CN104538670B - A kind of full solid state polymer electrolyte, its preparation method and application - Google Patents
A kind of full solid state polymer electrolyte, its preparation method and application Download PDFInfo
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- CN104538670B CN104538670B CN201410683144.1A CN201410683144A CN104538670B CN 104538670 B CN104538670 B CN 104538670B CN 201410683144 A CN201410683144 A CN 201410683144A CN 104538670 B CN104538670 B CN 104538670B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a kind of full solid state polymer electrolyte, its preparation method and application, belong to field of lithium ion battery, full solid state polymer electrolyte includes PEO, lithium salts, inorganic nanoparticles and ionic liquid, and the lithium salts and the PEO mass ratio are 0.1~0.5, inorganic nanoparticles and ionic liquid quality sum is the 10%~30% of the full solid state polymer electrolyte quality；The lithium salts includes double trifluoromethanesulfonimide lithiums, LiBF4, lithium perchlorate, lithium hexafluoro phosphate, hexafluoroarsenate lithium, the one or more of trifluoromethyl sulfonic acid lithium and dioxalic acid lithium borate；Inorganic nanoparticles include one or more kinds of in nano aluminium oxide, nano silicon oxide, nano zircite and nano barium phthalate.Full solid state polymer electrolyte has preferable mechanical strength and higher ionic conductivity in the present invention.The inventive method technique is simple, and with low cost, raw material are easily obtained.
Description
Technical field
The invention belongs to the preparation field of lithium ion battery electrolyte materials, more particularly, to all solid state polymerization of one kind
Thing electrolyte, its preparation method and application.
Background technology
Currently, lithium ion battery generates tremendous influence to people's daily life and national economy, its be applied to mobile phone,
In terms of the electronic products such as computer, automotive powerplant and renewable energy power generation station.The performance of battery largely takes
Certainly in the development of material, in lithium ion battery, crucial material components include positive pole, negative pole and electrolyte, wherein electrolyte
Material is to influence the key factor of cell safety stability.
At present, the perishable positive and negative electrode of wide variety of liquid electrolyte, so as to cause battery capacity irreversible loss.Together
When the heat that produces of exothermic reaction can also decompose liquid electrolyte, so as to produce fuel gas, and cause fire and blast etc.
Severe safety problem.These drawbacks of liquid electrolyte can be avoided using solid electrolyte, and its shape can arbitrarily be cut out
And change so that battery design is easier, and quality is lighter and handier, in addition, the good mechanical strength of solid electrolyte also has battery
There are more preferable security and persistence.
Organic polyelectrolyte is because its relatively low modulus of elasticity is more suitable for use in polymorphic battery, and it was prepared
Journey is simple and with low cost, so as to receive much attention.Organic polyelectrolyte can be further divided into full solid state polymer electrolysis again
Matter and gel polymer electrolyte.Gel polymer electrolyte is usually that solvent and liquid electrolyte directly are carried out into mixing generation
Gel state, or leaching is made after microporous membrane in polymer puts the imbibition in liquid electrolyte, substantially or liquid electrolyte exists
Conducting, although ionic conductivity performance reaches commercial batteries demand, but the mechanical performance of this electrolyte is poor, and not yet in effect
Solve cathode of lithium dendrite problems, actually transitional product of the liquid electrolyte to solid electrolyte.Comparatively, it is all solid state poly-
Polymer electrolyte has good mechanical performance, and can effectively suppress the generation of cathode of lithium dendrite, therefore turns into current research
Emphasis.
PEO (polyethylene oxide, abbreviation PEO) is generally acknowledged at present most suitable to prepare all solid state electricity
Solve the matrix of matter.The complexing body that PEO can be coordinated with sodium salt or the sylvite formation of alkali metal, the complexing body has certain
Electrical conductivity.At present, the subject matter that PEO base polymer electrolytes face is：Electrical conductivity at room temperature is about also than relatively low
10-6Scm-1, with traditional liquid electrolyte about 10-3Scm-1Still have than larger gap.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of full solid state polymer electrolyte,
Its preparation method and application, its object is to provide that a kind of room-temperature conductivity is higher and mechanical strength preferably all solid state PEO
Base polymer electrolyte, is prepared, it can be applied in lithium ion battery as electrolyte using simple production technology.Thus solve
Certainly all solid state PEO base polymer electrolyte room-temperature conductivities are low, it is impossible to apply the technical problem in lithium ion battery.
To achieve the above object, according to one aspect of the present invention there is provided a kind of full solid state polymer electrolyte, it is special
Levy and be, including PEO, lithium salts, inorganic nanoparticles and ionic liquid, the lithium salts quality and the polycyclic oxygen second
Alkane mass ratio is 0.1~0.5, and inorganic nanoparticles quality and ionic liquid quality sum are electrolysed for the full solid state polymer
The 10%~30% of matter quality；Wherein, the lithium salts includes double trifluoromethanesulfonimide lithiums, LiBF4, lithium perchlorate,
One or more in lithium hexafluoro phosphate, hexafluoroarsenate lithium, trifluoromethyl sulfonic acid lithium and dioxalic acid lithium borate；It is described inorganic
Nano particle includes one or more kinds of in nano aluminium oxide, nano silicon oxide, nano zircite and nano barium phthalate.
Further, the particle diameter of the inorganic nanoparticles is 10nm~100nm.
Further, the thickness of the full solid state polymer electrolyte is 100 μm~300 μm.
It is another aspect of this invention to provide that a kind of method for preparing full solid state polymer electrolyte as described above is also provided,
It is characterised in that it includes following steps：
S1：First lithium salts is mixed with organic solvent, inorganic nanoparticles and ionic liquid are subsequently added into, then stirs equal
It is even, polyethylene oxide powder is eventually adding, and stir until obtaining leucosol；The organic solvent quality and the polycyclic oxygen
Ethane mass ratio is 15~25, and the ratio can ensure follow-up drying property and obtain all solid state polymerization of predetermined thickness
Thing electrolyte；
S2：The step S1 leucosols obtained are placed in culture dish, spontaneously dries, obtains in protective atmosphere environment
Obtain solid film；
S3：The step S2 solid films obtained are dried in vacuo, the vacuum drying temperature is 60~80 DEG C,
The vacuum drying time is 12h~48h, that is, obtains full solid state polymer electrolyte.
Further, ionic liquid described in step S1 is 1- butyl -1- crassitude bis trifluoromethyl sulfimides.
Ionic liquid also liquid, but it is not volatile, even toasts for a long time, it still will not volatilize.
Further, polyethylene oxide molecules amount described in step S1 is 100,000~1,000,000.Such molecular weight of scope,
The intensity and processing performance of full solid state polymer electrolyte prepared can be ensured.
Further, organic solvent described in step S1 includes the one or more in acetonitrile, acetone or tetrahydrofuran.
Organic solvent is used to dissolving and disperse lithium salts, inorganic nanoparticles, polyethylene oxide powder etc., the organic solvent is by certain temperature
During baking, can all it vapor away.
Further, stirring is stirred using magnetic agitation or ultrasonic wave described in step S1, and mixing time be 30min~
Preferably various composition can be made dispersed in 60min, the mixing time.
Further, culture dish described in step S2 is polytetrafluoroethylene (PTFE) culture dish, only using polytetrafluoroethylene (PTFE) culture
Ware just can guarantee that peels off full solid state polymer electrolyte easily, and material is caused during without causing and peel off full solid state polymer electrolyte
The damage of material.
According to the third aspect of the invention, a kind of lithium ion battery is also provided, it is characterised in that it includes as described above
Full solid state polymer electrolyte.
In general, the contemplated above technical scheme of the present invention can obtain following beneficial effect：
1st, to improve PEO base solid electrolyte electrical conductivity, inorganic nanoparticles and ionic liquid are added, nano inorganic is added
Particle can improve mechanical performance, and addition ionic liquid at room temperature then improves electrical conductivity, this is sent out by both synergy
Bright middle full solid state polymer electrolyte has preferable mechanical strength and higher ionic conductivity；
2nd, the addition of inorganic nanoparticles can reduce PEO percent crystallization in massecuite, PEO is in noncrystalline state, favourable conduction lithium
Passing through for ion, electrical conductivity is further improved so as to additionally aid.
3rd, preparation method technique of the present invention is simple, and raw material are easily obtained, with low cost so that PEO bases solid polymer electricity
Solution matter large-scale application is possibly realized in lithium ion battery industry.
Brief description of the drawings
Fig. 1 is the electrochemical impedance spectroscopy EIS figures of comparative example 1, comparative example 2, embodiment 1, embodiment 2；
Fig. 2 is the X-ray diffractogram of full solid state polymer electrolyte prepared by the embodiment of the present invention 1.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below
Not constituting conflict each other can just be mutually combined.
Embodiment 1：
The present embodiment is used to prepare the full solid state polymer electrolyte that thickness is 100 μm, and its composition includes：Molecular weight is 60
Ten thousand PEO, trifluoromethanesulfonimide lithium, particle diameter are 10nm barium titanate, ionic liquid 1- butyl -1- methyl pyrroles
Cough up alkane bis trifluoromethyl sulfimide.Wherein, lithium salts and PEO mass ratio are 0.36, inorganic nanoparticles and ion
Liquid quality sum is the 10% of full solid state polymer electrolyte quality.Ionic liquid is liquid, its it is micro exist with it is all solid state
In polymer dielectric, and ionic liquid is not volatile.
Its preparation method is as follows：
S1：First trifluoromethanesulfonimide lithium is mixed with organic solvent acetonitrile, the metatitanic acid that particle diameter is 10nm is subsequently added into
Barium and ionic liquid 1- butyl -1- crassitude bis trifluoromethyl sulfimides, then magnetic agitation 60min, is eventually adding
Molecular weight is 600,000 polyethylene oxide powder, and further stirs until obtaining leucosol.Any of the above material is added
It is stirred into conical flask.Wherein, the quality 2.05g of polyethylene oxide powder, the quality of trifluoromethanesulfonimide lithium is
0.74g, organic solvent quality is 41g, and organic solvent quality is 20 with PEO mass ratio.The quality of barium titanate is
0.15g, the quality of ionic liquid is 0.16g, and both quality sums are 0.31g.Lithium salts quality and PEO mass ratio
For 0.36.
S2：The step S1 leucosols obtained are placed in polytetrafluoroethylene (PTFE) culture dish, in the protective atmosphere ring of high-purity Ar gas
Spontaneously dried in border, obtain solid film.During using polytetrafluoroethylene (PTFE) culture dish, the solid film of acquisition is easily separated from.
S3：It is dried in vacuo to obtaining solid film in the step S2, vacuum drying chamber is the neat glad DZF- in Shanghai
Vacuum drying temperature is 70 DEG C in 6050 types, the present embodiment, and vacuum drying time is 18h, that is, obtains thickness complete solid for 100 μm
State polymer dielectric.
Full solid state polymer electrolyte quality is 3.1g, inorganic nanoparticles quality and ionic liquid matter in the present embodiment
Amount sum accounts for the 10% of whole full solid state polymer electrolyte quality；
The present embodiment obtains the film that thickness is 100 μm, cuts into disk, electrical conductivity test is carried out with AC impedence method,
As a result it is 7.4E in the electrical conductivity of 25 DEG C of room temperature to show it-5S/cm。
Organic solvent acetonitrile is all volatized into air in 70 DEG C of degree bakings.
Embodiment 2：
The present embodiment is used to prepare the full solid state polymer electrolyte that thickness is 300 μm, and its composition includes：Molecular weight is 80
Ten thousand PEO, LiBF4, particle diameter are 100nm zirconium oxide, ionic liquid 1- butyl -1- crassitudes double three
Methyl fluoride sulfimide.Wherein, lithium salts and PEO mass ratio are 0.5, inorganic nanoparticles and ionic liquid quality
Sum is the 30% of full solid state polymer electrolyte quality.Ionic liquid is liquid, its micro presence and full solid state polymer electricity
Xie Zhizhong.
Its preparation method is as follows：
S1：First trifluoromethanesulfonimide lithium is mixed with organic solvent-acetone, the oxidation that particle diameter is 100nm is subsequently added into
Zirconium and ionic liquid 1- butyl -1- crassitude bis trifluoromethyl sulfimides, then magnetic agitation 30min, is eventually adding
Molecular weight is 800,000 polyethylene oxide powder, and further stirs until obtaining leucosol.Wherein, polyethylene oxide powder
Quality 0.97g, the quality of trifluoromethanesulfonimide lithium is 0.48g, and acetone quality is 14.47g, organic solvent-acetone quality
It is 15 with PEO mass ratio.The quality of barium titanate is 0.30g, and the quality of ionic liquid is 0.32g, both quality it
With for 0.62g.Lithium salts quality is 0.5 with PEO mass ratio.
S2：With step S2 in implementing 1.
S3：It is dried in vacuo to obtaining solid film in the step S2, vacuum drying chamber producer and model are with implementation
Example 1.Vacuum drying temperature is 60 DEG C in the present embodiment, and vacuum drying time is 48h, that is, obtains thickness all solid state for 300 μm
Polymer dielectric.
Full solid state polymer electrolyte quality is 2.07g in the present embodiment, inorganic nanoparticles quality and ionic liquid
Quality sum accounts for the 30% of whole full solid state polymer electrolyte quality.
The present embodiment obtains the film that thickness is 300 μm, cuts into disk, electrical conductivity test is carried out with AC impedence method,
As a result it is 1.4E in the electrical conductivity of 25 DEG C of room temperature to show it-4S/cm。
Embodiment 3：
The present embodiment is used to prepare the full solid state polymer electrolyte that thickness is 120 μm, and its composition includes：Molecular weight is
1000000 PEO, lithium perchlorate and lithium hexafluoro phosphate, the silica that particle diameter is 50nm, ionic liquid 1- butyl -1- first
Base pyrrolidines bis trifluoromethyl sulfimide.Wherein, lithium salts and PEO mass ratio are 0.1, inorganic nanoparticles and
Ionic liquid quality sum is the 15% of full solid state polymer electrolyte quality.Ionic liquid is liquid, its it is micro exist with it is complete
In solid polymer electrolyte.
Its preparation method is as follows：
S1：First lithium perchlorate, lithium hexafluoro phosphate and organic solvent tetrahydrofuran are mixed, particle diameter is subsequently added into for 50nm
Silica and ionic liquid 1- butyl -1- crassitude bis trifluoromethyl sulfimides, then magnetic agitation 39min, most
Molecular weight is added afterwards and is 1,000,000 polyethylene oxide powder, and is further stirred until obtaining leucosol.Wherein, polycyclic oxygen
The quality 3.19g of ethane powder, the quality of trifluoromethanesulfonimide lithium is 0.32g, and acetone quality is 80g, organic solvent third
Ketone quality is 25 with PEO mass ratio.The quality of silica is 0.30g, and the quality of ionic liquid is 0.32g, both
Quality sum is 0.62g.Lithium salts quality is 0.1 with PEO mass ratio.
S2：With step S2 in implementing 1.
S3：It is dried in vacuo to obtaining solid film in the step S2, vacuum drying chamber producer and model are with implementation
Example 1.Vacuum drying temperature is 80 DEG C in the present embodiment, and vacuum drying time is 12h, that is, obtains thickness all solid state for 120 μm
Polymer dielectric.
Full solid state polymer electrolyte quality is 4.13g in the present embodiment, inorganic nanoparticles quality and ionic liquid
Quality sum accounts for the 15% of whole full solid state polymer electrolyte quality.
The present embodiment obtains the film that thickness is 120 μm, cuts into disk, electrical conductivity test is carried out with AC impedence method,
As a result it is 8.9E in the electrical conductivity of 25 DEG C of room temperature to show it-5S/cm。
Embodiment 4：
The present embodiment is used to prepare the full solid state polymer electrolyte that thickness is 200 μm, and its composition includes：Molecular weight is 40
Ten thousand PEO, lithium hexafluoro phosphate and hexafluoroarsenate lithium, particle diameter are 80nm aluminum oxide, ionic liquid 1- butyl -1- first
Base pyrrolidines bis trifluoromethyl sulfimide.Wherein, lithium salts and PEO mass ratio are 0.25, inorganic nanoparticles and
Ionic liquid quality sum is the 20% of full solid state polymer electrolyte quality.Ionic liquid is liquid, its it is micro exist with it is complete
In solid polymer electrolyte.
Its preparation method is as follows：
S1：First lithium salts trifluoromethanesulfonimide lithium is mixed with organic solvent acetonitrile, it is 10nm's to be subsequently added into particle diameter
Barium titanate and ionic liquid 1- butyl -1- crassitude bis trifluoromethyl sulfimides, then magnetic agitation 60min, finally
Add molecular weight and be 600,000 polyethylene oxide powder, and further stir until obtaining leucosol.
Wherein, the quality 1.98g of polyethylene oxide powder, the quality of trifluoromethanesulfonimide lithium is 0.496g, acetone
Quality is 35.64g, and organic solvent-acetone quality is 18 with PEO mass ratio.The quality of silica is 0.30g, from
The quality of sub- liquid is 0.32g, and both quality sums are 0.62g.Lithium salts quality is 0.25 with PEO mass ratio.
S2：With step S2 in implementing 1.
S3：It is dried in vacuo to obtaining solid film in the step S2, vacuum drying chamber producer and model are with implementation
Example 1.Vacuum drying temperature is 70 DEG C in the present embodiment, and vacuum drying time is 40h, that is, obtains thickness all solid state for 200 μm
Polymer dielectric.
Full solid state polymer electrolyte quality is 3.1g, inorganic nanoparticles quality and ionic liquid matter in the present embodiment
Amount sum accounts for the 20% of whole full solid state polymer electrolyte quality；
The present embodiment obtains the film that thickness is 200 μm, cuts into disk, electrical conductivity test is carried out with AC impedence method,
As a result it is 1.01E in the electrical conductivity of 25 DEG C of room temperature to show it-4S/cm。
Embodiment 5：
The present embodiment is used to prepare the full solid state polymer electrolyte that thickness is 250 μm, and its composition includes：Molecular weight is 10
Ten thousand PEO, trifluoromethyl sulfonic acid lithium and dioxalic acid lithium borate, the zirconium oxide that particle diameter is 30nm, ionic liquid 1- fourths
Base -1- crassitude bis trifluoromethyl sulfimides.Wherein, lithium salts and PEO mass ratio are 0.30, inorganic to receive
Rice grain and ionic liquid quality sum are the 20% of full solid state polymer electrolyte quality.Ionic liquid is liquid, and its is micro
In the presence of with full solid state polymer electrolyte.
Its preparation method is as follows：
S1：First trifluoromethyl sulfonic acid lithium and dioxalic acid lithium borate are mixed with organic solvent acetonitrile, being subsequently added into particle diameter is
30nm zirconium oxide and ionic liquid 1- butyl -1- crassitude bis trifluoromethyl sulfimides, then magnetic agitation
50min, is eventually adding molecular weight and is 100,000 polyethylene oxide powder, and further stir until obtaining leucosol.Wherein,
The quality 1.91g of polyethylene oxide powder, the quality of trifluoromethanesulfonimide lithium is 0.572g, and acetonitrile quality is 32.47g,
Organic solvent acetonitrile quality is 17 with PEO mass ratio.The quality of silica is 0.30g, and the quality of ionic liquid is
0.32g, both quality sums are 0.62g.Lithium salts quality is 0.30 with PEO mass ratio.
S2：With step S2 in implementing 1.
S3：It is dried in vacuo to obtaining solid film in the step S2, vacuum drying chamber producer and model are with implementation
Example 1.Vacuum drying temperature is 72 DEG C in the present embodiment, and vacuum drying time is 30h, that is, obtains thickness all solid state for 250 μm
Polymer dielectric.
Full solid state polymer electrolyte quality is 3.1g, inorganic nanoparticles quality and ionic liquid matter in the present embodiment
Amount sum accounts for the 20% of whole full solid state polymer electrolyte quality.
The present embodiment obtains the film that thickness is 250 μm, cuts into disk, electrical conductivity test is carried out with AC impedence method,
As a result it is 1.1E in the electrical conductivity of 25 DEG C of room temperature to show it-4S/cm。
Comparative example 1
This comparative example preparation process is identical with embodiment 1, does not only add nano barium titanate titanate particle and ionic liquid
Body, other compositions are identical.The sample prepared is subjected to electrical conductivity test with AC impedence method, as a result 25 DEG C of conductances of its room temperature
Rate is 6.3E-6S/cm。
Comparative example 2
This comparative example preparation process is identical with embodiment 1, does not only add ionic liquid, and other compositions are identical.
The sample prepared is subjected to electrical conductivity test with AC impedence method, as a result 25 DEG C of electrical conductivity of its room temperature are 1.3E-5S/cm。
Fig. 1 is the electrochemical impedance spectroscopy EIS figures of comparative example 1, comparative example 2, embodiment 1, embodiment 2, it can be seen that right
The room-temperature conductivity for the full solid state polymer electrolyte that ratio 1, comparative example 2, example 1, example 2 are obtained is raised successively, it is seen that received
The room temperature conductance of full solid state polymer electrolyte in the present invention all greatly improved in the addition of rice barium titanate and ionic liquid at room temperature
Rate.
Inorganic nano is indicated in the XRD for the full solid state polymer electrolyte that Fig. 2 is prepared for the embodiment of the present invention 1, figure
The phase of particle, PEO, wherein, ionic liquid is micro in full solid state polymer to be present, and it exists in liquid form,
It is dissolved in PEO matrixes, for conducting lithium ions, X-ray diffractometer can not display it, so, do not have in the XRD
Indicate the material.Without the double trifluoromethanesulfonimide lithium peaks of display in its figure, same explanation lithium salts is dissolved completely in PEO bases
In body.Bag peak in figure illustrates there are a large amount of amorphous phases in the polymer dielectric, this help to greatly improve lithium from
Son improves electrical conductivity in the transmission of polymer dielectric.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, it is not used to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the invention etc., it all should include
Within protection scope of the present invention.
Claims (6)
1. a kind of method for preparing full solid state polymer electrolyte, the full solid state polymer electrolyte include PEO,
Lithium salts, inorganic nanoparticles and ionic liquid, the lithium salts quality are 0.1~0.5, nothing with the PEO mass ratio
Machine nanoparticle mass and ionic liquid quality sum are the 10%~30% of the full solid state polymer electrolyte quality；
Wherein, the lithium salts includes double trifluoromethanesulfonimide lithiums, LiBF4, lithium perchlorate, lithium hexafluoro phosphate, hexafluoro
One or more in arsenic acid lithium, trifluoromethyl sulfonic acid lithium and dioxalic acid lithium borate；The inorganic nanoparticles bag is to receive
Rice barium titanate, the particle diameter of the inorganic nanoparticles is 10nm~100nm, it is characterised in that comprised the following steps：
S1：First lithium salts is mixed with organic solvent, nano barium phthalate and ionic liquid is subsequently added into, then stirs, finally
Polyethylene oxide powder is added, and is stirred until obtaining leucosol；The organic solvent quality and the PEO matter
The ratio between amount is 15~25；
S2：The step S1 leucosols obtained are placed in culture dish, spontaneously dried in protective atmosphere environment, consolidate
Body thin film；
S3：The step S2 solid films obtained are dried in vacuo, the vacuum drying temperature is 60~80 DEG C, described
Vacuum drying time is 12h~48h, that is, obtains full solid state polymer electrolyte.
2. the method as described in claim 1, it is characterised in that ionic liquid described in step S1 is 1- butyl -1- methyl pyrroles
Cough up alkane bis trifluoromethyl sulfimide.
3. method as claimed in claim 2, it is characterised in that polyethylene oxide molecules amount described in step S1 is 100,000~
1000000.
4. method as claimed in claim 2 or claim 3, it is characterised in that organic solvent described in step S1 includes acetonitrile, acetone or
One or more in tetrahydrofuran.
5. method as claimed in claim 4, it is characterised in that stirring is stirred using magnetic agitation or ultrasonic wave described in step S1
Mix, and mixing time is 30min~60min.
6. method as claimed in claim 5, it is characterised in that culture dish described in step S2 is polytetrafluoroethylene (PTFE) culture dish.
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| WO2015195595A1 (en) | 2014-06-17 | 2015-12-23 | Medtronic, Inc. | Semi-solid electrolytes for batteries |
| US10333173B2 (en) | 2014-11-14 | 2019-06-25 | Medtronic, Inc. | Composite separator and electrolyte for solid state batteries |
| CN104952634B (en) * | 2015-06-05 | 2019-07-19 | 北京大学 | A kind of ionic liquid-lithium salts gel polymer electrolyte and its preparation and application |
| KR20180021797A (en) | 2015-06-24 | 2018-03-05 | 콴텀스케이프 코포레이션 | Composite electrolyte |
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