CN109904439B - Low-temperature preparation method of novel titanium-based material - Google Patents
Low-temperature preparation method of novel titanium-based material Download PDFInfo
- Publication number
- CN109904439B CN109904439B CN201711305482.1A CN201711305482A CN109904439B CN 109904439 B CN109904439 B CN 109904439B CN 201711305482 A CN201711305482 A CN 201711305482A CN 109904439 B CN109904439 B CN 109904439B
- Authority
- CN
- China
- Prior art keywords
- precursor
- molten salt
- titanium
- based material
- lithium ion
- 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
Images
Classifications
-
- 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a novel titanium-based material, in particular to a low-temperature preparation method for a negative electrode material of a lithium ion secondary battery. The low-temperature preparation method is a molten salt method, and in the reaction process, the existence of molten salt provides a liquid phase environment for the reaction process, so that the reaction is carried out faster, and the effect of reducing the reaction temperature is achieved. The powder material with the nano willow leaf-shaped microstructure is obtained through reaction, and the powder is high in specific surface area, high in reaction activity and excellent in rate performance. In addition, the molten salt can be recycled after the reaction is finished, and energy conservation and environmental protection are facilitated.
Description
Technical Field
The invention belongs to the technical field of material preparation methods, and particularly relates to a low-temperature preparation method of a novel titanium-based negative electrode material applied to a lithium battery.
Background
In recent years, with the development of the field of lithium ion batteries, the demand for advanced negative electrode materials has been increasing. TiO 22Has attracted extensive attention due to the advantages of high safety, stability, no toxicity, rich reserves, low price and the like. In TiO2Of the numerous crystal forms, TiO with monoclinic phase2(B) Due to the presence of a rim [010 ] in the crystal structure]The directional characteristic is parallel to the channel, which is beneficial to the combination and diffusion of lithium ions in the channel, so that the lithium ion composite material is more suitable to be used as an ideal lithium ion intercalation/deintercalation matrix compared with other crystal forms.
TiO2(B) The theoretical specific capacity of the material is 335mAh g-1The volume change of the material after lithium ion intercalation is small (< 4%), and the material has very good structural stability. Literature (Norio Takami et al, Micro-size pharmacological TiO)2(B) TiO reported in second particulate as anode materials for high-power and low-power lithium-ion batteries, J.Power sources, 2015,273,923)2(B) The reversible capacity of the secondary microsphere can reach 220mAh/g within the voltage range of 1.3-3V, and the specific capacity is higher. Voltage plateau 1.6V vs. li+And Li, an SEI film cannot be formed in the charge-discharge process, and the safety performance is good. The specific capacity can still reach 176mAh/g after discharging at the rate of 20C. Is a high-safety high-multiplying-power cathode with great development prospectA material.
Currently most commonly used for the preparation of monoclinic TiO2(B) The methods mainly include a solid-phase reaction method, a hydrothermal method, a solvothermal method and the like. The hydrothermal method and the solvothermal synthesis method have the advantages of controllable components and crystal phases, the activity of the prepared powder is high, the preparation cost is high, the reaction process is finished in a high-pressure reaction kettle, and the industrial production is not facilitated. TiO prepared by the traditional solid phase method2(B) The calcination temperature of the powder is over 800 ℃, the energy consumption in the production process is high, and the energy conservation and emission reduction are not facilitated. In addition, the powder prepared by the solid phase method has large particle size, low activity and poor crystallinity, and further optimization is still needed.
Disclosure of Invention
The invention aims to reduce the solid phase method for preparing monoclinic phase TiO2(B) The calcination temperature of the material. The invention adopts a low-temperature molten salt method to achieve the purpose, the molten salt method is a green chemical method, and in the reaction process, the existence of molten salt provides a liquid phase environment for the reaction process, so that the reaction is carried out more quickly, and the effect of reducing the reaction temperature is achieved. The microstructure obtained by the reaction is nano-scale willow leaf-shaped powder with higher specific surface area and high reaction activity. In addition, the molten salt can be recycled after the reaction is finished, and energy conservation and environmental protection are facilitated.
The invention provides a low-temperature preparation method of a novel titanium-based material, which comprises the following steps:
(1) the molar ratio (3-6) is 1: (1-30) weighing TiO2Mixing alkali metal carbonate and a molten salt compound in a solvent, and drying the mixed slurry in an oven at 50-120 ℃ for 2-6 hours to obtain mixed powder;
(2) placing the mixed powder obtained in the step (1) in a crucible, and calcining for 1-10 h (preferably 3-7h) at 300-900 ℃ (preferably 300-;
(3) adding a solvent (deionized water or absolute ethyl alcohol) into the precursor mixed with the molten salt obtained in the step (2) to wash away the molten salt, and drying the precursor in an oven at the temperature of 50-120 ℃ for 2-6 hours to obtain a precursor A;
(4) adding the precursor A obtained in the step (3) into an acid solution with the concentration of 1-5 mol/L, stirring at room temperature for 6-100 h (preferably 40-100h), washing with deionized water, and drying to obtain a precursor B;
(5) placing the precursor B in a crucible, calcining for 1-10 h (preferably 2-8h) at 250-500 ℃ (preferably 250-2(B) And (3) powder.
Wherein the crystal form of the titanium dioxide in the step (1) is anatase, and the average grain diameter is 20-500 nm.
The alkali metal carbonate used in the step (1) is Na2CO3、K2CO3、Cs2CO3、BaCO3One kind of (1).
The molten salt used in the step (1) is one or a mixture of more than two of potassium chloride, sodium chloride, barium nitrate, cesium chloride, potassium nitrate, sodium nitrate and cesium nitrate.
The solvent used in the step (1) is methanol, ethanol, isopropanol, methyl acetate, ethyl acetate, propyl acetate, acetone, methyl butanone or methyl isobutyl ketone.
The acid solvent used in the step (4) is a diluted solution of concentrated acid such as hydrochloric acid, sulfuric acid, nitric acid and the like. The proportion of the precursor A to the acid solution is 1 g: 50-400 ml.
Preparing the novel titanium-based negative electrode material TiO2(B) The method has the advantages of low preparation temperature, low energy consumption and correspondingly improved operation safety, and the low-temperature method is particularly set according to the condition of the required characteristics of the target material, so that the obtained material has a nano willow-leaf-shaped microstructure, a high specific surface area, high reaction activity, high capacity and excellent cycle performance. In addition, the method can recycle and continuously recycle the molten salt after the reaction is finished, is beneficial to energy conservation and environmental protection, has simple process and low cost, and is easy for industrialization.
Drawings
Fig. 1 is an XRD pattern of the novel titanium-based negative electrode prepared in example 1.
Fig. 2 is an SEM image of the novel titanium-based negative electrode prepared in example 2.
Fig. 3 is a charge and discharge curve of the materials of the novel titanium-based negative electrodes prepared in example 2 and comparative example at a rate of 0.2C and 10C, respectively.
Detailed Description
The method for preparing the novel titanium-based material for the lithium ion battery at low temperature provided by the invention is further explained by combining specific examples. However, the present invention is not limited to the following examples.
Example 1: weighing TiO according to the molar ratio of 4:1:52、K2CO3And mixing the obtained product and KCl in an absolute ethyl alcohol solvent, and drying the mixed slurry in a 60 ℃ oven for 5 hours to obtain mixed powder. And calcining the obtained powder at 750 ℃ for 4h to obtain a precursor material mixed with molten salt. Adding deionized water into the precursor mixed with the molten salt to wash away the molten salt, and drying in an oven at 60 ℃ for 4 hours to obtain a precursor K2Ti4O9. 10g of K2Ti4O9Adding the precursor into 700ml hydrochloric acid solution with the solubility of 1mol/L, stirring for 72H at room temperature, washing with deionized water, and drying to obtain a precursor H2Ti4O9. H is to be2Ti4O9Placing in a crucible, calcining at 400 ℃ for 6h to obtain monoclinic-phase TiO2(B) Powder, the obtained powder is pure TiO2(B) Phase (fig. 1).
Example 2: weighing TiO according to the molar ratio of 4:1:62、K2CO3And KCl: NaCl (molar ratio 1: 1) mixed molten salt is placed in an absolute ethyl alcohol solvent for mixing, and the mixed slurry is placed in a 100 ℃ oven for drying for 4 hours to obtain mixed powder. Calcining the obtained powder at 550 ℃ for 4h to obtain a precursor material mixed with molten salt. Adding deionized water into the precursor mixed with the molten salt to wash away the molten salt, and drying in an oven at 100 ℃ for 4 hours to obtain a precursor K2Ti4O9. 10g of K2Ti4O9Adding the precursor into 500ml hydrochloric acid solution with the solubility of 2mol/L, stirring for 48H at room temperature, washing with deionized water, and drying to obtain a precursor H2Ti4O9. H is to be2Ti4O9Placing in a crucible, calcining at 350 ℃ for 4h to obtain monoclinic-phase TiO2(B) And (3) powder. The obtained TiO2(B) The powder is willow leaf-shaped (figure 2) with length of about 50-70nm, the first discharge specific capacity is 243mAh/g within 1.3-3.0V voltage range and 0.2C multiplying power, and is slightly higher than TiO prepared by solid phase method2(B) Material (comparative) first efficiency was 90.9%. The charging specific capacity of 10C is 189mAh/g, and the TiO is prepared by a solid phase method2(B) The rate capability is obviously improved by more than 2 times of the material (comparative example). (see fig. 3).
Example 3: weighing TiO according to the molar ratio of 3:1:152、Na2CO3And NaNO3And (3) melting the salt, mixing the salt in an absolute ethyl alcohol solvent, and drying the mixed slurry in a 120 ℃ oven for 6 hours to obtain mixed powder. Calcining the obtained powder at 350 ℃ for 2h to obtain a precursor material mixed with molten salt. Adding deionized water into the precursor mixed with the molten salt to wash away the molten salt, and drying in a 120 ℃ oven for 4 hours to obtain a precursor Na2Ti3O7. Adding 10g of Na2Ti3O7Adding the mixture into 500ml of nitric acid solution with the solubility of 2mol/L, stirring the mixture for 80 hours at room temperature, washing the mixture by deionized water, and drying the mixture to obtain a precursor H2Ti3O7. H is to be2Ti3O7Placing in a crucible, calcining at 300 deg.C for 4 hr to obtain monoclinic phase TiO2(B) And (3) powder.
Example 4: weighing TiO according to the molar ratio of 5:1:62、Cs2CO3And CsNO3And mixing the molten salt to obtain mixed powder. Calcining the obtained powder at 420 ℃ for 3h to obtain a precursor material mixed with molten salt. Adding deionized water into the precursor mixed with the molten salt to wash away the molten salt, and drying in an oven at 100 ℃ for 4 hours to obtain a precursor Cs2Ti5O11. 10g of Cs2Ti5O11Adding the solution into 1000ml of nitric acid solution with the solubility of 1mol/L, stirring for 96H at room temperature, washing with deionized water, and drying to obtain a precursor H2Ti5O11. H is to be2Ti5O11Placing in a crucible, calcining at 380 ℃ for 6h to obtain monoclinic-phase TiO2(B) And (3) powder.
Example 5: weighing TiO according to the molar ratio of 4:1:62、BaCO3And Ba (NO)3)2And (3) melting the salt, mixing the melted salt in a methanol solvent, and drying the mixed slurry in an oven at 80 ℃ for 8 hours to obtain mixed powder. Calcining the obtained powder at 600 ℃ for 4h to obtain a precursor material mixed with molten salt. Adding deionized water into the precursor mixed with the molten salt to wash away the molten salt, and drying in an oven at 80 ℃ for 8 hours to obtain a precursor BaTi4O9. 10g of BaTi4O9Adding the mixture into 500ml of nitric acid solution with the solubility of 2mol/L, stirring the mixture for 90 hours at room temperature, washing the mixture by deionized water, and drying the mixture to obtain a precursor H2Ti4O9. H is to be2Ti4O9Placing in a crucible, calcining at 300 ℃ for 10h to obtain monoclinic-phase TiO2(B) And (3) powder.
Comparative example: weighing TiO according to the molar ratio of 4:12、K2CO3Mixing the mixture in absolute ethyl alcohol solvent, and drying the mixed slurry in a 100 ℃ oven for 5 hours to obtain mixed powder. Calcining the obtained powder at 900 ℃ for 8h to obtain a precursor K2Ti4O9. 10g of K2Ti4O9Adding the precursor into 700ml hydrochloric acid solution with the solubility of 1mol/L, stirring for 72H at room temperature, washing with deionized water, and drying to obtain a precursor H2Ti4O9. H is to be2Ti4O9Placing in a crucible, calcining at 450 ℃ for 8h to obtain monoclinic-phase TiO2(B) And (3) powder. TiO obtained in this comparative example2(B) The electrochemical properties of the powder are shown in FIG. 3.
The electrochemical properties of the above materials were tested as follows: by synthetic TiO2(B) The material is a negative active material, and the lithium sheet is a counter electrode, so as to assemble the button type experimental battery. The composition mass ratio of the negative electrode film is m (active material), m (acetylene black), m (PVDF)And (5) testing by adopting a blue test system, wherein the charging and discharging voltage is 1.3-3V, and the charging and discharging performance is carried out in the environment of normal temperature (25 ℃). The test results are shown in table 1 below:
table 1 charge and discharge performance of examples 1-5 are compared to comparative examples.
As is apparent from the above table, the materials prepared by the low temperature method of the present invention (examples 1 to 4) have a slightly improved specific capacity (except example 1) in the first discharge test with a smaller rate (0.2C) compared to the materials prepared by the conventional solid phase method (comparative example), and the first charging efficiency is substantially maintained at the same level; however, the specific charge capacity was greatly improved at a high rate (10C) (the highest improvement was 114%, example 2). This is mainly due to the low temperature molten salt process for preparing TiO2(B) The material is nano-scale particles, which is more beneficial to the rapid intercalation and deintercalation of lithium ions.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (5)
1. Monoclinic phase TiO2The titanium-based material is applied to improving the high-rate charge-discharge specific capacity of the lithium ion battery, and is characterized in that: the monoclinic phase TiO2The titanium-based material is a negative electrode active material of the lithium ion battery, and is prepared by the following steps:
(1) the molar ratio (3-6): 1: (1-30) weighing anatase TiO2Mixing alkali metal carbonate and a molten salt compound in a solvent, and drying the mixed slurry in an oven at 50-120 ℃ for 2-6 hours to obtain mixed powder; wherein the solvent is methanol, ethanol, isopropanol, methyl acetate, ethyl acetate, propyl acetate, acetone, methyl butanone or methyl isobutyl ketone; the molten salt compoundIs one or more of potassium chloride, sodium chloride, barium nitrate, cesium chloride, potassium nitrate, sodium nitrate and cesium nitrate;
(2) calcining the mixed powder obtained in the step (1) at 300-900 ℃ for 1-10 h to obtain a precursor material mixed with molten salt;
(3) adding deionized water into the precursor mixed with the molten salt obtained in the step (2) to wash away the molten salt, and drying in an oven at 50-120 ℃ for 2-6 hours to obtain a precursor A;
(4) adding the precursor A obtained in the step (3) into an acid solution with the concentration of 1-5 mol/L, stirring at room temperature for 6-100 h, washing with deionized water, and drying to obtain a precursor B; the ratio of the precursor A to the acid solution is 1 g: 50-400 ml;
(5) and calcining the precursor B at 250-380 ℃ for 1-10 h to obtain the nano-scale willow-leaf-shaped titanium-based material.
2. Monoclinic phase TiO according to claim 12The titanium-based material is applied to improving the high-rate charge-discharge specific capacity of the lithium ion battery, and is characterized in that: the crystal form of the titanium dioxide used in the step (1) is anatase, and the average grain diameter is 20 nm-500 nm.
3. Monoclinic phase TiO according to claim 12The titanium-based material is applied to improving the high-rate charge-discharge specific capacity of the lithium ion battery, wherein the alkali metal carbonate is Na2CO3、K2CO3And Cs2CO3One kind of (1).
4. Monoclinic phase TiO according to claim 12The titanium-based material is applied to improving the high-rate charge-discharge specific capacity of the lithium ion battery, and is characterized in that: the acid solution used in the step (4) is hydrochloric acid, sulfuric acid or nitric acid.
5. A lithium ion battery, characterized in that the negative active material of the lithium ion battery is prepared by the steps of any one of claims 1 to 4The monoclinic phase TiO thus obtained2The titanium-based material of (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711305482.1A CN109904439B (en) | 2017-12-11 | 2017-12-11 | Low-temperature preparation method of novel titanium-based material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711305482.1A CN109904439B (en) | 2017-12-11 | 2017-12-11 | Low-temperature preparation method of novel titanium-based material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109904439A CN109904439A (en) | 2019-06-18 |
| CN109904439B true CN109904439B (en) | 2022-02-22 |
Family
ID=66941843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711305482.1A Active CN109904439B (en) | 2017-12-11 | 2017-12-11 | Low-temperature preparation method of novel titanium-based material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109904439B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024049697A1 (en) * | 2022-08-31 | 2024-03-07 | Pacific Industrial Development Corporation | A preparation process for monoclinic titanium dioxide |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5962367A (en) * | 1994-11-04 | 1999-10-05 | Dequing Chemical Industry And Technologies Co., Ltd. | Titania (TiO2) support and process for preparation and use of the same |
| KR20010005862A (en) * | 1997-04-01 | 2001-01-15 | 오쯔까 유우지로 | Photocatalyst, process for producing the same and multifunctional members |
| JP2007247002A (en) * | 2006-03-16 | 2007-09-27 | Keio Gijuku | Electrochemical reduction method for titanium oxide |
| CN102315427A (en) * | 2010-06-29 | 2012-01-11 | 比亚迪股份有限公司 | Cathode active substance for lithium ion secondary battery, preparation method and lithium ion secondary battery |
| JP2012166966A (en) * | 2011-02-10 | 2012-09-06 | Doshisha | B type titanium oxide and method of manufacturing the same, and lithium ion battery using the same |
| JP2013030420A (en) * | 2011-07-29 | 2013-02-07 | Doshisha | Negative electrode material for lithium ion battery containing surface-fluorinated b-type titanium oxide and manufacturing method thereof, and lithium ion battery using the same |
| CN102324511B (en) * | 2011-10-09 | 2013-06-12 | 北京科技大学 | Preparation method for lithium ion battery composite cathode material |
| CN103427076B (en) * | 2013-07-12 | 2016-08-10 | 新疆大学 | A kind of solid state reaction prepares TiO2the method of-B nano material |
| CN103950976A (en) * | 2014-04-04 | 2014-07-30 | 中国科学院过程工程研究所 | Method for preparing titanium dioxide by utilizing mixed alkali of sodium hydroxide and sodium nitrate |
| CN104466155B (en) * | 2014-12-23 | 2018-01-09 | 北京理工大学 | A kind of preparation method of high coulombic efficiency lithium ion battery negative material chrysanthemum shape nano titanium oxide |
| CN104894636B (en) * | 2015-04-29 | 2017-10-27 | 华东理工大学 | The preparation method of eight potassium titanate crystal whiskers |
-
2017
- 2017-12-11 CN CN201711305482.1A patent/CN109904439B/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024049697A1 (en) * | 2022-08-31 | 2024-03-07 | Pacific Industrial Development Corporation | A preparation process for monoclinic titanium dioxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109904439A (en) | 2019-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105206831B (en) | One kind is used for sodium-ion battery positive material Na3V2O2x(PO4)2F3‑2xThe preparation method of microballoon | |
| CN110326136B (en) | Novel high-potential multilayer carbon-coated polyanionic sodium-ion battery positive electrode material and preparation method thereof | |
| WO2016165262A1 (en) | Preparation method for doped lithium titanate negative electrode material | |
| CN114933293B (en) | Preparation of sodium vanadium fluorophosphate and application of sodium vanadium fluorophosphate in sodium ion battery | |
| CN110233261B (en) | Preparation method of single crystal ternary lithium battery positive electrode material and lithium ion battery | |
| CN107507976B (en) | Lithium aluminum boron composite doped lithium manganate cathode material and preparation method thereof | |
| CN106920959A (en) | A kind of lithium-rich manganese-based polynary positive pole material of monocrystalline and preparation method thereof | |
| CN108172808A (en) | A kind of method of modifying of cerium tin composite oxides cladding lithium-rich manganese-based anode material | |
| CN115312698A (en) | Sodium ion battery layered oxide positive electrode material, preparation method and application | |
| CN108598456A (en) | A kind of preparation method of lithium ion battery porous composite oxide negative material | |
| CN114242968A (en) | Carbon-coated sodium iron fluorophosphate material and preparation method and application thereof | |
| CN112736233B (en) | Lithium ion battery electrode active material, preparation method thereof, electrode and battery | |
| CN115472899A (en) | Sodium ion battery layered oxide positive electrode material, preparation method and application thereof | |
| WO2018121101A1 (en) | Method for preparing high-cycle and high-voltage modified lithium-rich lithium manganate positive electrode material | |
| CN107017399A (en) | A kind of doping type lithium vanadate anode material and its synthetic method | |
| CN110957478B (en) | Titanium yttrium lithium phosphate modified high-nickel cathode composite material and preparation method thereof | |
| CN102070187B (en) | Method for preparing spinel lithium titanate serving as negative material of lithium ion battery | |
| CN103693632B (en) | A kind of preparation method of lithium vanadyl phosphate positive material for lithium ion battery | |
| CN103441257A (en) | Preparation method for lithium titanate material | |
| CN106684350B (en) | Preparation method of high-voltage positive electrode material lithium nickel manganese oxide | |
| CN113651360B (en) | Synthesis method and application of vanadium oxide | |
| CN110649263A (en) | Nickel-ion battery lithium vanadium phosphate positive electrode material, sol-gel preparation method and application | |
| WO2019104948A1 (en) | Molybdenum doping-modified lithium manganese oxide composite material, preparation method therefor and lithium ion battery | |
| CN103187566A (en) | Tubular lithium-rich anode material, preparation method and application thereof | |
| CN109904439B (en) | Low-temperature preparation method of novel titanium-based material |
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 |