CN117247045B - Aluminum-doped tin dioxide composite titanium niobate material, and preparation method and application thereof - Google Patents
Aluminum-doped tin dioxide composite titanium niobate material, and preparation method and application thereof Download PDFInfo
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- CN117247045B CN117247045B CN202311541127.XA CN202311541127A CN117247045B CN 117247045 B CN117247045 B CN 117247045B CN 202311541127 A CN202311541127 A CN 202311541127A CN 117247045 B CN117247045 B CN 117247045B
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 101
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000010936 titanium Substances 0.000 title claims abstract description 71
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 68
- 239000000463 material Substances 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002270 dispersing agent Substances 0.000 claims abstract description 28
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 19
- 239000010955 niobium Substances 0.000 claims abstract description 17
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 15
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 14
- 239000007921 spray Substances 0.000 claims abstract description 10
- 238000005469 granulation Methods 0.000 claims abstract description 7
- 230000003179 granulation Effects 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000007773 negative electrode material Substances 0.000 claims description 13
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 11
- 229910001415 sodium ion Inorganic materials 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 3
- 238000005507 spraying Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000001694 spray drying Methods 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 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
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides an aluminum-doped tin dioxide composite titanium niobate material, and a preparation method and application thereof, and relates to the technical field of batteries. The preparation method comprises the following steps: preparing a mixed solution of aluminum-doped tin oxide, a high molecular dispersing agent, a niobium source and a titanium source, and then sequentially carrying out spray granulation and sintering on the mixed solution to prepare the aluminum-doped tin dioxide composite titanium niobate material. According to the invention, after the conductive oxide ASO is compounded with the titanium niobate, a three-dimensional conductive structure can be formed in the titanium niobate, so that the conductivity and the multiplying power performance of the material are improved, and the material capacity is increased; and spraying and granulating the mixed solution, and adhering ASO (ASO) into titanium niobate particles by using a high-molecular dispersing agent to form a uniform conductive network, so that the conductive performance of the material is improved. The preparation method is simple and convenient, has low cost, and the prepared aluminum-doped tin dioxide composite titanium niobate material has good conductivity and can be used for preparing batteries.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to an aluminum-doped tin dioxide composite titanium niobate material, and a preparation method and application thereof.
Background
The secondary battery plays an increasingly important role in daily life of people, influences daily life, work, travel and other aspects of people, and in recent years, the lithium ion battery gradually replaces the lead-acid battery with excellent electrochemical performance, however, the lithium ion battery also has the problems of high cost, high potential safety hazard and the like, and a product capable of replacing the lithium ion battery is needed to be searched.
Titanium niobate becomes an ideal lithium ion battery anode material due to the deintercalation mechanism, and the Goodenough group in 2011 firstly uses TiNb 2 O 7 As a negative electrode material of a lithium ion battery, the lithium ion battery has excellent electrochemical performance, and Ti-based can be generated in the processes of removing and inserting lithium 4+ And Ti is 3+ Single electron reaction between and Nb 5+ And Nb (Nb) 3+ The theoretical specific capacity of the 5 electron transfer of the two electron reaction corresponds to the redox reaction of 5 electron pairs, which reaches 387.6mAh/g (commercial lithium titanate Li) 4 Ti 5 O 12 About twice as many as a carbon-based negative electrode material), and no dendrite is generated during charge and discharge, and a battery using the same as the negative electrode material does not undergo volume change, and has a higher discharge potential (e.g., tiNb) 2 O 7 The discharge potential of (1.6V) is about), the high voltage platform theory can effectively avoid the formation of SEI film (the most applied LiPF at present) 6 In the electrolyte system dissolved in the mixed solvent of EC and DEC, the reduction potential of the anode is about 1.3V, i.e., if the charge-discharge potential of the anode material is 1.3V or more, an SEI film is not theoretically generated during battery cycle), li + During the embedding and removing process of TiNb 2 O 7 The unit cell volume change of (2) was only 3.6%, and in situ XRD studies found that the volume of the crystals increased from 0.794 to 0.833nm after the charging process 3 Can be recovered to 0.794nm after discharge 3 Indicating TiNb 2 O 7 Has excellent stability and highly reversible cycle process. Has higher safety and better circulation stability.
However, titanium niobate has lower electron and ion conductivity, and the defects of low diffusion rate of lithium ions therein limit the industrialized application thereof, and in order to solve the bottleneck, the current common improvement strategies include carbon coating, element doping (doping by heterogeneous metal ions and improving electron conduction by oxygen defects), micro-nano structure design and multi-hollow structure design (reducing Li) + Depth of deintercalation, shorten Li + Transmission path, increased electrolyte/electrode contact, increased active sites for electrode reactionsDots) to modify and improve conductivity, however, these methods are not ideal and need to be improved.
In view of this, the present invention has been made.
Disclosure of Invention
A first object of the present invention is to provide a method for preparing an aluminum doped tin dioxide (ASO) composite titanium niobate material, so as to solve at least one of the above problems.
The second object of the invention is to provide an aluminum-doped tin dioxide composite titanium niobate material.
The third object of the invention is to provide the application of the aluminum-doped tin dioxide composite titanium niobate material in sodium ion batteries.
A fourth object of the present invention is to provide a sodium ion battery.
In a first aspect, the invention provides a preparation method of an aluminum-doped tin dioxide composite titanium niobate material, which comprises the following steps:
preparing a mixed solution of aluminum-doped tin oxide, a high molecular dispersing agent, a niobium source and a titanium source, and then sequentially carrying out spray granulation and sintering on the mixed solution to prepare an aluminum-doped tin dioxide composite titanium niobate material;
the mass of the aluminum-doped tin oxide is 0.5-8% of that of the aluminum-doped tin dioxide composite titanium niobate material;
the mass of the high molecular dispersing agent is 0.5-5% of the mass of the aluminum-doped tin dioxide composite titanium niobate material;
the mass ratio of the niobium element to the titanium element in the niobium source and the titanium source is 3:1-5:1.
As a further technical scheme, the mass ratio of aluminum in the aluminum-doped tin oxide is 0.5% -10%.
As a further technical scheme, the polymer dispersant comprises at least one of PVP, PAN, PAM or nylon 66.
As a further technical scheme, the niobium source comprises at least one of niobium ethoxide or niobium pentoxide;
the titanium source comprises at least one of titanium dioxide, tetraethyl titanate, tetrabutyl titanate, tetraisopropyl titanate or titanyl sulfate.
As a further technical scheme, the preparation method of the mixed solution comprises the following steps: mixing aluminum doped tin oxide, a high molecular dispersing agent, a niobium source and a titanium source in water, and grinding to prepare a mixed solution;
the grinding is to grind the solid particles in the mixed solution to a particle size of less than 10 mu m.
As a further technical scheme, spray granulation is carried out by adopting a spray dryer.
As a further technical scheme, the sintering temperature is 750-1100 ℃.
In a second aspect, the invention provides an aluminum-doped tin dioxide composite titanium niobate material, which is prepared by the preparation method.
In a third aspect, the invention provides application of the aluminum-doped tin dioxide composite titanium niobate material in sodium ion batteries.
In a fourth aspect, the invention provides a sodium ion battery, wherein the sodium ion battery takes the aluminum doped tin dioxide composite titanium niobate material as a negative electrode active material.
Compared with the prior art, the invention has the following beneficial effects:
1. compared with carbon coating, the conductive oxide ASO has more excellent electrochemical performance, and can form a three-dimensional conductive structure in the titanium niobate after being compounded with the titanium niobate, thereby improving the ion and electron conductivity and the multiplying power performance of the material and increasing the material capacity.
2. And spraying and granulating the mixed solution, and adhering ASO (ASO) into titanium niobate particles by using a high-molecular dispersing agent to form a uniform conductive network, so that the conductive performance of the material is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow of the preparation method of example 1;
FIG. 2 is a scanning electron microscope image of the aluminum doped tin dioxide composite titanium niobate material provided in example 1;
FIG. 3 is a graph showing the results of precursor particles after spray drying and evaporative drying;
FIG. 4 effect of different ASO doping levels on cell cycle performance;
fig. 5 is a comparison of battery cycle performance of example 1, comparative example 3 and comparative example 4;
fig. 6 is a comparison of battery cycle performance of example 1, comparative example 1 and comparative example 2;
fig. 7 is a comparison of battery cycle performance of example 1 and comparative example 5.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to embodiments and examples, but it will be understood by those skilled in the art that the following embodiments and examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not specified, and the process is carried out according to conventional conditions or conditions suggested by manufacturers. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In a first aspect, the invention provides a preparation method of an aluminum-doped tin dioxide composite titanium niobate material, which comprises the following steps:
preparing a mixed solution of aluminum-doped tin oxide, a high molecular dispersing agent, a niobium source and a titanium source, and then sequentially carrying out spray granulation and sintering on the mixed solution to prepare an aluminum-doped tin dioxide composite titanium niobate material;
the mass of the aluminum doped tin oxide is 0.5% -8% of that of the aluminum doped tin dioxide composite titanium niobate material, for example, but not limited to, 0.5%, 1%, 2%, 4% or 8%;
the mass of the high molecular dispersing agent is 0.5% -5% of the mass of the aluminum-doped tin dioxide composite titanium niobate material, for example, but not limited to, 0.5%, 1%, 2%, 4% or 5%;
the mass ratio of the niobium element to the titanium element in the niobium source and the titanium source can be, for example, but not limited to, 3:1, 4:1 or 5:1.
Compared with carbon coating, the conductive oxide ASO has obvious capacity improvement and cycle stability, and after a proper amount of ASO is compounded with titanium niobate, a three-dimensional conductive structure can be formed inside the titanium niobate, so that the ion and electron conductivity and multiplying power performance of the material are improved, and the material capacity is increased.
And spraying and granulating the mixed solution, and adhering ASO (ASO) into titanium niobate particles by using a high-molecular dispersing agent to form a uniform conductive network, so that the conductive performance of the material is improved.
The preparation method provided by the invention is simple and convenient, has low cost, and the prepared aluminum-doped tin dioxide composite titanium niobate material has good conductivity and can be used for preparing batteries.
Compared with tin dioxide, the aluminum doped tin oxide has better electric conductivity. In some alternative embodiments, the aluminum doped tin oxide may include, for example, but not limited to, 0.5%, 1%, 2%, 4%, 8%, or 10% by mass of aluminum.
The electrochemical performance of the prepared aluminum-doped tin dioxide composite titanium niobate material is better through further optimization and adjustment of the aluminum mass ratio in the aluminum-doped tin oxide.
In some alternative embodiments, the polymeric dispersant includes, but is not limited to, at least one of PVP, PAN, PAM or nylon 66.
The inventor researches show that the polymer dispersing agent can be adsorbed on the surfaces of the solid particles, and an adsorption layer is formed on the surfaces of the solid particles, so that the charges on the surfaces of the solid particles are increased, the reaction force among particles forming three-dimensional obstruction is improved, the system is uniform, and the suspension performance is increased; compared with an ionic dispersing agent, the high-molecular dispersing agent has strong stability and good material consistency; the high molecular dispersant has larger molecular weight and high solution viscosity, and is easy to form homogeneous colloid solution.
In some alternative embodiments, the niobium source includes, but is not limited to, at least one of niobium ethoxide or niobium pentoxide;
the titanium source includes, but is not limited to, at least one of titanium dioxide, tetraethyl titanate, tetrabutyl titanate, tetraisopropyl titanate, or titanyl sulfate.
In some alternative embodiments, the method of preparing the mixed solution includes: mixing aluminum doped tin oxide, a high molecular dispersing agent, a niobium source and a titanium source in water, and grinding to prepare a mixed solution;
the grinding is to grind the solid particles in the mixed solution to a particle size of less than 10 mu m.
The titanium niobate precursor (niobium source, titanium source), the high molecular dispersant and the ASO are mixed and then ground, so that a highly dispersed homogeneous colloid solution can be formed, the dispersion degree of the ASO in the titanium niobate can be increased, and the conductive network is more compact.
In some alternative embodiments, spray granulation is performed using a spray dryer.
The precursor particles obtained by spray drying have the advantages of uniform particle size, good consistency and the like compared with the precursor particles obtained by evaporation drying.
In some alternative embodiments, the sintering temperature may be, for example, but not limited to, 750 ℃, 800 ℃, 900 ℃, 1000 ℃, or 1100 ℃.
In a second aspect, the invention provides an aluminum-doped tin dioxide composite titanium niobate material, which is prepared by the preparation method.
The aluminum-doped tin dioxide composite titanium niobate material provided by the invention has good electrochemical properties such as conductivity and the like.
In a third aspect, the invention provides application of the aluminum-doped tin dioxide composite titanium niobate material in sodium ion batteries.
The aluminum-doped tin dioxide composite titanium niobate material provided by the invention has good electrochemical properties such as conductivity and the like, and can be used for preparing batteries.
In a fourth aspect, the invention provides a sodium ion battery, wherein the sodium ion battery takes the aluminum doped tin dioxide composite titanium niobate material as a negative electrode active material.
The invention is further illustrated by the following specific examples and comparative examples, however, it should be understood that these examples are for the purpose of illustration only in greater detail and should not be construed as limiting the invention in any way.
Example 1
The preparation flow of the aluminum-doped tin dioxide composite titanium niobate material is shown in figure 1, and the preparation method comprises the following steps:
1. nb is set to 2 O 5 And TiO 2 Dissolving in a mixed solution of water and ethanol (volume ratio of water to ethanol=9/1), and uniformly stirring;
2. adding the aluminum-doped tin dioxide material into the mixed solution in the step 1, and uniformly stirring;
3. adding the high molecular dispersant PAM into the mixed solution in the step 2, and uniformly stirring;
4. sanding the mixed solution in the step 3 by using a sand mill for 200-600min;
5. spray drying the homogeneous solution obtained in the step 4 to obtain dry precursor powder;
6. and (3) placing the precursor powder obtained in the step (5) into a high-temperature furnace, and calcining for 6-10h at 750-1100 ℃. The aluminum-doped tin dioxide composite titanium niobate material is prepared, and a scanning electron microscope image is shown in figure 2.
Wherein the amounts of the raw materials are shown in Table 1.
Examples 2 to 7
Examples 2-7 each provide an aluminum doped tin dioxide composite titanium niobate material differing from example 1 in the amount of raw materials, each of which is shown in table 1.
TABLE 1
Comparative example 1
A negative electrode active material is different from example 1 in that it does not include a conductive oxide ASO.
Comparative example 2
A negative electrode active material is different from example 1 in that the conductive oxide ASO is replaced with tin dioxide.
Comparative example 3
The negative electrode active material was different from example 1 in that a polymeric dispersant was not added.
Comparative example 4
The negative electrode active material is different from example 1 in that the polymeric dispersant is replaced with an ionic dispersant (polyvinylpyrrolidone).
Comparative example 5
The negative electrode active material is different from example 1 in that step b is that the solution in step a is evaporated to dryness. As shown in fig. 3, spray drying is performed on the left side of the figure, evaporation drying is performed on the right side, the material is agglomerated due to the evaporation drying process, and the precursor particles obtained by spray drying have the advantages of uniform particle size, good consistency and the like compared with the evaporation drying.
Test example 1
The negative electrode active materials provided in examples 1 to 7 and comparative examples 1 to 5 were prepared into batteries by the same preparation method, and the specific steps were as follows:
the resulting materials of examples 1 to 7 and comparative examples 1 to 5 were high temperature sintered and sieved to obtain test samples, and the test samples, SP (conductive carbon black), PVDF (polyvinylidene fluoride) were prepared according to a ratio of 8:1:1, adding the mixture into an agate mortar, adding NMP (N-methyl pyrrolidone) for grinding, after the viscosity of the mixed slurry is proper, uniformly coating the slurry on a copper foil by using a film pulling device, then transferring into a vacuum oven for baking for 60-300min, cutting a dressing area by using a slicing machine after baking to obtain a negative pole piece, transferring the obtained pole piece into a glove box, assembling the button cell by using a 2032 button cell shell, a pp cell diaphragm, a lithium piece and lithium hexafluorophosphate (D001), and performing electrochemical performance test by using a blue electric test cabinet after the assembly is completed (performing 1C cycle on the cell under normal temperature). The results are shown in FIGS. 4 to 7 (in the figures, "Cycle number" is the number of cycles; and "Capacity" is the Capacity).
Fig. 4 (in the figure, "undoped" is comparative example 1, "0.5%" is example 3, "1%" is example 2, "2%" is example 1, "4%" is example 4, "8%" is example 5,) shows the effect of different ASO doping amounts on the cycle performance of the battery, and it can be seen from the figure that the cycle performance of the battery can be significantly improved when the ASO doping amount is in the range of 0.5% -8%, wherein the ASO doping amount is optimal when it is 2%.
Fig. 5 shows that the addition of the dispersing agent can improve the uniformity of the mixing of the conductive oxide and the titanium niobate, thereby improving the electrochemical performance of the prepared battery, and the result shows that the effect of the high molecular dispersing agent is better than that of the ionic dispersing agent.
Fig. 6 shows that doping of tin dioxide or ASO into the titanium niobate material can significantly improve the electrochemical performance of the battery, and ASO is more pronounced.
Fig. 7 shows that the material prepared by the spray drying method has better conductivity and can further improve the electrochemical performance of the battery compared with the conventional evaporation drying method.
In addition, it was examined that the batteries prepared with examples 6 to 7 as the negative electrode materials had a slightly lower retention of cyclic capacitance than example 1, but were significantly superior to comparative example 2.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (8)
1. The preparation method of the aluminum-doped tin dioxide composite titanium niobate material is characterized by comprising the following steps of:
preparing a mixed solution of aluminum-doped tin oxide, a high molecular dispersing agent, a niobium source and a titanium source, and then sequentially carrying out spray granulation and sintering on the mixed solution to prepare an aluminum-doped tin dioxide composite titanium niobate material;
the mass of the aluminum-doped tin oxide is 0.5-8% of that of the aluminum-doped tin dioxide composite titanium niobate material;
the mass of the high molecular dispersing agent is 0.5-5% of the mass of the aluminum-doped tin dioxide composite titanium niobate material;
the mass ratio of the niobium element to the titanium element in the niobium source and the titanium source is 3:1-5:1;
the high molecular dispersing agent comprises at least one of PVP, PAN, PAM or nylon 66;
the sintering temperature is 750-1100 ℃.
2. The preparation method according to claim 1, wherein the mass ratio of aluminum in the aluminum-doped tin oxide is 0.5% -10%.
3. The method of claim 1, wherein the niobium source comprises at least one of niobium ethoxide or niobium pentoxide;
the titanium source comprises at least one of titanium dioxide, tetraethyl titanate, tetrabutyl titanate, tetraisopropyl titanate or titanyl sulfate.
4. The method of preparing the mixed solution according to claim 1, wherein the method of preparing the mixed solution comprises: mixing aluminum doped tin oxide, a high molecular dispersing agent, a niobium source and a titanium source in water, and grinding to prepare a mixed solution;
the grinding is to grind the solid particles in the mixed solution to a particle size of less than 10 mu m.
5. The method according to claim 1, wherein spray granulation is performed by a spray dryer.
6. An aluminum-doped tin dioxide composite titanium niobate material, characterized in that the aluminum-doped tin dioxide composite titanium niobate material is prepared by the preparation method of any one of claims 1 to 5.
7. The use of the aluminum-doped tin dioxide composite titanium niobate material of claim 6 in sodium ion batteries.
8. A sodium ion battery characterized in that the sodium ion battery uses the aluminum-doped tin dioxide composite titanium niobate material as a negative electrode active material according to claim 6.
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| CN112736250A (en) * | 2020-12-30 | 2021-04-30 | 安徽科达铂锐能源科技有限公司 | Carbon-coated niobium-doped modified titanium niobate material and preparation method thereof |
| CN114122392A (en) * | 2021-11-10 | 2022-03-01 | 云南中晟新材料有限责任公司 | High-capacity quick-charging graphite composite material and preparation method thereof |
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| CN116897439A (en) * | 2020-12-29 | 2023-10-17 | I-Ten公司 | Method for preparing a porous anode for a lithium ion secondary battery, resulting anode and microbattery comprising said anode |
| CN112736250A (en) * | 2020-12-30 | 2021-04-30 | 安徽科达铂锐能源科技有限公司 | Carbon-coated niobium-doped modified titanium niobate material and preparation method thereof |
| CN114122392A (en) * | 2021-11-10 | 2022-03-01 | 云南中晟新材料有限责任公司 | High-capacity quick-charging graphite composite material and preparation method thereof |
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