CN108598550A - A kind of high security solid state composite electrolyte, preparation method and lithium battery - Google Patents
A kind of high security solid state composite electrolyte, preparation method and lithium battery Download PDFInfo
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- CN108598550A CN108598550A CN201810353945.XA CN201810353945A CN108598550A CN 108598550 A CN108598550 A CN 108598550A CN 201810353945 A CN201810353945 A CN 201810353945A CN 108598550 A CN108598550 A CN 108598550A
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- H01M10/00—Secondary cells; Manufacture thereof
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The present invention relates to a kind of high security solid state composite electrolyte, preparation method and lithium batteries, belong to lithium secondary battery electrolyte technical field.The electrolyte is distributed in zirconium dioxide nanometer skeleton after being mixed by lithium salts, ionic liquid and cathode film formation additive and constitutes；The skeleton is three-dimensional net structure made of being stacked by nano zirconium dioxide particle, is distributed irregular and interconnected mesopore orbit.Mixed solution containing lithium salts, ionic liquid and cathode film formation additive is solidificated in the skeleton by the ester-based organic compound containing zirconium during hydrolysis generates zirconium dioxide and is made by the electrolyte.The electrolyte can play all the components respectively advantage, excellent combination property：High ionic conductivity, thermal stability and fixedness, good chemical stability, bio-compatibility, nontoxicity and mechanical strength, can form stable solid electrolyte membrane in negative terminal surface；The method realization large-scale production easy to operate, environmentally protective, easy.
Description
Technical field
The present invention relates to a kind of high security solid state composite electrolyte, preparation method and lithium batteries, belong to the secondary electricity of lithium
Pond electrolyte technical field.
Background technology
Lithium ion battery as energy storage of new generation and conversion main force medium, how processability is more excellent, safety more
The good and lower lithium ion battery of cost is one of the key points and difficulties realized new energy development and utilized.Electrolyte is as battery
An essential and crucial part carries the key player for transmitting charge in inside battery, to the safety of battery, each
Item chemical property and cost play decisive role.Want fundamentally to solve the inflammable, explosive of liquid electrolyte and easily let out
The problem of dew, need to jump out the scope of liquid electrolyte, develop novel high security electrolyte system.Therefore, tradition is organic
Electrolyte is substituted for solid electrolyte and is just attract more and more concerns, especially in recent years energy storage field to high-energy density
Active demand with high security lithium metal battery is just pushing the research and development of solid-state lithium metal battery significantly.
For the lithium ion solid electrolyte of current conventional study, solid polyelectrolyte system is due to organic polymer
Object nature it is restricted, in mechanical performance, thermal stability and electrochemical stability etc., there is also clearly disadvantageous.Entirely
Most of electrolyte in Solid inorganic solid electrolytic plastidome is difficult at two aspects of ionic conductivity and electrochemical stability
It gets both.Therefore, in order to combine the performance of both, the better lithium ion solid electrolyte of comprehensive performance, researcher are obtained
Also propose various composite solid electrolytes in succession, so that it is provided simultaneously with the respective advantage of two or more electrolyte,
And make up the single electrolyte deficiency of itself.But the selection of composite electrolyte internal material and complex method are ever-changing, such as
What screening also becomes the important problem in science in the field with optimization.
A kind of existing composite electrolyte being fixed on ionic liquid in zirconium dioxide nanoparticles of report
(Angew.Chem.2010,122,9344-9347), the electrolyte have preferable thermal stability and suitable conductivity.But
Be the electrolyte it is in integrally gel, is first to synthesize zirconium dioxide nanoparticles and then ionic liquid to be passed through covalent bond
Effect grafting fix.Ionic liquid adsorbance is less, and conductivity is also not up to desirable, and has not been reported and lithium metal electricity
Related data after the matching of pond.In view of the above-mentioned problems, it is necessory to synthesize one kind have both excellent heat stability and chemical stability,
High ionic conductivity, excellent electrochemical performance and the solid electrolyte that lithium an- ode can be protected.
Invention content
In view of this, one of the objects of the present invention is to provide a kind of high security solid state composite electrolyte, the electricity
Solving matter has good thermal stability and chemical stability, high ionic conductivity, good filming performance and excellent electricity
Chemical property.
The second object of the present invention is to provide a kind of system of high security solid state composite electrolyte of the present invention
Preparation Method.
The third object of the present invention is to provide a kind of lithium battery, and the electrolyte of the lithium battery is of the present invention one
Kind high security solid state composite electrolyte.
The purpose of the present invention is what is be achieved through the following technical solutions.
A kind of high security solid state composite electrolyte, the electrolyte are added by lithium salts, ionic liquid and cathode film formation
It is distributed in zirconium dioxide nanometer skeleton and constitutes after agent mixing.
The lithium salts is conventional use of lithium salts in field of lithium；It is preferred that the lithium salts is di-oxalate lithium borate (LiB
(C2O4)2, LiBOB), difluorine oxalic acid boracic acid lithium (LiBF2(C2O4), LiODFB), trifluoromethanesulfonic acid lithium (LiCF3SO3), double trifluoros
Sulfonyl methane imine lithium (Li (CF3SO2)2N, LiTFSI), double fluorine sulfimide lithium (Li (FSO2)2N, LiFSI), hexafluoroethane sulphur
Imide li (Li (C2F5SO2)2) and perfluoromethane sulfonymethyl lithium (LiC (CF N3SO2)3One or more of).
The ionic liquid is conventional use of ionic liquid in field of lithium；It is preferred that the ionic liquid is 1- second
Base -3- methylimidazole bis-trifluoromethylsulfoandimides salt, 1- propyl -3- methylimidazole bis-trifluoromethylsulfoandimides salt, 1- butyl -3-
The double fluorine sulfonamides of methylimidazole bis-trifluoromethylsulfoandimide salt, 1- ethyl-3-methylimidazoles, 1- propyl -3- methyl miaows
The double fluorine sulfonamides of azoles, the double fluorine sulfonamides of 1- butyl -3- methylimidazoles, N- methyl, the double fluoroforms of propyl pyrrole
Sulfimide salt, N- methyl, butyl pyrroles's bis-trifluoromethylsulfoandimide salt, N- methyl, the double fluorine sulfonamides of propyl pyrrole
With N- methyl, one or more of butyl pyrroles's bis-trifluoromethylsulfoandimide salt.
The cathode film formation additive is conventional use of cathode film formation additive in field of lithium；It is preferred that the cathode
Film for additive is fluorinated ethylene carbonate (FEC), vinylene carbonate (VC), vinylethylene carbonate (VEC) and sulfurous acid
One or more of acrylic ester (PS).
The nano zirconium dioxide skeleton is three-dimensional net structure made of being stacked by nano zirconium dioxide particle, is had point
The irregular and interconnected mesopore orbit of cloth；It is preferred that the particle size of nano zirconium dioxide is 10nm~40nm.
A kind of preparation method of high security solid state composite electrolyte of the present invention, steps are as follows for the method：
In the environment of being less than or equal to 0.1ppm full of inert gas and moisture, lithium salts is mixed with ionic liquid,
Mixed solution is obtained after lithium salts is completely dissolved, and the mixing of cathode film formation additive is added；Then the ester-based organic compound containing zirconium is added
It mixes to solution at uniformly thick, adds formic acid and be constantly uniformly mixed, stop stirring in after class milk shape after solution
It mixes, a kind of high security solid state composite electrolyte is obtained after standing solidification.
Wherein, preferably in mixed solution lithium salts a concentration of 0.2molKg–1~1.2molKg–1。
It is preferred that the quality of cathode film formation additive accounts for the 1%~5% of mixed solution quality.
The ester-based organic compound containing zirconium is tetrabutyl zirconate, four n-propyl zirconates and four (triethanolamine) zirconates
One or more of.
The molar ratio of preferred ion liquid and the ester-based organic compound containing zirconium is 0.5~2:1.
It is preferred that mixing time is 5min, preferably mixing speed is 400rmin–1。
A kind of high security solid state composite electrolyte of the present invention is suitable for lithium battery, is preferably applied to lithium metal
Battery.
The electrolyte of a kind of lithium battery, the lithium battery is a kind of high security solid state combined electrolysis of the present invention
Matter；It is preferred that the lithium battery is lithium metal battery.
Advantageous effect
1. the present invention provides a kind of high security solid state composite electrolyte, the electrolyte can play it is all at
The respective advantage divided, has excellent comprehensive performance：Zirconium dioxide and ionic liquid itself all have high safety, therefore institute
It states electrolyte and had both had the high ionic conductivity of ionic liquid, thermal stability and fixedness, it is good but also with zirconium dioxide skeleton
Good chemical stability, bio-compatibility, nontoxicity and mechanical strength, simultaneously because the addition of film for additive, the electrolysis
Matter can also form stable solid electrolyte membrane (SEI) in negative terminal surface, can protect lithium anode；
2. the present invention provides a kind of preparation method of high security solid state composite electrolyte, the electrolyte is by containing zirconium
Ester-based organic compound will be containing lithium salts, ionic liquid and cathode film formation additive during hydrolysis generates zirconium dioxide it is mixed
Conjunction solution, which is solidificated in nano particle skeleton, to be prepared；The preparation method belongs to " one kettle way ", easy to operate, green ring
It protects, be easily achieved large-scale production；
3. the present invention provides a kind of lithium battery, the electrolyte of the lithium battery is a kind of high security of the present invention
Solid state composite electrolyte, especially when lithium battery is lithium metal battery, lithium anode contacts well with electrolyte interface
And interface stability, dendrite are inhibited well, battery shows good cyclical stability and high security.
Description of the drawings
Fig. 1 is that the transmission of the high security solid state composite electrolyte for preparing after remove ionic liquid is electric in embodiment 2
Sub- microscope figure.
Fig. 2 is the scanning electron microscope diagram of the high security solid state composite electrolyte prepared in embodiment 2.
Fig. 3 is the thermal gravimetric analysis curve figure of the high security solid state composite electrolyte prepared in embodiment 2.
Fig. 4 is that the lithium metal battery that the high security solid state composite electrolyte prepared in embodiment 2 is assembled into is recycling 5
The scanning electron microscope diagram on lithium an- ode surface after week.
Specific implementation mode
The present invention is described in further detail with reference to the accompanying drawings and examples.But the present invention is not limited to following implementations
Example.
In following embodiment, used analysis test method is as follows：
Transmission electron microscope (TEM) is tested：Model FEI Tecnai G2F20, the U.S.；
Scanning electron microscope (SEM) is tested：Model HITACHI S-4800, Japan；
Thermogravimetric analysis (TGA) is tested：Model Netzsch STA 499F3, Germany；
Electrochemical AC impedance (EIS) is tested：Model C HI604D, China.
Embodiment 1
By the bis- trifluoromethanesulfonimide lithiums of 0.861g in the glove box full of argon gas and moisture less than 0.1ppm
It is mixed with 2.5g 1- ethyl-3-methylimidazole bis-trifluoromethylsulfoandimide salt, waits for that double trifluoromethanesulfonimide lithiums are completely molten
0.168g fluorinated ethylene carbonates are added after solution；Then be added 2.45g tetrabutyl zirconates, stirring to solution at uniformly it is thick,
It adds dropwise formic acid and is stirred continuously, with 400rmin–1Speed stir 5min, it is to be mixed uniformly, solution be in homogeneous class
Stop stirring after milk shape, the solid product of white is obtained after standing solidification, is a kind of high security solid-state of the present invention
Change composite electrolyte.
By LiFePO4Electrode slice, above-mentioned gained solid state composite electrolyte and lithium metal are assembled into lithium metal battery,
Battery is disassembled after recycling 5 weeks on LAND battery test systems, metal lithium sheet is taken out, electron microscope is scanned to its surface
(SEM) it tests.
A kind of high security solid state composite electrolyte manufactured in the present embodiment is tested, it is as a result as follows：
(1) transmission electron microscope (TEM) is tested：
After the electrolyte is removed ionic liquid, carry out TEM tests the result shows that titanium dioxide in the electrolyte
A diameter of 20nm~30nm of zirconium particle, particle are the low crystalline phases of low temperature, belong to polycrystalline material, have crystallite area also and have and is amorphous
Area can be distributed more Lewis acidic sites, promote the dissociation and transmission of lithium ion.
(2) scanning electron microscope (SEM) is tested：
SEM test results show that the electrolyte has and abundant interconnected are received by what zirconium dioxide particle was assembled into
Rice grain pattern road, ionic liquid is attached to nano grain surface, and can be moved in nano pore and transmit lithium ion；Lithium metal table
The SEM tests in face show that the electrolyte can form fine and close SEI films on lithium anode surface, are given birth to almost without Li dendrite
At playing a very good protection to lithium metal.
(3) thermogravimetric analysis (TGA) is tested：
TGA test results show that the electrolyte has good thermal stability, only a small amount of matter when less than 400 DEG C
Amount loss.
(4) electrochemical AC impedance (EIS) is tested：
EIS test results show that room temperature (25 DEG C) ionic conductivity of the electrolyte is 0.80 × 10–3S·cm–1。
Embodiment 2
By the bis- trifluoromethanesulfonimide lithiums of 0.717g in the glove box full of argon gas and moisture less than 0.1ppm
It is mixed with 2.5g 1- ethyl-3-methylimidazole bis-trifluoromethylsulfoandimide salt, waits for that double trifluoromethanesulfonimide lithiums are completely dissolved
0.161g fluorinated ethylene carbonates are added afterwards；Then be added 2.45g tetrabutyl zirconates, stirring to solution at uniformly it is thick, then
Formic acid is added dropwise dropwise and is stirred continuously, with 400rmin–1Speed stir 5min, wait for solution be uniformly mixed, be in homogeneous class ox
Stop stirring after creamy, the solid product of white is obtained after standing solidification, is a kind of high security solid state of the present invention
Composite electrolyte.
By LiFePO4Electrode slice, above-mentioned gained solid state composite electrolyte and lithium metal are assembled into lithium metal battery,
Battery is disassembled after recycling 5 weeks on LAND battery test systems, metal lithium sheet is taken out, electron microscope is scanned to its surface
(SEM) it tests.
A kind of high security solid state composite electrolyte manufactured in the present embodiment is tested, it is as a result as follows：
(1) transmission electron microscope (TEM) is tested：
After the electrolyte is removed ionic liquid, TEM tests are carried out, the results are shown in Figure 1, shows in the electrolyte
Zirconium dioxide particle a diameter of 20nm~30nm, particle is the low crystalline phase of low temperature, belongs to polycrystalline material, there is crystallite area
There is amorphous region, more Lewis acidic sites can be distributed, promotes the dissociation and transmission of lithium ion.
(2) scanning electron microscope (SEM) is tested：
As shown in Fig. 2, SEM test results show that the electrolyte has the abundant phase being assembled by zirconium dioxide particle
Intercommunicated nanochannel, ionic liquid are attached to nano grain surface, and can be moved in nano pore and transmit lithium from
Son；As shown in figure 4, the SEM tests of metallic lithium surface show that the electrolyte can form densification on lithium anode surface
SEI films are generated almost without Li dendrite, are played a very good protection to lithium metal.
(3) thermogravimetric analysis (TGA) is tested：
As shown in figure 3, TGA test results show that the electrolyte has good thermal stability, when less than 400 DEG C only
There is a small amount of mass loss.
(4) electrochemical AC impedance (EIS) is tested：
EIS test results show that room temperature (25 DEG C) ionic conductivity of the electrolyte is 0.74 × 10–3S·cm–1。
Embodiment 3
In the glove box contained full of argon gas and moisture less than 0.1ppm by the bis- trifluoromethanesulfonimide lithiums of 0.576g and
2.5g 1- ethyl-3-methylimidazole bis-trifluoromethylsulfoandimide salt mixes, after double trifluoromethanesulfonimide lithiums are completely dissolved
0.154g fluorinated ethylene carbonates are added；Then be added 2.45g tetrabutyl zirconates, stirring to solution at uniformly it is thick, then by
Drop is added dropwise formic acid and is stirred continuously, with 400rmin–1Speed stir 5min, wait for solution be uniformly mixed, be in homogeneous class milk
Stop stirring after shape, the solid product of white is obtained after standing solidification, it is multiple for a kind of high security solid state of the present invention
Close electrolyte.
By LiFePO4Electrode slice, above-mentioned gained solid state composite electrolyte and lithium metal are assembled into lithium metal battery,
Battery is disassembled after recycling 5 weeks on LAND battery test systems, metal lithium sheet is taken out, electron microscope is scanned to its surface
(SEM) it tests.
A kind of high security solid state composite electrolyte manufactured in the present embodiment is tested, it is as a result as follows：
(1) transmission electron microscope (TEM) is tested：
TEM tests are carried out after the electrolyte is removed ionic liquid, the results showed that the zirconium dioxide in the electrolyte
A diameter of 20nm~30nm of particle, particle are the low crystalline phases of low temperature, belong to polycrystalline material, have crystallite area also and have and is amorphous
Area can be distributed more Lewis acidic sites, promote the dissociation and transmission of lithium ion.
(2) scanning electron microscope (SEM) is tested：
SEM test results show that the electrolyte has and abundant interconnected are received by what zirconium dioxide particle was assembled into
Rice grain pattern road, ionic liquid is attached to nano grain surface, and can be moved in nano pore and transmit lithium ion；Lithium metal table
The SEM tests in face show that the electrolyte can form fine and close SEI films on lithium anode surface, are given birth to almost without Li dendrite
At playing a very good protection to lithium metal.
(3) thermogravimetric analysis (TGA) is tested：
TGA test results show that the electrolyte has good thermal stability, only a small amount of matter when less than 400 DEG C
Amount loss.
(4) electrochemical AC impedance (EIS) is tested：
EIS test results show that room temperature (25 DEG C) ionic conductivity of the electrolyte is 0.68 × 10–3S·cm–1。
Embodiment 4
By the bis- trifluoromethanesulfonimide lithiums of 0.717g in the glove box full of argon gas and moisture less than 0.1ppm
With 2.5g N- methyl, propyl pyrrole bis-trifluoromethylsulfoandimide salt mixing, after double trifluoromethanesulfonimide lithiums are completely dissolved
0.161g fluorinated ethylene carbonates are added；Then be added 2.35g tetrabutyl zirconates, stirring to solution at uniformly it is thick, then by
Drop is added dropwise formic acid and is stirred continuously, with 400rmin–1Speed stir 5min, wait for solution be uniformly mixed, be in homogeneous class milk
Stop stirring after shape, the solid product of white is obtained after standing solidification, it is multiple for a kind of high security solid state of the present invention
Close electrolyte.
By LiFePO4Electrode slice, above-mentioned gained solid state composite electrolyte and lithium metal are assembled into lithium metal battery,
Battery is disassembled after recycling 5 weeks on LAND battery test systems, metal lithium sheet is taken out, electron microscope is scanned to its surface
(SEM) it tests.
A kind of high security solid state composite electrolyte manufactured in the present embodiment is tested, it is as a result as follows：
(1) transmission electron microscope (TEM) is tested：
TEM tests are carried out after the electrolyte is removed ionic liquid, the results showed that the zirconium dioxide in the electrolyte
A diameter of 20nm~30nm of particle, particle are the low crystalline phases of low temperature, belong to polycrystalline material, have crystallite area also and have and is amorphous
Area can be distributed more Lewis acidic sites, promote the dissociation and transmission of lithium ion.
(2) scanning electron microscope (SEM) is tested：
SEM test results show that the electrolyte has and abundant interconnected are received by what zirconium dioxide particle was assembled into
Rice grain pattern road, ionic liquid is attached to nano grain surface, and can be moved in nano pore and transmit lithium ion；Lithium metal table
The SEM tests in face show that the electrolyte can form fine and close SEI films on lithium anode surface, are given birth to almost without Li dendrite
At playing a very good protection to lithium metal.
(3) thermogravimetric analysis (TGA) is tested：
TGA test results show that the electrolyte has good thermal stability, only a small amount of matter when less than 400 DEG C
Amount loss.
(4) electrochemical AC impedance (EIS) is tested：
EIS test results show that room temperature (25 DEG C) ionic conductivity of the electrolyte is 0.72 × 10–3S·cm–1。
Embodiment 5
By the bis- trifluoromethanesulfonimide lithiums of 0.717g in the glove box full of argon gas and moisture less than 0.1ppm
With 2.5g N- methyl, propyl pyrrole bis-trifluoromethylsulfoandimide salt mixing, after double trifluoromethanesulfonimide lithiums are completely dissolved
0.161g fluorinated ethylene carbonates are added；Then 4.7g tetrabutyl zirconates are added, stirring to solution is at uniformly thick, then dropwise
Formic acid is added dropwise and is stirred continuously, with 400rmin–1Speed stir 5min, wait for solution be uniformly mixed, be in homogeneous class milk shape
Stop stirring afterwards, the solid product of white is obtained after standing solidification, is that a kind of high security solid state of the present invention is compound
Electrolyte.
By LiFePO4Electrode slice, above-mentioned gained solid state composite electrolyte and lithium metal are assembled into lithium metal battery,
Battery is disassembled after recycling 5 weeks on LAND battery test systems, metal lithium sheet is taken out, electron microscope is scanned to its surface
(SEM) it tests.
A kind of high security solid state composite electrolyte manufactured in the present embodiment is tested, it is as a result as follows：
(1) transmission electron microscope (TEM) is tested：
TEM tests are carried out after the electrolyte is removed ionic liquid, the results showed that the zirconium dioxide in the electrolyte
A diameter of 20nm~30nm of particle, particle are the low crystalline phases of low temperature, belong to polycrystalline material, have crystallite area also and have and is amorphous
Area can be distributed more Lewis acidic sites, promote the dissociation and transmission of lithium ion.
(2) scanning electron microscope (SEM) is tested：
SEM test results show that the electrolyte has and abundant interconnected are received by what zirconium dioxide particle was assembled into
Rice grain pattern road, ionic liquid is attached to nano grain surface, and can be moved in nano pore and transmit lithium ion；Lithium metal table
The SEM tests in face show that the electrolyte can form fine and close SEI films on lithium anode surface, are given birth to almost without Li dendrite
At playing a very good protection to lithium metal.
(3) thermogravimetric analysis (TGA) is tested：
TGA test results show that the electrolyte has good thermal stability, only a small amount of matter when less than 400 DEG C
Amount loss.
(4) electrochemical AC impedance (EIS) is tested：
EIS test results show that room temperature (25 DEG C) ionic conductivity of the electrolyte is 0.58 × 10–4S·cm–1。
Embodiment 6
By the bis- trifluoromethanesulfonimide lithiums of 0.717g in the glove box full of argon gas and moisture less than 0.1ppm
With 2.5g N- methyl, propyl pyrrole bis-trifluoromethylsulfoandimide salt mixing, after double trifluoromethanesulfonimide lithiums are completely dissolved
0.161g fluorinated ethylene carbonates are added；Then be added 3.52g tetrabutyl zirconates, stirring to solution at uniformly it is thick, then by
Drop is added dropwise formic acid and is stirred continuously, with 400rmin–1Speed stir 5min, wait for solution be uniformly mixed, be in homogeneous class milk
Stop stirring after shape, the solid product of white is obtained after standing solidification, it is multiple for a kind of high security solid state of the present invention
Close electrolyte.
By LiFePO4Electrode slice, above-mentioned gained solid state composite electrolyte and lithium metal are assembled into lithium metal battery,
Battery is disassembled after recycling 5 weeks on LAND battery test systems, metal lithium sheet is taken out, electron microscope is scanned to its surface
(SEM) it tests.
A kind of high security solid state composite electrolyte manufactured in the present embodiment is tested, it is as a result as follows：
(1) transmission electron microscope (TEM) is tested：
TEM tests are carried out after the electrolyte is removed ionic liquid, the results showed that the zirconium dioxide in the electrolyte
A diameter of 20nm~30nm of particle, particle are the low crystalline phases of low temperature, belong to polycrystalline material, have crystallite area also and have and is amorphous
Area can be distributed more Lewis acidic sites, promote the dissociation and transmission of lithium ion.
(2) scanning electron microscope (SEM) is tested：
SEM test results show that the electrolyte has and abundant interconnected are received by what zirconium dioxide particle was assembled into
Rice grain pattern road, ionic liquid is attached to nano grain surface, and can be moved in nano pore and transmit lithium ion；Lithium metal table
The SEM tests in face show that the electrolyte can form fine and close SEI films on lithium anode surface, are given birth to almost without Li dendrite
At playing a very good protection to lithium metal.
(3) thermogravimetric analysis (TGA) is tested：
TGA test results show that the electrolyte has good thermal stability, only a small amount of matter when less than 400 DEG C
Amount loss.
(4) electrochemical AC impedance (EIS) is tested：
EIS test results show that room temperature (25 DEG C) ionic conductivity of the electrolyte is 0.89 × 10–4S·cm–1。
Embodiment 7
By the bis- trifluoromethanesulfonimide lithiums of 0.717g in the glove box full of argon gas and moisture less than 0.1ppm
With 2.5g N- methyl, propyl pyrrole bis-trifluoromethylsulfoandimide salt mixing, after double trifluoromethanesulfonimide lithiums are completely dissolved
0.161g fluorinated ethylene carbonates are added；Then be added 1.17g tetrabutyl zirconates, stirring to solution at uniformly it is thick, then by
Drop is added dropwise formic acid and is stirred continuously, with 400rmin–1Speed stir 5min, wait for solution be uniformly mixed, be in homogeneous class milk
Stop stirring after shape, the solid product of white is obtained after standing solidification, it is multiple for a kind of high security solid state of the present invention
Close electrolyte.
By LiFePO4Electrode slice, above-mentioned gained solid state composite electrolyte and lithium metal are assembled into lithium metal battery,
Battery is disassembled after recycling 5 weeks on LAND battery test systems, metal lithium sheet is taken out, electron microscope is scanned to its surface
(SEM) it tests.
A kind of high security solid state composite electrolyte manufactured in the present embodiment is tested, it is as a result as follows：
(1) transmission electron microscope (TEM) is tested：
TEM tests are carried out after the electrolyte is removed ionic liquid, the results showed that the zirconium dioxide in the electrolyte
A diameter of 20nm~30nm of particle, particle are the low crystalline phases of low temperature, belong to polycrystalline material, have crystallite area also and have and is amorphous
Area can be distributed more Lewis acidic sites, promote the dissociation and transmission of lithium ion.
(2) scanning electron microscope (SEM) is tested：
SEM test results show that the electrolyte has and abundant interconnected are received by what zirconium dioxide particle was assembled into
Rice grain pattern road, ionic liquid is attached to nano grain surface, and can be moved in nano pore and transmit lithium ion；Lithium metal table
The SEM tests in face show that the electrolyte can form fine and close SEI films on lithium anode surface, are given birth to almost without Li dendrite
At playing a very good protection to lithium metal.
(3) thermogravimetric analysis (TGA) is tested：
TGA test results show that the electrolyte has good thermal stability, only a small amount of matter when less than 300 DEG C
Amount loss.
(4) electrochemical AC impedance (EIS) is tested：
EIS test results show that room temperature (25 DEG C) ionic conductivity of the electrolyte is 1.23 × 10–3S·cm–1。
Embodiment 8
By the bis- trifluoromethanesulfonimide lithiums of 0.717g in the glove box full of argon gas and moisture less than 0.1ppm
With 2.5g N- methyl, propyl pyrrole bis-trifluoromethylsulfoandimide salt mixing, after double trifluoromethanesulfonimide lithiums are completely dissolved
0.161g fluorinated ethylene carbonates are added；Then be added tetra- n-propyl zirconates of 2.08g, stirring to solution at uniformly it is thick,
It adds dropwise formic acid and is stirred continuously, with 400rmin–1Speed stir 5min, wait for solution be uniformly mixed, be in homogeneous class
Stop stirring after milk shape, the solid product of white is obtained after standing solidification, is a kind of high security solid-state of the present invention
Change composite electrolyte.
By LiFePO4Electrode slice, above-mentioned gained solid state composite electrolyte and lithium metal are assembled into lithium metal battery,
Battery is disassembled after recycling 5 weeks on LAND battery test systems, metal lithium sheet is taken out, electron microscope is scanned to its surface
(SEM) it tests.
A kind of high security solid state composite electrolyte manufactured in the present embodiment is tested, it is as a result as follows：
(1) transmission electron microscope (TEM) is tested：
TEM tests are carried out after the electrolyte is removed ionic liquid, the results showed that the zirconium dioxide in the electrolyte
A diameter of 20nm~30nm of particle, particle are the low crystalline phases of low temperature, belong to polycrystalline material, have crystallite area also and have and is amorphous
Area can be distributed more Lewis acidic sites, promote the dissociation and transmission of lithium ion.
(2) scanning electron microscope (SEM) is tested：
SEM test results show that the electrolyte has and abundant interconnected are received by what zirconium dioxide particle was assembled into
Rice grain pattern road, ionic liquid is attached to nano grain surface, and can be moved in nano pore and transmit lithium ion；Lithium metal table
The SEM tests in face show that the electrolyte can form fine and close SEI films on lithium anode surface, are given birth to almost without Li dendrite
At playing a very good protection to lithium metal.
(3) thermogravimetric analysis (TGA) is tested：
TGA test results show that the electrolyte has good thermal stability, only a small amount of matter when less than 400 DEG C
Amount loss.
(4) electrochemical AC impedance (EIS) is tested：
EIS test results show that room temperature (25 DEG C) ionic conductivity of the electrolyte is 0.77 × 10–3S·cm–1。
Embodiment 9
By the bis- trifluoromethanesulfonimide lithiums of 0.717g in the glove box full of argon gas and moisture less than 0.1ppm
It is mixed with 2.5g 1- ethyl-3-methylimidazole bis-trifluoromethylsulfoandimide salt, waits for that double trifluoromethanesulfonimide lithiums are completely dissolved
0.064g fluorinated ethylene carbonates are added afterwards；Then be added 2.45g tetrabutyl zirconates, stirring to solution at uniformly it is thick, then
Formic acid is added dropwise dropwise and is stirred continuously, with 400rmin–1Speed stir 5min, wait for solution be uniformly mixed, be in homogeneous class ox
Stop stirring after creamy, the solid product of white is obtained after standing solidification, is a kind of high security solid state of the present invention
Composite electrolyte.
By LiFePO4Electrode slice, above-mentioned gained solid state composite electrolyte and lithium metal are assembled into lithium metal battery,
Battery is disassembled after recycling 5 weeks on LAND battery test systems, metal lithium sheet is taken out, electron microscope is scanned to its surface
(SEM) it tests.
A kind of high security solid state composite electrolyte manufactured in the present embodiment is tested, it is as a result as follows：
(1) transmission electron microscope (TEM) is tested：
TEM tests are carried out after the electrolyte is removed ionic liquid, the results showed that the zirconium dioxide in the electrolyte
A diameter of 20nm~30nm of particle, particle are the low crystalline phases of low temperature, belong to polycrystalline material, have crystallite area also and have and is amorphous
Area can be distributed more Lewis acidic sites, promote the dissociation and transmission of lithium ion.(2) scanning electron microscope (SEM) is surveyed
Examination：
SEM test results show that the electrolyte has and abundant interconnected are received by what zirconium dioxide particle was assembled into
Rice grain pattern road, ionic liquid is attached to nano grain surface, and can be moved in nano pore and transmit lithium ion；Lithium metal table
The SEM tests in face show that the electrolyte can form fine and close SEI films on lithium anode surface, are given birth to almost without Li dendrite
At playing a very good protection to lithium metal.
(3) thermogravimetric analysis (TGA) is tested：
TGA test results show that the electrolyte has good thermal stability, only a small amount of matter when less than 400 DEG C
Amount loss.
(4) electrochemical AC impedance (EIS) is tested：
EIS test results show that room temperature (25 DEG C) ionic conductivity of the electrolyte is 0.69 × 10–3S·cm–1。
Embodiment 10
By the bis- trifluoromethanesulfonimide lithiums of 0.717g in the glove box full of argon gas and moisture less than 0.1ppm
It is mixed with 2.5g 1- ethyl-3-methylimidazole bis-trifluoromethylsulfoandimide salt, waits for that double trifluoromethanesulfonimide lithiums are completely dissolved
0.161g vinylene carbonates are added afterwards；Then be added 2.45g tetrabutyl zirconates, stirring to solution at uniformly it is thick, then by
Drop is added dropwise formic acid and is stirred continuously, with 400rmin–1Speed stir 5min, wait for solution be uniformly mixed, be in homogeneous class milk
Stop stirring after shape, the solid product of white is obtained after standing solidification, it is multiple for a kind of high security solid state of the present invention
Close electrolyte.
By LiFePO4Electrode slice, above-mentioned gained solid state composite electrolyte and lithium metal are assembled into lithium metal battery,
Battery is disassembled after recycling 5 weeks on LAND battery test systems, metal lithium sheet is taken out, electron microscope is scanned to its surface
(SEM) it tests.
A kind of high security solid state composite electrolyte manufactured in the present embodiment is tested, it is as a result as follows：
(1) transmission electron microscope (TEM) is tested：
TEM tests are carried out after the electrolyte is removed ionic liquid, the results showed that the zirconium dioxide in the electrolyte
A diameter of 20nm~30nm of particle, particle are the low crystalline phases of low temperature, belong to polycrystalline material, have crystallite area also and have and is amorphous
Area can be distributed more Lewis acidic sites, promote the dissociation and transmission of lithium ion.
(2) scanning electron microscope (SEM) is tested：
SEM test results show that the electrolyte has and abundant interconnected are received by what zirconium dioxide particle was assembled into
Rice grain pattern road, ionic liquid is attached to nano grain surface, and can be moved in nano pore and transmit lithium ion；Lithium metal table
The SEM tests in face show that the electrolyte can form fine and close SEI films on lithium anode surface, are given birth to almost without Li dendrite
At playing a very good protection to lithium metal.
(3) thermogravimetric analysis (TGA) is tested：
TGA test results show that the electrolyte has good thermal stability, only a small amount of matter when less than 400 DEG C
Amount loss.
(4) electrochemical AC impedance (EIS) is tested：
EIS test results show that room temperature (25 DEG C) ionic conductivity of the electrolyte is 0.81 × 10–3S·cm–1。
Embodiment 11
By the bis- fluorine sulfimide lithiums of 0.467g and 2.5g in the glove box full of argon gas and moisture less than 0.1ppm
1- ethyl-3-methylimidazole bis-trifluoromethylsulfoandimide salt mixes, and 0.148g is added after double fluorine sulfimide lithiums are completely dissolved
Fluorinated ethylene carbonate；Then be added 2.45g tetrabutyl zirconates, stirring to solution at uniformly it is thick, add dropwise formic acid
And be stirred continuously, with 400rmin–1Speed stir 5min, wait for that solution is uniformly mixed, in stopping stirring after homogeneous class milk shape
It mixes, the solid product of white is obtained after standing solidification, be a kind of high security solid state composite electrolyte of the present invention.
By LiFePO4Electrode slice, above-mentioned gained solid state composite electrolyte and lithium metal are assembled into lithium metal battery,
Battery is disassembled after recycling 5 weeks on LAND battery test systems, metal lithium sheet is taken out, electron microscope is scanned to its surface
(SEM) it tests.
A kind of high security solid state composite electrolyte manufactured in the present embodiment is tested, it is as a result as follows：
(1) transmission electron microscope (TEM) is tested：
TEM tests are carried out after the electrolyte is removed ionic liquid, the results showed that the zirconium dioxide in the electrolyte
A diameter of 20nm~30nm of particle, particle are the low crystalline phases of low temperature, belong to polycrystalline material, have crystallite area also and have and is amorphous
Area can be distributed more Lewis acidic sites, promote the dissociation and transmission of lithium ion.
(2) scanning electron microscope (SEM) is tested：
SEM test results show that the electrolyte has and abundant interconnected are received by what zirconium dioxide particle was assembled into
Rice grain pattern road, ionic liquid is attached to nano grain surface, and can be moved in nano pore and transmit lithium ion；Lithium metal table
The SEM tests in face show that the electrolyte can form fine and close SEI films on lithium anode surface, are given birth to almost without Li dendrite
At playing a very good protection to lithium metal.
(3) thermogravimetric analysis (TGA) is tested：
TGA test results show that the electrolyte has good thermal stability, only a small amount of matter when less than 400 DEG C
Amount loss.
(4) electrochemical AC impedance (EIS) is tested：
EIS test results show that room temperature (25 DEG C) ionic conductivity of the electrolyte is 0.65 × 10–3S·cm–1。
Embodiment 12
By 0.36g difluorine oxalic acid boracic acid lithiums and 2.5g in the glove box full of argon gas and moisture less than 0.1ppm
1- ethyl-3-methylimidazole bis-trifluoromethylsulfoandimide salt mixes, and 0.143g is added after difluorine oxalic acid boracic acid lithium is completely dissolved
Fluorinated ethylene carbonate；Then be added 2.45g tetrabutyl zirconates, stirring to solution at uniformly it is thick, add dropwise formic acid
And be stirred continuously, with 400rmin–1Speed stir 5min, wait for that solution is uniformly mixed, in stopping stirring after homogeneous class milk shape
It mixes, the solid product of white is obtained after standing solidification, be a kind of high security solid state composite electrolyte of the present invention.
By LiFePO4Electrode slice, above-mentioned gained solid state composite electrolyte and lithium metal are assembled into lithium metal battery,
Battery is disassembled after recycling 5 weeks on LAND battery test systems, metal lithium sheet is taken out, electron microscope is scanned to its surface
(SEM) it tests.
A kind of high security solid state composite electrolyte manufactured in the present embodiment is tested, it is as a result as follows：
(1) transmission electron microscope (TEM) is tested：
TEM tests are carried out after the electrolyte is removed ionic liquid, the results showed that the zirconium dioxide in the electrolyte
A diameter of 20nm~30nm of particle, particle are the low crystalline phases of low temperature, belong to polycrystalline material, have crystallite area also and have and is amorphous
Area can be distributed more Lewis acidic sites, promote the dissociation and transmission of lithium ion.(2) scanning electron microscope (SEM) is surveyed
Examination：
SEM test results show that the electrolyte has and abundant interconnected are received by what zirconium dioxide particle was assembled into
Rice grain pattern road, ionic liquid is attached to nano grain surface, and can be moved in nano pore and transmit lithium ion；Lithium metal table
The SEM tests in face show that the electrolyte can form fine and close SEI films on lithium anode surface, are given birth to almost without Li dendrite
At playing a very good protection to lithium metal.
(3) thermogravimetric analysis (TGA) is tested：
TGA test results show that the electrolyte has good thermal stability, only a small amount of matter when less than 400 DEG C
Amount loss.
(4) electrochemical AC impedance (EIS) is tested：
EIS test results show that room temperature (25 DEG C) ionic conductivity of the electrolyte is 0.57 × 10–3S·cm–1。
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a kind of high security solid state composite electrolyte, it is characterised in that：The electrolyte is by lithium salts, ionic liquid and cathode
It is distributed in zirconium dioxide nanometer skeleton and constitutes after film for additive mixing；The nano zirconium dioxide skeleton is by nanometer two
Three-dimensional net structure made of zirconia particles stack, is distributed irregular and interconnected mesopore orbit.
2. a kind of high security solid state composite electrolyte according to claim 1, it is characterised in that：Nano zirconium dioxide
Particle size be 10nm~40nm.
3. a kind of high security solid state composite electrolyte according to claim 1, it is characterised in that：The lithium salts is double
It is Lithium bis (oxalate) borate, difluorine oxalic acid boracic acid lithium, trifluoromethanesulfonic acid lithium, double trifluoromethanesulfonimide lithiums, double fluorine sulfimide lithiums, complete
One or more of fluoroethane sulfimide lithium and perfluoromethane sulfonymethyl lithium.
4. a kind of high security solid state composite electrolyte according to claim 1, it is characterised in that：The ionic liquid
For 1- ethyl-3-methylimidazole bis-trifluoromethylsulfoandimides salt, 1- propyl -3- methylimidazole bis-trifluoromethylsulfoandimides salt, 1-
The double fluorine sulfonamides of butyl -3- methylimidazole bis-trifluoromethylsulfoandimides salt, 1- ethyl-3-methylimidazoles, 1- propyl -3-
The double fluorine sulfonamides of methylimidazole, the double fluorine sulfonamides of 1- butyl -3- methylimidazoles, N- methyl, propyl pyrrole are double
Trifluoro sulfonamide, N- methyl, butyl pyrroles's bis-trifluoromethylsulfoandimide salt, N- methyl, the double fluorine methylsulfonyls of propyl pyrrole
Inferior amine salt and N- methyl, one or more of butyl pyrroles's bis-trifluoromethylsulfoandimide salt.
5. a kind of high security solid state composite electrolyte according to claim 1, it is characterised in that：The cathode film formation
Additive is one or more of fluorinated ethylene carbonate, vinylene carbonate, vinylethylene carbonate and propylene sulfite.
6. a kind of high security solid state composite electrolyte according to claim 1, it is characterised in that：The lithium salts is double
It is Lithium bis (oxalate) borate, difluorine oxalic acid boracic acid lithium, trifluoromethanesulfonic acid lithium, double trifluoromethanesulfonimide lithiums, double fluorine sulfimide lithiums, complete
One or more of fluoroethane sulfimide lithium and perfluoromethane sulfonymethyl lithium；
The ionic liquid is 1- ethyl-3-methylimidazole bis-trifluoromethylsulfoandimides salt, the double trifluoros of 1- propyl -3- methylimidazoles
The double fluorine methylsulfonyls of sulfonamide, 1- butyl -3- methylimidazole bis-trifluoromethylsulfoandimides salt, 1- ethyl-3-methylimidazoles
The double fluorine sulfonamides of inferior amine salt, 1- propyl -3- methylimidazoles, the double fluorine sulfonamides of 1- butyl -3- methylimidazoles, N-
Methyl, propyl pyrrole bis-trifluoromethylsulfoandimide salt, N- methyl, butyl pyrroles's bis-trifluoromethylsulfoandimide salt, N- methyl, propyl
The double fluorine sulfonamides of pyrroles and N- methyl, one or more of butyl pyrroles's bis-trifluoromethylsulfoandimide salt；
The cathode film formation additive is fluorinated ethylene carbonate, vinylene carbonate, vinylethylene carbonate and sulfurous acid third
One or more of enester.
7. a kind of preparation method of such as high security solid state composite electrolyte according to any one of claims 1 to 6, special
Sign is：Steps are as follows for the method：
In the environment of being less than or equal to 0.1ppm full of inert gas and moisture, lithium salts is mixed with ionic liquid, waits for lithium
Salt obtains mixed solution after being completely dissolved, the mixing of cathode film formation additive is added；Then the ester-based organic compound mixing containing zirconium is added
To solution at uniformly thick, stop stirring after adding formic acid and being constantly uniformly mixed, stand obtain after solidification it is described
A kind of high security solid state composite electrolyte；
The ester-based organic compound containing zirconium is in tetrabutyl zirconate, four n-propyl zirconates and four (triethanolamine) zirconates
More than one.
8. a kind of preparation method of high security solid state composite electrolyte according to claim 7, it is characterised in that：It is mixed
Close a concentration of 0.2molKg of lithium salts in solution–1~1.2molKg–1；The quality of cathode film formation additive accounts for mixed solution
The 1%~5% of quality；The molar ratio of ionic liquid and the ester-based organic compound containing zirconium is 0.5~2:1；Mixing time is 5min；It stirs
It is 400rmin to mix speed–1。
9. a kind of lithium battery, it is characterised in that：The electrolyte of the lithium battery is as according to any one of claims 1 to 6
A kind of high security solid state composite electrolyte.
10. a kind of lithium battery according to claim 9, it is characterised in that：The lithium battery is lithium metal battery.
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