CN104466155A - Method for preparing high-coulombic-efficiency lithium ion battery negative pole material chrysanthemum-shaped nanometer titania - Google Patents
Method for preparing high-coulombic-efficiency lithium ion battery negative pole material chrysanthemum-shaped nanometer titania Download PDFInfo
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- CN104466155A CN104466155A CN201410815575.9A CN201410815575A CN104466155A CN 104466155 A CN104466155 A CN 104466155A CN 201410815575 A CN201410815575 A CN 201410815575A CN 104466155 A CN104466155 A CN 104466155A
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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
- H01M4/48—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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- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
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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
Abstract
The invention discloses a method for preparing high-coulombic efficiency lithium ion battery negative pole material chrysanthemum-shaped nanometer titania. The method comprises the following steps: dissolving a titanium source compound in short-chain monohydric alcohol, stirring to form a clarified solution, adding polyhydric alcohols, further stirring to form a clarified solution, carrying out a hydrothermal reaction, forming a complex with the titanium source compound by utilizing the polyhydric alcohols as guide agents and inducers, controlling hydrolysis of the titanium source compound by taking the short-chain monohydric alcohol as a dispersing agent so at to generate a titania precursor, and performing low-temperature heat treatment, thereby obtaining the lithium ion battery negative pole material chrysanthemum-shaped nanometer titania. The preparation method disclosed by the invention is simple in process and easy to operate, and raw materials are readily available; the high-coulombic efficiency lithium ion battery negative pole material chrysanthemum-shaped nanometer titania is low in cost and environmentally friendly, special equipment is not needed in the whole reaction process, the industrial production is promoted, the final product is high in quality, and according to the prepared nanometer/micron grading structure, the aims of shortening the ion transport distance and improving the conductivity and ion diffusion rate of the material can be simultaneously achieved, so that the material has excellent rate capability, stable cycle performance and high coulombic efficiency. The material prepared by the invention is an ideal lithium ion negative pole material with wide commercial application prospects.
Description
Technical field
The invention belongs to new energy materials preparation and application field, be specifically related to a kind of preparation method synthesizing the chrysanthemum shape nano-titanium oxide of high invertibity and high coulombic efficiency based on solvent thermal process.
Background technology
Lithium ion battery is as the clean energy resource of a new generation, the outstanding person in numerous novel energy, it is described as " 21 century green secondary cell ", because its energy density is high, have extended cycle life, environmental pollution is little, and the advantages such as self discharge is little, nothing " memory effect " are widely used in communication equipment, mancarried electronic aid, static energy-storage system and electric automobile market field, and its chemical property depends primarily on both positive and negative polarity electrode material.At present, material with carbon element is the most frequently used lithium ion battery negative material of commercialization, but due to operating voltage and metal lithium electrode current potential close, in charge and discharge process, may at carbon electrodes precipitating metal lithium, and the Zhi Jinghui formed causes short circuit, especially in high power charging-discharging process, very large safety problem can be caused.In addition, in first charge-discharge process, material with carbon element and the electrolyte surface that reacts forms the solid electrolyte interface film (SEI film) of one deck electronic isolation, causes electrolyte consumption and lower first run coulombic efficiency.Therefore, to have the negative material of good cyclical stability and fail safe significant for development of new.
Titanium dioxide is as a kind of " zero strain " material, in charge and discharge process, structure changes hardly, there is high security, stable cycle performance, aboundresources, cheap, advantages of environment protection, become the negative material of lithium ion cell electrode with prospects.But titanium dioxide conductivity is low by (~ 10
-13s cm
-1), cause high rate performance poor, be especially applied to electric automobile, large-scale energy-storage battery field is subject to great restriction.Thus, improve the conductivity of titanium dioxide electrodes material, and then raising high rate performance is that it is in lithium ion battery applications field problem demanding prompt solution.The usual conductivity improving titanium dioxide electrodes material has two kinds of methods, and the first, compound highly conductor phase material, comprising: metal, metal oxide, carbon-based material etc.; The second, synthesis of nano/micron hierarchy, improves the electrode performance of titanium dioxide with this.But compound highly conductor phase material needs complicated technical process usually, is not suitable for large-scale production, therefore synthesis of nano/micron hierarchy is widely regarded as one of best selection.Nano structural material shortens the diffusion length of lithium ion in solid phase, increases the contact area between electrode and electrolyte simultaneously and then increases reactivity region, causing the current density of per unit area to reduce, and then increasing charge-discharge velocity.Hierarchy shortens the diffusion length of electronics and lithium ion, strengthen lithium ion the embedding repeated with deviate from stress-strain in process and discharge.The titanium dioxide microballoon sphere that Wei etc. (J.Mater.Chem.A, 2014,2:1102) synthesize hierarchy is applied to lithium ion battery, and when current density is 1C, after 100 charge and discharge cycles, capacity is only 160.4mAh g
-1, when current density brings up to 5C and 10C, capacity is reduced to 128.4 and 105.6mAh g respectively
-1.Although the titanium dioxide developing hierarchy is devoted in a lot of research work, but be applied to lithium ion battery and not yet obtain satisfied capacity and stable cycle performance, and some research work needs to introduce surfactant to obtain hierarchy, which greatly limits large-scale production and application.
Summary of the invention
Object of the present invention is exactly the defect existed to overcome above-mentioned prior art, a kind of simple, eco-friendly method preparing lithium ion battery negative material chrysanthemum shape nano titanium oxide is provided, the method is by synthesizing hierarchy, shorten lithium ion and electrons spread distance, increase specific area to increase the contact area between electrode and electrolyte, thus improve large multiplying power discharging property and high coulombic efficiency, to meet the current demand to lithium ion battery.
Object of the present invention can be achieved through the following technical solutions:
A nano titanium oxide preparation method for lithium ion battery negative material chrysanthemum shape, comprises the following steps:
(1) a certain amount of titanium source compound (1.2 ~ 6g) is dissolved in the unit alcohol of short chain, magnetic agitation forms settled solution in 10 ~ 15 minutes, then be (3 ~ 8) according to short chain units alcohol and polyalcohol volume ratio: 1 adds polyalcohol, continue stirring and form settled solution in 15 ~ 20 minutes.
(2) above-mentioned solution is transferred in autoclave, (120 ~ 230 DEG C) carry out hydro-thermal reaction 10 ~ 36 hours at a certain temperature, after question response terminates, naturally cool to room temperature, centrifuge washing obtains TiO 2 precursor nano material after being separated drying.
(3) the TiO 2 precursor nano material that upper step obtains is put into high temperature furnace 400 ~ 600 DEG C of heat treatments after 4 ~ 8 hours, after naturally cooling to room temperature, just obtain chrysanthemum shape nano titanium oxide.
Above-described titanium source compound is: butyl titanate, isopropyl titanate, tetraethyl titanate, one or more in titanium tetrachloride; Short chain units alcohol is: ethanol, isopropyl alcohol, normal propyl alcohol, n-butanol, one or more mixed solvents in isobutanol; Polyalcohol is: ethylene glycol, one or both mixed solvents in glycerol.
(4) material that upper step is synthesized is used for lithium ion battery negative material, take conductive black as conductive agent, polyvinylidene fluoride (PVDF) makes anode plate for lithium ionic cell for binding agent, be to electrode with lithium metal, microporous polypropylene membrane is barrier film, take volume ratio as the 1M LiPF of ethylene carbonate (EC)/dimethyl carbonate (the DMC)/diethyl carbonate (DEC) of 1:1:1
6for electrolyte, in argon gas glove box, be assembled into 2025 type button cells.LAND CT-2001A tester is adopted at room temperature to carry out electrochemical property test.
The nano titanium oxide pattern of the chrysanthemum shape obtained produced according to the present invention is homogeneous, and good dispersion degree, does not have agglomeration to occur, better crystallinity degree, has abundant meso-hole structure, is a kind of lithium ion battery negative material of excellent electrochemical performance.
The present invention is based on and use titanium source compound and polyalcohol to form presoma complex compound, wherein polyalcohol plays template and directed agents effect, and short chain units alcohol, as dispersion solvent, controls titanium source compound hydrolysis rate, and then form chrysanthemum shape TiO 2 precursor, obtain product by calcining.Preparation method of the present invention has that output is high, technique is simple, easy to operate, raw material is easy to get, with low cost, advantages of environment protection, and whole course of reaction does not need special installation, is beneficial to suitability for industrialized production.Finally obtain product quality higher, show good chemical property as lithium ion battery negative material, there is high invertibity, high coulombic efficiency and stable cycle performance.
Accompanying drawing explanation
The X-ray diffracting spectrum of the chrysanthemum shape nano titanium oxide of Fig. 1 prepared by embodiment 1;
The scanning electron microscope diagram of the chrysanthemum shape nano titanium oxide of Fig. 2 prepared by embodiment 1;
Chrysanthemum shape nano titanium oxide when current density the be 5C charge-discharge performance figure of Fig. 3 prepared by embodiment 4;
Chrysanthemum shape nano titanium oxide when current density the be 10C charge-discharge performance figure of Fig. 4 prepared by embodiment 6;
The high rate performance figure of the chrysanthemum shape nano titanium oxide of Fig. 5 prepared by embodiment 7.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in detail, contributes to understanding the present invention, but the present invention is also not only confined to following examples.
Embodiment 1
(1) butyl titanate of 2.3g is dissolved in certain volume isopropanol solvent, magnetic agitation formed settled solution after 15 minutes, then be that 4:1 adds a certain amount of glycerol reagent according to the volume ratio of isopropyl alcohol and glycerol, continue stirring and form settled solution in 20 minutes.
(2) be transferred in autoclave by above-mentioned solution, carry out hydro-thermal reaction 14 hours, after question response terminates, naturally cool to room temperature at 180 DEG C, centrifuge washing obtains TiO 2 precursor nano material after being separated drying.
(3) the TiO 2 precursor nano material that upper step obtains is put into high temperature furnace 500 DEG C of heat treatments after 5 hours, after naturally cooling to room temperature, just obtain chrysanthemum shape nano titanium oxide.
(4) material that upper step is synthesized is used for lithium ion battery negative material, take conductive black as conductive agent, polyvinylidene fluoride (PVDF) makes anode plate for lithium ionic cell for binding agent, be to electrode with lithium metal, microporous polypropylene membrane is barrier film, take volume ratio as the 1M LiPF of ethylene carbonate (EC)/dimethyl carbonate (the DMC)/diethyl carbonate (DEC) of 1:1:1
6for electrolyte, in argon gas glove box, be assembled into 2025 type button cells.Adopt LAND CT-2001A tester at room temperature to carry out electrochemical property test, test voltage scope is 1.0-3.0V.Assembled battery is at 0.59C (100mA g
-1) first discharge specific capacity 305.4mAh g under current density
-1.
The X ray diffracting spectrum of the chrysanthemum shape nano titanium oxide of Fig. 1 obtained by the present embodiment, as can be seen from the figure obtained material is pure Anatase, does not have other phase and other impurity to occur, and the well-crystallized of material.Fig. 2 is the scanning electron microscope diagram sheet of chrysanthemum shape nano titanium oxide, and as seen from the figure, titanium dioxide pattern and size are comparatively even, are class chrysanthemum shape.
Embodiment 2
(1) isopropyl titanate of 1.2g is dissolved in the normal propyl alcohol solvent of certain volume, magnetic agitation formed settled solution after 10 minutes, then be that 3:1 adds a certain amount of glycerol reagent according to the volume ratio of normal propyl alcohol and glycerol, continue stirring and form settled solution in 15 minutes.
(2) be transferred in autoclave by above-mentioned solution, carry out hydro-thermal reaction 36 hours, after question response terminates, naturally cool to room temperature at 120 DEG C, centrifuge washing obtains TiO 2 precursor nano material after being separated drying.
(3) the TiO 2 precursor nano material that upper step obtains is put into high temperature furnace 450 DEG C of heat treatments after 8 hours, after naturally cooling to room temperature, just obtain chrysanthemum shape nano titanium oxide.
(4) after being assembled into battery according to embodiment one method, at 5C (850mA g
-1) test first discharge specific capacity 195.8mAh g under current density
-1, after 100 circulations, specific discharge capacity remains on 178.9mAh g
-1.
Embodiment 3
(1) titanium tetrachloride of 3.5g is dissolved in certain volume n-butanol solvent, magnetic agitation formed settled solution after 15 minutes, then be that 7:1 adds a certain amount of ethylene glycol and glycerol mix reagent according to the volume ratio of n-butanol and ethylene glycol and glycerol mixed solvent, continue stirring and form settled solution in 20 minutes.
(2) be transferred in autoclave by above-mentioned solution, carry out hydro-thermal reaction 10 hours, after question response terminates, naturally cool to room temperature at 230 DEG C, centrifuge washing obtains TiO 2 precursor nano material after being separated drying.
(3) the TiO 2 precursor nano material that upper step obtains is put into high temperature furnace 600 DEG C of heat treatments after 5 hours, after naturally cooling to room temperature, just obtain chrysanthemum shape nano titanium oxide.
(4), after being assembled into battery according to embodiment one method, under 5C current density, first discharge specific capacity 187.5mAhg is tested
-1, after 100 circulations, specific discharge capacity remains on 176.2mAh g
-1.
Embodiment 4
(1) tetraethyl titanate of 4.3g is dissolved in the mixed solvent of certain volume ethanol and isopropyl alcohol, magnetic agitation formed settled solution after 10 minutes, then be that 6:1 adds a certain amount of glycerol reagent according to ethanol and the mixed solvent cumulative volume of isopropyl alcohol and the volume ratio of glycerol, continue stirring and form settled solution in 15 minutes.
(2) be transferred in autoclave by above-mentioned solution, carry out hydro-thermal reaction 12 hours, after question response terminates, naturally cool to room temperature at 200 DEG C, centrifuge washing obtains TiO 2 precursor nano material after being separated drying.
(3) the TiO 2 precursor nano material that upper step obtains is put into high temperature furnace 450 DEG C of heat treatments after 7 hours, after naturally cooling to room temperature, just obtain chrysanthemum shape nano titanium oxide.
(4), after being assembled into battery according to embodiment one method, test under 5C current density, result as shown in Figure 3.
Fig. 3 is the charge-discharge performance figure under 5C current density of prepared class chrysanthemum shape nano titanium oxide, first discharge specific capacity 215.6mAh g
-1, after 100 circulations, specific discharge capacity remains on 198.3mAh g
-1, capability retention is 92%, and coulombic efficiency, close to 100%, shows this material and has excellent chemical property.
Embodiment 5
(1) tetraethyl titanate of 5.5g is dissolved in the mixed solvent of certain volume isobutanol, magnetic agitation formed settled solution after 10 minutes, then be that 8:1 adds a certain amount of glycerol reagent according to the volume ratio of isobutanol and glycerol, continue stirring and form settled solution in 15 minutes.
(2) be transferred in autoclave by above-mentioned solution, carry out hydro-thermal reaction 15 hours, after question response terminates, naturally cool to room temperature at 170 DEG C, centrifuge washing obtains TiO 2 precursor nano material after being separated drying.
(3) the TiO 2 precursor nano material that upper step obtains is put into high temperature furnace 450 DEG C of heat treatments after 6 hours, after naturally cooling to room temperature, just obtain chrysanthemum shape nano titanium oxide.
(4), after being assembled into battery according to embodiment one method, under 5C current density, first discharge specific capacity 191.9mAhg is tested
-1, after 100 circulations, specific discharge capacity remains on 180.2mAh g
-1.
Embodiment 6
(1) butyl titanate of 6g is dissolved in the solvent of certain volume isopropyl alcohol, magnetic agitation formed settled solution after 10 minutes, then be that 5:1 adds a certain amount of glycerol reagent according to the volume ratio of isopropyl alcohol and glycerol, continue stirring and form settled solution in 15 minutes.
(2) be transferred in autoclave by above-mentioned solution, carry out hydro-thermal reaction 24 hours, after question response terminates, naturally cool to room temperature at 150 DEG C, centrifuge washing obtains TiO 2 precursor nano material after being separated drying.
(3) the TiO 2 precursor nano material that upper step obtains is put into high temperature furnace 400 DEG C of heat treatments after 8 hours, after naturally cooling to room temperature, just obtain chrysanthemum shape nano titanium oxide.
(4), after being assembled into battery according to embodiment one method, under 5C current density, first discharge specific capacity 195.4mAhg is tested
-1, after 100 circulations, specific discharge capacity remains on 181.5mAh g
-1.
Fig. 4 is the prepared charge-discharge performance figure of class chrysanthemum shape nano titanium oxide under 10C current density, first discharge specific capacity 146.8mAh g
-1, after 200 circulations, specific discharge capacity remains on 134.6mAh g
-1capability retention is 91.7%, and coulombic efficiency, close to 100%, shows this material and has excellent chemical property, show can realize heavy-current discharge by synthesis of nano/micron hierarchy, and keep long-term cyclical stability and high first run coulombic efficiency.
Embodiment 7
(1) isopropyl titanate of 4.5g is dissolved in certain volume alcohol solvent, magnetic agitation formed settled solution after 10 minutes, then be that 4.5:1 adds a certain amount of glycerol reagent according to the volume ratio of ethanol contend and glycerol, continue stirring and form settled solution in 15 minutes.
(2) be transferred in autoclave by above-mentioned solution, carry out hydro-thermal reaction 18 hours, after question response terminates, naturally cool to room temperature at 160 DEG C, centrifuge washing obtains TiO 2 precursor nano material after being separated drying.
(3) the TiO 2 precursor nano material that upper step obtains is put into high temperature furnace 550 DEG C of heat treatments after 4 hours, after naturally cooling to room temperature, just obtain chrysanthemum shape nano titanium oxide.
(4), after being assembled into battery according to embodiment one method, under 5C current density, first discharge specific capacity 200.5mAhg is tested
-1, after 100 circulations, specific discharge capacity remains on 195mAh g
-1.
Fig. 5 is prepared class chrysanthemum shape nano titanium oxide high rate performance figure, shows excellent high rate performance, presents high first run coulombic efficiency simultaneously, suitable practical application.
In sum, the preparation method of a kind of lithium ion battery negative material chrysanthemum shape nano titanium oxide of the present invention, the method is by synthesizing Nano/micron hierarchy, can realize shortening ion transfer Distance geometry simultaneously and improve the conductivity of material, the ion diffusion rates of material, make the material prepared have excellent specific capacity, stable cycle performance and high coulombic efficiency.
Claims (10)
1. a preparation method for high coulombic efficiency lithium ion battery negative material chrysanthemum shape nano titanium oxide, comprises the steps:
(1) the titanium source compound of 1.2 ~ 6g is dissolved in the unit alcohol of the short chain of certain volume, magnetic agitation forms settled solution in 10 ~ 15 minutes, then be (3 ~ 8) according to short chain units alcohol and polyalcohol volume ratio: 1 adds polyalcohol, continue stirring and form settled solution in 15 ~ 20 minutes.
(2) solution of step (1) gained is transferred in autoclave, hydro-thermal reaction is carried out 10 ~ 36 hours at 120 ~ 230 DEG C of temperature, after question response terminates, naturally cool to room temperature, centrifuge washing obtains TiO 2 precursor nano material after being separated drying.
(3) the TiO 2 precursor nano material that upper step obtains is put into high temperature furnace 400 ~ 600 DEG C of heat treatments after 4 ~ 8 hours, after naturally cooling to room temperature, just obtain chrysanthemum shape nano titanium oxide.
(4) material that upper step is synthesized is used for lithium ion battery negative material, take conductive black as conductive agent, polyvinylidene fluoride (PVDF) makes anode plate for lithium ionic cell for binding agent, be to electrode with lithium metal, microporous polypropylene membrane is barrier film, take volume ratio as the 1M LiPF6 of ethylene carbonate (EC)/dimethyl carbonate (the DMC)/diethyl carbonate (DEC) of 1:1:1 be electrolyte, in argon gas glove box, be assembled into 2025 type button cells, adopt LAND CT-2001A tester to carry out electrochemical property test.
2. preparation method as claimed in claim 1, is characterized in that: described titanium source compound is butyl titanate, isopropyl titanate, tetraethyl titanate, one or more in titanium tetrachloride, and volume is 1.2 ~ 6g.
3. preparation method as claimed in claim 1, is characterized in that: described short chain units alcohol is ethanol, isopropyl alcohol, normal propyl alcohol, n-butanol, one or more mixed solvents in isobutanol.
4. preparation method as claimed in claim 1, is characterized in that: described polyalcohol is ethylene glycol, one or both mixed solvents in glycerol.
5. preparation method as claimed in claim 1, is characterized in that: the volume ratio of short chain units alcohol and polyalcohol is 3 ~ 8:1.
6. preparation method as claimed in claim 1, is characterized in that: be settled solution in magnetic agitation process, turbid phenomenon can not be had to occur.
7. preparation method as claimed in claim 1, is characterized in that: the condition of described Hydrothermal Synthesis is: hydrothermal temperature 120 ~ 230 DEG C; The hydro-thermal reaction time is 10 ~ 36 hours.
8. preparation method as claimed in claim 1, is characterized in that: described Low Temperature Heat Treatment temperature is 400 ~ 600 DEG C; Heat treatment time is 4 ~ 8 hours.
9. preparation method as claimed in claim 1, is characterized in that: described hydro-thermal reaction method synthesis chrysanthemum shape nano titanium oxide.
10. preparation method as claimed in claim 1, is characterized in that: the lithium ion battery negative material chrysanthemum shape nano titanium oxide that step (3) obtains is Anatase.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106830069A (en) * | 2017-02-15 | 2017-06-13 | 齐鲁工业大学 | A kind of flower-shaped mesoporous TiO 2 hierarchy and preparation method thereof |
| CN109879313A (en) * | 2017-12-06 | 2019-06-14 | 天津发洋环保科技有限公司 | A kind of flower-shape photocatalyst of titanium dioxide |
| CN109904439A (en) * | 2017-12-11 | 2019-06-18 | 中信国安盟固利动力科技有限公司 | A kind of low temperature preparation method of novel titanium base material |
| CN112447957A (en) * | 2020-11-30 | 2021-03-05 | 桐乡市融杭科技合伙企业(有限合伙) | P, N doped porous carbon fiber-TiO2Preparation method of lithium ion battery cathode material |
| CN112479254A (en) * | 2020-12-28 | 2021-03-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of three-dimensional hollow flower-shaped titanium dioxide nano material, product and application |
| CN115676878A (en) * | 2022-11-23 | 2023-02-03 | 宜兴市佳信数控科技有限公司 | Preparation method of titanium dioxide lithium ion battery cathode material |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106830069A (en) * | 2017-02-15 | 2017-06-13 | 齐鲁工业大学 | A kind of flower-shaped mesoporous TiO 2 hierarchy and preparation method thereof |
| CN109879313A (en) * | 2017-12-06 | 2019-06-14 | 天津发洋环保科技有限公司 | A kind of flower-shape photocatalyst of titanium dioxide |
| CN109904439A (en) * | 2017-12-11 | 2019-06-18 | 中信国安盟固利动力科技有限公司 | A kind of low temperature preparation method of novel titanium base material |
| CN112447957A (en) * | 2020-11-30 | 2021-03-05 | 桐乡市融杭科技合伙企业(有限合伙) | P, N doped porous carbon fiber-TiO2Preparation method of lithium ion battery cathode material |
| CN112447957B (en) * | 2020-11-30 | 2021-09-17 | 上海彤程电子材料有限公司 | P, N doped porous carbon fiber-TiO2Preparation method of lithium ion battery cathode material |
| CN112479254A (en) * | 2020-12-28 | 2021-03-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of three-dimensional hollow flower-shaped titanium dioxide nano material, product and application |
| CN115676878A (en) * | 2022-11-23 | 2023-02-03 | 宜兴市佳信数控科技有限公司 | Preparation method of titanium dioxide lithium ion battery cathode material |
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