CN114843494B - Rare earth titanate electrode material with tube centerline structure and preparation method thereof - Google Patents
Rare earth titanate electrode material with tube centerline structure and preparation method thereof Download PDFInfo
- Publication number
- CN114843494B CN114843494B CN202210210230.5A CN202210210230A CN114843494B CN 114843494 B CN114843494 B CN 114843494B CN 202210210230 A CN202210210230 A CN 202210210230A CN 114843494 B CN114843494 B CN 114843494B
- Authority
- CN
- China
- Prior art keywords
- electrode material
- rare earth
- tube
- titanate
- nitrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000007772 electrode material Substances 0.000 title claims abstract description 31
- -1 Rare earth titanate Chemical class 0.000 title claims abstract description 28
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002071 nanotube Substances 0.000 claims abstract description 13
- 239000002070 nanowire Substances 0.000 claims abstract description 5
- 239000002105 nanoparticle Substances 0.000 claims abstract description 3
- 238000009987 spinning Methods 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 11
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010041 electrostatic spinning Methods 0.000 claims description 10
- 239000002121 nanofiber Substances 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 5
- APRNQTOXCXOSHO-UHFFFAOYSA-N lutetium(3+);trinitrate Chemical group [Lu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O APRNQTOXCXOSHO-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 238000001523 electrospinning Methods 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 abstract description 19
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 238000004146 energy storage Methods 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 238000003487 electrochemical reaction Methods 0.000 abstract description 2
- 239000002149 hierarchical pore Substances 0.000 abstract description 2
- 238000006479 redox reaction Methods 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 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 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 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
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052786 argon Inorganic materials 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
- 239000011230 binding agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002074 nanoribbon Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 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
- H01M4/36—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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
-
- 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
-
- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention belongs to the technical field of electrode materials, and particularly relates to a rare earth titanate electrode material with a tube centerline structure and a preparation method thereof. The electrode material is in a tube neutral line structure; in the tube centerline structure, the wall thickness of the nanotube is 20-30nm, the outer diameter is 180-300nm, and the diameter of the nanowire in the nanotube is 80-120nm, and the nanotube is obtained by interconnecting nano particles. The electrode material with the nano structure has special secondary morphology, has a large number of hierarchical pore structures and larger specific surface area, is favorable for realizing charge transfer and ion diffusion from the inside to the interface surface, shortens the ion diffusion distance, improves the electron transmission performance, accelerates the Faraday process in the electrochemical reaction process, can strengthen the contact area between an active center for oxidation-reduction reaction and an electrode and electrolyte by a high percentage of exposed surface atoms, and provides a possibility for adjusting the energy storage performance at an atomic level.
Description
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to a rare earth titanate electrode material with a tube centerline structure and a preparation method thereof.
Background
In order to cope with the aggravated crisis of fossil energy and environmental pollution due to the consumption of conventional energy, the proportion of clean energy including solar energy, wind energy and tidal energy in energy structures has been slowly rising in recent years. Secondary batteries and electrochemical capacitors as "bridges" for new energy conversion processes are also attracting attention.
For solar cells as primary energy sources or secondary batteries and electrochemical capacitors as energy storage devices, the structure and morphology of the electrode materials have a critical impact on the performance of the device. The main research interest at present focuses on how to reasonably control and accurately design electrode materials with special morphology, and to realize nano-functional materials with customized properties.
Among the various nanostructured materials, one-dimensional (1D) nanostructured materials are a two-dimensional limited nanosystem, which has great potential in applications such as catalysis, energy conversion and storage devices, gas sensors, etc., due to unique physicochemical properties (e.g., small size effects, surface effects, etc.), becoming increasingly attractive nanostructured materials. Various physical, chemical synthesis techniques have been heretofore successful in preparing 1D nanostructured materials (e.g., nanofibers, nanoribbons, and nanotubes). Among them, the nanotube material is a special 1D structure, which exhibits stronger competitive advantages in various applications due to its advantages of both hollow structure and 1D structure. However, most of the literature and patent reports on 1D tubular structures are relatively simple due to limitations in the manufacturing process. Compared with the simple nano-tubular structure material, the complex nano-tubular structure is expected to provide a richer research carrier for basic research, and bring about various changes of physical and chemical properties. The current method for synthesizing the complex nano-tubular structure mainly comprises a template method, a solvothermal secondary coating method of electrospun fibers and the like. However, these methods are complex in synthesis steps, costly, and have poor reproducibility, and the nanostructure yields that can be produced during each synthesis process are relatively limited.
The rare earth titanate material has very wide application prospect in the aspects of light, electricity, magnetism, heat, photocatalysis, energy storage and the like. After rare earth titanate is nanocrystallized, the catalytic and electrochemical properties of the rare earth titanate can be greatly changed, and the rare earth titanate can be more suitable for the fields of secondary batteries, electrochemical capacitors, photovoltaic devices and the like. The conventional synthesis of rare earth titanate materials requires high temperature of above 1000 ℃, and the titanium source as a titanate precursor is easily and rapidly hydrolyzed in the air under the influence of water vapor in the air, so the conventional way for synthesizing rare earth titanate materials with complex morphology is a difficulty in the field all the time.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing a line nano-structure electrode material in a rare earth titanate tube. The centerline nanostructure of the tube adopts an electrostatic spinning technology, precursor fibers are obtained by controlling the environment temperature and the environment humidity of spinning, and the centerline nanostructure of the rare earth titanate tube is finally obtained by combining the subsequent high-temperature annealing process.
In order to achieve the above object, the technical method of the present invention is as follows:
the invention provides a rare earth titanate electrode material with a tube centerline structure, which is characterized in that the electrode material is of a tube centerline structure; in the tube centerline structure, the wall thickness of the nanotube is 20-30nm, the outer diameter is 180-300nm, and the diameter of the nanowire in the nanotube is 80-120nm, and the nanotube is obtained by interconnecting nano particles.
In the above technical solution, further, the length of the line structure in the tube is 200-1000nm.
In another aspect, the present invention provides a method for preparing a rare earth titanate electrode material having a tube-in-tube line structure, the method comprising the steps of:
(1) Dissolving butyl titanate and rare earth nitrate in a solvent, then dissolving polyvinylpyrrolidone in a mixed solution containing butyl titanate and rare earth nitrate, stirring and standing to obtain a clear and transparent spinning solution, wherein the mass concentration of polyvinylpyrrolidone in the spinning solution is 7-20%;
(2) Transferring the spinning solution obtained in the step (1) into an electrostatic spinning device, and carrying out electrostatic spinning by adopting a single nozzle spinning head to obtain precursor nanofiber;
(3) And (3) carrying out vacuum drying on the precursor nanofiber obtained in the step (2), and carrying out annealing treatment through a temperature programming process to obtain the rare earth titanate nano electrode material with the line structure in the tube.
In the above technical scheme, in the step (1), the solvent is a mixed solution of ethanol, N-N dimethylformamide and acetic acid, and the volume ratio of the ethanol, the N-N dimethylformamide and the acetic acid is 0.46-0.49:0.46-0.49:0.02-0.08.
In the technical scheme, in the step (1), the molar ratio of the butyl titanate to the rare earth nitrate is (1-1.05): 1.
In the above technical scheme, further, the rare earth nitrate comprises lutetium nitrate, yttrium nitrate, lanthanum nitrate and ytterbium nitrate.
In the above technical scheme, further, in the step (2), the electrostatic spinning process parameters are as follows: the spinning voltage is 14-18kV, the collecting distance is 15-20cm, the caliber of the nozzle is 0.9-1.5mm, the ambient temperature is 20-30 ℃, and the ambient humidity is 40-45%.
In the above technical scheme, in the step (3), the temperature programming rate is 1-2 ℃/min, the temperature is raised to 700-900 ℃ for annealing treatment, and the temperature is kept for 4-8h.
In yet another aspect, the invention provides the use of a rare earth titanate electrode material having a tubular centerline structure.
The nano electrode material has potential application advantages in the fields of lithium ion batteries, sodium ion batteries, super capacitors and the like.
In addition, the nano-structure in the tube can also load dye, and has potential application prospect in the aspect of dye solar cells.
The beneficial effects of the invention are as follows:
the electrode material with the nano structure has special secondary morphology, has a large number of hierarchical pore structures and larger specific surface area, is favorable for realizing charge transfer and ion diffusion from the inside to the interface surface, shortens the ion diffusion distance, improves the electron transmission performance, accelerates the Faraday process in the electrochemical reaction process, can strengthen the contact area between an active center for oxidation-reduction reaction and an electrode and electrolyte by a high percentage of exposed surface atoms, and provides a possibility for adjusting the energy storage performance at an atomic level. The internal space of the material nanostructure can weaken the volume expansion in the continuous charge and discharge process, and realize favorable cycle and rate performance.
Drawings
FIG. 1 is a schematic view of a line structure of a nanotube according to the present invention;
in the figure: 1. nanotube, 2, nanowire;
FIG. 2 shows the Lu obtained in example 1 2 Ti 2 O 7 SEM images of nanomaterials;
FIG. 3 shows the Lu obtained in example 1 2 Ti 2 O 7 TEM image of nanomaterial;
FIG. 4 shows the Lu obtained in example 1 2 Ti 2 O 7 XRD pattern of nanomaterial;
FIG. 5 is a Y obtained in example 2 2 Ti 2 O 7 SEM images of nanomaterials;
FIG. 6 is a Y prepared in example 2 2 Ti 2 O 7 TEM image of nanomaterial;
FIG. 7 is a Y obtained in example 2 2 Ti 2 O 7 XRD pattern of nanomaterial;
FIG. 8 shows the Lu obtained in example 1 2 Ti 2 O 7 Capacitance-potential curve of nanomaterial.
Detailed Description
The invention is further illustrated below with reference to specific examples.
Example 1
(1) Dissolving 4.0g PVP (Mw= 130,0000) into a mixed solvent of 40ml absolute ethanol and DMF (absolute ethanol: DMF=1:1, volume ratio), stirring for 2-6h until the mixture is clear, adding 2ml glacial acetic acid and a certain amount of lutetium nitrate and tetrabutyl titanate into the solution, and stirring until the mixture is clear to obtain spinning solution;
wherein the molar ratio of lutetium nitrate to butyl titanate is 1.0:1.02, the mass ratio of the total mass of lutetium nitrate and butyl titanate to PVP is 0.5:1.0;
(2) Transferring the spinning solution obtained in the step (1) into an electrostatic spinning device, and carrying out electrostatic spinning by adopting a single nozzle spinning head, wherein the spinning voltage is 15kV, the collecting distance is 15cm, the spinning environment temperature is 22 ℃, and the air humidity is 40%, so as to obtain precursor nanofiber;
(3) And (3) putting the precursor nanofiber obtained in the step (2) into a vacuum oven, drying at 80 ℃ for 8 hours, then heating to 800 ℃ at a heating rate of 1 ℃/min, and preserving heat at 800 ℃ for 4 hours to obtain the nano lutetium titanate electrode material with the tube-in-tube line structure.
Grinding the sample prepared in the example 1 as an active substance, mixing with graphite powder and a binder (polyvinylidene fluoride is dissolved in N-methyl pyrrolidone to be 50 mg/mL) according to a ratio of 8:1:1, and stirring uniformly; the mass of active material loaded on each pole piece was about 2mg. And uniformly coating the stirred slurry on the surface of the copper foil, and then placing the copper foil in a 70 ℃ oven for drying for 3 hours until the slurry on the copper foil is completely dried. Cutting the dried copper foil into 1.0X1.0 cm pieces 2 Is hot-pressed three times at 50 ℃ and 0.4kPa by a pneumatic gilding press (518-G2) to obtain the prepared electrode slice.
The lithium ion battery was assembled in an argon-filled glove box with both oxygen and water contents of less than 0.1ppm. The button cell is assembled by adopting a LIR2032 type button cell shell: 1mol/L LiPF 6 EC: DEC (volume ratio 1:1) electrolyte and glass fiber filter paper GF/D are used as diaphragms, and the assembly is carried out according to the sequence of a positive electrode shell, an electrode plate, the diaphragms, the electrolyte, a metal lithium plate, a gasket, a spring piece and a negative electrode shell, wherein the metal lithium plate is easy to oxidize to form an oxide film on the surface, so that the surface oxide film needs to be scraped before the assembly, and the contact between the metal lithium plate and the electrolyte is increased, so that the cycle performance of the battery is improved. Then tabletting treatment is carried out on a hand-operated tablet press, and the pressure is kept at 0.5MPa. And standing the assembled button cell for 5 hours, so that the electrolyte is fully contacted with the electrode plate for wetting, and the circulation stability of the button cell is improved.
In the experiment, a blue battery test system (CT 3002A) is adopted to perform constant current charge and discharge test on the LIR2032 type button battery, and the Lu prepared in the example 1 2 Ti 2 O 7 The charge-discharge curves for different turns of wire material in the nanotubes are shown in figure 8.
Example 2
(1) 8.0g PVP (Mw= 130,0000) is dissolved in 40ml of mixed solvent of absolute ethanol and DMF (absolute ethanol: DMF=1:1, volume ratio) and stirred for 2-6h until the mixture is clear, 2ml of glacial acetic acid and a certain amount of yttrium nitrate and tetrabutyl titanate are added into the solution and stirred until the mixture is clear;
wherein the molar ratio of yttrium nitrate to butyl titanate is 1.0:1.02, and the mass ratio of the total mass of yttrium nitrate and butyl titanate to PVP is 0.3:1.0;
(2) Transferring the spinning solution obtained in the step (1) into an electrostatic spinning device, and carrying out electrostatic spinning by adopting a single nozzle spinning head, wherein the spinning voltage is 15kV, the collecting distance is 15cm, the spinning environment temperature is 24 ℃, and the air humidity is 40%, so as to obtain precursor nanofiber;
(3) And (3) putting the precursor nanofiber obtained in the step (2) into a vacuum oven, drying at 80 ℃ for 8 hours, then heating to 800 ℃ at a heating rate of 1 ℃/min, and preserving heat at 800 ℃ for 4 hours to obtain the nano yttrium titanate electrode material with the tube-in-tube line structure.
The above examples are only preferred embodiments of the present invention and are not limiting of the implementation. The protection scope of the present invention shall be subject to the scope defined by the claims. Other variations or modifications may be made in the various forms based on the above description. Obvious variations or modifications of the embodiments are within the scope of the invention.
Claims (6)
1. The rare earth titanate electrode material with the tube centerline structure is characterized in that the electrode material is of the tube centerline structure; in the tube centerline structure, the wall thickness of the nanotube is 20-30nm, the outer diameter is 180-300nm, the diameter of the nanowire in the nanotube is 80-120nm, and the nanowire is obtained by interconnecting nano particles;
the method of the electrode material comprises the following steps:
(1) Dissolving butyl titanate and rare earth nitrate in a molar ratio in a solvent, then dissolving polyvinylpyrrolidone in a mixed solution containing butyl titanate and rare earth nitrate, stirring and standing to obtain a clear and transparent spinning solution, wherein the mass concentration of polyvinylpyrrolidone in the spinning solution is 7-20%;
(2) Transferring the spinning solution obtained in the step (1) into an electrostatic spinning device, and carrying out electrostatic spinning by adopting a single nozzle spinning head to obtain precursor nanofiber;
(3) Vacuum drying the precursor nanofiber obtained in the step (2), and annealing the precursor nanofiber through a temperature programming process to obtain a rare earth titanate nano electrode material with a line structure in a tube;
in the step (1), the rare earth nitrate is lutetium nitrate or yttrium nitrate;
in the step (2), the ambient temperature is 20-30 ℃ and the air humidity is 40%;
in the step (3), the temperature programming rate is 1-2 ℃/min, the temperature is raised to 700-900 ℃ for annealing treatment, and the temperature is kept for 4-8 hours;
the rare earth titanate nano electrode material is lutetium titanate Lu2Ti2O7 or yttrium titanate Y2Ti2O7 nano electrode material.
2. The electrode material of claim 1, wherein the length of the line-in-tube structure is 200-1000nm.
3. The electrode material according to claim 1, wherein in the step (1), the solvent is a mixture of ethanol, N-N dimethylformamide and acetic acid, and the volume ratio of ethanol, N-N dimethylformamide and acetic acid is 0.46-0.49:0.46-0.49:0.02-0.08.
4. The electrode material according to claim 1, wherein in the step (1), the molar ratio of butyl titanate to rare earth nitrate is (1-1.05): 1.
5. The electrode material according to claim 1, wherein in the step (2), the electrospinning process parameters are as follows: the spinning voltage is 14-18kV, the collecting distance is 15-20cm, and the caliber of the nozzle is 0.9-1.5mm.
6. Use of a rare earth titanate electrode material having a tube-in-tube wire structure according to any one of claims 1-5 in a lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210210230.5A CN114843494B (en) | 2022-03-04 | 2022-03-04 | Rare earth titanate electrode material with tube centerline structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210210230.5A CN114843494B (en) | 2022-03-04 | 2022-03-04 | Rare earth titanate electrode material with tube centerline structure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114843494A CN114843494A (en) | 2022-08-02 |
| CN114843494B true CN114843494B (en) | 2024-02-20 |
Family
ID=82561427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210210230.5A Active CN114843494B (en) | 2022-03-04 | 2022-03-04 | Rare earth titanate electrode material with tube centerline structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114843494B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116356439B (en) * | 2023-04-12 | 2024-04-09 | 大连海事大学 | One-dimensional rare earth titanate zirconate nano luminescent material with multi-layer tube-in-tube nano structure and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101545158A (en) * | 2009-05-07 | 2009-09-30 | 南京大学 | Tubular and tube-in-tube structure organic oxide and preparation method thereof |
| CN102820460A (en) * | 2012-08-20 | 2012-12-12 | 上海交通大学 | Electrostatic spinning method for preparing rare-earth metal doped nanometer lithium titanate |
| EP2889272A1 (en) * | 2013-12-27 | 2015-07-01 | Commissariat à l'Energie Atomique et aux Energies Alternatives | Method for producing a carbonaceous powder comprising a mixed oxide of yttrium and titanium |
| CN104928800A (en) * | 2015-06-02 | 2015-09-23 | 济南大学 | Ferrous-manganese combined metal oxide magnetic nanofiber with pipe-in-pipe structure and preparation method of ferrous-manganese combined metal oxide magnetic nanofiber |
| CN105375028A (en) * | 2015-12-08 | 2016-03-02 | 武汉理工大学 | Contractive inner-structure-adjustable mesoporous inorganic salt nanotube material, preparation method therefor and application thereof |
| CN110783541A (en) * | 2019-10-21 | 2020-02-11 | 刘怀金 | Based on cellulose-carbon nano tube-Li 4Ti 5O 12Hybrid battery negative electrode material |
| CN111809273A (en) * | 2020-07-20 | 2020-10-23 | 大连海事大学 | Preparation method of rare earth ion doped yttrium vanadate nanotube and nanotube |
| CN114015444A (en) * | 2021-10-25 | 2022-02-08 | 大连海事大学 | Preparation method of rare earth titanate nanotube material with up-conversion luminescence/photo-thermal performance |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130337321A1 (en) * | 2011-01-24 | 2013-12-19 | Sanyo Electric Co., Ltd. | Positive electrode for nonaqueous electrolyte secondary battery, method for producing the positive electrode, and nonaqueous electrolyte secondary battery using the positive electrode |
| US11309538B2 (en) * | 2018-10-06 | 2022-04-19 | University Of Tehran | Porous wire-in-tube structures |
-
2022
- 2022-03-04 CN CN202210210230.5A patent/CN114843494B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101545158A (en) * | 2009-05-07 | 2009-09-30 | 南京大学 | Tubular and tube-in-tube structure organic oxide and preparation method thereof |
| CN102820460A (en) * | 2012-08-20 | 2012-12-12 | 上海交通大学 | Electrostatic spinning method for preparing rare-earth metal doped nanometer lithium titanate |
| EP2889272A1 (en) * | 2013-12-27 | 2015-07-01 | Commissariat à l'Energie Atomique et aux Energies Alternatives | Method for producing a carbonaceous powder comprising a mixed oxide of yttrium and titanium |
| CN104928800A (en) * | 2015-06-02 | 2015-09-23 | 济南大学 | Ferrous-manganese combined metal oxide magnetic nanofiber with pipe-in-pipe structure and preparation method of ferrous-manganese combined metal oxide magnetic nanofiber |
| CN105375028A (en) * | 2015-12-08 | 2016-03-02 | 武汉理工大学 | Contractive inner-structure-adjustable mesoporous inorganic salt nanotube material, preparation method therefor and application thereof |
| CN110783541A (en) * | 2019-10-21 | 2020-02-11 | 刘怀金 | Based on cellulose-carbon nano tube-Li 4Ti 5O 12Hybrid battery negative electrode material |
| CN111809273A (en) * | 2020-07-20 | 2020-10-23 | 大连海事大学 | Preparation method of rare earth ion doped yttrium vanadate nanotube and nanotube |
| CN114015444A (en) * | 2021-10-25 | 2022-02-08 | 大连海事大学 | Preparation method of rare earth titanate nanotube material with up-conversion luminescence/photo-thermal performance |
Non-Patent Citations (1)
| Title |
|---|
| Electrospinning preparation and electrochemical properties of Lu2Ti2O7 nanowires, nanotubes and wire-in-tube architectures for their potential lithium-ion battery applications;Yu hongquan et al.,;《Journal of Physics and Chemistry of Solids》;20220707;第169卷;1-6 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114843494A (en) | 2022-08-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103337641A (en) | Oxygen electrode composite catalyst used for lithium-air batteries and preparation method of the oxygen electrode composite catalyst | |
| CN110042503B (en) | MoSe2@ C electrospun hollow nanofiber and preparation method and application thereof | |
| CN104900861B (en) | A kind of lithium hydrogentitanate Li H Ti O material and preparation method thereof | |
| CN111193014B (en) | Cobaltosic oxide-nitrogen doped carbon/carbon nanocage composite material with eggshell-yolk structure and preparation method and application thereof | |
| CN110459755A (en) | A kind of sulphur/polypyrrole/graphene/carbon nano-tube coextruded film, preparation method and applications | |
| CN109616331A (en) | A kind of hud typed nickel hydroxide nano piece/manganese cobalt/cobalt oxide combination electrode material and preparation method thereof | |
| CN107541811A (en) | A kind of carbon nano rod composite and its preparation method and application | |
| CN114843494B (en) | Rare earth titanate electrode material with tube centerline structure and preparation method thereof | |
| CN104852042A (en) | Preparation method and application of cobalt-iron composite oxide nanorods for lithium ion battery anode material | |
| CN114149024A (en) | Boron-doped porous titanium dioxide/carbon fiber negative electrode material and preparation method thereof | |
| CN107857308B (en) | Nickel-cobalt composite hydroxide ultra-long nanobelt, nickel-cobalt composite oxide ultra-long nanobelt and preparation method thereof | |
| CN106067550A (en) | A kind of vanadium phosphate cathode material and its preparation method and application | |
| CN110474023B (en) | Fibrous nickel-bismuth battery and preparation method thereof | |
| CN110993359B (en) | Flexible solid-state asymmetric supercapacitor device and preparation method and application thereof | |
| CN110002429B (en) | Carbon nanotube/transition metal hydroxide composite electrode material and preparation method thereof | |
| CN114717687B (en) | Hollow fibrous sodium ion battery positive electrode material, and preparation method and application thereof | |
| CN110957145A (en) | Flexible all-solid-state asymmetric fibrous energy storage device and manufacturing method thereof | |
| CN112599737B (en) | Sodium ion battery transition metal sulfide carbon composite negative electrode material and preparation method and application thereof | |
| CN111945252B (en) | Method for preparing hollow antimony-based binary alloy composite nanofiber material based on electrostatic spinning and potassium storage application thereof | |
| CN112447957B (en) | P, N doped porous carbon fiber-TiO2Preparation method of lithium ion battery cathode material | |
| CN110350174B (en) | Lithium manganate, lithium titanate and TiO2Composite nanowire and preparation method thereof | |
| CN112670478B (en) | Carbon sphere packaged amorphous vanadium-oxygen cluster composite material, preparation method thereof and sodium storage application | |
| CN110112396B (en) | Preparation of Na from titanium dioxide carbon fiber 8 Ti 5 O 14 Method for preparing-C nanofiber negative electrode material | |
| CN110085841B (en) | Preparation of Na from titanium dioxide carbon fiber 4 Ti 5 O 12 Method for preparing-C nano fiber negative electrode material | |
| CN109921005B (en) | Blue phosphate radical doped titanium dioxide (B) nanowire and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |