CN109818053A - Composite solid electrolyte film and its preparation method and application - Google Patents
Composite solid electrolyte film and its preparation method and application Download PDFInfo
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- CN109818053A CN109818053A CN201910063954.XA CN201910063954A CN109818053A CN 109818053 A CN109818053 A CN 109818053A CN 201910063954 A CN201910063954 A CN 201910063954A CN 109818053 A CN109818053 A CN 109818053A
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- electrolyte film
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- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 239000003292 glue Substances 0.000 claims abstract description 51
- 210000002966 serum Anatomy 0.000 claims abstract description 39
- 239000003792 electrolyte Substances 0.000 claims abstract description 37
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 32
- 210000002469 basement membrane Anatomy 0.000 claims abstract description 30
- 239000011230 binding agent Substances 0.000 claims abstract description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 21
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 18
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 14
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 14
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims abstract description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 claims abstract description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims abstract description 7
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims abstract description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012528 membrane Substances 0.000 claims description 37
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 21
- 229910052744 lithium Inorganic materials 0.000 claims description 21
- 210000004379 membrane Anatomy 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 14
- 229920002799 BoPET Polymers 0.000 claims description 7
- 229910000614 lithium tin phosphorous sulfides (LSPS) Inorganic materials 0.000 claims description 7
- 229910003405 Li10GeP2S12 Inorganic materials 0.000 claims description 6
- 239000002019 doping agent Substances 0.000 claims description 6
- 229910010848 Li6PS5Cl Inorganic materials 0.000 claims description 5
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 4
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 150000002732 mesitylenes Chemical class 0.000 claims description 3
- 229910009161 xLi2S-(1-x)P2S5 Inorganic materials 0.000 claims description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical group COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 11
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 7
- 239000002002 slurry Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920006335 epoxy glue Polymers 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- -1 further Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
Abstract
The present invention discloses a kind of composite solid electrolyte film and its preparation method and application.Wherein, the method for preparing composite solid electrolyte film includes: that (1) mixes organic solvent and binder, to obtain mixed glue solution；(2) by the mixed glue solution and sulfide electrolyte mixed pulp, to obtain mixed serum；(3) mixed serum is formed at least part of the basement membrane, to obtain composite solid electrolyte film, wherein, in step (1), the organic solvent is selected from methylene chloride, tetrahydrofuran, n-hexane, normal heptane, toluene, 2,4- dimethyl-propione, monochlor-benzene, dimethylbenzene, methyl phenyl ethers anisole, cyclohexanone, 1, at least one of 3,5- trimethylbenzenes, n-decane and methylformamide.The composite solid electrolyte film that is obtained using the present processes while having flexible, intensity is high, good toughness, ionic conductivity height and the good advantage of thermal stability.
Description
Technical field
The invention belongs to technical field of lithium batteries, in particular to a kind of composite solid electrolyte film and preparation method thereof and answer
With.
Background technique
In numerous battery systems, lithium battery is with its high-energy density, memory-less effect and relatively good environment friend
Good property and become energy storage and conversion system in main force.As people are to the energy density of lithium battery and security performance
It is required that increasingly improving, the battery that solid state lithium battery will become high-energy density and high security of new generation is preferred.Solid state battery
In key technology first is that solid electrolyte membrane technique, the quality of diaphragm directly affects the energy density of battery, safety,
High rate performance and high temperature performance etc..
Solid electrolyte divides three categories: oxide electrolyte, sulfide electrolyte and polymer dielectric.Using these three
The pure material of electrolyte has respective problem as the membrane layer of solid state battery, and oxide can be prepared into fine and close ceramics
Piece, but practical film cannot be prepared and conductivity at room temperature is low because brittleness is big；The room-temperature ion conductance of sulfide
Rate is high, but can not prepare fine and close film；Polymer is although easily prepared at film, but intensity is very low is easy to be pierced by Li dendrite
It wears, and is unable to high temperature resistant.Currently, there are no developments worldwide there are no there is ideal solid electrolyte membrane technology
With develop intensity height, good toughness, ionic conductivity is high and has solid electrolyte membrane flexible.
Summary of the invention
In view of this, the present invention is directed to propose a kind of method for preparing composite solid electrolyte film, existing solid to solve
State dielectric film poor toughness, intensity and the low problem of conductivity at room temperature.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
The method according to the present invention for preparing solid electrolyte membrane includes: that (1) mixes organic solvent and binder, so as to
Obtain mixed glue solution；(2) by the mixed glue solution and the sulfide electrolyte mixed pulp, to obtain mixed serum；(3)
The mixed serum is formed at least part of the basement membrane, to obtain composite solid electrolyte film,
Wherein, in step (1), the organic solvent is selected from methylene chloride, tetrahydrofuran, n-hexane, normal heptane, first
Benzene, 2,4- dimethyl-propione, monochlor-benzene, dimethylbenzene, methyl phenyl ethers anisole, cyclohexanone, 1,3,5- trimethylbenzenes, n-decane and methyl
At least one of formamide.
According to some embodiments of the present invention, the mass ratio of the organic solvent and the binder is 5~50:1, preferably
10~20:1.
According to some embodiments of the present invention, in step (1), the binder be selected from PVDF5130,
At least one of PVDF75130, PVDF21216, PVDF6020, PVDF-HVS900, PVDF-HFP and PEO.
Further, the molecular weight of the binder is 200,000~5,000,000.
According to some embodiments of the present invention, in step (2), the matter of the mixed glue solution and the sulfide electrolyte
Amount is than being 0.9~3:1, preferably 1.2~1.6:1.
According to some embodiments of the present invention, in step (2), the sulfide electrolyte is xLi2S(1-x)P2S5And
Its derivative, wherein x is 0.2~0.8.
Further, in step (2), the sulfide electrolyte is Li10GeP2S12、Li6PS5Cl、Li10SnP2S12And
Its compound for containing dopant.
Further, in step (2), the dopant is Si, Ta, Hf, Sc, LiI, ZnO and P2O5In at least it
One.
According to some embodiments of the present invention, in step (3), the liquid of the mixed serum and the basement membrane consolidates mass ratio
For 80~400:1, preferably 120~160:1.
According to some embodiments of the present invention, in step (3), the basement membrane is porous membrane.
Further, in step (3), the porous membrane is PAN film, compound PAN film, PP-PE composite membrane or PET
Film.
According to some embodiments of the present invention, the mixed serum is formed in the upper surface and/or lower surface of the basement membrane.
According to some embodiments of the present invention, the dielectric film with a thickness of 10~150 microns.
Compared with the existing technology, the method for the present invention for preparing solid electrolyte membrane has the advantage that
By by methylene chloride, tetrahydrofuran, n-hexane, normal heptane, toluene, 2,4- dimethyl-propione, a chloro
Benzene, dimethylbenzene, methyl phenyl ethers anisole, cyclohexanone, 1, at least one of 3,5- trimethylbenzenes, n-decane and methylformamide are mixed with binder
Glue after conjunction, then by obtained mixed glue solution and sulfide electrolyte mixed pulp, sulfide electrolyte is in the mixed of the composition
It closes in glue and stablizes, and obtained mixed serum is formed at least part of basement membrane, it is strong that basement membrane can provide support
Degree, toughness and elasticity, sulfide electrolyte can be embedded into basement membrane in mixed serum, so that obtained solid electrolyte membrane tool
There are the mechanical performances such as good mechanical property and higher intensity, toughness, elasticity and flexibility, so that gained composite solid
Dielectric film not only has good processing performance, is easily assembled, and can be subjected to battery inside in charge and discharge process and answer
Change and stress impact, so that battery has longer service life, while sulfide electrolyte runs through basement membrane, so that is obtained consolidates
State dielectric film has excellent ionic conductance, is conducive to the performance of battery capacity, to ensure that the high rate performance of battery
And high temperature performance, in addition, the composite electrolyte membrane has good thermal stability.It is obtained as a result, using the present processes
Composite solid electrolyte film have simultaneously flexible, intensity is high, good toughness, ionic conductivity height and good excellent of thermal stability
Gesture.
Another object of the present invention is to propose that a kind of composite solid electrolyte film, the composite solid electrolyte film use
Method described above is prepared.
Composite solid electrolyte film of the invention, is prepared by using above-mentioned method, simultaneously have it is flexible,
Intensity is high, good toughness, ionic conductivity height and the good advantage of thermal stability.
Another object of the present invention is to propose that a kind of lithium battery, the lithium battery have using obtained by the above method multiple
Close solid electrolyte membrane or above-mentioned composite solid electrolyte film.
Lithium battery of the invention has flexible by using above-mentioned, and intensity is high, good toughness, ionic conductivity height and
The solid electrolyte membrane of the good advantage of thermal stability, to ensure that the high-energy density and security performance of lithium battery.
Another object of the present invention is to propose that a kind of vehicle, the vehicle have lithium battery described above.
Vehicle of the invention can mentioned by using the above-mentioned lithium battery with high-energy density and security performance
Its service life is improved while high vehicle course continuation mileage, thus by consumers.
Detailed description of the invention
The attached drawing for constituting a part of the invention is used to provide further understanding of the present invention, schematic reality of the invention
It applies example and its explanation is used to explain the present invention, do not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 is the method flow schematic diagram for preparing solid electrolyte membrane of the embodiment of the present invention；
Fig. 2 is the micro-structure diagram of the PP-PE composite membrane of embodiment 1；
Fig. 3 is the section SEM figure for the composite solid electrolyte film that embodiment 1 obtains；
Fig. 4 is the fiber surface SEM figure for the composite solid electrolyte film that embodiment 1 obtains；
Fig. 5 is the optical photograph for the composite solid electrolyte film that embodiment 1 obtains；
Fig. 6 is the surface SEM figure for the composite solid electrolyte film that embodiment 2 obtains；
Fig. 7 is the fibre optics photo for the composite solid electrolyte film that embodiment 2 obtains.
Specific embodiment
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the present invention can phase
Mutually combination.
Come that the present invention will be described in detail below with reference to Fig. 1 and in conjunction with the embodiments.
The method for preparing composite solid electrolyte film of one aspect includes: according to the present invention
S100: organic solvent and binder are mixed
According to some embodiments of the present invention, organic solvent and binder are mixed, to obtain mixed glue solution, wherein
Organic solvent is selected from methylene chloride, tetrahydrofuran, n-hexane, normal heptane, toluene, 2,4- dimethyl-propione, a chloro
Benzene, dimethylbenzene, methyl phenyl ethers anisole, cyclohexanone, 1, at least one of 3,5- trimethylbenzenes, n-decane and methylformamide.Invention human hair
Existing, the above solvent can dissolve a variety of pairs of stable binders of sulfide, these solvent boiling points are moderate, and residual moisture was at 24 hours
It is interior to remove to less than 10ppm, in room temperature or under the conditions of to 80 DEG C of high temperature, it is sufficiently mixed with above-mentioned electrolyte small more than 24
When, conductivity is maintained between 50%-100%, show its to sulfide electrolyte stable, these solvents principally fall into ketone,
Ethers, benzene class and alkanes prepare uniform and stable large area toughness high conductivity sulfide dielectric film for wet process and provide
Powerful guarantee, greatly reduces the technology difficulty and cost for preparing dielectric film.
According to some embodiments of the present invention, the mass ratio of organic solvent and binder be 5~50:1, such as 5:1,7:1,
9:1、10:1、12:1、15:1、17:1、19:1、20:1、、22:1、25:1、27:1、29:1、30:1、32:1、35:1、37:1、
39:1,40:1,42:1,45:1,47:1,49:1,50:1, preferably 10~20:1.Inventors have found that the matter of solvent and binder
For amount than excessively high, made slurry is diluter, it is difficult to form a film, and be easy to cause binder and electrolyte segregation phenomenon, if solvent ratios
Smaller, slurry fluidity is poor, and ball milling is difficult, and material is difficult to be uniformly mixed.It can protected using the proportional region of the application as a result,
Card slurry is uniformly mixed slurry while being easy to form a film.
Further, binder can be for selected from PVDF5130, PVDF75130, PVDF21216, PVDF6020, PVDF-
At least one of HVS900, PVDF-HFP and PEO, it is preferred that the molecular weight of binder be 200,000~5,000,000, such as 200,000,
400000,600,000,800,000,1,000,000,1,200,000,1,400,000,1,600,000,1,800,000,2,000,000,2,200,000,2,400,000,2,600,000,2,800,000,
3000000,3,200,000,3,400,000,3,600,000,3,800,000,4,000,000,4,200,000,4,400,000,4,600,000,4,800,000,5,000,000.Inventors have found that
If binder molecular weight is too low, bad adhesion, binder demand is more, and if molecular weight is excessively high, dissolubility is bad, slurrying viscosity
It is excessively high, it is easily formed gel, is unfavorable for expect coating.Binder can guaranteed using the binder of the application as a result,
Ensure that slurry being capable of even spread simultaneously.
S200: by mixed glue solution and sulfide electrolyte mixed pulp
According to some embodiments of the present invention, by mixed glue solution obtained above and sulfide electrolyte mixed pulp.Tool
Body, by mixed glue solution obtained above and sulfide electrolyte mixed pulp, epoxy glue of the sulfide electrolyte in the composition
Stablize in liquid, so as to be prepared uniformly, viscosity is appropriate and the good mixed serum of caking property, and then obtain colleague and have
Flexible, intensity is high, good toughness, the composite solid electrolyte film of ionic conductivity height and the good advantage of thermal stability.
According to some embodiments of the present invention, in the step, the quality of the mixed glue solution and the sulfide electrolyte
Than for 0.9~3:1, for example, 0.9:1,1.1:1,1.2:1,1.3:1,1.4:1,1.5:1,1.6:1,1.8:1,2.0:1,2.2:1,
2.4:1,2.6:1,2.8:1,3.0:1, preferably 1.2~1.6:1, inventors have found that if mixed glue solution and sulfide electrolyte
Mass ratio is too low, and made slurry is excessively sticky, and the coating of dielectric film difficulty is thin, and is difficult to be uniformly dispersed between material, film it is uniform
Property not can guarantee, and if ratio is excessively high, made slurry is difficult to form the preferable film of mechanical strength and film resistance is excessive.It adopts as a result,
With the proportional region of the application can be improved while guaranteeing material dielectric film homogeneity dielectric film mechanical strength and
Resistance.Further, the sulfide electrolyte is xLi2S(1-x)P2S5And its derivative, wherein x is 0.2~0.8, such as
0.2,0.3,0.4,0.5,0.6,0.7,0.8.Preferably, sulfide electrolyte is Li10GeP2S12、Li6PS5Cl、Li10SnP2S12
And its compound containing dopant, further, dopant Si, Ta, Hf, Sc, LiI, ZnO and P2O5At least one of.
S300: mixed serum is formed at least part of basement membrane
According to some embodiments of the present invention, mixed serum obtained above is formed at least part of basement membrane,
Such as can using blade coating, infiltration or the techniques such as inkjet printing, and mixed serum can be formed in basement membrane upper surface and/or
On lower surface.Further, basement membrane can be porous membrane, it is preferred that porous membrane is PAN film, compound PAN film, PP-PE multiple
Close film or PET film.Inventors have found that basement membrane can provide support strength, toughness and elasticity, sulfide electrolyte in mixed serum
Can be embedded into basement membrane so that obtained solid electrolyte membrane have good mechanical property and higher intensity, toughness,
The mechanical performances such as elasticity and flexibility are easy to so that gained composite solid electrolyte film not only has good processing performance
Assembly, and it can be subjected to battery internal strain and stress impact in charge and discharge process, so that battery has longer use
Service life, while sulfide electrolyte runs through basement membrane, so that obtained solid electrolyte membrane has excellent ionic conductance, favorably
In the performance of battery capacity, to ensure that the high rate performance and high temperature performance of battery, in addition, the composite electrolyte membrane has
Good thermal stability.
According to some embodiments of the present invention, it is 80~400:1 that the liquid of the mixed serum and the basement membrane, which consolidates mass ratio,
Such as 80:1,100:1,120:1,140:1,160:1,180:1,200:1,220:1,240:1,260:1,280:1,300:1,
320:1,340:1,360:1,380:1,400:1, preferably 120~160:1.Inventors have found that if the two mixed proportion is excessively high, institute
Be film-made blocked up, impedance is big, and basement membrane enabling capabilities reduce, and when use is easy to be broken, and if ratio is too low, slurries can not uniformly cover
Lid basement membrane, basement membrane local material and gap exposure, cause film to be scrapped, are not available.It as a result, can using the mixed proportion of the application
To avoid film impedance excessive while guaranteeing slurries uniform fold basement membrane.
According to some embodiments of the present invention, the dielectric film with a thickness of 10~150 microns, such as 10 microns, 30
Micron, 50 microns, 70 microns, 90 microns, 100 microns, 120 microns, 130 microns, 150 microns.Inventors have found that if film thickness
Excessively high, impedance is high, and after deflector roll pressure, the decline of resistant to shearing ability is easily broken, and if film thickness is excessively thin, bad mechanical strength, resistance to compression energy
Power is poor, and basement membrane is easy to damage by pressure, is easy to produce partial short-circuit.It can guaranteed using the dielectric film of the application thickness as a result,
Avoid its impedance excessively high while mechanical strength.
The method for preparing composite solid electrolyte is by by methylene chloride, tetrahydro furan according to embodiments of the present invention
It mutters, n-hexane, normal heptane, toluene, 2,4- dimethyl-propione, monochlor-benzene, dimethylbenzene, methyl phenyl ethers anisole, cyclohexanone, 1,3,5-
Glue after at least one of trimethylbenzene, n-decane and methylformamide are mixed with binder, the mixed glue solution that then will be obtained
With sulfide electrolyte mixed pulp, sulfide electrolyte is stablized in the mixed glue solution of the composition, and the mixing that will be obtained
Slurries are formed at least part of basement membrane, and basement membrane can provide support strength, toughness and elasticity, sulfide in mixed serum
Electrolyte can be embedded into basement membrane, so that obtained solid electrolyte membrane has good mechanical property and higher strong
The mechanical performances such as degree, toughness, elasticity and flexibility, so that gained composite solid electrolyte film not only has good processability
Can, it is easily assembled, and battery internal strain and stress impact in charge and discharge process can be subjected to, so that battery is with longer
Service life, while sulfide electrolyte run through basement membrane so that obtained solid electrolyte membrane have excellent ionic conductance
Property, be conducive to the performance of battery capacity, to ensure that the high rate performance and high temperature performance of battery, in addition, the combined electrolysis
Plasma membrane has good thermal stability.The composite solid electrolyte film that is obtained as a result, using the present processes while having soft
Property it is good, intensity is high, good toughness, ionic conductivity height and the good advantage of thermal stability.
Another aspect of the invention is to propose that a kind of composite solid electrolyte film, the composite solid electrolyte film use
Method described above is prepared.Composite solid electrolyte film of the invention, is prepared by using above-mentioned method,
Have simultaneously flexible, intensity is high, good toughness, ionic conductivity height and the good advantage of thermal stability.It should be noted that above-mentioned
It is equally applicable to the composite solid electrolyte film for feature and advantage described in composite solid electrolyte film are prepared, herein not
It repeats again.
Another aspect of the present invention is to propose that a kind of lithium battery, the lithium battery have using obtained by the above method multiple
Close solid electrolyte membrane or above-mentioned composite solid electrolyte film.Lithium battery of the invention has flexibility by using above-mentioned
Good, intensity is high, good toughness, the solid electrolyte membrane of ionic conductivity height and the good advantage of thermal stability, to ensure that lithium electricity
The high-energy density and security performance in pond.It should be noted that it is above-mentioned for feature described in composite solid electrolyte film and
Advantage is equally applicable to the lithium battery, and details are not described herein again.
Another object of the present invention is to propose that a kind of vehicle, the vehicle have lithium battery described above.The present invention
Vehicle vehicle course continuation mileage can improved by using the above-mentioned lithium battery with high-energy density and security performance
While improve its service life, thus by consumers.It should be noted that above-mentioned for spy described in lithium battery
Advantage of seeking peace is equally applicable to the vehicle, and details are not described herein again.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only to describe
Property, without limiting the invention in any way.
Embodiment 1
(1) it is 25:1 according to mass ratio by methylene chloride and PVDF5130 (molecular weight 200,000), mixes glue, mixed
Glue；
(2) by mixed glue solution and Li10SnP2S12It is 1.2:1 according to mass ratio, mixed pulp obtains mixed serum；
It (3) is that 130:1 is coated in PP-PE composite membrane according to solid-to-liquid ratio by mixed serum (its microstructure is as shown in Figure 2)
Surface on, obtain composite solid electrolyte film (its section SEM figure as shown in figure 3, surface SEM figure as shown in figure 4, optics shine
Piece is as shown in Figure 5).
Embodiment 2
(1) it is 22:1 mixing glue according to mass ratio by tetrahydrofuran and PEO (molecular weight 550,000), obtains mixed glue solution；
(2) by mixed glue solution and Li10GeP2S12It is 1.2:1 mixed pulp according to mass ratio, obtains mixed serum；
(3) it is that 140:1 is coated on the surface of PAN film according to solid-to-liquid ratio by mixed serum, obtains composite solid electrolyte
Film (its surface texture figure is as shown in fig. 6, optical photograph is as shown in Figure 7).
Embodiment 3
(1) it is 20:1 mixing glue according to mass ratio by n-hexane and PVDF75130 (molecular weight 1,220,000), is mixed
Glue；
(2) by mixed glue solution and Li6PS5Cl is 1.3:1 mixed pulp according to mass ratio, obtains mixed serum；
(3) it is that 140:1 is coated on the surface of PET film according to solid-to-liquid ratio by mixed serum, obtains composite solid electrolyte
Film.
Embodiment 4
(1) it is 18:1 mixing glue according to mass ratio by normal heptane and PVDF21216 (molecular weight 1,570,000), is mixed
Glue；
(2) by mixed glue solution and Li10GeP2S12The compound of doping Si is 1.4:1 mixed pulp according to mass ratio, is obtained
Mixed serum；
(3) be 140 according to solid-to-liquid ratio by PET film: infiltration obtains composite solid electrolyte film in mixed serum.
Embodiment 5
(1) it is 20:1 mixing glue according to mass ratio by toluene and PVDF6020 (molecular weight 2,120,000), obtains epoxy glue
Liquid；
(2) by mixed glue solution and Li6PS5The compound of Cl doping Ta is 1.4:1 mixed pulp according to mass ratio, is mixed
Close slurries；
(3) it is that 140:1 infiltrates in mixed serum according to solid-to-liquid ratio by PAN film, obtains composite solid electrolyte film.
Embodiment 6
(1) 2,4- dimethyl-propione and PVDF-HVS900 (molecular weight 2,680,000) are mixed according to mass ratio for 15:1
Glue obtains mixed glue solution；
(2) by mixed glue solution and Li10SnP2S12The compound of doping Hf is 1.5:1 mixed pulp according to mass ratio, is obtained
Mixed serum；
(3) it is that 130:1 infiltrates in mixed serum according to solid-to-liquid ratio by PP-PE composite membrane, obtains composite solid electrolyte
Film.
Embodiment 7
(1) it is 27:1 mixing glue according to mass ratio by monochlor-benzene and PVDF-HFP (molecular weight 3,250,000), is mixed
Glue；
(2) by mixed glue solution and Li10SnP2S12The compound of doping Sc is 1.5:1 mixed pulp according to mass ratio, is obtained
Mixed serum；
(3) it is that 160:1 is coated on the surface of PET film according to solid-to-liquid ratio by mixed serum, obtains composite solid electrolyte
Film.
Embodiment 8
(1) it is 20:1 mixing glue according to mass ratio by dimethylbenzene and PVDF75130 (molecular weight 4,250,000), is mixed
Glue；
(2) by mixed glue solution and Li6PS5The compound of Cl doping LiI is 1.4:1 mixed pulp according to mass ratio, is mixed
Close slurries；
(3) it is that 140:1 is coated on the surface of PP-PE composite membrane film according to solid-to-liquid ratio by mixed serum, obtains composite solid
State dielectric film.
Embodiment 9
(1) methyl phenyl ethers anisole and PVDF5130 (molecular weight 2,570,000) are 15:1 mixing glue according to mass ratio, obtain epoxy glue
Liquid；
(2) by mixed glue solution and Li10GeP2S12The compound of doping ZnO is 1.4:1 mixed pulp according to mass ratio, is obtained
Mixed serum；
(3) it is that 150:1 is coated on the surface of PAN film according to solid-to-liquid ratio by mixed serum, obtains composite solid electrolyte
Film.
Embodiment 10
(1) cyclohexanone, 1,3,5- trimethylbenzenes and PEO (molecular weight 5,000,000) are 20:1 mixing glue according to mass ratio, are obtained
Mixed glue solution；
(2) by mixed glue solution and Li6PS5Cl adulterates P2O5Compound according to mass ratio be 1.3:1 mixed pulp, obtain
Mixed serum；
(3) it is that 140:1 is coated on the surface of PET film according to solid-to-liquid ratio by mixed serum, obtains composite solid electrolyte
Film.
Embodiment 11
(1) n-decane, methylformamide and PVDF75130 (molecular weight 4,850,000) are 18:1 mixing glue according to mass ratio,
Obtain mixed glue solution；
(2) by mixed glue solution and Li10SnP2S12It is 1.4:1 mixed pulp according to mass ratio, obtains mixed serum；
(3) it is that 140:1 is coated on the surface of compound PAN film according to solid-to-liquid ratio by mixed serum, obtains composite solid electricity
Solve plasma membrane.
Evaluation: small to the ionic conductivity of the obtained composite solid electrolyte film of embodiment 1-11,130 degrees Celsius of processing 2
At present shrinking percentage is measured, and test result is as shown in table 1.
The composite solid electrolyte film properties that 1 embodiment 1-11 of table is obtained
Conclusion: as shown in Figure 2, the maximum diameter of hole of PP-PE composite membrane is up to 100 μm, and the porosity is up to 70%, non-woven fabrics
With a thickness of 25 μm, from figure 3, it can be seen that PP-PE composite membrane is not attached to the surface of composite membrane, and it has been embedded in compound
It in film, can not only make composite membrane that there is good mechanical property in this way, but also can make sulfide electrolyte through non-woven fabrics to make
Composite membrane solid electrolyte membrane has ideal ionic conductance, it can be seen that carrying out the micro- of composite electrolyte membrane from Fig. 4 and 6
Structure is highly uniform, from Fig. 5 and 7 it can be seen that obtained composite solid electrolyte film has good toughness, and is counted by table 1
According to it is found that the ionic conductivity for adopting the composite solid electrolyte film being obtained by the present invention is all larger than 10-4S/cm, and
2 hours are handled under 80 degrees Celsius without any contraction, i.e., institute's composite solid electrolyte film have good ionic conductance and
Stability, this is conducive to the performance of battery capacity, is the guarantee of the high rate performance and high temperature performance of battery.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of method for preparing composite solid electrolyte film characterized by comprising
(1) organic solvent and binder are mixed, to obtain mixed glue solution；
(2) by the mixed glue solution and sulfide electrolyte mixed pulp, to obtain mixed serum；
(3) mixed serum is formed at least part of the basement membrane, to obtain composite solid electrolyte film,
Wherein, in step (1), the organic solvent be selected from methylene chloride, tetrahydrofuran, n-hexane, normal heptane, toluene,
2,4- dimethyl-propione, monochlor-benzene, dimethylbenzene, methyl phenyl ethers anisole, cyclohexanone, 1,3,5- trimethylbenzenes, n-decane and methyl formyl
At least one of amine.
2. the method according to claim 1, wherein in step (1), the organic solvent and the binder
Mass ratio be 5~50:1, preferably 10~20:1,
It is optional, in step (1), the binder be selected from PVDF5130, PVDF75130, PVDF21216, PVDF6020,
At least one of PVDF-HVS900, PVDF-HFP and PEO,
Optional, in step (1), the molecular weight of the binder is 200,000~5,000,000.
3. the method according to claim 1, wherein in step (2), the mixed glue solution and the sulfide
The mass ratio of electrolyte be 0.9~3:1, preferably 1.2~1.6:1,
Optional, in step (2), the sulfide electrolyte is xLi2S(1-x)P2S5And its derivative, wherein x 0.2
~0.8,
Optional, in step (2), the sulfide electrolyte is Li10GeP2S12、Li6PS5Cl、Li10SnP2S12And its contain
The compound of dopant,
Optional, in step (2), the dopant is Si, Ta, Hf, Sc, LiI, ZnO and P2O5At least one of.
4. the method according to claim 1, wherein in step (3), the mixed serum and the basement membrane
Liquid consolidate mass ratio be 80~400:1, preferably 120~160:1,
Optional, in step (3), the basement membrane is porous membrane.
5. according to the method described in claim 4, it is characterized in that, in step (3), the porous membrane is PAN film, compound
PAN film, PP-PE composite membrane or PET film.
6. the method according to claim 1, wherein the mixed serum is formed in the upper surface of the basement membrane
The lower surface and/or.
7. the method according to claim 1, wherein the dielectric film with a thickness of 10~150 microns.
8. a kind of composite solid electrolyte film, which is characterized in that the composite solid electrolyte film is appointed using in claim 1-7
Method described in one is prepared.
9. a kind of lithium battery, which is characterized in that the lithium battery has to be obtained using method of any of claims 1-7
The composite solid electrolyte film or use composite solid electrolyte film according to any one of claims 8 arrived.
10. a kind of vehicle, which is characterized in that the vehicle has lithium battery as claimed in claim 9.
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