adapted to change greatly.
Current existing composite solid electrolyte is the solid electrolyte that with the addition of lithium salts.Although the addition of lithium salts is advantageous to
The ionic conductance of electrolyte is improved, but lithium salts can make polymer decrystallized with the crosslinking before polymer or coupled reaction, so as to drop
The fusing point of low polymer, and then have impact on the operating temperature range of electrolyte.In addition, the addition of lithium salts can make polymeric matrix by
One ion insulator phase transition is ion conductor, when charge and discharge cycles to a certain extent when, lithium ion can deposit, and gradually
Li dendrite is grown, final electrolyte can fail because of penetrating for Li dendrite.Therefore, there is an urgent need to research and develop one kind without lithium salts to add
Add, macroion conductance, operating temperature range is wide, can suppress the composite solid electrolyte of lithium dendrite growth.
The content of the invention
The problem of existing for prior art, it is an object of the invention to provide one kind without lithium salts addition, macroion conductance,
Operating temperature range is wide, can suppress lithium dendrite growth composite solid electrolyte material, dielectric film and preparation method thereof and
Lithium secondary battery containing the dielectric film.
In a first aspect, the present invention provides a kind of composite solid electrolyte material, it is characterised in that including polymeric matrix material
Material and fast-ionic conductor powder body material, the chemical formula of the fast ion conducting material is Li7-xLa3Zr2-xMxO12, wherein M is
At least one of Al, Ta, Nb, W, Ga, Y, Te, 0≤x≤1, the composite solid electrolyte material do not include lithium
Salt.
The composite solid electrolyte material of the present invention is in the charge and discharge process of battery, the Li in fast-ionic conductor inorganic particle+
Movement is quickly conducted in the powder granule and particle of mutual UNICOM and the interface of polymer, so as to conduct Li+.The present invention exists
Any type of lithium salts is not added in polymer, lithium is difficult that deposition forms Li dendrite in polymeric matrix, therefore is not susceptible to interior
Portion's short circuit, there is higher security when applied to lithium secondary battery, and between fast-ionic conductor inorganic particle and polymer not
It can crosslink or couple, polymer can be avoided decrystallized, therefore operating temperature range is wide.Meanwhile composite solid of the invention
State electrolyte still keeps excellent ionic conductivity, its at room temperature ionic conductivity up to 10-4S cm-1, and with lithium from
The advantages that sub- transport number is close to 1, electrochemical window wide (more than 5V).
It is preferred that the composite solid electrolyte material is by the polymeric matrix material and the fast-ionic conductor powder material
Material composition, the wherein mass content of polymeric matrix material are 95~20%, and the mass content of fast-ionic conductor powder body material is
5~80%.
It is preferred that the polymeric matrix material can be polyoxyethylene (PEO), polyethylene terephthalate
(PET), polyimides (PI), Kynoar (PVdF), polymethyl methacrylate (PMMA), polyacrylonitrile
(PAN), at least one of poly (propylene carbonate) (PPC), polyvinyl chloride (PVC) and its copolymer.
It is preferred that the grain diameter of the fast-ionic conductor powder body material is 20nm~20 μm.
The present invention composite solid electrolyte material operating temperature can be room temperature to 120 DEG C, preferably 60~100 DEG C.
High temperature helps to strengthen the activity at powder granule and polymer interface, therefore ionic conductivity when temperature improves within the specific limits
It is higher.
Second aspect, the present invention provide a kind of composite solid electrolyte film, and it is by above-mentioned composite solid electrolyte material shape
Into.
The third aspect, the present invention provide the preparation method of above-mentioned composite solid electrolyte film, comprised the following steps：
1) fast-ionic conductor powder body material and polymeric matrix material are dispersed in organic solvent, obtain composite solid electrolyte
Slurry；
2) composite solid electrolyte slurry is coated on substrate, dries, obtain composite solid electrolyte film.
Present invention process is simple, and cost is cheap, reproducible, can large-scale application.
It is preferred that the fast-ionic conductor powder body material carries out anhydrous processing in advance, the step 1) is under protective atmosphere
Carry out.
It is preferred that the solid content of the composite solid electrolyte slurry is 6%~15%.
Fourth aspect, the present invention provide a kind of all solid lithium secondary battery, and it includes：Positive pole, negative pole and it is arranged at institute
State the above-mentioned composite solid electrolyte film between positive pole and the negative pole.
The present invention has the advantages that：
What the 1st, the present invention was maximum compared with other composite solid electrolytes is not both no any type of lithium salts of addition in polymer, and herein
Under the conditions of its conductivity at room temperature can reach 10-4S cm-1；
2nd, the composite solid electrolyte film in the present invention has good when applied to lithium secondary battery at room temperature (25 DEG C) and 60 DEG C
Good cycle performance and high rate performance；
3rd, the present invention in composite solid electrolyte film for it is a kind of can self-supporting dielectric film, be easy to process and transport；
4th, the energy density of battery can be remarkably improved directly using lithium metal as negative material.
Brief description of the drawings
Fig. 1 a are the composite solid electrolyte film digital photograph of the present invention, and the composite solid electrolyte film, which is shown, in figure is
It is a kind of can self-supporting flexible membrane electrolyte；
Fig. 1 b are SEM (SEM) figure of composite solid electrolyte film of the present invention；
Fig. 2 a are Li in the embodiment of the present invention 17La3Zr2O12(LLZTO):The X-ray diffraction spectrogram of PEO composite solid electrolyte films
(XRD)；
Fig. 2 b are LLZTO:The room temperature ac impedance spectroscopy of PEO composite solid electrolyte films；
Fig. 3 a are all-solid-state battery in the embodiment of the present invention 3 in 0.05C multiplying powers, 25 DEG C of first charge-discharge curve；
Fig. 3 b be in the embodiment of the present invention 3 all-solid-state battery at 25 DEG C, 0.05,0.1,0.2,1.0, the circulation under 2.0C multiplying powers it is bent
Line；
Fig. 4 a are all-solid-state battery in the embodiment of the present invention 4 in 0.05C multiplying powers, 60 DEG C of first charge-discharge curve；
Fig. 4 b be in the embodiment of the present invention 4 all-solid-state battery at 60 DEG C, 0.05,0.1,0.2,1.0, the circulation under 2.0C multiplying powers it is bent
Line.
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing and following embodiments, it should be appreciated that accompanying drawing and following embodiments are only
For illustrating the present invention, it is not intended to limit the present invention.
The invention provides it is a kind of can be applied to all solid lithium secondary battery without lithium salts addition composite solid electrolyte, its
Polymer and fast-ionic conductor powder is compound, and do not add lithium salts.Preferably, composite solid electrolyte is by polymeric matrix material
Material forms with fast-ionic conductor inorganic powder material.
Selected polymeric matrix material can be conventional solid electrolyte polymer matrix material, include but is not limited to
PEO, PET, PI, PVdF, PMMA, PAN, PPC, PVC etc. and the blending of one or both of its copolymer.
The fast-ionic conductor inorganic particle is Li7La3Zr2O12Original washing powder body, by Li7La3Zr2O12Base adulterates with different ions
Formed, such as the element doping such as Al, Ta, Nb, W, Ga, Y, Te or one or more of mixtures for being co-doped with.It is changed
Formula can be expressed as Li7-xLa3Zr2-xMxO12, the wherein doping of doped chemical can be 0≤x≤1.Li7La3Zr2O12Original washing powder body
Grain graininess can be 20nm~20 μm, preferably 20nm~200nm.
Fast-ionic conductor inorganic particle can uniformly mix with polymeric matrix material.Wherein, fast-ionic conductor inorganic particle
Mass content can be 5~80%, preferably 10~70%, more preferably 20~60%；The mass content of polymeric matrix material
For 95~20%, preferably 90~30%, more preferably 80~40%.
The composite solid electrolyte of the present invention is formed as membranaceous composite solid electrolyte, i.e., the present invention also provides one kind without lithium
The macroion conductance composite solid electrolyte film of salt addition, it is the film formed by above-mentioned composite solid electrolyte.
The working mechanism of solid electrolyte membrane of the present invention is：
Solid electrolyte membrane does not add any organic solvent and any type of lithium salts.In the charge and discharge process of battery, fast ion is led
Li in body inorganic particle+Movement is quickly conducted in the powder granule and particle of mutual UNICOM and the interface of polymer, so as to
Conduct Li+.High temperature helps to strengthen the activity at powder granule and polymer interface, therefore when temperature improves within the specific limits
Ionic conductivity is higher.The operating temperature range of the solid electrolyte membrane of the present invention can be room temperature to 120 DEG C, preferably 60~
100℃。
The solid electrolyte membrane of the present invention has ionic conductivity high, and conductivity at room temperature can reach 10-4S cm-1；Lithium from
Sub- transport number is close to 1；Electrochemical window is wide, through cyclic voltammetry its electrochemical window can reach more than 5V (5V with
On) the advantages that.The ionic conductivity of the solid electrolyte membrane of the present invention will be apparently higher than with the addition of other nonionic conductor inorganic powders
The composite solid electrolyte film of body.The solid electrolyte membrane of the present invention can be used for high voltage, the secondary electricity of the lithium of high-energy-density system
Pond, or the field such as ultracapacitor, fuel cell.Composite solid electrolyte film in the present invention is applied to lithium secondary battery
When, there are good cycle performance and high rate performance at room temperature (25 DEG C) and 60 DEG C.
Fig. 1 a show the composite solid electrolyte film digital photograph of an example of the present invention, it can be seen that solid-state of the invention
Dielectric film can be the flexible membrane of self-supporting, have mechanical stability, be easy to process and transport.The solid electrolyte membrane of the present invention
Thickness can be 20 μm~150 μm.Fig. 1 b show the composite solid electrolyte film SEM figures of an example of the present invention, can be with
Find out, fast-ionic conductor powder is distributed evenly in polymeric matrix.
The composite solid electrolyte film of the present invention can be made by antivacuum coating method.In one example, can will soon from
Sub- conductor powder body material and polymeric matrix material are dispersed in organic solvent, obtain composite solid electrolyte slurry；Then
Composite solid electrolyte slurry is coated on substrate, dries, obtains composite solid electrolyte film.
The source of fast-ionic conductor powder is unlimited, can use commercial goods, can also voluntarily prepare.In one example,
Its preparation method is as follows：By chemical formula Li7-xLa3Zr2-xMxO12(x=0~1, M=Al, Ta, Nb, W, Ga, Y, Te
Deng) in Li, La, Zr, M mol ratio, choose LiOH, La (OH)3、ZrO2With corresponding oxide MxOyMake former
Material, wherein LiOH excessive 15%, by it, ball milling is dried after 24 hours in alcoholic media, then small in 900 DEG C of calcinings 12
When, 3 DEG C/min of heating rate, obtain Li7-xLa3Zr2-xMxO12Fast-ionic conductor powder..
Fast-ionic conductor powder can carry out anhydrous processing in advance, such as be dried in vacuo 24h at 100 DEG C, so as to remove
The micro-moisture contained in powder, reduce influence of the moisture to its ionic conductivity.
The preparation of composite solid electrolyte slurry
Fast-ionic conductor powder is disperseed in organic solvent, to promote its dispersed, to be ultrasonically treated, such as
1h is handled in ultrasound reactor under 80% power, fast-ionic conductor powder is well-dispersed in organic solvent.As organic molten
Agent, including but not limited to 1-METHYLPYRROLIDONE, acetonitrile, N-N- dimethylformamides, dimethyl carbonate, ethylene carbonate
Deng.The concentration of fast-ionic conductor powder can be 0.01~0.2g/mL.Then, to being dispersed with the organic molten of fast-ionic conductor powder
Polymeric matrix material is added in liquid, such as can be slowly added to feeder, while can also aid in stirring (such as 24h), by
This obtains composite solid electrolyte slurry.The wherein mass content of fast-ionic conductor inorganic particle can be 5-80%, polymeric matrix
The mass content of material is 95-20%.The preparation of composite solid electrolyte slurry is preferably carried out under protective atmosphere, such as in height
Carried out in pure argon glove box.
It should be understood that composite solid electrolyte slurry preparation steps (fast-ionic conductor powder and polymeric matrix material plus
Material order) it is not limited to above-mentioned, such as first polymeric matrix material can also be dissolved in organic solvent, add fast ion and lead
Body powder；Or polymeric matrix material and fast-ionic conductor powder are added in organic solvent simultaneously.It is furthermore, it is to be understood that multiple
Other possible additives can also be contained such as dispersing aid by closing solid electrolyte slurry.
Composite solid electrolyte slurry is coated on substrate, after drying, obtains the composite solid electrolyte film of flexibility.Make
For substrate, it is not particularly limited, such as can is polyfluortetraethylene plate etc..Coating method for example can be spin coating, roller coat, spraying
Deng.Drying mode can be heating or organic solvent is volatilized naturally.Obtained flexible membrane is taken off from substrate, can obtain from branch
The composite solid electrolyte film of support.
The composite solid electrolyte and its film of the present invention can be applied to all solid lithium secondary battery.Present invention also offers one kind
All solid lithium secondary battery, it includes the composite solid electrolyte of the present invention.In one example, all solid lithium secondary battery bag
The composite solid electrolyte film of positive pole, negative pole and the present invention is included, it is arranged between positive pole and negative pole.In addition, the present invention
All solid lithium secondary battery can also include other compositions, such as conductive additive etc..The composite solid electrolyte film of the present invention exists
The growth of Li dendrite can be suppressed in lithium secondary battery, room-temperature conductivity is high and has stable circulating battery.
The composite solid electrolyte of the present invention has splendid adaptability and stability in the lithium secondary battery, and of the invention is complete
Solid lithium secondary cell is not particularly limited to positive electrode and negative material.
Can be LiFePO4 as positive electrode, cobalt acid lithium, LiMn2O4, nickel ion doped, ternary nickel cobalt manganese composite wood
One or more of mixing materials in material.
Can be acetylene black, graphite, graphene, graphene oxide, porous carbon, carbon nanometer as conductive additive
One or more of mixing in pipe, carbon fiber, nitrogen-doped carbon, KB (Ketjen black).
Can be metal lithium sheet or graphitic carbonaceous materials as negative material.The present invention can be directly using lithium metal as negative
Pole material, it is remarkably improved the energy density of battery.
The present invention has the advantages of following notable：
(1) provide it is a kind of can self-supporting membranaceous composite solid electrolyte, there is mechanical stability, ionic conductivity is reachable at room temperature
10-4S cm-1；
(2) good to the stability of lithium metal, because being added without lithium salts, lithium is difficult that deposition forms Li dendrite in polymeric matrix, because
This is not susceptible to internal short-circuit, has higher security when applied to lithium secondary battery；
(3) electrochemical operation window is wide, and through cyclic voltammetry, its electrochemical window can reach more than 5V, therefore available for high electricity
Pressure, the lithium secondary battery of high-energy-density system, or the field such as ultracapacitor, fuel cell；
(4) it is demonstrated experimentally that composite solid electrolyte in the present invention is applied to during lithium secondary battery, in room temperature (25 DEG C) and
All there is good cyclical stability at 60 DEG C；
(5) during composite solid electrolyte and the positive pole in the present invention, negative pole form all solid lithium secondary battery, it is used just
Pole material and negative material are not particularly limited, and the composite solid electrolyte has splendid adaptability and stability.
With reference to specific experiment example and accompanying drawing, the invention will be further described, but the present invention is used merely to explain invention mesh
, however it is not limited to following examples.Method described in following embodiments is conventional method unless otherwise instructed.The material is such as
It can be bought without special instruction from open commercial sources.Those skilled in the art according to the present invention the above make some
Nonessential modifications and adaptations belong to protection scope of the present invention.Following specific technological parameters of example etc. are also only OK ranges
In an example, i.e., those skilled in the art can be done in suitable scope by this paper explanation and be selected, and not really want to limit
In the concrete numerical value of hereafter example.
Method of testing：
Diameter of particle：The particle size distribution of gained fast-ionic conductor powder is determined by laser diffraction granularity tester, is aided in simultaneously
SEM further looks at determination；
Ac impedance spectroscopy：The composite electrolyte membrane of preparation is assembled into stainless steel substrates<Stainless steel substrates/dielectric film/stainless steel substrates>Obstruction
Battery, Based on AC Impedance Measurements is carried out to the battery with electrochemical workstation；
Ionic conductivity：Pass through the ac impedance spectroscopy and formula obtained in the above-mentioned methodsCalculate the ionic conductance of dielectric film
Rate.Wherein t is the thickness of dielectric film, and R is the resistance of dielectric film, and A is the cross-sectional area of dielectric film；
Lithium ion transference number：The composite electrolyte membrane of preparation is assembled into metal lithium sheet<Metal lithium sheet/dielectric film/metal lithium sheet>Resistance
Battery is filled in, direct current polarization measure is carried out to the battery with electrochemical workstation.With reference to ac impedance spectroscopy and direct current polarization curve, root
According to formula TLi+={ I(t=∞)[ΔV-I(t=0)R(t=0)]}/{I(t=0)[VΔ-I(t=∞)R(t=∞)], the lithium ion transference number of dielectric film can be calculated
TLi+.Wherein, Δ V is voltage amplitude, I(t=0)For initial current value, R(t=0)For electrolyte resistance, I before polarization(t=∞)It is steady to polarize
Determine current value, R(t=∞)For electrolyte resistance after polarization；
Electrochemical window：The composite electrolyte membrane of preparation is assembled into metal lithium sheet and stainless steel substrates<Metal lithium sheet/dielectric film/stainless
Steel disc>Battery, cyclic voltammetric and linear volt-ampere curve measure are carried out to the battery with electrochemical workstation to determine dielectric film
Electrochemical operation window.Wherein cyclic voltammetry voltage range is usually -0.5V~6.0V, and linear volt-ampere test voltage is usual
For 2.0V~6.0V.
Embodiment 1
It is a kind of available for macroion conductance composite solid electrolyte film of all solid lithium secondary battery without lithium salts addition, its digital photograph and
SEM pictures are shown in accompanying drawing 1a and 1b, and its preparation process is specific as follows：
Stirring 1 gram of PEO in 10mL organic solvent 1-METHYLPYRROLIDONEs in Ar atmosphere glove box makes it fully dissolve,
Then by a certain amount of Li7La3Zr2O12(LLZO, particle diameter are 10 μm) adds and continuing stirring makes its dispersed, wherein
PEO and LLZO mass ratio is 10：X, x=1-8, x=5 in this embodiment.A certain amount of composite solid electrolyte is starched
Material is applied on substrate, is stood 24h at room temperature, solvent is volatilized completely, that is, obtains composite solid electrolyte film.Wherein,
LLZO raw powder's production technologies are as follows：By chemical formula Li7La3Zr2O12Middle Li, La, Zr mol ratio, selection LiOH,
La(OH)3、ZrO2Make raw material, wherein LiOH excessive 15%, ball milling is dried after 24 hours in alcoholic media by it, then
Calcined 12 hours at 900 DEG C, 3 DEG C/min of heating rate, obtain Li7La3Zr2O12Fast-ionic conductor powder.
Embodiment 2
A kind of NEW TYPE OF COMPOSITE solid electrolyte membrane, preparation method is the same as embodiment 1.Wherein selected LLZO particle diameters are 200nm,
PEO is 10 with LLZO mass ratioes：3.The XRD of dielectric film is as shown in Figure 2 a, it is seen that dielectric film principal phase is cube
Garnet structure.Using circular Li electrodes as electrode is tested, electric performance test is carried out to electrolyte membrane samples at room temperature,
Obtain shown in its ac impedance spectroscopy 2b, calculate conductivity at room temperature be 2.0 × 10-4S·cm-1.After tested, its lithium ion
Transport number is 0.46, and electrochemical window is 0V~4.8V.
Embodiment 3
A kind of all solid lithium secondary battery based on composite solid electrolyte film, the negative pole and positive electrode of use are specific as follows：
The composite solid electrolyte film of use is the same as example 1；
Negative pole directly uses metal lithium sheet；
Positive pole LiFePO4:SP:PEO:LiTFSI；Every mass ratio is 8：1：7：0.3；
Battery testing temperature：25℃；
Fig. 3 a the present embodiment all-solid-state batteries first charge-discharge curve under 25 DEG C, 0.05C multiplying powers, Fig. 3 b are that all-solid-state battery exists
25 DEG C, 0.05,0.1,0.2,1.0, the cyclic curve under 2.0C multiplying powers, it can be seen that it has good circulation at 25 DEG C
Stability.
Embodiment 4
A kind of all solid lithium secondary battery based on composite solid electrolyte film, the negative pole and positive electrode of use are specific as follows：
The composite solid electrolyte film of use is the same as example 1；
The negative pole of use is the same as embodiment 3；
The positive pole of use is the same as embodiment 3；
Battery testing temperature：60℃；
Fig. 4 a are all-solid-state battery first charge-discharge curve under 60 DEG C, 0.05C multiplying powers, Fig. 4 b be all-solid-state battery at 60 DEG C,
0.05th, 0.1,0.2, the 1.0, cyclic curve under 2.0C multiplying powers, it can be seen that it has good stable circulation at 60 DEG C
Property.
Embodiment 5
Fast-ionic conductor inorganic particle is the Li of doping6.7La3Zr1.7Ta0.3O12(LLZTO) raw powder's production technology is as follows：By chemistry
Formula Li6.7La3Zr1.7Ta0.3O12Middle Li, La, Zr, Ta mol ratio, choose LiOH, La (OH)3、ZrO2And corresponding oxidation
Thing TaO makees raw material, and wherein LiOH excessive 15%, by it, ball milling is dried after 24 hours in alcoholic media, Ran Hou
900 DEG C are calcined 12 hours, 3 DEG C/min of heating rate, obtain Li6.7La3Zr1.7Ta0.3O12Fast-ionic conductor powder.Then, exist
Stirring 1 gram of PEO in 10mL organic solvent 1-METHYLPYRROLIDONEs in Ar atmosphere glove box makes it fully dissolve, then
By a certain amount of Li6.7La3Zr1.7Ta0.3O12(LLZTO, particle diameter are 10 μm) adds and continuing stirring makes its dispersed, its
Middle PEO and LLZTO mass ratio are 10：X, x=1-8, x=5 in this embodiment.A certain amount of composite solid is electrolysed
Chylema material is applied on substrate, stands 24h at room temperature, solvent is volatilized completely, obtains composite solid electrolyte film.
Comparative example 1
A kind of composite solid electrolyte film, preparation method is the same as embodiment 1.Wherein selected LLZO particle diameters are 200nm, PEO
It is 10 with LLZO mass ratioes：3, it (can be LiClO to add lithium salts4、LiPF6、LiAsF6、LiBF4、
LiCF3SO3、LiN(CF3SO2)2(LiTFSI)、LiN(C2F5SO2)2(LiBETI)、LiPF3(CF3CF2)3(LiFAP)、
LiBF3CF3CF2(LiFAB)、LiC(CF3SO2)3(LiTFSM)、LiB(C2O4)2(LiBOB)、LiBF2(CO2)2
(LiODFB), polymerize the one or more in lithium borate salt PLTB) in lithium ion and PEO in [EO] unit mole
Than for 1：12.Using circular Li electrodes as electrode is tested, electric performance test is carried out to electrolyte membrane samples at room temperature,
Calculate conductivity at room temperature be 4.3 × 10-4S·cm-1.After tested, its lithium ion transference number is 0.47, and electrochemical window is
0V~4.65V.Compared with the composite electrolyte membrane without lithium salts addition in the present invention, with the addition of the electrolyte of lithium salts its film from
Electron conductivity and lithium ionic mobility slightly have raising and raising is not notable, but electrochemical operation window has obvious reduction.Separately
Outside, on the one hand the addition of lithium salts adds the preparation cost and complexity of dielectric film, on the other hand make it that dielectric film is easy
The moisture absorption and the measure for influenceing its ionic conductivity, while also add assembled battery lithium dendrite growth in charge and discharge process
Risk.
Claims (10)
1. a kind of composite solid electrolyte material, it is characterised in that including polymeric matrix material and fast-ionic conductor powder body material, the chemical formula of the fast ion conducting material is Li7-xLa3Zr2-xMxO12, wherein M is at least one of Al, Ta, Nb, W, Ga, Y, Te, and 0≤x≤1, the composite solid electrolyte material does not include lithium salts.
2. composite solid electrolyte material according to claim 1, it is characterized in that, it is made up of the polymeric matrix material and the fast-ionic conductor powder body material, wherein the mass content of polymeric matrix material is 95~20%, and the mass content of fast-ionic conductor powder body material is 5~80%.
3. composite solid electrolyte material according to claim 1 or 2, characterized in that, the polymeric matrix material is at least one of polyoxyethylene, polyethylene terephthalate, polyimides, Kynoar, polymethyl methacrylate, polyacrylonitrile, poly (propylene carbonate), polyvinyl chloride and its copolymer.
4. composite solid electrolyte material according to any one of claim 1 to 3, it is characterised in that the grain diameter of the fast-ionic conductor powder body material is 20 nm~20 μm.
5. composite solid electrolyte material according to any one of claim 1 to 4, it is characterised in that the operating temperature of the composite solid electrolyte material be room temperature to 120 DEG C, preferably 60~100 DEG C.
6. a kind of composite solid electrolyte film, it is characterised in that formed as the composite solid electrolyte material any one of claim 1 to 5.
7. the preparation method of the composite solid electrolyte film described in a kind of claim 6, it is characterised in that comprise the following steps：
1）Fast-ionic conductor powder body material and polymeric matrix material are dispersed in organic solvent, obtain composite solid electrolyte slurry；
2）Composite solid electrolyte slurry is coated on substrate, dries, obtains composite solid electrolyte film.
8. preparation method according to claim 7, it is characterised in that the fast-ionic conductor powder body material carries out anhydrous processing, the step 1 in advance）Carried out under protective atmosphere.
9. the preparation method according to claim 7 or 8, it is characterised in that the solid content of the composite solid electrolyte slurry is 6~15%.
A kind of 10. all solid lithium secondary battery, it is characterised in that including：Positive pole, negative pole and the composite solid electrolyte film as claimed in claim 6 being arranged between the positive pole and the negative pole.
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