CN116314697A - Nanometer lithium titanate composite material and preparation method and application thereof - Google Patents
Nanometer lithium titanate composite material and preparation method and application thereof Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 138
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 135
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 29
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 24
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- 238000000137 annealing Methods 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 238000004108 freeze drying Methods 0.000 claims abstract description 13
- 238000004140 cleaning Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000008139 complexing agent Substances 0.000 claims abstract description 10
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 9
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims description 48
- 238000007254 oxidation reaction Methods 0.000 claims description 48
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 36
- 229910052782 aluminium Inorganic materials 0.000 claims description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 29
- 239000003792 electrolyte Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 230000007797 corrosion Effects 0.000 claims description 18
- 238000005260 corrosion Methods 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 235000006408 oxalic acid Nutrition 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 238000005530 etching Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- 239000007773 negative electrode material Substances 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 6
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 5
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 claims description 3
- 229910001637 strontium fluoride Inorganic materials 0.000 claims description 3
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 5
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 51
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 lithium titanate ions Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/582—Halogenides
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The application provides a nano lithium titanate composite material, a preparation method and application thereof, and relates to the technical field of nano materials. The preparation method comprises the following steps: mixing titanium dioxide serving as a titanium source and lithium hydroxide serving as a lithium source under the conditions of a solvent and a complexing agent to prepare a lithium titanate precursor solution; immersing a porous alumina template into the precursor solution, standing in a vacuum environment, drying, preheating and calcining, and removing the template by adopting a sodium hydroxide solution to obtain nano lithium titanate; and (3) cleaning and drying the nano lithium titanate, dispersing the nano lithium titanate into a solvent, adding fluoride, stirring to obtain a mixture, freeze-drying the mixture to obtain powder, annealing the powder in an argon atmosphere, and cooling to obtain the nano lithium titanate composite material. The nano lithium titanate composite material prepared by the method has the advantages of controllable growth morphology such as pore diameter, pore spacing and the like, and improved conductivity and circulation stability.
Description
Technical Field
The application relates to the technical field of nano materials, in particular to a nano lithium titanate composite material and a preparation method and application thereof.
Background
In recent years, the increasing demand for electric vehicles and renewable energy integration devices has driven the rapid development of rechargeable, long-life, high-capacity, low-cost energy storage devices. The lithium ion battery has the advantages of large capacity, long period, environmental friendliness and the like, and becomes a good power source for portable electronic equipment and electric automobiles.
In the basic development of lithium batteries, the positive electrode materials and the negative electrode materials of the batteries are all hot spots for research. In the aspect of the cathode material, most of lithium-embedded graphitized carbon materials at present have the advantages of wide raw materials, low price, simple preparation method, good performance and the like, but the following defects exist in practical application: the first charge and discharge efficiency is lower, the volume change is larger in the charge and discharge process, the short circuit of the battery is easily caused by the formation of lithium dendrites, the risk of decomposition of the electrolyte is higher, and potential safety hazards exist.
In contrast, lithium titanate having a spinel structure has excellent properties, and when used as a battery anode material, the lithium titanate can effectively overcome the defects of the carbon material as an anode material. The lithium titanate is a composite oxide composed of metal lithium and low-potential transition metal titanium, and has the biggest characteristics of zero strain, and the lattice constant and the volume change of lithium titanate are very small in the process of intercalation or deintercalation of lithium ions, and the change rate is within 1%; in the charge-discharge cycle, the zero strain can avoid the structural damage caused by the back-and-forth expansion of the electrode material, thereby improving the cycle performance and the service life of the electrode, reducing the specific capacity attenuation caused by the cycle and having very good overcharge and overdischarge resistance.
However, lithium titanate still has some disadvantages as a negative electrode material, for example, the low conductivity of the lithium titanate itself makes the lithium titanate have poor performance and rapid specific capacity decay during high-rate charge and discharge, and the high-current discharge performance is not ideal. Thus, the current research on modification of lithium titanate is a hot spot.
Disclosure of Invention
The purpose of the application is to provide a preparation method of a nano lithium titanate composite material, which is used for modifying nano lithium titanate and combining the advantages of the nano lithium titanate and fluoride.
Another object of the present application is to provide a nano lithium titanate composite material having an advantage of charge-discharge cycle stability.
Another object of the present application is to provide the use of the above nano lithium titanate composite material as a negative electrode material in the field of batteries
In order to solve the technical problems, the application adopts the technical scheme that:
in one aspect, the present application provides a method for preparing a nano lithium titanate composite material, comprising the steps of:
preparing a lithium titanate precursor liquid: mixing titanium dioxide serving as a titanium source and lithium hydroxide serving as a lithium source under the conditions of a solvent and a complexing agent to prepare a lithium titanate precursor solution;
preparing nano lithium titanate: immersing a porous alumina template into the precursor solution, standing in a vacuum environment, drying, preheating and calcining, and removing the template by adopting a sodium hydroxide solution to obtain nano lithium titanate;
preparing a nano lithium titanate composite material: and (3) cleaning and drying the nano lithium titanate, dispersing the nano lithium titanate into a solvent, adding fluoride, stirring to obtain a mixture, freeze-drying the mixture to obtain powder, annealing the powder in an argon atmosphere, and cooling to obtain the nano lithium titanate composite material.
On the other hand, the application provides a nano lithium titanate composite material prepared by the method.
In yet another aspect, the present application provides the use of the above-described nano lithium titanate composite material as a negative electrode material in the field of batteries.
Compared with the prior art, the embodiment of the application has at least the following advantages or beneficial effects:
according to the preparation method, porous alumina is used as a template, lithium titanate precursor solution is filled into pores of the porous alumina, stable and compact nano lithium titanate is formed after standing, drying, preheating and calcining, then the alumina template is removed by adopting sodium hydroxide solution, and hollow nano lithium titanate is obtained.
According to the method, fluoride is wrapped on the surface of the nano lithium titanate through the steps of mixing and dispersing, freeze drying and high-temperature annealing, and the fluoride conductive substance is applied to lithium titanate ions, so that the conductive substance can not only improve the conductive performance of the material, but also prevent electrolyte from directly contacting with negative electrode material lithium titanate, further reduce side reaction of the electrolyte, and the fluoride can reduce the activity of oxygen release, inhibit electrolyte decomposition, and further improve conductivity and cycling stability of the electrolyte.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present application will be described in detail with reference to specific examples.
The preparation method of the nano lithium titanate composite material comprises the following steps:
preparing a lithium titanate precursor liquid: mixing titanium dioxide serving as a titanium source and lithium hydroxide serving as a lithium source under the conditions of a solvent and a complexing agent to prepare a lithium titanate precursor solution;
preparing nano lithium titanate: immersing a porous alumina template into the precursor solution, standing in a vacuum environment, drying, preheating and calcining, and removing the template by adopting a sodium hydroxide solution to obtain nano lithium titanate;
preparing a nano lithium titanate composite material: and (3) cleaning and drying the nano lithium titanate, dispersing the nano lithium titanate into a solvent, adding fluoride, stirring to obtain a mixture, freeze-drying the mixture to obtain powder, annealing the powder in an argon atmosphere, and cooling to obtain the nano lithium titanate composite material.
According to the preparation method, porous alumina is used as a template, lithium titanate precursor solution is filled into pores of the porous alumina, stable and compact nano lithium titanate is formed after standing, drying, preheating and calcining, then the alumina template is removed by adopting sodium hydroxide solution, and hollow nano lithium titanate is obtained.
According to the method, fluoride is wrapped on the surface of the nano lithium titanate through the steps of mixing and dispersing, freeze drying and high-temperature annealing, and the fluoride conductive substance is applied to lithium titanate ions, so that the conductive substance can not only improve the conductive performance of the material, but also prevent electrolyte from directly contacting with negative electrode material lithium titanate, further reduce side reaction of the electrolyte, and the fluoride can reduce the activity of oxygen release, inhibit electrolyte decomposition, and further improve conductivity and cycling stability of the electrolyte.
In some embodiments of the present application, the molar ratio of the titanium source to the lithium source in the step of preparing the lithium titanate precursor solution is 1: (0.8-0.9), wherein the solvent is absolute ethyl alcohol, 1, 4-butanediol, glycerol or 1, 5-pentanediol, and the complexing agent is acetic acid, triethanolamine or acetylacetone.
In some embodiments of the present application, the porous alumina template in the step of preparing nano lithium titanate is prepared by the following method: after surface pretreatment and polishing are carried out on the aluminum sheet, the aluminum sheet is used as an anode, a platinum sheet is used as a cathode, and the aluminum sheet subjected to first anodic oxidation, corrosion liquid aluminum sheet corrosion and second anodic oxidation is used as the porous alumina template.
In some embodiments of the present application, the electrolyte for the first anodic oxidation is an oxalic acid solution with a concentration of 0.1-0.3 mol/L, an oxidation voltage of 40-60V, an oxidation temperature of 20-30 ℃ and an oxidation time of 1-3h.
In some embodiments of the present application, the etching solution for etching the aluminum sheet is prepared from phosphoric acid, chromic acid and water according to a mass ratio of 4-5: 1-2: 94, and the corrosion temperature is 50-60 ℃.
In some embodiments of the present application, the electrolyte for the second anodic oxidation is an oxalic acid solution with a concentration of 0.1-0.3 mol/L, an oxidation voltage of 40-60V, an oxidation temperature of 50-60 ℃ and an oxidation time of 4-5 h.
In some embodiments of the present application, the standing time in the step of preparing the nano lithium titanate is 12-24 hours; the temperature of the drying step is 30-40 ℃ and the time is 10-30 min; the temperature of the preheating step is 150-200 ℃ and the time is 1-3 h; the calcination temperature is 800-1000 ℃ and the calcination time is 4-8 h.
In some embodiments of the present application, the solvent in the step of preparing the nano lithium titanate composite material is deionized water, the fluoride is calcium fluoride, magnesium fluoride or strontium fluoride, the temperature of freeze drying is-40 to-20 ℃, the annealing temperature is 400 to 600 ℃, and the annealing time is 1 to 3 hours.
The nano lithium titanate composite material is prepared by adopting the preparation method.
The nano lithium titanate composite material is applied to the field of batteries as a negative electrode material.
The features and capabilities of the present application are described in further detail below in connection with the examples.
Example 1
A preparation method of the nano lithium titanate composite material comprises the following steps:
preparing a porous alumina template: soaking an aluminum sheet in acetone for 20min, taking out, and performing ultrasonic treatment in deionized water for 8min to perform surface pretreatment; polishing in a mixed solution of perchloric acid and ethanol for 15min, and washing with deionized water; taking an aluminum sheet as an anode and a platinum sheet as a cathode, putting the anode and the cathode into an oxalic acid solution with the concentration of 0.2mol/L for first anodic oxidation, wherein the oxidation voltage is 50V, the temperature of the electrolyte is 25 ℃, and the oxidation time is 2 hours; taking out the aluminum sheet after the first anodic oxidation, and putting the aluminum sheet into an etching solution, wherein the etching solution comprises phosphoric acid, chromic acid and water according to a mass ratio of 4:2:94, the corrosion temperature is 55 ℃, and the corrosion treatment is carried out for 20min; after corrosion treatment, the solution is put into oxalic acid solution with the concentration of 0.2mol/L for secondary anodic oxidation, the oxidation voltage is 50V, the temperature of the electrolyte is 55 ℃, and the oxidation time is 5 hours; and cleaning the oxidized aluminum sheet by distilled water to obtain the porous alumina template.
Preparing a lithium titanate precursor liquid: titanium dioxide and lithium hydroxide are mixed according to a mole ratio of 1:0.8, weighing, placing in absolute ethyl alcohol, adding triethyl alcohol as a complexing agent, stirring and mixing for 2 hours, and preparing the lithium titanate precursor solution.
Preparing nano lithium titanate: immersing the prepared porous alumina template into the precursor solution, standing for 16 hours in a vacuum environment, naturally airing, sending into a constant temperature oven at 200 ℃ for preheating for 2 hours, calcining for 6 hours at 800 ℃, taking out, cooling to room temperature, soaking by using a sodium hydroxide solution with the concentration of 25% to remove the alumina template, and cleaning to neutrality to obtain the hollow nano lithium titanate.
Preparing a nano lithium titanate composite material: dispersing nano lithium titanate into deionized water after drying, adding calcium fluoride, rapidly dispersing to obtain a mixture, and freeze-drying the mixture at-30 ℃ to obtain powder; and in an argon atmosphere, placing the powder at 500 ℃ for roasting and annealing for 2 hours, and cooling to room temperature to obtain the nano lithium titanate composite material of the embodiment.
Example 2
A preparation method of the nano lithium titanate composite material comprises the following steps:
preparing a porous alumina template: soaking an aluminum sheet in acetone for 15min, taking out, and performing ultrasonic treatment in deionized water for 8min to perform surface pretreatment; polishing in a mixed solution of perchloric acid and ethanol for 12min, and washing with deionized water; taking an aluminum sheet as an anode and a platinum sheet as a cathode, putting the anode and the cathode into an oxalic acid solution with the concentration of 0.1mol/L for first anodic oxidation, wherein the oxidation voltage is 40V, the temperature of the electrolyte is 20 ℃, and the oxidation time is 2 hours; taking out the aluminum sheet after the first anodic oxidation, and putting the aluminum sheet into an etching solution, wherein the etching solution comprises phosphoric acid, chromic acid and water according to a mass ratio of 5:1:94, the corrosion temperature is 60 ℃, and the corrosion treatment is carried out for 15min; after corrosion treatment, the solution is put into oxalic acid solution with the concentration of 0.2mol/L for secondary anodic oxidation, the oxidation voltage is 50V, the temperature of the electrolyte is 60 ℃, and the oxidation time is 6 hours; and cleaning the oxidized aluminum sheet by distilled water to obtain the porous alumina template.
Preparing a lithium titanate precursor liquid: titanium dioxide and lithium hydroxide are mixed according to a mole ratio of 1:0.85 of the lithium titanate precursor solution is weighed and placed in absolute ethyl alcohol, and is added with the triethyl alcohol as a complexing agent, and the mixture is stirred and mixed for 1.5 hours to prepare the lithium titanate precursor solution.
Preparing nano lithium titanate: immersing the prepared porous alumina template into the precursor solution, standing for 24 hours in a vacuum environment, naturally airing, sending into a constant temperature oven at 150 ℃ for preheating for 2 hours, calcining for 8 hours at 800 ℃, taking out, cooling to room temperature, soaking by using a sodium hydroxide solution with the concentration of 25% to remove the alumina template, and cleaning to neutrality to obtain the hollow nano lithium titanate.
Preparing a nano lithium titanate composite material: dispersing nano lithium titanate into deionized water after drying, adding calcium fluoride, rapidly dispersing to obtain a mixture, and freeze-drying the mixture at-40 ℃ to obtain powder; and in an argon atmosphere, placing the powder at 600 ℃ for roasting and annealing for 2 hours, and cooling to room temperature to obtain the nano lithium titanate composite material of the embodiment.
Example 3
A preparation method of the nano lithium titanate composite material comprises the following steps:
preparing a porous alumina template: soaking an aluminum sheet in acetone for 15min, taking out, and performing ultrasonic treatment in deionized water for 8min to perform surface pretreatment; polishing in a mixed solution of perchloric acid and ethanol for 12min, and washing with deionized water; taking an aluminum sheet as an anode and a platinum sheet as a cathode, putting the anode and the cathode into an oxalic acid solution with the concentration of 0.3mol/L for first anodic oxidation, wherein the oxidation voltage is 55V, the temperature of the electrolyte is 30 ℃, and the oxidation time is 2 hours; taking out the aluminum sheet after the first anodic oxidation, and putting the aluminum sheet into an etching solution, wherein the etching solution comprises phosphoric acid, chromic acid and water according to a mass ratio of 5:1:94, the corrosion temperature is 60 ℃, and the corrosion treatment is carried out for 15min; after corrosion treatment, the solution is put into oxalic acid solution with the concentration of 0.1mol/L for secondary anodic oxidation, the oxidation voltage is 55V, the temperature of the electrolyte is 60 ℃, and the oxidation time is 4 hours; and cleaning the oxidized aluminum sheet by distilled water to obtain the porous alumina template.
Preparing a lithium titanate precursor liquid: titanium dioxide and lithium hydroxide are mixed according to a mole ratio of 1:0.83 is weighed and placed in absolute ethyl alcohol, and is added with triethyl alcohol as a complexing agent, and is stirred and mixed for 3 hours, so that the lithium titanate precursor solution is prepared.
Preparing nano lithium titanate: immersing the prepared porous alumina template into the precursor solution, standing for 12 hours in a vacuum environment, naturally airing, sending into a constant temperature oven at 180 ℃ for preheating for 2 hours, calcining for 5 hours at 1000 ℃, taking out, cooling to room temperature, soaking by using a sodium hydroxide solution with the concentration of 25% to remove the alumina template, and cleaning to neutrality to obtain the hollow nano lithium titanate.
Preparing a nano lithium titanate composite material: dispersing nano lithium titanate into deionized water after drying, adding calcium fluoride, rapidly dispersing to obtain a mixture, and freeze-drying the mixture at-25 ℃ to obtain powder; and in an argon atmosphere, placing the powder at 450 ℃ for roasting and annealing for 3 hours, and cooling to room temperature to obtain the nano lithium titanate composite material of the embodiment.
Example 4
A preparation method of the nano lithium titanate composite material comprises the following steps:
preparing a porous alumina template: soaking an aluminum sheet in acetone for 10min, taking out, and performing ultrasonic treatment in deionized water for 10min to perform surface pretreatment; polishing in a mixed solution of perchloric acid and ethanol for 12min, and washing with deionized water; taking an aluminum sheet as an anode and a platinum sheet as a cathode, putting the anode and the cathode into an oxalic acid solution with the concentration of 0.2mol/L for first anodic oxidation, wherein the oxidation voltage is 45V, the temperature of the electrolyte is 30 ℃, and the oxidation time is 2 hours; taking out the aluminum sheet after the first anodic oxidation, and putting the aluminum sheet into an etching solution, wherein the etching solution comprises phosphoric acid, chromic acid and water according to a mass ratio of 4:2:94, the corrosion temperature is 60 ℃, and the corrosion treatment is carried out for 15min; after corrosion treatment, the solution is put into oxalic acid solution with the concentration of 0.1mol/L for secondary anodic oxidation, the oxidation voltage is 45V, the temperature of the electrolyte is 60 ℃, and the oxidation time is 5 hours; and cleaning the oxidized aluminum sheet by distilled water to obtain the porous alumina template.
Preparing a lithium titanate precursor liquid: titanium dioxide and lithium hydroxide are mixed according to a mole ratio of 1:0.83 is weighed and placed in 1, 4-butanediol, acetylacetone with the mass of 0.5 times of titanium dioxide is added as a complexing agent, and the mixture is stirred and mixed for 3 hours to prepare the lithium titanate precursor solution.
Preparing nano lithium titanate: immersing the prepared porous alumina template into the precursor solution, standing for 15 hours in a vacuum environment, naturally airing, sending into a constant temperature oven at 150 ℃ for preheating for 2 hours, calcining for 6 hours at 900 ℃, taking out, cooling to room temperature, soaking by using a sodium hydroxide solution with the concentration of 25% to remove the alumina template, and cleaning to neutrality to obtain the hollow nano lithium titanate.
Preparing a nano lithium titanate composite material: dispersing nano lithium titanate into deionized water after drying, adding strontium fluoride, rapidly dispersing to obtain a mixture, and freeze-drying the mixture at-25 ℃ to obtain powder; and in an argon atmosphere, placing the powder at 550 ℃ for roasting and annealing for 1h, and cooling to room temperature to obtain the nano lithium titanate composite material of the embodiment.
Comparative example
This comparative example differs from example 1 in that the hollow nano lithium titanate was not fluoride coated.
Experimental example
Preparing a capacitor: the nano lithium titanate composite material or the hollow nano lithium titanate prepared by adopting the examples 1-4 and the comparative example, the acetylene black conductive agent and the polyvinylidene fluoride binder are prepared according to the mass ratio of 8:1:1 is added into N-methyl pyrrolidone, uniformly stirred and coated on a copper foil to form a membrane, then a lithium sheet is used as a negative electrode, and LiPF is used 6 the/CAN was dissolved as an electrolyte, and assembled in a glove box filled with argon, to obtain capacitors of each experimental group.
The capacitors of each experimental group were tested for charge and discharge cycles using a battery performance tester, and the results are shown in table 1.
TABLE 1
As can be seen from Table 1, the cycle performance of the nano lithium titanate composite material capacitors prepared in examples 1 to 4 is very good, and is remarkably improved compared with the comparative example. In the comparative example, fluoride is not coated on the outer surface of the hollow lithium titanate material, and the capacity retention rate is only 90% after 1000 times of circulation.
In summary, the nano lithium titanate composite material, the preparation method and the application thereof in the embodiment of the application have the following advantages:
according to the preparation method, porous alumina is used as a template, lithium titanate precursor solution is filled into pores of the porous alumina, stable and compact nano lithium titanate is formed after standing, drying, preheating and calcining, then the alumina template is removed by adopting sodium hydroxide solution, and hollow nano lithium titanate is obtained.
According to the method, fluoride is wrapped on the surface of the nano lithium titanate through the steps of mixing and dispersing, freeze drying and high-temperature annealing, and the fluoride conductive substance is applied to lithium titanate ions, so that the conductive substance can not only improve the conductive performance of the material, but also prevent electrolyte from directly contacting with negative electrode material lithium titanate, further reduce side reaction of the electrolyte, and the fluoride can reduce the activity of oxygen release, inhibit electrolyte decomposition, and further improve conductivity and cycling stability of the electrolyte.
The embodiments described above are some, but not all, of the embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present application based on the embodiments herein.
Claims (10)
1. The preparation method of the nano lithium titanate composite material is characterized by comprising the following steps:
preparing a lithium titanate precursor liquid: mixing titanium dioxide serving as a titanium source and lithium hydroxide serving as a lithium source under the conditions of a solvent and a complexing agent to prepare a lithium titanate precursor solution;
preparing nano lithium titanate: immersing a porous alumina template into the precursor solution, standing in a vacuum environment, drying, preheating and calcining, and removing the template by adopting a sodium hydroxide solution to obtain nano lithium titanate;
preparing a nano lithium titanate composite material: and (3) cleaning and drying the nano lithium titanate, dispersing the nano lithium titanate into a solvent, adding fluoride, stirring to obtain a mixture, freeze-drying the mixture to obtain powder, annealing the powder in an argon atmosphere, and cooling to obtain the nano lithium titanate composite material.
2. The method for preparing a nano lithium titanate composite material according to claim 1, wherein in the step of preparing a lithium titanate precursor solution, the molar ratio of a titanium source to a lithium source is 1: (0.8-0.9), wherein the solvent is absolute ethyl alcohol, 1, 4-butanediol, glycerol or 1, 5-pentanediol, and the complexing agent is acetic acid, triethanolamine or acetylacetone.
3. The method for preparing the nano lithium titanate composite material according to claim 1, wherein the porous alumina template in the step of preparing the nano lithium titanate is prepared by the following method: after surface pretreatment and polishing are carried out on the aluminum sheet, the aluminum sheet is used as an anode, a platinum sheet is used as a cathode, and the aluminum sheet subjected to first anodic oxidation, corrosion liquid aluminum sheet corrosion and second anodic oxidation is used as the porous alumina template.
4. The method for preparing nano lithium titanate composite material according to claim 3, wherein the electrolyte for the first anodic oxidation is oxalic acid solution with concentration of 0.1-0.3 mol/L, oxidation voltage of 40-60V, oxidation temperature of 20-30 ℃ and oxidation time of 1-3h.
5. The preparation method of the nano lithium titanate composite material according to claim 3, wherein the etching solution is prepared from phosphoric acid, chromic acid and water according to a mass ratio of 4-5: 1-2: 94, and the corrosion temperature is 50-60 ℃.
6. The method for preparing nano lithium titanate composite material according to claim 3, wherein the electrolyte for the second anodic oxidation is oxalic acid solution with concentration of 0.1-0.3 mol/L, oxidation voltage of 40-60V, oxidation temperature of 50-60 ℃ and oxidation time of 4-5 h.
7. The method for preparing a nano lithium titanate composite material according to claim 1, wherein the standing time in the step of preparing the nano lithium titanate is 12-24 hours; the temperature of the drying step is 30-40 ℃ and the time is 10-30 min; the temperature of the preheating step is 150-200 ℃ and the time is 1-3 h; the calcination temperature is 800-1000 ℃ and the calcination time is 4-8 h.
8. The method for preparing the nano lithium titanate composite material according to claim 1, wherein the solvent in the step of preparing the nano lithium titanate composite material is deionized water, the fluoride is calcium fluoride, magnesium fluoride or strontium fluoride, the freeze-drying temperature is-40 to-20 ℃, the annealing temperature is 400 to 600 ℃, and the annealing time is 1 to 3 hours.
9. The nano lithium titanate composite material is characterized by being prepared by the preparation method of any one of claims 1-8.
10. The use of the nano lithium titanate composite material according to claim 9 as a negative electrode material in the field of batteries.
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