CN113161606A - Ultrathin composite solid electrolyte membrane and preparation method thereof - Google Patents
Ultrathin composite solid electrolyte membrane and preparation method thereof Download PDFInfo
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 93
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 239000012528 membrane Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 34
- 239000011159 matrix material Substances 0.000 claims abstract description 28
- 229910003480 inorganic solid Inorganic materials 0.000 claims abstract description 22
- 239000011230 binding agent Substances 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 239000011256 inorganic filler Substances 0.000 claims abstract description 10
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 229920002545 silicone oil Polymers 0.000 claims abstract description 5
- 239000000919 ceramic Substances 0.000 claims description 16
- 239000005518 polymer electrolyte Substances 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 13
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 12
- 229910010252 TiO3 Inorganic materials 0.000 claims description 11
- 229910020721 Li0.33La0.557TiO3 Inorganic materials 0.000 claims description 10
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims description 10
- 159000000002 lithium salts Chemical class 0.000 claims description 10
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 9
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 7
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- -1 lithium hexafluorophosphate Chemical group 0.000 claims description 6
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 229920002799 BoPET Polymers 0.000 claims description 4
- 229910009511 Li1.5Al0.5Ge1.5(PO4)3 Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 229910021102 Li0.5La0.5TiO3 Inorganic materials 0.000 claims description 3
- 229910009274 Li1.4Al0.4Ti1.6 (PO4)3 Inorganic materials 0.000 claims description 3
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 claims description 3
- 229910013075 LiBF Inorganic materials 0.000 claims description 3
- 229910010941 LiFSI Inorganic materials 0.000 claims description 3
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 claims description 3
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- 239000000945 filler Substances 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- 238000010345 tape casting Methods 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 17
- 229910001416 lithium ion Inorganic materials 0.000 description 17
- 239000000843 powder Substances 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 229960002303 citric acid monohydrate Drugs 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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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
-
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses an ultrathin composite solid electrolyte membrane and a preparation method thereof, wherein the ultrathin composite solid electrolyte membrane is a membrane formed by compounding inorganic solid electrolyte filler and a polymer matrix. The film material of the composite solid electrolyte is prepared by introducing the binder into the composite system and adopting a tape casting method on the substrate with the silicone oil attached to the surface, and has the advantages of easy demoulding, extremely small thickness, uniform and compact components, flat and smooth surface and the like. Has better electrochemical performance, and particularly, the ionic conductivity of the film is obviously improved. Meanwhile, the adhesive tightly combines the inorganic filler and the polymer matrix, so that the mechanical property of the film is obviously improved, the growth of dendritic crystals can be effectively inhibited, and the safety of the solid-state battery is ensured.
Description
Technical Field
The invention relates to an electrolyte membrane and preparation thereof, in particular to an ultrathin composite solid electrolyte membrane and a preparation method thereof.
Background
With the continuous development of human society, higher demands are put on energy storage systems. Lithium ion of conventional liquid electrolyteCompared with the battery, the all-solid-state lithium ion battery based on the solid electrolyte has higher energy density and safety, and is the most potential battery system in the future energy storage field. The solid electrolytes are various in types, and mainly include three major systems of sulfides, oxides and polymers, and both of them belong to inorganic solid electrolytes. Wherein the inorganic solid electrolyte has high ion conductivity (10)-4～10-2S/cm) and mechanical strength, but has the defects of unstable air, large grain boundary resistance, poor interface stability with electrode materials and the like; meanwhile, because the inorganic electrolyte has high density and large thickness, the energy density of the solid-state battery assembled by the inorganic electrolyte is obviously lower. The polymer solid electrolyte has the characteristics of good flexibility, easy processing and the like, so that the polymer solid electrolyte has good contact with an electrode material and can effectively solve the problem of large electrode/electrolyte interface resistance; in addition, the polymer solid electrolyte is easy to prepare into a film form, and the thickness and the quality of the battery are reduced, so that the energy density of the all-solid-state lithium ion battery is effectively improved. However, the ionic conductivity of polymer solid electrolytes is generally low, and is only 10-7～10-5S/cm; and the mechanical property is poor, particularly the tensile mechanical strength is far lower than that of the inorganic solid electrolyte, which is not beneficial to solving the safety problem caused by the growth of the lithium dendrite.
In recent years, composite solid electrolytes have attracted much attention, i.e., inorganic/organic composite materials prepared by adding inorganic solid electrolytes as fillers to polymer matrices can effectively combine the advantages of both. For example, the Chinese patent 201910233460.1 discloses an inorganic/polymer composite solid electrolyte and a preparation method thereof, which is prepared by mixing Li1.5Al0.5Ge1.5(PO4)3The ceramic nano particles are mixed with polyethylene oxide and soaked in the solvated ionic liquid to prepare the composite solid electrolyte film, so that the ionic conductivity of a polymer matrix is improved, good interface compatibility with an electrode material is shown, and the electrochemical stability and safety of the composite solid electrolyte film are improved. However, due to the lack of effective bonding between the two, when the volume content of the ceramic powder particles is high and the particle size is small,non-uniform dispersion and even agglomeration easily occur in a polymer matrix, so that a continuous transmission channel of lithium ions cannot be effectively formed, and the mechanical property of the composite solid electrolyte is reduced.
On the other hand, the casting method is a common method for producing a polymer film, but a common polymer electrolyte has a problem that molding and demolding are difficult when a film is produced due to high viscosity and low mechanical strength.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide an ultrathin composite solid electrolyte membrane and a preparation method thereof, and solves the problems of poor mechanical property, difficult demoulding and insufficient electrochemical property of the conventional composite solid electrolyte membrane.
The technical scheme is as follows:
the ultrathin composite solid electrolyte membrane comprises a polymer matrix and an inorganic solid electrolyte, wherein the content of the inorganic solid electrolyte is 5-30 wt%, the inorganic solid electrolyte is ceramic nanoparticles of an oxide solid electrolyte modified by a binder, the polymer matrix is composed of a polymer electrolyte and a lithium salt, and the inorganic solid electrolyte is added into the polymer matrix as an inorganic filler.
In order to improve the mechanical tensile properties, the oxide-based solid electrolyte is Li1.4Al0.4Ti1.6(PO4)3、Li1.5Al0.5Ge1.5(PO4)3、Li0.24La0.587TiO3、Li0.33La0.557TiO3、Li0.36La0.547TiO3、Li0.5La0.5TiO3And Li7La3Zr2O12At least one of (1).
For better compatibility of the inorganic filler with the polymer matrix and for intimate bonding of the two together, the binder is polyvinylpyrrolidone.
In order to ensure the electrochemical performance, the polymer electrolyte is at least one of polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), Polyacrylonitrile (PAN), polymethyl methacrylate (PMMA) and polyvinylidene fluoride (PVDF-HFP).
The lithium salt is lithium hexafluorophosphate LiPF6Lithium tetrafluoroborate (LiBF)4Lithium perchlorate LiClO4Lithium bis (fluorosulfonyl) imide LiFSI, lithium bis (trifluoromethanesulfonyl) imide LiTFSI, lithium bis (trifluoromethanesulfonyl) imide LiN (CF)3SO2)2Lithium nitrate LiNO3And lithium fluoride LiF.
A film with too low binder content has low tensile strain, poor film forming property and difficult demoulding, and the electrochemical performance of the material is reduced due to too high content of the binder, and the content of the binder in the inorganic solid electrolyte is about 10 wt%.
The preparation method of the ultrathin composite solid electrolyte membrane comprises the following steps:
(1) putting an oxide solid electrolyte and a binder into a crucible for grinding and mixing, and adding the mixture into an organic solvent for ultrasonic dispersion to form a white suspension;
(2) dispersing polymer electrolyte and lithium salt in the white suspension liquid obtained in the step (1), and performing magnetic stirring for sufficient time to form white viscous solution as slurry;
(3) pouring the slurry obtained in the step (2) on a substrate, and uniformly coating the slurry on the substrate by using a scraper at a constant speed;
(4) and (4) putting the substrate coated with the slurry in the step (3) into a vacuum drying oven, and heating to remove the solvent to obtain the ultrathin composite solid electrolyte membrane.
Wherein the organic solvent in the step (1) is acetonitrile.
The mass ratio of the polymer electrolyte to the lithium salt in the step (2) is (75-60): (25-40).
In order to prepare a thin film with uniform density and thin thickness, the substrate in the step (3) is a polyester PET film with silicone oil attached to the surface, the coating speed of a scraper is 1-2 cm/s, and the height of the scraper is 50-100 μm.
The technical principle is as follows: the composite solid electrolyte membrane has the advantages of both inorganic solid electrolyte and polymer electrolyte material, has good chemical stability, electrochemical performance and mechanical performance, can effectively inhibit the growth of lithium dendrite in the charge and discharge process of a solid lithium ion battery, and promotes the transmission of lithium ions; and the lithium ion battery has good flexibility, can be bent and deformed at will, and promotes the application of the lithium ion battery in flexible devices, soft package batteries and the like. The addition of the binder can enable the inorganic filler to be more tightly combined with the polymer matrix, and an interfacial intermediate phase is formed between the inorganic filler and the polymer matrix, so that a continuous channel for lithium ion transmission can be provided; the PET substrate with the silicone oil attached to the surface can increase the ductility of the composite solid electrolyte membrane, and is easy to demould. Meanwhile, the ultrathin composite solid electrolyte membrane can also obviously reduce the quality of the battery, improve the energy density of the battery and meet the development requirement of the solid lithium ion battery.
Has the advantages that: the polyvinylpyrrolidone is introduced into the composite solid electrolyte membrane as a binder, so that the prepared membrane has more uniform components and smoother surface, the interface between the inorganic filler and the polymer matrix is more tightly combined, and the mechanical property of the composite solid electrolyte membrane is obviously improved, thereby effectively hindering the growth of lithium dendrites and improving the energy density and the safety of the all-solid-state lithium ion battery; the polyester PET film is selected as the substrate in the preparation process of the composite solid electrolyte film, and because the silicone oil is attached to the surface of the polyester PET film, the fluidity of slurry in the preparation process can be increased, the film forming property of the material is improved, the thickness of the film is reduced, and the dried film can be easily demoulded, so that the surface of the film is more uniform and smooth; inorganic solid electrolyte Li0.33La0.557TiO3Compared with the traditional polymer electrolyte material, the thin film material compounded with the polymer matrix has better electrochemical performance, particularly higher ionic conductivity and more excellent mechanical tensile property; the lithium ion battery has better cycle stability in the all-solid-state lithium ion battery, and the ultra-thin thickness and the good electrochemical performance can bring higher energy density to the all-solid-state lithium ion battery.
Drawings
FIG. 1 is Li0.33La0.557TiO3Oxide-based solid state powerSEM pictures of ceramic nanoparticles of the electrolyte;
fig. 2 is an SEM picture of the composite solid electrolyte thin film, in which (a) is a cross-sectional SEM picture of the composite solid electrolyte thin film; (b) surface SEM pictures of the composite solid electrolyte film;
FIG. 3 is a tensile test curve of a composite solid electrolyte membrane with a neat polymer matrix;
FIG. 4 is a resistance test curve of a composite solid electrolyte membrane at different binder contents;
FIG. 5 is a graph of impedance testing of a composite solid electrolyte membrane with a pure polymer matrix;
fig. 6 is a graph showing cycle performance at 60 c of a battery fabricated using the composite solid electrolyte membrane of the present invention.
Detailed Description
The present application is further described below with reference to the drawings and examples.
The invention discloses an ultrathin composite solid electrolyte membrane, which has the thickness of about 20-50 mu m, and is a film prepared by compounding an inorganic solid electrolyte and a polymer matrix on a substrate with a surface treated by adopting a tape casting method, wherein the content of the inorganic solid electrolyte is 5-30 wt%, the inorganic solid electrolyte is ceramic nanoparticles of an oxide solid electrolyte modified by a binder, the polymer matrix is composed of a polymer electrolyte and a lithium salt, and the ceramic nanoparticles are used as an inorganic filler and added into the polymer matrix to obtain the composite solid electrolyte material. The oxide-based solid electrolyte is Li1.4Al0.4Ti1.6(PO4)3、Li1.5Al0.5Ge1.5(PO4)3、Li0.24La0.587TiO3、Li0.33La0.557TiO3、Li0.36La0.547TiO3、Li0.5La0.5TiO3And Li7La3Zr2O12At least one of (1). The binder is polyvinylpyrrolidone, and the polymer electrolyte is polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), Polyacrylonitrile (PAN) or polymethyl methacrylate (PMMA)At least one of methyl acrylate PMMA and polyvinylidene fluoride PVDF-HFP. The lithium salt is lithium hexafluorophosphate LiPF6Lithium tetrafluoroborate (LiBF)4Lithium perchlorate LiClO4Lithium bis (fluorosulfonyl) imide LiFSI, lithium bis (trifluoromethanesulfonyl) imide LiTFSI, lithium bis (trifluoromethanesulfonyl) imide LiN (CF)3SO2)2Lithium nitrate LiNO3And lithium fluoride LiF. The content of the binder in the inorganic solid electrolyte was about 10 wt%.
With Li0.33La0.557TiO3The method for preparing the ultrathin composite solid electrolyte membrane of the invention as an oxide-based solid electrolyte comprises the following steps:
first of all, Li is prepared0.33La0.557TiO3Ceramic powder comprising the steps of:
(1) reacting LiNO with a catalyst3、La(NO3)3·6H2O、Ti(OC4H9)4And citric acid monohydrate in a molar ratio of 0.33:0.557:1:0.887, wherein the citric acid is used as a complexing agent;
(2) first La (NO)3)3·6H2Dissolving O in absolute ethyl alcohol, stirring at normal temperature until the O is completely dissolved, and dissolving the rest raw materials in absolute ethyl alcohol and stirring until the O is completely dissolved;
(3) adding La (NO)3)3·6H2Dropwise adding the O solution into the other solution, and stirring at 80 ℃ for 30min to obtain a white suspension;
(4) pouring the white suspension into a reaction kettle, reacting for 10 hours at 180 ℃, centrifuging the turbid solution, washing the turbid solution for a plurality of times by using absolute ethyl alcohol, and finally pouring the solution into a culture dish;
(5) drying the culture dish in an oven at 80 ℃ for 12h to obtain white Li0.33La0.557TiO3Precursor powder;
(6) grinding the precursor powder, sieving with 200# sieve, placing into an air-tube furnace, heating at 500 deg.C for 2 hr at a temperature rise rate of 2 deg.C/min, calcining at 1000 deg.C for 6 hr at a temperature rise rate of 1 deg.C/min, and calcining at the maximumWhite Li is finally obtained0.33La0.557TiO3A ceramic powder.
And then using the obtained Li0.33La0.557TiO3The preparation of the ultrathin composite solid electrolyte membrane by using the ceramic powder comprises the following steps:
(1) weighing 20 wt% of Li0.33La0.557TiO3Ceramic powder is used as a filler, polyvinylpyrrolidone accounting for 10 wt% of the inorganic solid electrolyte material is used as a binder, and the ceramic powder and the polyvinylpyrrolidone are added into a mortar and fully ground to be uniformly mixed;
(2) pouring the mixed powder into 10mL of acetonitrile solvent, and performing ultrasonic dispersion for 30min to obtain white suspension;
(3) then weighing PEO and LiTFSI with the mass ratio of 2:1 as raw materials of a polymer matrix, adding the raw materials into the white suspension, and stirring for 24 hours at normal temperature to obtain white slurry;
(4) pouring the slurry on a PET substrate, and uniformly coating the slurry by using a scraper with adjustable thickness at the height of 50 mu m and the speed of 1 cm/s;
(5) and (3) putting the PET substrate coated with the slurry into a vacuum drying oven, drying at 60 ℃ for 12h, and stripping the PET substrate to obtain the uniform and compact ultrathin composite solid electrolyte membrane.
For the prepared Li0.33La0.557TiO3The ceramic powder was subjected to SEM test, and the results are shown in FIG. 1, from which Li can be seen in FIG. 10.33La0.557TiO3The ceramic particles are uniformly distributed, and the particle size is about 100-200 nm. SEM test of the ultra-thin composite solid electrolyte membrane showed that Li in the composite solid electrolyte membrane was observed according to FIG. 2a as shown in FIG. 20.33La0.557TiO3The ceramic particles and the polymer electrolyte matrix are tightly combined together to form a compact and stable structure, and the thickness of the film is only about 24 mu m; the SEM picture shown in FIG. 2b reveals Li in the composite solid electrolyte thin film0.33La0.557TiO3The ceramic particles are uniformly distributed in the polymer electrolyte matrix
The tensile test is carried out on the prepared ultrathin composite solid electrolyte membrane at the temperature of 25 ℃ at the speed of 2mm/min according to a membrane sample of 10mm multiplied by 50mm, and a pure polymer matrix without inorganic filler is taken as a control experiment group, and the result is shown in figure 3, and as can be known from figure 3, the tensile property of the membrane of the composite solid electrolyte material is obviously superior to that of the polymer matrix, and the strain is up to 950%, which indicates that the mechanical property of the composite membrane is obviously improved, and the composite membrane is beneficial to the solid battery to bear larger bending deformation.
The proportion of the prepared ultrathin composite solid electrolyte membrane is 0.1-106The frequency of Hz and the amplitude of 5mV were measured by ac impedance test at 25 ℃, and the influence of the content of different binders on the ionic conductivity of the composite film was investigated, and as a result, as shown in fig. 4, it can be seen from fig. 4 that the electrochemical impedance of the composite film with a binder content of 10 wt% is the lowest, and when the content is less than 10 wt%, the film is difficult to be demolded and cannot be used for performance test, and when the content is more than 10 wt%, the electrochemical impedance of the composite film increases, indicating that the binder content is too high and rather hinders the transmission of lithium ions in the composite film.
The proportion of the prepared ultrathin composite solid electrolyte membrane is 0.1-106The frequency of Hz and the amplitude of 5mV were measured at 25 deg.C, and the results are shown in FIG. 5, where the electrochemical impedance of the composite solid electrolyte material is significantly lower than that of the polymer matrix, indicating that the ionic conductivity of the composite film is higher, which is beneficial to the transmission of lithium ions in the solid electrolyte, as can be seen from FIG. 5.
The battery adopting the ultrathin composite solid electrolyte membrane is subjected to charge-discharge cycle test at 60 ℃ according to the current density of 0.1C and the voltage range of 2-4V, a pure polymer matrix without inorganic filler is taken as a control experiment group, and the result is shown in fig. 6, as can be seen from fig. 6, the cycle performance of the solid battery prepared by the composite solid electrolyte material is better than that of the polymer matrix, and the capacity of 50 cycles of cycle is still maintained at about 110mAh/g, which shows that the impedance in the battery is better relieved, and the transmission of lithium ions in the battery is more facilitated.
Claims (10)
1. The ultrathin composite solid electrolyte membrane is characterized by comprising a polymer matrix and an inorganic solid electrolyte, wherein the content of the inorganic solid electrolyte is 5-30 wt%, the inorganic solid electrolyte is ceramic nanoparticles of an oxide solid electrolyte modified by a binder, the polymer matrix is composed of a polymer electrolyte and a lithium salt, and the inorganic solid electrolyte is added into the polymer matrix as an inorganic filler.
2. The ultrathin composite solid electrolyte membrane according to claim 1, wherein the oxide-based solid electrolyte is Li1.4Al0.4Ti1.6(PO4)3、Li1.5Al0.5Ge1.5(PO4)3、Li0.24La0.587TiO3、Li0.33La0.557TiO3、Li0.36La0.547TiO3、Li0.5La0.5TiO3And Li7La3Zr2O12At least one of (1).
3. The ultrathin composite solid electrolyte membrane of claim 1, wherein the binder is polyvinylpyrrolidone.
4. The ultra-thin composite solid electrolyte membrane according to claim 1, wherein the polymer-based electrolyte is at least one of polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), Polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), and polyvinylidene fluoride (PVDF-HFP).
5. The ultrathin composite solid electrolyte membrane according to claim 1, wherein the lithium salt is lithium hexafluorophosphate LiPF6Lithium tetrafluoroborate (LiBF)4Lithium perchlorate LiClO4Lithium bis (fluorosulfonyl) imide LiFSI, lithium bis (trifluoromethanesulfonyl) imide LiTFSI, lithium bis (trifluoromethanesulfonyl) imide LiN (CF)3SO2)2Lithium nitrate LiNO3And lithium fluoride LiF.
6. The ultra-thin composite solid electrolyte membrane according to claim 1, wherein the binder content in the inorganic solid electrolyte is about 10 wt%.
7. The method for preparing an ultra-thin composite solid electrolyte membrane according to any one of claims 1 to 6, comprising the steps of:
(1) putting an oxide solid electrolyte and a binder into a crucible for grinding and mixing, and adding the mixture into an organic solvent for ultrasonic dispersion to form a suspension;
(2) dispersing polymer electrolyte and lithium salt in the white suspension liquid obtained in the step (1), and performing magnetic stirring for sufficient time to form viscous solution as slurry;
(3) pouring the slurry obtained in the step (2) onto a substrate, and uniformly coating the slurry on the substrate by using a scraper at a constant speed;
(4) and (4) putting the substrate coated with the slurry in the step (3) into a vacuum drying oven, and heating to remove the solvent to obtain the ultrathin composite solid electrolyte membrane.
8. The method for preparing an ultra-thin composite solid electrolyte membrane according to claim 7, wherein the organic solvent in the step (1) is acetonitrile.
9. The method for preparing the ultrathin composite solid electrolyte membrane according to claim 7, wherein the mass ratio of the polymer electrolyte to the lithium salt in the step (2) is (75-60): (25-40).
10. The method for preparing the ultrathin composite solid electrolyte membrane according to claim 7, wherein the substrate in the step (3) is a polyester PET film with silicone oil attached to the surface, the coating speed of a scraper is 1-2 cm/s, and the height of the scraper is 50-100 μm.
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Application publication date: 20210723 |