CN108598561A - A kind of quasi- solid lithium ion conducting electrolyte and its preparation method and application - Google Patents
A kind of quasi- solid lithium ion conducting electrolyte and its preparation method and application Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
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Abstract
The invention discloses a kind of quasi- solid lithium ion conducting electrolyte, raw material composition includes polymer, ceramic electrolyte, lithium salts and ionic liquid；The polymer includes Kynoar hexafluoropropene and poly (propylene carbonate)；The ceramic electrolyte includes main phase lithium lanthanum zirconium oxygen and dephasign La2Zr2O7；The ionic liquid is fluorine-containing glyoxaline ion liquid.The invention discloses a kind of quasi- solid lithium ion conducting electrolytes, with high mechanical strength and take into account toughness, high room temperature lithium ion conductivity, and the high chemical/electrochemical stability with lithium anode and oxide anode, for lithium metal battery, lithium-air battery and lithium-sulfur cell, it can be achieved that good chemical property.
Description
Technical field
The present invention relates to novel lithium battery solid electrolyte fields, and in particular to a kind of quasi- solid lithium ion conducting electrolyte
And its preparation method and application.
Background technology
With the rapid development of new-energy automobile industry, the requirement to power battery energy density is higher and higher, and traditional
The energy density of lithium ion battery have been approached bottleneck value, exploitation novel lithium battery cell system become it is current there is an urgent need to.It will be golden
Belong to the graphite cathode that lithium replaces lithium ion battery, the energy density of battery can be significantly improved and reduces the volume of battery.But
The compatibility of lithium metal and liquid electrolyte is poor, and lithium metal easily forms dendrite in charge and discharge process repeatedly, easily pierces
Broken diaphragm is to cause safety problem.By the way that solid electrolyte is replaced liquid electrolyte, lithium branch can be alleviated to a certain extent
Brilliant problem, but common solid electrolyte (such as polymer, ceramics, polymer/ceramic compound) lithium ion room-temperature conductivity
It is universal relatively low, need addition liquid plasticizer that could improve room temperature lithium ion conductivity.But the machine plasticizer of common are is often
The cycle life of cathode of lithium can be reduced with lithium metal reaction.
On the other hand, in above-mentioned solid electrolyte, although polymer have preferable mechanical performance and with good compatible of lithium
Property, but room temperature lithium ion conductivity is relatively low, and common inorganic solid electrolyte, such as NASICON types, sulfide, Ca-Ti ore type,
Although room temperature lithium ion conductivity is higher, and mechanical strength poor with the compatibility of lithium is poor, often needs in practical applications
Polymer and inorganic electrolyte is mutually compound, improve overall performance, i.e. mechanical stability and lithium compatibility, lithium ion conductance
Rate etc..
As 105070946 A of Publication No. CN Chinese patent literature in disclose and a kind of being used for lithium ion battery or lithium
Quasi- solid electrolyte of nanostructure of sulphur battery and its preparation method and application, the quasi- solid electrolyte of the nanostructure is by inorganic
Macroscopical solid electrolyte material that organic hybrid frame material adion conductive agent is formed；Preparation method is in protective atmosphere
Lower inorganic-organic hybrid frame material is immersed in ionic conductive agent is sufficiently mixed, and then excess of solvent volatilizees；It is obtained
The quasi- solid electrolyte of nanostructure has higher lithium ion conductivity, can replace simultaneously organic in conventional lithium ion battery
Electrolyte and diaphragm.But it is different from solid ceramic electrolyte, inorganic-organic hybrid frame material only serves the function of adion,
In itself without lithium ion transport performance, and as the key component of quasi-solid electrolyte film since brittleness can influence dielectric film
Mechanical performance.In addition, cited polymer is used generally as the binder of lithium battery, and usage amount is relatively low, in quasi- solid-state
It is difficult to improve dielectric film flexibility and absorption liquid electrolyte as film forming bulk composition to become lithium ion conductor in electrolyte
Effect.
For another example a kind of compound quasi-solid electrolyte is disclosed in the Chinese patent literature of 107645013 A of Publication No. CN
Film and preparation method thereof, the compound quasi-solid electrolyte film include solid electrolyte, liquid electrolyte containing lithium salt, inorganic nano
Particle and binder.The compound quasi-solid electrolyte has high conductance, can effectively reduce the content of liquid electrolyte.
But ceramic electrolyte and lithium metal Presence of an interface stability problem, there is also the interface stabilities with lithium metal to ask for liquid electrolyte
Topic, to influence the stable circulation sex chromosome mosaicism of cathode of lithium.
Invention content
The present invention has high mechanical strength in view of the above-mentioned problems, disclosing a kind of quasi- solid lithium ion conducting electrolyte
And toughness is taken into account, high room temperature lithium ion conductivity, and the chemical/electrochemical high with lithium anode and oxide anode are steady
It is qualitative, for lithium metal battery, lithium-air battery and lithium-sulfur cell, it can be achieved that good chemical property.
Specific technical solution is as follows：
A kind of quasi- solid lithium ion conducting electrolyte, raw material composition includes polymer, ceramic electrolyte, lithium salts and ionic liquid
Body；
The polymer includes Kynoar-hexafluoropropene and poly (propylene carbonate)；
The ceramic electrolyte includes main phase lithium lanthanum zirconium oxygen and dephasign La2Zr2O7；
The ionic liquid is fluorine-containing glyoxaline ion liquid.
In the present invention, by optimizing component, the component of ceramic electrolyte of polymer, and the ionic liquid of specific composition is introduced
Body plasticizer, to the quasi-solid electrolyte for obtaining mechanical property and chemical/electrochemical is had excellent performance.
By mass percentage, the raw material composition of the quasi- solid lithium ion conducting electrolyte includes：
In the present invention, the polymer is made of Kynoar-hexafluoropropene and poly (propylene carbonate), wherein gathering inclined fluorine
Ethylene-hexafluoropropene is that quasi-solid electrolyte mainly provides mechanical strength, and poly (propylene carbonate) mainly provides toughness, in addition, poly-
The introducing of propylene carbonate is conducive to improve the film-formation result of solid electrolyte, and individually Kynoar-hexafluoropropene is difficult
Film forming, and toughness is poor.It has been investigated that in quasi-solid electrolyte, the polymer of the specific composition also acts as package pottery
The effect of porcelain electrolyte reduces the contact of ceramic electrolyte and cathode of lithium and oxide anode, improves quasi-solid electrolyte and lithium
The chemical/electrochemical compatibility of cathode and oxide anode, and sulfide ceramic electrolyte is inhibited to decompose.And pass through further examination
It issues after examination and approval now, if poly (propylene carbonate) is replaced with polyvinyl alcohol (PVA), polyethylene glycol oxide (PEO) or poly-methyl methacrylate
Ester (PMMA), otherwise the quasi-solid electrolyte being prepared can not form a film or will be unable to take into account mechanical property and chemistry/electrification
Learn performance.
In the raw material composition of the quasi- solid lithium ion conducting electrolyte, the content of polymer is 30~50%；As excellent
It selects, in the polymer, the content of poly (propylene carbonate) is 30~70%.Within the above range, the quasi- solid-state lithium prepared
The mechanical strength of ionic conductivity electrolyte, toughness, film forming, lithium ion conductivity, the interface with lithium metal and oxide anode
Overall balance, any quasi- solid lithium ion for deviateing above-mentioned composition and cannot get excellent combination property can be obtained in the performances such as stability
Conducting electrolyte.
Unless otherwise instructed, the content in the present invention is clearly mass percentage content.
In the present invention, it is prepared by main phase lithium lanthanum zirconium oxygen and dephasign La using agglutinating nature yeast2Zr2O7The ceramics of composition
Electrolyte.The chemical formula of the main phase lithium lanthanum zirconium oxygen is Li7La3Zr2O12.The special composition and the dephasign of content can protect lithium
Lanthanum zirconium oxygen inhibits its interfacial reaction with oxide anode, improves the interface stability of main phase and oxide anode.
In the raw material composition of the quasi- solid lithium ion conducting electrolyte, the content of ceramic electrolyte is 2~10%；As
It is preferred that in the ceramic electrolyte, dephasign content is 2~10%.Excessive ceramic electrolyte by influence electrolyte toughness and
Film forming, very few ceramic electrolyte will influence its mechanical strength and lithium ion conductivity and mobility；More dephasigns will reduce
The lithium ion conductivity and mobility of solid electrolyte, very few dephasign are unfavorable for improving the interface stability with oxide anode
Property.Further preferably, in the ceramic electrolyte, dephasign content is 3~7%.Standard prepared by the ceramic electrolyte of the dephasign content is solid
The comprehensive performance of state lithium ion conducting electrolyte is best.
Further preferably, the ceramic electrolyte, particle size are 100~500nm, and even size distribution.Particle
The small mechanical strength for being conducive to improve polymer in the evenly dispersed of polymer of size, particle is small also can be improved its own lithium from
The lithium ion conductivity and transport number of polymer/ceramic pentalyte also can be improved in electron conductivity and transport number, excessive
Particle is unfavorable in the evenly dispersed and lithium ion conductivity of polymer and the raising of transport number, and too small particle is easily rolled into a ball
It is poly-, it is unfavorable in the polymer evenly dispersed.
Preferably, the lithium salts includes but not limited to lithium perchlorate, lithium hexafluoro phosphate, trifluoromethanesulfonic acid lithium, double trifluoros
The one or more of sulfonyl methane imine lithium.The content of lithium salts is 2~10%, and very few lithium salts is unfavorable for lithium ion conductivity
It improves, excessive lithium salts is unfavorable for the raising of quasi- solid lithium ion conducting electrolyte mechanical strength, and can improve manufacturing cost.
Introducing ionic liquid carries out plasticising to film-form solid electrolyte and forms quasi-solid electrolyte in solid electrolyte.
In the present invention, the ionic liquid is selected from fluorine-containing glyoxaline ion liquid, including but not limited to -3 methylimidazole of 1- propyl
At least one of bis- (trifyl) imines of bis- (trifyl) imines, -3 methylimidazole of 1- ethyls.Through experiment
It was found that on the one hand such ionic liquid and lithium contact generation reduction reaction generate fluorine-containing compound and can inhibit the shape of Li dendrite
At and inhibit ceramic electrolyte and lithium metal interfacial reaction；On the other hand solid electrolyte also can be improved in such ionic liquid
Lithium ion conductivity, and with the poly (propylene carbonate) collective effect in polymer, further increase the conductive electricity of quasi- solid lithium ion
Solve the toughness of matter.In addition, ionic liquid also functions to the effect of bridge joint solid electrolyte particle and polymer, solid-state electricity can be fixed
Solve matter particle.
Preferably, in the raw material composition of the quasi- solid lithium ion conducting electrolyte, the content of ionic liquid is 35~
65%, very few content is unfavorable for improving the lithium ion conductivity of solid electrolyte and quasi- solid lithium ion conducting electrolyte and lithium
The interfacial reaction of the inhibition of dendrite and lithium metal and ceramic electrolyte, it is conductive that excessive ionic liquid is unfavorable for quasi- solid lithium ion
The raising of electrolyte mechanical strength.
The invention also discloses the preparation method of the quasi- solid lithium ion conducting electrolyte, step includes：
1) zirconium source and solvent I are mixed to get solution A, lithium source and lanthanum source is mixed to get solution B with solvent II；
2) solution A prepared in step 1) is mixed with solution B, gluey presoma is obtained after stirring evenly, then chilled
Dry and repetition obtains ceramic electrolyte after roasting；
3) polymer is mixed with solvent III, polymer solution is obtained after being sufficiently stirred, then ceramics prepared by step 2)
Electrolyte is scattered in lithium salts in the polymer solution, sticky colloid is formed after being sufficiently stirred, through pouring into a mould, being dried
To film-form solid electrolyte；
4) compound concentration is lithium salts/ionic liquid of 0.5~2mol/L, film-form solid electrolyte prepared by step 3)
It soaks and sets 12~36 hours in the lithium salts/ionic liquid, remove extra ionic liquid solution, obtain the quasi- solid-state lithium
Ionic conductivity electrolyte.
Preferably, in step 1)：
The zirconium source is selected from zirconium-n-propylate, zirconium iso-propoxide, zirconium-n-butylate, and lithium source is selected from LiNO3、Li2SO4, lithium acetate or its
Hydrate, lanthanum source are selected from lanthanum nitrate, lanthanum sulfate, lanthanum acetate and its hydrate；
The molar ratio in the zirconium source, lithium source and lanthanum source is 1.95~2.05:7:2.95~3.05；
The solvent I is for dissolving the zirconium source, selected from but not limited to ethyl acetoacetate, methyl acetoacetate, acetyl
Tert-butyl acetate, a concentration of 2~7 grams per milliliter in zirconium source in solution A；
The needs of the solvent II can dissolve lithium source and lanthanum source simultaneously, molten selected from but not limited to ethyl alcohol, propyl alcohol, ethylene glycol
A concentration of 0.1~0.9 grams per milliliter of lithium source in liquid B.
The dosage of each raw material is limited under above range, is conducive to that the nano level of high-lithium ion conductivity is prepared
Lithium lanthanum zirconium oxygen main phase and La2Zr2O7Dephasign, and in a certain range the control of dephasign content, to which quasi- solid-state electricity both can be improved
The conductivity of matter is solved, and main phase can be improved and aoxidize the interface stability of positive object pole.
Preferably, in step 2)：
The stirring, time are 1.5~3 hours, and temperature is 40~60 DEG C.
The repetition, which roasts, is specially：
Air atmosphere by the product after freeze-drying at 550~750 DEG C roasts 6~15h next time, by a product of roasting
After tabletting, then 6~15h of after baking is carried out under 550~750 DEG C of air atmosphere.
Further preferably, the heating rate of the primary roasting and after baking is independently selected from 1~3 DEG C/min；
The pressure of the tabletting is 5~15MPa.
It is found through experiment that be conducive to inhibit growing up and reuniting for particle using freeze-drying, the rational heating rate of material,
Rational roasting time and temperature and double roasting technique can be realized well-crystallized, nano level and even size distribution
Ceramic electrolyte powder, and realize the lithium lanthanum zirconium oxygen main phase and La of high-lithium ion conductivity2Zr2O7The active balance of dephasign, obtains
To rational phase structure.
Preferably, in step 3)：
The solvent III is selected from methyl pyrrolidone, one or both of anhydrous acetonitrile, polymer a concentration of 20~
40 grams per liters；When prepared polymer solution, it is sufficiently stirred at 70~90 DEG C；
The mass ratio of the polymer, ceramic electrolyte and lithium salts is 30~50：2~10：1~8；
The drying is carried out in two steps, 12~48 hours dry in air atmosphere first at 50~70 DEG C, then 50
It is 12~36 hours dry in vacuum at~70 DEG C.
Above each technological parameter is mutually related, and will be more conducive to obtain nanoscale, particle size distribution by optimization
Uniformly, agglomeration does not occur and realizes the lithium lanthanum zirconium oxygen main phase and La of high-lithium ion conductivity2Zr2O7The effective of dephasign puts down
Weighing apparatus, obtains rational phase structure.
Preferably, in step 3)：
The solvent Ι Ι are selected from one or both of methyl pyrrolidone, anhydrous acetonitrile, polymer solution concentration 20
~40 grams per liters；When prepared polymer solution, it is sufficiently stirred at 70~90 DEG C；
The mass ratio of the polymer, ceramic electrolyte and lithium salts is 30~50：2~10：1~8；
The drying is carried out in two steps, 12~36 hours dry in air atmosphere first at 50~70 DEG C, then 50
It is 12~36 hours dry in vacuum at~70 DEG C.
Above-mentioned whipping temp, drying temperature and time are close associations, can be prepared by the restriction to above-mentioned parameter
To the solid electrolyte film of uniform bubble-free, without other film forming agents, defrother or surfactant is separately added.
In step 4)：
In the lithium salts/ionic liquid, a concentration of 0.5~2mol/L of lithium salts, in solid electrolyte film ionic liquid
Leaching set the time be 12~36 hours, too low lithium salt be unfavorable for improve quasi-solid electrolyte in lithium salts content, influence
The raising of lithium ion conductivity, excessive lithium salts can improve the manufacturing cost of quasi-solid electrolyte, and disadvantage in time is set in too short leaching
It is fully plasticized by ionic liquid in solid electrolyte film, it is strong in quasi-solid electrolyte film machinery that disadvantage in time is set in long leaching
The raising of degree, and the lithium salts being present in polymer can be partly dissolved.
In the present invention, lithium salts is added in two portions, and is the warp during preparation of film-form solid electrolyte and leaching are set respectively
Experiment finds that the technique can improve the interface lithium ion transport rate between polymer, ceramic electrolyte, ionic liquid three,
To improve the lithium ion conductivity of quasi-solid electrolyte on the whole.
The quasi- solid lithium ion conducting electrolyte being prepared through above-mentioned technique has high mechanical strength and takes into account toughness,
High room temperature lithium ion conductivity, and the chemical/electrochemical stability high with lithium anode and oxide anode, therefore,
It can be applied in lithium battery, lithium sky battery, lithium-sulfur cell.
Compared with prior art, the invention has the advantages that：
1, quasi- solid lithium ion conducting electrolyte of the invention is polymer/inorganic filler composite solid electrolyte, inorganic
Filler uses the lithium lanthanum zirconium oxygen of high-lithium ion conduction and containing the dephasign of a small amount of special composition, on the one hand which can carry
The lithium ion conductivity and transport number of high solid electrolyte, on the other hand can be improved solid electrolyte and oxide anode and lithium are negative
The interface stability of pole.
2, it is plasticized using fluorine-containing glyoxaline ion liquid in quasi- solid lithium ion conducting electrolyte of the invention, introducing should
The conductivity of solid electrolyte can be improved in ionic liquid latter aspect, can also pass through with the compound further improvement toughness of polymer
Bridge joint polymer and solid ceramic electrolyte particle play the role of fixed solid electrolyte particle, and on the other hand the ionic liquid can
It is reacted with lithium metal and forms fluoride in lithium surface in situ, which can inhibit the formation of Li dendrite and inhibit ceramics electrolysis
The interfacial reaction of matter and lithium anode improves the interface stability of cathode of lithium and solid electrolyte.
Description of the drawings
Fig. 1 is the photo of quasi- solid lithium ion conducting electrolyte prepared by embodiment 1；
Fig. 2 is the XRD diagram of ceramic electrolyte prepared by embodiment 1；
Fig. 3 is the stereoscan photograph of ceramic electrolyte prepared by embodiment 1；
Fig. 4 is the chemical property of the lithium battery of the quasi- solid lithium ion conducting electrolyte assembling prepared with embodiment 1.
Specific implementation mode
Embodiment 1
Ceramic electrolyte is prepared using sol-gel method, 3.27 grams of zirconium-n-propylates are dissolved in 0.71 gram of ethyl acetoacetate
In, obtain solution A through being sufficiently stirred；By 2.41 grams of LiNO3With 6.49 grams of La (NO3)3·6H2O is dissolved in 7.53 grams of absolute ethyl alcohols
Obtain solution B；Solution B is added in solution A, is stirred 2 hours at 40 DEG C and obtains gel；It is dry that above-mentioned gel is subjected to freezing
It is dry to obtain presoma, then presoma is roasted under air atmosphere, heating rate is 2 DEG C/min, and calcination temperature is 600 DEG C, roasting
Time is 8 hours, then will roast gained powder in 10MPa lower sheetings, and repeat roasting with above-mentioned roasting technique and obtain ceramic electrical
Xie Zhi；0.8 gram of Kynoar-hexafluoropropene and 0.8 gram of poly (propylene carbonate) are placed in 50mL methyl pyrrolidones, 80
It is sufficiently stirred to obtain homogeneous solution at DEG C, then by 0.32 gram of ceramic electrolyte and 0.32 gram of double trifluoromethanesulfonimide lithium point
It dissipates in polymer solution, forms sticky colloid after being sufficiently stirred, then colloid is cast in Teflon container；It will be upper
The container for being loaded with colloid is stated first at 60 DEG C dry 48 hours in air atmosphere, it is then 24 hours dry in vacuum at 60 DEG C again
Obtain film-form solid electrolyte；By above-mentioned solid electrolyte film in the ionic liquid 1- third containing 1mol/L lithium perchlorates
It soaks and sets 24 hours in bis- (trifyl) imines of -3 methylimidazole of base, remove extra ionic liquid solution, obtain standard
Solid lithium ion conducting electrolyte.
Quasi- solid lithium ion conducting electrolyte appearance photo manufactured in the present embodiment is shown in Fig. 1, from figure it is found that quasi- solid-state lithium from
Conductive electrolyte can form a film well.The XRD of ceramic electrolyte is shown in Fig. 2, and LLZO is lithium lanthanum zirconium oxygen in figure, it is found that should from figure
Ceramic electrolyte is by lithium lanthanum zirconium oxygen main phase and La2Zr2O7Dephasign forms, and the mass percent of lithium lanthanum zirconium oxygen main phase is 96%,
La2Zr2O7The mass percent of dephasign is 4%.Stereoscan photograph shows, the particle size of ceramic electrolyte is about 100 to receive
Rice, and even size distribution, are shown in Fig. 3.
Using quasi- solid lithium ion conducting electrolyte manufactured in the present embodiment as electrolyte, using lithium metal as cathode, with
LiFePO4For anode, (active material, conductive carbon, PVDF weight of binder ratio are 8:1:1) it is assembled into quasi- solid state battery, in electric current
Density 17mA/g, voltage range 2.5V~4.3V carry out charge and discharge at room temperature, and discharge capacity reaches 150mAh/g, shows very
Good electro-chemical activity, and and LiFePO4Just high interface stability.
Comparative example 1
The preparation of quasi- solid lithium ion conducting electrolyte is a difference in that substantially with embodiment 1 in polymer, by 0.8
Gram poly (propylene carbonate) replaces with 0.8 gram of PMMA, and gained colloid cannot effectively form a film, and gained film mechanical strength is poor.
Comparative example 2
The preparation of quasi- solid lithium ion conducting electrolyte is a difference in that substantially with embodiment 1 in polymer, by 0.8
Gram poly (propylene carbonate) replaces with 0.8 gram of PVA, and PVA cannot can effectively be formed a film by ion etching.
Comparative example 3
The preparation of quasi- solid lithium ion conducting electrolyte is a difference in that substantially with embodiment 1 in polymer, by 0.8
Gram poly (propylene carbonate) replaces with 0.8 gram of PEO, and gained membrane electrochemical performance is poor, and assembled battery capacity is less than 130mAh/g.
Comparative example 4
The preparation of quasi- solid lithium ion conducting electrolyte is a difference in that substantially with embodiment 1 by ionic liquid 1- third
Bis- (trifyl) imines of -3 methylimidazole of base replace with pyrrole ionic liquid, such as 1- butyl -1- crassitudes
Bis- (trifluoro methylsulfonyl) imines, gained quasi-solid electrolyte mechanical performance are not so good as embodiment 1, and assembled battery capacity is less than
140mAh/g。
Comparative example 5
The preparation of quasi- solid lithium ion conducting electrolyte is a difference in that lithium salts is disposable adds substantially with embodiment 1
Enter, i.e., is only added at one time when preparing lithium salts/ionic liquid, 0.32 is added without in film-form solid electrolyte preparation process
Gram double trifluoromethanesulfonimide lithiums, gained quasi-solid electrolyte membrane ion conductivity is relatively low, and assembled battery capacity is less than
130mAh/g。
Comparative example 6
The preparation of quasi- solid lithium ion conducting electrolyte is a difference in that when synthesizing lithium lanthanum zirconium oxygen, does not have with embodiment 1
Using freeze-drying, but uses and be air-dried at 90 DEG C.The experimental results showed that when without using freeze-drying, lithium lanthanum zirconium oxygen
Particle is larger and Size Distribution is uneven, and under 1 identical test condition of embodiment, the capacity of quasi- solid state battery is less than with freezing
Dry situation.
Embodiment 2
Ceramic electrolyte is prepared using sol-gel method, 3.22 grams of zirconium-n-propylates are dissolved in 0.71 gram of ethyl acetoacetate
In, obtain solution A through being sufficiently stirred；By 2.41 grams of LiNO3With 6.33 grams of La (NO3)3·6H2O is dissolved in 7.53 grams of absolute ethyl alcohols
Obtain solution B；Solution B is added in solution A, is stirred 2 hours at 40 DEG C and obtains gel；It is dry that above-mentioned gel is subjected to freezing
It is dry to obtain presoma, then presoma is roasted under air atmosphere, heating rate is 2 DEG C/min, and calcination temperature is 650 DEG C, roasting
Time is 6 hours, then will roast gained powder in 10MPa lower sheetings, and repeat roasting with above-mentioned roasting technique and obtain ceramic electrical
Xie Zhi；1.12 grams of Kynoar-hexafluoropropenes and 0.48 gram of poly (propylene carbonate) are placed in 50mL methyl pyrrolidones,
It is sufficiently stirred to obtain homogeneous solution at 80 DEG C, then by 0.32 gram of ceramic electrolyte and 0.32 gram of double trifluoromethanesulfonimide lithium
It is scattered in polymer solution, forms sticky colloid after being sufficiently stirred, then colloid is cast in Teflon container；It will
The above-mentioned container for being loaded with colloid is first 48 hours dry in air atmosphere at 60 DEG C, and then drying 24 is small in vacuum at 60 DEG C again
When obtain film-form solid electrolyte；By above-mentioned solid electrolyte film in the ionic liquid 1- third containing 1mol/L lithium perchlorates
It soaks and sets 24 hours in bis- (trifyl) imines of -3 methylimidazole of base, remove extra ionic liquid solution, obtain standard
Solid lithium ion conducting electrolyte.
Quasi- solid lithium ion conducting electrolyte manufactured in the present embodiment can form a film well.XRD characterization shows that ceramics are electrolysed
Matter is by lithium lanthanum zirconium oxygen main phase and La2Zr2O7Dephasign forms, and the mass percent of lithium lanthanum zirconium oxygen main phase is 93%, La2Zr2O7Dephasign
Mass percent be 7%.Stereoscan photograph shows that the particle size of ceramic electrolyte is about 100 nanometers, and Size Distribution
Uniformly.
Using quasi- solid lithium ion conducting electrolyte manufactured in the present embodiment as electrolyte, using lithium metal as cathode, with
LiFePO4For anode, (active material, conductive carbon, PVDF weight of binder ratio are 8:1:1) it is assembled into quasi- solid state battery, in electric current
Density 17mA/g, voltage range 2.5V~4.3V carry out charge and discharge at room temperature, and discharge capacity reaches 152mAh/g, shows very
Good electro-chemical activity, and and LiFePO4Just high interface stability.
Embodiment 3
Ceramic electrolyte is prepared using sol-gel method, 3.32 grams of zirconium-n-propylates are dissolved in 0.71 gram of ethyl acetoacetate
In, obtain solution A through being sufficiently stirred；By 2.41 grams of LiNO3With 6.65 grams of La (NO3)3·6H2O is dissolved in 7.53 grams of absolute ethyl alcohols
Obtain solution B；Solution B is added in solution A, is stirred 2 hours at 40 DEG C and obtains gel；It is dry that above-mentioned gel is subjected to freezing
It is dry to obtain presoma, then presoma is roasted under air atmosphere, heating rate is 2 DEG C/min, and calcination temperature is 550 DEG C, roasting
Time is 12 hours, then will roast gained powder in 10MPa lower sheetings, and repeat roasting with above-mentioned roasting technique and obtain ceramic electrical
Xie Zhi；0.48 gram of Kynoar-hexafluoropropene and 1.12 grams of poly (propylene carbonate)s are placed in 50mL methyl pyrrolidones,
It is sufficiently stirred to obtain homogeneous solution at 80 DEG C, then by 0.32 gram of ceramic electrolyte and 0.32 gram of double trifluoromethanesulfonimide lithium
It is scattered in polymer solution, forms sticky colloid after being sufficiently stirred, then colloid is cast in Teflon container；It will
The above-mentioned container for being loaded with colloid is first 48 hours dry in air atmosphere at 60 DEG C, and then drying 24 is small in vacuum at 60 DEG C again
When obtain film-form solid electrolyte；By above-mentioned solid electrolyte film in the ionic liquid 1- containing 1mol/L lithium hexafluoro phosphates
It soaks and sets 24 hours in bis- (trifyl) imines of -3 methylimidazole of propyl, remove extra ionic liquid solution, obtain
Quasi- solid lithium ion conducting electrolyte.
Quasi- solid lithium ion conducting electrolyte manufactured in the present embodiment can form a film well.XRD characterization shows that ceramics are electrolysed
Matter is by lithium lanthanum zirconium oxygen main phase and La2Zr2O7Dephasign forms, and the mass percent of lithium lanthanum zirconium oxygen main phase is 97%, La2Zr2O7Dephasign
Mass percent be 3%.Stereoscan photograph shows that the particle size of ceramic electrolyte is about 100 nanometers, and Size Distribution
Uniformly.
Using quasi- solid lithium ion conducting electrolyte manufactured in the present embodiment as electrolyte, using lithium metal as cathode, with
LiFePO4For anode, (active material, conductive carbon, PVDF weight of binder ratio are 8:1:1) it is assembled into quasi- solid state battery, in electric current
Density 17mA/g, voltage range 2.5V~4.3V carry out charge and discharge at room temperature, and discharge capacity reaches 148mAh/g, shows very
Good electro-chemical activity, and and LiFePO4Just high interface stability.
Embodiment 4
Ceramic electrolyte is prepared using sol-gel method, 3.27 grams of zirconium-n-propylates are dissolved in 0.65 gram of ethyl acetoacetate
In, obtain solution A through being sufficiently stirred；By 2.41 grams of LiNO3With 6.49 grams of La (NO3)3·6H2O is dissolved in 4.60 grams of absolute ethyl alcohols
Obtain solution B；Solution B is added in solution A, is stirred 2 hours at 40 DEG C and obtains gel；It is dry that above-mentioned gel is subjected to freezing
It is dry to obtain presoma, then presoma is roasted under air atmosphere, heating rate is 2 DEG C/min, and calcination temperature is 600 DEG C, roasting
Time is 8 hours, then will roast gained powder in 10MPa lower sheetings, and repeat roasting with above-mentioned roasting technique and obtain ceramic electrical
Xie Zhi；0.8 gram of Kynoar-hexafluoropropene and 0.8 gram of poly (propylene carbonate) are placed in 50mL methyl pyrrolidones, 80
It is sufficiently stirred to obtain homogeneous solution at DEG C, then by 0.32 gram of ceramic electrolyte and 0.32 gram of double trifluoromethanesulfonimide dispersion
In polymer solution, sticky colloid is formed after being sufficiently stirred, then colloid is cast in Teflon container；It will be above-mentioned
The container for being loaded with colloid is first 48 hours dry in air atmosphere at 60 DEG C, then obtains within dry 24 hours in vacuum at 60 DEG C again
To film-form solid electrolyte；By above-mentioned solid electrolyte film in the ionic liquid 1- ethyls -3 containing 1mol/L lithium perchlorates
It soaks and sets 24 hours in bis- (trifyl) imines of methylimidazole, remove extra ionic liquid solution, obtain quasi- solid-state lithium
Ionic conductivity electrolyte.
Quasi- solid lithium ion conducting electrolyte manufactured in the present embodiment can form a film well.XRD characterization shows that ceramics are electrolysed
Matter is by lithium lanthanum zirconium oxygen main phase and La2Zr2O7Dephasign forms, and the mass percent of lithium lanthanum zirconium oxygen main phase is 96%, La2Zr2O7Dephasign
Mass percent be 4%.Stereoscan photograph shows that the particle size of ceramic electrolyte is about 100 nanometers, and Size Distribution
Uniformly.
Using quasi- solid lithium ion conducting electrolyte manufactured in the present embodiment as electrolyte, using lithium metal as cathode, with
LiFePO4For anode, (active material, conductive carbon, PVDF weight of binder ratio are 8:1:1) it is assembled into quasi- solid state battery, in electric current
Density 17mA/g, voltage range 2.5V~4.3V carry out charge and discharge at room temperature, and discharge capacity reaches 151mAh/g, shows very
Good electro-chemical activity, and and LiFePO4High interface stability.
Claims (10)
1. a kind of quasi- solid lithium ion conducting electrolyte, which is characterized in that raw material composition includes polymer, ceramic electrolyte, lithium
Salt and ionic liquid；
The polymer includes Kynoar-hexafluoropropene and poly (propylene carbonate)；
The ceramic electrolyte includes main phase lithium lanthanum zirconium oxygen and dephasign La2Zr2O7；
The ionic liquid is fluorine-containing glyoxaline ion liquid.
2. quasi- solid lithium ion conducting electrolyte according to claim 1, which is characterized in that by mass percentage, former
Material forms：
3. quasi- solid lithium ion conducting electrolyte according to claim 1 or 2, which is characterized in that in the polymer, gather
The mass percent of propylene carbonate is 30~70%.
4. quasi- solid lithium ion conducting electrolyte according to claim 1 or 2, which is characterized in that the ceramic electrolyte,
Particle size is 100~500nm；
In the ceramic electrolyte, the mass percent of dephasign is 2~10%.
5. quasi- solid lithium ion conducting electrolyte according to claim 1 or 2, which is characterized in that the lithium salts is selected from height
One or more of lithium chlorate, lithium hexafluoro phosphate, trifluoromethanesulfonic acid lithium, double trifluoromethanesulfonimide lithiums；
It is double that the ionic liquid is selected from bis- (trifyl) imines of -3 methylimidazole of 1- propyl, -3 methylimidazole of 1- ethyls
At least one of (trifyl) imines.
6. a kind of preparation method of quasi- solid lithium ion conducting electrolyte according to Claims 1 to 5 any claim,
It is characterized in that, step includes：
1) zirconium source and solvent I are mixed to get solution A, lithium source and lanthanum source is mixed to get solution B with solvent II；
2) solution A prepared in step 1) is mixed with solution B, gluey presoma is obtained after stirring evenly, then freeze-dried
Ceramic electrolyte is obtained after being roasted with repetition；
3) polymer is mixed with solvent III, polymer solution is obtained after being sufficiently stirred, then ceramics prepared by step 2) are electrolysed
Matter is scattered in lithium salts in the polymer solution, and sticky colloid is formed after being sufficiently stirred, thin through pouring into a mould, being dried to obtain
Membranaceous solid electrolyte；
4) compound concentration is lithium salts/ionic liquid of 0.5~2mol/L, and film-form solid electrolyte prepared by step 3) is in institute
It states leaching in lithium salts/ionic liquid to set 12~36 hours, removes extra ionic liquid solution, obtain the quasi- solid lithium ion
Conducting electrolyte.
7. the preparation method of quasi- solid lithium ion conducting electrolyte according to claim 6, which is characterized in that step 1)
In：
The molar ratio in the zirconium source, lithium source and lanthanum source is 1.95~2.05:7:2.95~3.05；
The solvent I is selected from least one of ethyl acetoacetate, methyl acetoacetate, tert-butyl acetoacetate, in solution A
A concentration of 2~7 grams per milliliter in zirconium source；
The solvent II is selected from ethyl alcohol, propyl alcohol, at least one of ethylene glycol, and a concentration of 0.1~0.9 gram of lithium source in solution B/
Milliliter.
8. the preparation method of quasi- solid lithium ion conducting electrolyte according to claim 6, which is characterized in that step 2)
In, the repetition roasting is specially：
Air atmosphere by the product after freeze-drying at 550~750 DEG C roasts 6~15h next time, by a product of roasting tabletting
Afterwards, then under 550~750 DEG C of air atmosphere 6~15h of after baking is carried out.
9. the preparation method of quasi- solid lithium ion conducting electrolyte according to claim 6, which is characterized in that step 3)
In：
The solvent III is selected from methyl pyrrolidone, one or both of anhydrous acetonitrile, a concentration of 20~40 grams of polymer/
It rises；
The mass ratio of the polymer, ceramic electrolyte and lithium salts is 30~50：2~10：1~8；
The drying is carried out in two steps, 12~48 hours dry in air atmosphere first at 50~70 DEG C, then 50~70
It is 12~36 hours dry in vacuum at DEG C.
10. a kind of quasi- solid lithium ion conducting electrolyte according to Claims 1 to 5 any claim lithium battery,
Application in lithium sky battery, lithium-sulfur cell.
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