CN113140786A - Solid electrolyte and preparation method and application thereof - Google Patents
Solid electrolyte and preparation method and application thereof Download PDFInfo
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- CN113140786A CN113140786A CN202110275335.4A CN202110275335A CN113140786A CN 113140786 A CN113140786 A CN 113140786A CN 202110275335 A CN202110275335 A CN 202110275335A CN 113140786 A CN113140786 A CN 113140786A
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002071 nanotube Substances 0.000 claims abstract description 85
- CEMTZIYRXLSOGI-UHFFFAOYSA-N lithium lanthanum(3+) oxygen(2-) titanium(4+) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Ti+4].[La+3] CEMTZIYRXLSOGI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 25
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 18
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 5
- 238000000197 pyrolysis Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 14
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical group [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 10
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 238000009987 spinning Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001523 electrospinning Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 150000002603 lanthanum Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 150000003608 titanium Chemical class 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 2
- 229910012464 LiTaF6 Inorganic materials 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 2
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 150000002500 ions Chemical class 0.000 abstract description 13
- 238000013508 migration Methods 0.000 abstract description 12
- 230000005012 migration Effects 0.000 abstract description 12
- 230000005540 biological transmission Effects 0.000 abstract description 11
- WVDJDYHWHDLSAZ-UHFFFAOYSA-N [O].[Ti].[La].[Li] Chemical compound [O].[Ti].[La].[Li] WVDJDYHWHDLSAZ-UHFFFAOYSA-N 0.000 abstract description 9
- 230000003993 interaction Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 229920002239 polyacrylonitrile Polymers 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 239000000945 filler Substances 0.000 description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical group [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 239000002001 electrolyte material Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000010041 electrostatic spinning Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006224 stepwise pyrolysis Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention belongs to the technical field of energy storage, and discloses a solid electrolyte and a preparation method and application thereof. The solid electrolyte comprises a polymer, lithium salt and a nanotube, wherein the nanotube comprises lithium lanthanum titanium oxide, and the surface of the nanotube is provided with holes and crystal grain gaps. The introduction of the lithium lanthanum titanium oxygen nanotube provides a three-dimensional continuous lithium ion transmission channel, and the formed stable and continuous ion transmission channel is beneficial to improving the migration capacity of lithium ions in the solid electrolyte; meanwhile, the lithium lanthanum titanium oxide nanotube has large specific surface area, and the surface has a porous structure and a crystal grain gap, so that the interaction between the nanotube and a polymer is improved, and the ionic conductivity of the solid electrolyte can be effectively improved. The invention provides a solid electrolyte, which has simple raw material components and low cost; the preparation method is simple, the synthesis time is short, large-scale preparation can be realized, and the progress of marketization of the solid-state battery is promoted.
Description
Technical Field
The invention belongs to the technical field of energy storage, and particularly relates to a solid electrolyte and a preparation method and application thereof.
Background
With the further increase of the demand of the electronic consumer market, the demand for efficient and safe electrochemical energy storage devices is higher and higher. Lithium ion batteries have received much attention from researchers as the most widely used electrochemical energy storage devices. However, the liquid organic electrolyte used in the current lithium ion battery has safety problems of flammability, easy leakage, toxicity, poor thermal stability and the like, and a diaphragm therein is also easily punctured by lithium dendrite to cause short circuit of the battery, thereby causing risks such as fire explosion and the like, and greatly limiting the development of the lithium ion battery. Compared with the prior art, the all-solid-state battery has the advantages of high safety, high energy density and the like due to the adoption of the solid electrolyte, and is considered to be the first choice direction of the next generation of novel power batteries and energy storage type batteries.
Currently, the major problems encountered during the development of solid-state batteries are the low lithium ion conductivity and the poor electrode/electrolyte interface contact. In view of the problem of poor interface contact, the interface contact can be improved to some extent by introducing a polymer component into the solid electrolyte. The low lithium ion conductivity can be improved by adding a suitable filler to the solid polymer electrolyte substrate to prepare the composite solid electrolyte. Generally, the ionic conductivity of the composite solid electrolyte can be effectively improved by optimally designing the filler structure to improve the overall electrochemical performance. In recent years, a great deal of research on filler structure design has been reported, including structures such as nanoparticles, nanofibers, three-dimensional networks, etc., all of which can improve ionic conductivity to some extent. However, the ion conductivity of the solid electrolyte is still to be further improved as compared with the conventional liquid electrolyte. Meanwhile, some solid electrolytes are easy to agglomerate due to poor structural continuity and small specific surface area of the filler, so that the ionic conductivity is seriously influenced, and the solid electrolytes are complex in components and complicated in preparation process, so that the application of solid batteries is not facilitated.
Therefore, it is desirable to provide a solid electrolyte, which has a continuous channel inside, a large specific surface area of the filler, and a uniform distribution in the solid electrolyte, and can effectively improve the ionic conductivity of the solid electrolyte.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides the solid electrolyte, which is internally provided with a channel with a continuous structure, has large specific surface area of the filler, is uniformly distributed in the solid electrolyte and can effectively improve the ionic conductivity of the solid electrolyte.
The nanotube comprises lithium lanthanum titanium oxide, is formed by connecting single nanoparticles, has holes and intercrystalline grains on the surface, and is shown in a scanning electron microscope and a transmission electron microscope picture shown in figure 2.
Preferably, the diameter of the nanoparticles is 30-50 nm.
The preparation method of the nanotube comprises the following steps:
adding a solvent into polyvinylpyrrolidone with the molecular weight of 1000000-1500000 and the molecular weight of 300000-400000 for dissolving, and then adding an organic acid, a lithium salt, a lanthanum salt and a titanium salt to prepare an electrospinning precursor liquid; then carrying out electrostatic gradient spinning and pyrolysis reaction to prepare the nanotube.
Polyvinylpyrrolidone with different molecular weights is used as a polymer carrier, polymer gradient distribution with low inside and high outside is formed in an electrospun material, and a tubular structure is formed by pyrolysis from inside to outside in a gradient way due to different pyrolysis speeds of the two polymers in the pyrolysis reaction. The nano tube has a channel with a continuous structure, has a large specific surface area, is uniformly distributed in the solid electrolyte as a filler, and does not generate an agglomeration phenomenon.
The nanotube is formed by connecting single small nanoparticles, the surface of the nanotube is porous, and a large number of crystal grain gaps are formed to form an open structure and provide a three-dimensional ion transmission channel. Meanwhile, the interface wettability between the nanotube and the polymer is increased by the porous and grain gaps on the surface of the nanotube, the Lewis acid-base effect is promoted, the lithium ion concentration in the solid electrolyte is improved, and the migration resistance of lithium ions is reduced.
Preferably, the mass ratio of the polyvinylpyrrolidone with the molecular weight of 1000000-1500000 and the molecular weight of 300000-400000 is (0.8-1.4) - (1.2-2).
Preferably, the solvent is N, N-dimethylformamide, and the volume of the N, N-dimethylformamide is 16-20 mL.
Preferably, the organic acid is at least one of acetic acid, propionic acid or butyric acid; further preferably, the organic acid is acetic acid.
Preferably, the lithium salt is lithium nitrate; the lanthanum salt is lanthanum nitrate; the titanium salt is tetrabutyl titanate.
Preferably, the ratio of the total mass of the polyvinylpyrrolidone to the amount of the lithium salt, lanthanum salt and titanium salt is (2-4.5): (0.02-0.08): (0.3-0.7): (0.6-1.2). Further preferably, the ratio of the total mass of the polyvinylpyrrolidone to the amount of the lithium salt, lanthanum salt and titanium salt is (2.5-4): (0.03-0.07): (0.4-0.6): (0.8-1.2).
Preferably, the voltage of the electrostatic gradient spinning is 10-20kV, the receiving distance is 5-25cm, and the injection speed is 0.05-0.1 mm/min; further preferably, the voltage of the electrostatic gradient spinning is 12-18kV, the receiving distance is 12-18cm, and the injection speed is 0.06-0.09 mm/min; more preferably, the voltage of the electrostatic gradient spinning is 15kV, the receiving distance is 15cm, and the injection speed is 0.08 mm/min.
The temperature of the pyrolysis reaction is 750-820 ℃, the heating rate is 5-10 ℃/min, and the heat preservation time is 1-5 h; more preferably, the temperature of the pyrolysis reaction is 780-820 ℃, the heating rate is 6-9 ℃/min, and the heat preservation time is 2-3 h. By controlling the time and the temperature of the pyrolysis reaction, the obtained lithium lanthanum titanium oxide nanotube has a large specific surface area, so that more interaction areas between the nanotube and the polymer are provided, more interfacial fast ion conducting layers are formed, and the transmission speed of lithium ions is further increased.
The present invention also provides a solid electrolyte comprising a polymer, a lithium salt and the nanotubes.
Preferably, the thickness of the solid electrolyte is 150-250 μm; further preferably, the thickness of the solid electrolyte is 200-220 μm.
Preferably, the lithium salt is LiClO4、LiPF6、LiAsF6、LiBF4、LiAlCl4LiSCN or LiTaF6At least one of (1). More preferably, the lithium salt is LiClO4(lithium perchlorate).
Preferably, the polymer is at least one of polyacrylonitrile, polymethyl methacrylate, polycarbonate or polyethylene oxide. Further preferably, the polymer is polyacrylonitrile. The solid electrolyte film formed by polyacrylonitrile and lithium perchlorate has stable structural strength and flexibility, and can improve the contact between electrolyte and electrodes.
Preferably, the mass ratio of the polymer, the lithium salt and the nanotubes is (0.5-1.5): 0.25-0.75): (0.05-0.3); further preferably, the mass ratio of the polymer, the lithium salt and the nanotube is (0.5-1.5): 0.3-0.7): (0.12-0.2); more preferably, the mass ratio of the polymer, the lithium salt and the nanotubes is (0.8-1.5): 0.3-0.7): (0.14-0.18).
The invention also provides a preparation method of the solid electrolyte, which comprises the following steps:
adding the nanotube, the polymer and the lithium salt into a solvent, heating and stirring to obtain a solid electrolyte solution; and then placing the solid electrolyte solution in a mould, and drying under vacuum to obtain the solid electrolyte.
Preferably, the solvent is N, N-Dimethylformamide (DMF); the volume of the N, N-dimethylformamide is 10-30 mL.
Preferably, the concentration of the polymer is 0.06-0.12g mL-1The concentration of the lithium salt is 0.03-0.06g mL-1。
Preferably, the mass of the nanotube is 40-320 mg; further preferably, the mass of the nanotube is 120-200 mg; more preferably, the mass of the nanotubes is 140-180 mg.
Preferably, the temperature of the heating and stirring is 50-70 ℃.
Preferably, the drying temperature is 50-90 ℃ and the drying time is 5-18 h; further preferably, the drying temperature is 60-80 ℃, and the drying time is 6-14 h.
The invention also provides application of the solid electrolyte in preparation of a lithium ion battery.
A lithium ion battery comprising the solid state electrolyte.
Compared with the prior art, the invention has the following beneficial effects:
(1) the solid electrolyte provided by the invention comprises a nanotube (lithium lanthanum titanium oxygen nanotube), a polymer and a lithium salt. The introduction of the open lithium lanthanum titanium oxygen nanotube provides a three-dimensional continuous lithium ion transmission channel, converts the random diffusion of the traditional lithium ions in the polymer electrolyte into the continuous rapid radial transmission along the nanotube, forms a stable and continuous ion transmission channel, and is beneficial to improving the mobility of the lithium ions in the solid electrolyte; meanwhile, the lithium lanthanum titanium oxide nanotube has large specific surface area, and the surface has a porous structure and a crystal grain gap, so that the interaction between the nanotube and a polymer is improved, and the ionic conductivity of the solid electrolyte can be effectively improved.
(2) In the solid electrolyte provided by the invention, the nano tubes are uniformly dispersed in the solid electrolyte, the agglomeration phenomenon is avoided, and the solid electrolyte has strong stability.
(3) The invention provides a solid electrolyte, which has simple raw material components and low cost; the preparation method is simple, the synthesis time is short, large-scale preparation can be realized, and the progress of marketization of the solid-state battery is promoted.
Drawings
FIG. 1 is an X-ray diffraction pattern of a nanotube;
FIG. 2 is a scanning electron microscope and a transmission electron microscope of the nanotubes prepared in example 1;
FIG. 3 is a scanning electron micrograph of a solid electrolyte prepared according to example 2;
FIG. 4 is a graph of impedance of a solid electrolyte containing 10 wt% nanotubes at various temperatures;
FIG. 5 is a graph of activation energy test results for solid electrolytes containing nanotubes of different masses;
fig. 6 is a graph showing the results of cycle performance tests of the battery prepared in example 2;
FIG. 7 is a scanning electron micrograph of nanotubes prepared according to comparative example 1;
FIG. 8 is a scanning electron micrograph of the nanotubes prepared in comparative example 2.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Example 1
A method for preparing nanotubes comprises the following steps:
adding 1.1g of high molecular weight polyvinylpyrrolidone (Mw is 1300000, HPVP) and 1.5g of low molecular weight polyvinylpyrrolidone (Mw is 360000, LPVP) into 20mL of DMF, adding 3mL of acetic acid, 0.33mmol of lithium nitrate, 0.55mmol of lanthanum nitrate and 1mmol of tetrabutyl titanate to prepare LLTO electrospinning precursor solution, and preparing a lithium lanthanum titanium oxygen nanotube through electrostatic gradient spinning and pyrolysis reaction, wherein the voltage of electrospinning is 15kV, the receiving distance is 15cm, and the injection speed is 0.08 mm/min; the temperature of the pyrolysis reaction is 800 ℃, the heating rate is 8 ℃/min, and the heat preservation time is 2 h.
Polyvinylpyrrolidone with different molecular weights is used as a polymer carrier, polymer gradient distribution with low inside and high outside is formed in an electrospun material, and a tubular structure is formed by stepwise pyrolysis from inside to outside due to the difference of pyrolysis speeds of the two polymers during sintering.
The prepared lithium lanthanum titanium oxide nanotube is subjected to X-ray diffraction (XRD) analysis, and the obtained X-ray diffraction pattern is shown in figure 1. From the curve shown in fig. 1 at 800 c, the nanotube material is pure Lithium Lanthanum Titanium Oxide (LLTO) and has no other impurity phases.
The prepared lithium lanthanum titanium oxide nanotube is tested by a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM), and the obtained result is shown in FIG. 2. As can be seen from a in fig. 2, the lithium lanthanum titanium oxygen nanotube has a one-dimensional structure and a porous surface. In fig. 2 b, the tubular structure inside the lithium lanthanum titanium oxide nanotube is shown, and the polymer can effectively permeate into the nanotube to form more interaction area between the lithium lanthanum titanium oxide nanotube and the polymer.
In fig. 2, c and d show the structural composition of the lithium lanthanum titanium oxygen nanotube, which is formed by connecting single small nanoparticles, has a porous surface and a large number of grain gaps, forms an open structure and provides a three-dimensional ion transmission channel. Meanwhile, the interface wettability between the nanotube and the polymer is increased by the porous and grain gaps on the surface of the lithium lanthanum titanium oxygen nanotube, the Lewis acid-base effect is promoted, the lithium ion concentration in the solid electrolyte is improved, and the migration resistance of lithium ions is reduced.
Example 2
A method of preparing a solid electrolyte comprising the steps of:
1) dispersing 160mg of the lithium lanthanum titanium oxide nanotube prepared in example 1 in 10mL of N, N-dimethylformamide, and uniformly dispersing the lithium lanthanum titanium oxide nanotube by using an ultrasonic mode;
2) taking 1g of Polyacrylonitrile (PAN) and 0.5g of lithium perchlorate (LiClO)4) Adding the electrolyte into the step 1), heating and stirring to obtain a uniform composite solid electrolyte solution;
3) taking out the product obtained in the step 2), inverting the product in a mould, and then placing the mould in a vacuum oven at 80 ℃ for drying for 12h to obtain the composite solid electrolyte.
The prepared solid electrolyte was subjected to morphological analysis, and the obtained results are shown in fig. 3. As can be seen from fig. 3, the nanotubes are uniformly dispersed in the solid electrolyte without significant agglomeration.
The obtained solid electrolyte is used as the dielectric material of the solid lithium ion battery, and lithium iron phosphate LiFePO is used4As the positive electrode, a metal lithium sheet is taken as the negative electrode material, and CR 2016 type button lithium ion is assembledAnd (4) a pool. Impedance (EIS) analysis was performed on the obtained solid lithium ion battery, and the obtained results are shown in FIG. 4, where FIG. 4 is impedance of a solid electrolyte containing 10 wt% of nanotubes at different temperatures, and in the figure, along the direction of the arrow, impedance curves at 20-80 ℃ are represented in order, and the ionic conductivity at room temperature can be calculated to be 3.6X 10-4S cm-1. FIG. 5 is a graph of solid electrolyte activation energy tests for different materials containing different qualities of nanotube filler; wherein, when 10 wt% of the nanotubes are added, the activation energy of the prepared solid electrolyte is 0.11eV, the prepared solid electrolyte shows the lowest lithium ion migration resistance, and the ion migration number is 0.38.
The lithium-lithium symmetric battery is assembled by adopting the solid electrolyte, a constant-current charge and discharge test is carried out, and fig. 6 shows the cycle performance test result of the battery, and the battery can stably run for 1000 hours under the current of 0.1mA at the test temperature of 25 ℃, so that the battery has good structural stability.
Example 3
A method of preparing a solid electrolyte comprising the steps of:
1) dispersing 120mg of the lithium lanthanum titanium oxide nanotube prepared in the embodiment 1 in 10mL of N, N-dimethylformamide, and uniformly dispersing the lithium lanthanum titanium oxide nanotube by using an ultrasonic mode;
2) taking 1g of Polyacrylonitrile (PAN) and 0.5g of lithium perchlorate (LiClO)4) Adding the electrolyte into the step 1), heating and stirring to obtain a uniform composite solid electrolyte solution;
3) taking out the product obtained in the step 2), inverting the product in a mould, and then placing the mould in a vacuum oven at 80 ℃ for drying for 12h to obtain the solid electrolyte.
The obtained solid electrolyte material was subjected to scanning electron microscope analysis, and the obtained result was similar to example 2.
The obtained solid electrolyte was used as a solid battery electrolyte material in the manner of example 2, and an impedance EIS test was performed to calculate an ionic conductivity of 8.6 × 10-5S cm-1。
Example 4
A method of preparing a solid electrolyte comprising the steps of:
1) dispersing 140mg of the lithium lanthanum titanium oxide nanotube prepared in the example 1 in 10mL of N, N-dimethylformamide, and uniformly dispersing the lithium lanthanum titanium oxide nanotube by using an ultrasonic mode;
2) taking 1g of Polyacrylonitrile (PAN) and 0.5g of lithium perchlorate (LiClO)4) Adding the electrolyte into the step 1), heating and stirring to obtain a uniform solid electrolyte solution;
3) taking out the product obtained in the step 2), inverting the product in a mould, and then placing the mould in a vacuum oven at 80 ℃ for drying for 12h to obtain the solid electrolyte.
The obtained solid electrolyte material was subjected to scanning electron microscope analysis, and the obtained result was similar to example 2.
The obtained solid electrolyte was used as a solid battery electrolyte material in the manner of example 2, and an impedance EIS test was performed to calculate an ionic conductivity of 1.3 × 10-4S cm-1。
Example 5
A method of preparing a solid electrolyte comprising the steps of:
1) dispersing 180mg of the lithium lanthanum titanium oxide nanotube prepared in the embodiment 1 in 10mL of N, N-dimethylformamide, and uniformly dispersing the lithium lanthanum titanium oxide nanotube by using an ultrasonic mode;
2) taking 1g of Polyacrylonitrile (PAN) and 0.5g of lithium perchlorate (LiClO)4) Adding the electrolyte into the step 1), heating and stirring to obtain a uniform solid electrolyte solution;
3) taking out the product obtained in the step 2), inverting the product in a mould, and then placing the mould in a vacuum oven at 80 ℃ for drying for 12h to obtain the solid electrolyte.
The obtained solid electrolyte material was subjected to scanning electron microscope analysis, and the obtained result was similar to example 2.
Using the solid electrolyte obtained as a solid battery electrolyte material in the manner of example 2, an impedance EIS test was conducted to calculate an ionic conductivity of 1.1X 10-4S cm-1。
Example 6
The preparation method of the open nanotube/polymer composite solid electrolyte comprises the following steps:
1) dispersing 200mg of the lithium lanthanum titanium oxide nanotube prepared in the embodiment 1 in 10mL of N, N-dimethylformamide, and uniformly dispersing the lithium lanthanum titanium oxide nanotube by using an ultrasonic mode;
2) taking 1g of Polyacrylonitrile (PAN) and 0.5g of lithium perchlorate (LiClO)4) Adding the electrolyte into the step 1), heating and stirring to obtain a uniform solid electrolyte solution;
3) taking out the product obtained in the step 2), inverting the product in a mould, and then placing the mould in a vacuum oven at 80 ℃ for drying for 12h to obtain the solid electrolyte.
The obtained solid electrolyte material was subjected to scanning electron microscope analysis, and the obtained result was similar to example 2. The obtained solid electrolyte was used as a solid battery electrolyte material in the manner of example 2, and an impedance EIS test was performed to calculate an ionic conductivity of 9 × 10-5S cm-1。
From the above examples, it can be seen that the ion conductivity of the solid electrolyte provided by the present application can reach 3.6 × 10 at 25 ℃ at room temperature-4S cm-1The ion migration number is 0.38, and the ion migration number can be kept stable in a long circulation process of 1000 hours, and the phenomena of short circuit structure rupture and the like are avoided, so that the ion migration number has great potential in practical application.
Comparative example 1
Adding 1.1g of high molecular weight polyvinylpyrrolidone (Mw is 1300000, HPVP) and 1.5g of low molecular weight polyvinylpyrrolidone (Mw is 360000, LPVP) into 20mL of DMF, adding 3mL of acetic acid, 0.33mmol of lithium nitrate, 0.557mmol of lanthanum nitrate and 1mmol of tetrabutyl titanate to prepare LLTO electrospinning precursor liquid, and preparing a lithium lanthanum titanium oxygen nanotube through electrostatic gradient spinning and pyrolysis reaction, wherein the voltage of electrostatic spinning is 15kV, the receiving distance is 15cm, and the injection speed is 0.08 mm/min; the temperature of the pyrolysis reaction is 700 ℃, the heating rate is 8 ℃/min, and the heat preservation time is 2 h.
The prepared lithium lanthanum titanium oxide nanotube is subjected to X-ray diffraction (XRD) analysis, and the obtained X-ray diffraction pattern is shown in figure 1. It can be seen from the graph shown in fig. 1 at 700 c that a certain amount of hetero-phase exists except that the nanotube material is a pure Lithium Lanthanum Titanium Oxide (LLTO).
The Scanning Electron Microscope (SEM) characterization of the lithium lanthanum titanium oxide nanotubes showed that the nanotubes prepared were good in structure, smooth in wall, but less porous on the surface, probably due to insufficient reaction caused by low reaction temperature, and the residual inorganic material on the surface was not completely decomposed, as shown in fig. 7.
Comparative example 2
Adding 1.1g of high molecular weight polyvinylpyrrolidone (Mw is 1300000, HPVP) and 1.5g of low molecular weight polyvinylpyrrolidone (Mw is 360000, LPVP) into 20mL of DMF, adding 3mL of acetic acid, 0.33mmol of lithium nitrate, 0.557mmol of lanthanum nitrate and 1mmol of tetrabutyl titanate to prepare LLTO electrospinning precursor liquid, and preparing a lithium lanthanum titanium oxygen nanotube through electrostatic gradient spinning and pyrolysis reaction, wherein the voltage of electrostatic spinning is 15kV, the receiving distance is 15cm, and the injection speed is 0.08 mm/min; the temperature of the pyrolysis reaction is 850 ℃, the heating rate is 8 ℃/min, and the heat preservation time is 2 h.
The X-ray diffraction (XRD) analysis of the lithium lanthanum titanium oxide nanotube resulted in an X-ray diffraction pattern as shown in FIG. 1. As can be seen from the graph shown in FIG. 1 at 850 deg.C, the nanotube material is pure Lithium Lanthanum Titanium Oxide (LLTO) and has no other impurity phase.
The lithium lanthanum titanium oxide nanotubes were characterized by Scanning Electron Microscopy (SEM), and the results are shown in fig. 8. It was found that the structure of some of the nanotubes had collapsed, probably due to excessive growth of some of the grains caused by excessive temperature.
Comparative example 3
The comparative example 3 is different from the example 2 in that the lithium lanthanum titanium oxide nanotube prepared in the comparative example 1 is used instead of the lithium lanthanum titanium oxide nanotube prepared in the example 1, and the rest of the raw materials and the preparation method are the same as those of the example 2.
The solid electrolyte obtained in comparative example 3 was used as a solid battery electrolyte material, and impedance EIS test was carried out to calculate an ionic conductivity of 4.4X 10-5S cm-1The prepared solid electrolyte has lithium ion migration activation energy of 0.21eV and ion migration number of 0.15.
Comparative example 4
Comparative example 4 is different from example 2 in that the lithium lanthanum titanium oxide nanotube prepared in comparative example 2 is used instead of the lithium lanthanum titanium oxide nanotube prepared in example 1, and the remaining raw materials and preparation method are the same as those of example 2.
The solid electrolyte obtained in comparative example 4 was used as a solid battery electrolyte material, and impedance EIS test was conducted to calculate an ionic conductivity of 7.2X 10-5S cm-1The prepared solid electrolyte has lithium ion migration activation energy of 0.17eV and ion migration number of 0.26.
Claims (10)
1. The nanotube is characterized in that the nanotube comprises lithium lanthanum titanium oxide, and the surface of the nanotube is provided with holes and crystal grain gaps.
2. A method of making nanotubes as claimed in claim 1, comprising the steps of:
adding a solvent into polyvinylpyrrolidone with the molecular weight of 1000000-1500000 and the molecular weight of 300000-400000 for dissolving, and then adding an organic acid, a lithium salt, a lanthanum salt and a titanium salt to prepare an electrospinning precursor liquid; then carrying out electrostatic gradient spinning and pyrolysis reaction to prepare the nanotube.
3. The method according to claim 2, wherein the mass ratio of the polyvinylpyrrolidone having a molecular weight of 1000000-1500000 and a molecular weight of 300000-400000 is (0.8-1.4): (1.2-2).
4. The preparation method as claimed in claim 2, wherein the temperature of the pyrolysis reaction is 600-1000 ℃, the heating rate is 5-10 ℃/min, and the holding time is 1-5 h.
5. A solid electrolyte comprising a polymer, a lithium salt and the nanotube of claim 1.
6. The solid electrolyte of claim 5, wherein the lithium salt is LiClO4、LiPF6、LiAsF6、LiBF4、LiAlCl4LiSCN or LiTaF6At least one of; the polymer is polypropyleneAt least one of an alkenenitrile, polymethylmethacrylate, polycarbonate, or polyethylene oxide.
7. The solid-state electrolyte of claim 5, wherein the thickness of the solid-state electrolyte is 150-250 μm.
8. The method for producing a solid electrolyte according to any one of claims 5 to 7, characterized by comprising the steps of:
adding the nanotube, the polymer and the lithium salt into a solvent, heating and stirring to obtain a solid electrolyte solution; and then, drying the solid electrolyte solution in vacuum to obtain the solid electrolyte.
9. Use of the solid-state electrolyte of any one of claims 5-7 in the preparation of a lithium ion battery.
10. A lithium ion battery comprising the solid state electrolyte of any one of claims 5-7.
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