CN100334261C - Rutile type structure TiO2 single dispersed nano-monocrystal and its synthesis method - Google Patents
Rutile type structure TiO2 single dispersed nano-monocrystal and its synthesis method Download PDFInfo
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- CN100334261C CN100334261C CNB2005100199251A CN200510019925A CN100334261C CN 100334261 C CN100334261 C CN 100334261C CN B2005100199251 A CNB2005100199251 A CN B2005100199251A CN 200510019925 A CN200510019925 A CN 200510019925A CN 100334261 C CN100334261 C CN 100334261C
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Abstract
The present invention relates to a TiO2 monodispersed nanometer single crystal with a rutile type structure, and a synthetic method thereof. The TiO2 monodispersed nanometer single crystal with a rutile type structure is a nanometer crystal with a multi-prism structure, and the size of the TiO2 monodispersed nanometer single crystal with a rutile type structure is from 50 nanometers to 0.5 micrometers. The synthetic method comprises that titanium tetrachloride is dissolved in hydrochloric acid solution; after the titanium tetrachloride and the hydrochloric acid solution are evenly mixed, the mixture is placed in an autoclave, and the temperature of the mixture is kept at the precompression of 0.1 to 1.5MPa at 200 to 400 DEG C for four to eight hours to obtain the TiO2 monodispersed nanometer single crystal with a rutile type structure and high crystallinity. The present invention has the characteristics that the hydrolyzing temperature of a precursor is increased through the acidity and the precompression of solution to cause the precursor to hydrolyze at high temperature; because the system is at the high pressure of 10 to 25MPa at the time, when TiO2 molecules are crystallized, TiO2 grows preferentially along a limited crystal face, and the TiO2 monodispersed nanometer single crystal with a rutile type structure and maximal density and without defects almost is directly grown. The crystal can be used as a negative electrode material of a lithium ion battery, and the crystal can effectively enhance the charging efficiency of the battery and can prolong the service life of the battery; the crystal is used as an auxiliary element of pressure point ceramic, and the anti-loading capacity and the working quality can be enhanced.
Description
Technical field
The present invention relates to a kind of rutile-type structure TiO
2Several its synthetic methods of monodisperse nano monocrystal.
Background technology
Nano-TiO
2Also claim transparent TiO
2Or crystallite TiO
2,, have a wide range of applications at aspects such as environmental protection, coating, printing ink, packaging material for food, makeup, solar cell, gas sensor and function ceramics because its reactive behavior height, visible light permeability are good and ultraviolet radiation absorption is strong.Therefore the application and development of titanium oxide has formed a new hot subject.The preparation method of nano-titanium oxide mainly contains: alkoxide hydrolysis, sol-gel method and inorganic salt hydrolytic precipitation method, gas-phase decomposition method and microemulsion method.The presoma of preparation is few, and the inorganic salt that are mainly pure oxide compound, titanium have Ti (SO
4)
2And TiCl
4
And the TiO of above-mentioned these method preparations
2, the common shortcoming is arranged: promptly surface imperfection is more, and surface energy is big, is difficult for disperseing, and is easy to reunite, and after particularly calcining in various degree, the crystal formation of titanium dioxide and grain-size all can change, can not preservation steady in a long-term.
Summary of the invention
The purpose of this invention is to provide a kind of rutile-type structure TiO
2Monodisperse nano monocrystal and synthetic method thereof.This rutile-type structure TiO
2Monodisperse nano monocrystal surface few defects is not easy to reunite; Have that preparation technology is simple to operate, advantage such as favorable reproducibility and product cut size are controlled.
The principle of foundation of the present invention is: TiCl
4Dissolve in the hydrochloric acid soln, during heating, after HCl was evaporated from solution, hydrochloric acid content reduced in the solution.Temperature raises and can strengthen the HCl steam output, after concentration of hydrochloric acid is reduced to certain value, and TiCl
4Hydrolysis generates TiO
2Because heating in confined conditions, when the precompressed of 0.1-1.5 MPa was arranged, reaction system was under the 10-25 MPa immense pressure (250 ℃ time water saturation vapour pressure greater than 8 MPas), newly-generated TiO
2Can be according to the crystallization of maximum density structure formation, grow up, and along certain crystal face and crystal orientation preferential growth, finally obtain size and be 50 nanometers～0.5 micron and be monodispersed rutile-type structure TiO
2Single crystal.Key condition: (1) adds inhibitor hydrochloric acid, makes its hydrolysis at low temperatures; (2) charge into precompressed, suppress the generation of too much nucleus, guarantee that nucleus growth speed is greater than forming nuclear speed; (3) temperature of reaction reaches 200-400 ℃, guarantees can directly generate rutile-type structure TiO under High Temperature High Pressure
2, avoid generating the crystal of lattice imperfection as far as possible.Organic cooperation of these three conditions can obtain that size is suitable, constitutionally stable TiO
2Single crystal.
A kind of rutile-type structure TiO provided by the invention
2Nano crystal, this rutile-type structure TiO
2Nano crystal is the nanocrystalline of multiple edge body structure, and size is 50 nanometers～0.5 micron.
Rutile-type structure TiO of the present invention
2The preparation method of nano crystal adopts hydro-thermal-hydraulic method preparation, and its preparation process is:
1st, titanium tetrachloride being dissolved in mass concentration is in the 36%-38% hydrochloric acid, is mixed with the hydrochloric acid soln that titanium tetrachloride concentration is 3.0 mol;
2nd, distilled water being added in the titanium tetrachloride hydrochloric acid soln that step 1 obtains, is that the volume ratio of 36%-38% hydrochloric acid is 1 to distilled water and mass concentration: 15-30, fully stir, and mix, obtain the titanium tetrachloride dilute hydrochloric acid solution;
3rd, the titanium tetrachloride dilute hydrochloric acid solution that obtains in the step 2 is put into autoclave, fill air pressurized to pressure and be the 0.1-1.5 MPa as precompressed, put into salt bath furnace, controlled temperature promptly obtains rutile-type structure TiO 200--400 ℃ of reaction 4-8 hour
2The thick product precipitation of nano crystal;
4th, the rutile-type structure TiO that step 3 is obtained
2The thick product of nano crystal precipitation repeatedly with distilled water wash and centrifugal anhydrating except that chlorion, does not have chlorion until the centrifugal water that goes out, and＜120 ℃ of oven dry, promptly obtains product then.
Rutile-type structure TiO of the present invention
2Nano crystal is applied in the lithium ion battery as negative active core-shell material.Its usage is the rutile-type structure TiO that will make by the present invention
2Nano crystal fully grinds and disperses, then in retort furnace in 650 ± 25 ℃ of roasting 30-60 minutes, grind again disperse after, at 900-1000 ℃ of roasting 3-4 hour, obtain the more rutile-type structure TiO of high-crystallinity
2Nano crystal is with this rutile-type structure TiO
2Nano crystal and conductive agent acetylene black, the poly-inclined to one side tetrafluoroethylene of binding agent mix by 75: 15: 10 mass ratio, are pressed into the negative pole of lithium ion battery.
Characteristics of the present invention are to utilize the acidity and the precompressed of solution, improve reaction precursor body hydrolysis temperature, make its crystallization under high temperature, high pressure, and then nucleus directly generates flawless rutile-type structure TiO along limited crystal face preferential growth
2Nano crystal.This crystal is as lithium ion battery negative material, charging efficiency and the work-ing life that can effectively improve battery; As solid electronic device,, can improve its anti-lotus ability and craftmanship as the pressure point pottery.
Description of drawings
Fig. 1 embodiment 1 synthetic TiO
2The TEM of nano crystal.
Fig. 2 embodiment 2 synthetic TiO
2The TEM of nano crystal.
Fig. 3 embodiment 3 synthetic TiO
2The TEM of nano crystal.
Fig. 4 embodiment 1 synthetic TiO
2XRD figure spectrum before the nano crystal roasting.
Fig. 5 embodiment 1 synthetic TiO
2XRD figure spectrum after the nano crystal roasting.
Nano-TiO from Fig. 1-3
2The electromicroscopic photograph of sample as can be seen, its TiO
2Nanocrystalline for the multiple edge body structure is uniformly dispersed no agglomeration.Size is 50 nanometers～0.5 micron.As seen from the figure, the TiO that makes
2Sample surfaces is smooth smooth, is specular reflection, and its diffractogram can be demarcated the TiO into rutile-type structure
2, this result with XRD is consistent.
Embodiment
Room temperature described in the following embodiment is 10-30 ℃
Embodiment 1
Get the analytical pure mass concentration and be 20 milliliters of the hydrochloric acid of 36%-38%, slowly add 10 milliliters of TiCl
4Solution (titanium tetrachloride concentration is the hydrochloric acid soln of 3.0 mol) drips distilled water then, is made into hydrochloric acid and distilled water volume ratio and is 1: 15 200 milliliters of solution, on magnetic stirring apparatus, stir, after mixing, put into autoclave, fill air pressurized to precompression to 1.0 MPas, put into High Temperature Salt Bath Furnace, temperature is controlled at 330 ℃, reacts 5 hours, is chilled to room temperature then, repeatedly with distilled water wash and centrifugal anhydrating, there is not chlorion until the centrifugal water that goes out except that chlorion.TEM (transmission electron microscope) analysis is done in sampling; 100 ± 10 ℃ of oven dry, fully grind and disperse, do XRD analysis.Roasting in retort furnace then 650 ℃ of roastings 30 minutes, grind to disperse again, again 900 ℃ of roastings 2 hours, obtains high purity, the TiO of high-crystallinity more
2Nano crystal carries out transmission electron microscope and XRD comparative analysis again.
Synthetic TiO
2The TEM of nano crystal such as Fig. 1, its TiO
2The forward and backward XRD figure spectrum of nano crystal roasting is respectively Fig. 4 and Fig. 5.As seen from Figure 1, synthetic TiO
2Nanocrystalline for the multiple edge body structure is uniformly dispersed no agglomeration.Size is 50 nanometers～0.5 micron.As seen from the figure, the TiO that makes
2Sample surfaces is smooth smooth, is specular reflection, and its diffractogram can be demarcated the TiO into rutile-type structure
2
Embodiment 2
Get the analytical pure mass concentration and be 20 milliliters of the hydrochloric acid of 36%-38%, slowly add 10 milliliters of TiCl
4Solution (titanium tetrachloride concentration is the hydrochloric acid soln of 3.0 mol) drips distilled water then, is made into hydrochloric acid and distilled water volume ratio and is 1: 30 200 milliliters of solution, on magnetic stirring apparatus, stir, after mixing, put into autoclave, fill air pressurized to precompression to 0.3 MPa, put into High Temperature Salt Bath Furnace, temperature is controlled at 310 ℃, reacts 5 hours, is chilled to room temperature then, repeatedly with distilled water wash and centrifugal anhydrating, there is not chlorion until the centrifugal water that goes out except that chlorion.TEM (transmission electron microscope) analysis is done in sampling.
Synthetic TiO
2The TEM of nano crystal such as Fig. 2.As seen from the figure, it is the nanocrystalline of multiple edge body structure, is uniformly dispersed, no agglomeration.Size is 50 nanometers～0.5 micron.As seen from the figure, the TiO that makes
2Sample surfaces is smooth smooth, is specular reflection, and its diffractogram can be demarcated the TiO into rutile-type structure
2
Embodiment 3
Get the analytical pure mass concentration and be 20 milliliters of the hydrochloric acid of 36%-38%, slowly add 10 milliliters of TiCl
4Solution (titanium tetrachloride concentration is the hydrochloric acid soln of 3.0 mol) drips distilled water then, is made into hydrochloric acid and distilled water volume ratio and is 1: 20 200 milliliters of solution, on magnetic stirring apparatus, stir, after mixing, put into autoclave, fill air pressurized to precompression to 0.3 MPa, put into High Temperature Salt Bath Furnace, temperature is controlled at 320 ℃, reacts 5 hours, is chilled to room temperature then, repeatedly with distilled water wash and centrifugal anhydrating, there is not chlorion until the centrifugal water that goes out except that chlorion.TEM (transmission electron microscope) analysis is done in sampling.
Synthetic TiO
2The TEM of nano crystal such as Fig. 3.As seen from the figure, it is the nanocrystalline of multiple edge body structure, is uniformly dispersed, no agglomeration.Size is 50 nanometers～0.5 micron.As seen from the figure, the TiO that makes
2Sample surfaces is smooth smooth, is specular reflection, and its diffractogram can be demarcated the TiO into rutile-type structure
2
Claims (1)
1, the described rutile-type structure TiO of a kind of claim 1
2The preparation method of nano crystal is characterized in that adopting hydro-thermal-hydraulic method preparation, and its preparation process is:
1st, titanium tetrachloride being dissolved in mass concentration is in the 36%-38% hydrochloric acid, is mixed with the hydrochloric acid soln that titanium tetrachloride concentration is 3.0 mol;
2nd, distilled water being added in the titanium tetrachloride hydrochloric acid soln that step 1 obtains, is that the volume ratio of 36%-38% hydrochloric acid is 1 to distilled water and mass concentration: 15-30, fully stir, and mix, obtain the titanium tetrachloride dilute hydrochloric acid solution;
3rd, the titanium tetrachloride dilute hydrochloric acid solution that obtains in the step 2 is put into autoclave, fill air pressurized to pressure and be the 0.1-1.5 MPa as precompressed, put into salt bath furnace, controlled temperature promptly obtains rutile-type structure TiO 200--400 ℃ of reaction 4-8 hour
2The thick product precipitation of nano crystal;
4th, the rutile-type structure TiO that step 3 is obtained
2The thick product of nano crystal precipitation repeatedly with distilled water wash and centrifugal anhydrating except that chlorion, does not have chlorion until the centrifugal water that goes out, and＜120 ℃ of oven dry, promptly obtains rutile-type structure TiO then
2Nano crystal is the nanocrystalline of multiple edge body structure, and size is 50 nanometers～0.5 a micron product.
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| CN100448782C (en) * | 2006-09-08 | 2009-01-07 | 中国科学技术大学 | Microsphere of titanium dioxide in dandelion shape, and prepartion method |
| CN102503166A (en) * | 2011-10-21 | 2012-06-20 | 厦门大学 | Preparation method of one-dimensional rutile TiO2 nanorod array film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1248550A (en) * | 1999-05-12 | 2000-03-29 | 中国科学院上海硅酸盐研究所 | Process for preparing titanic schorl phase titanium dioxide nanometer crystal under room temp. |
| KR100420275B1 (en) * | 2001-04-06 | 2004-03-02 | (주)아해 | Preparation of TiO2 fine powder from titanium tetrachloride with inorganic acid |
| CN1172856C (en) * | 2002-03-01 | 2004-10-27 | 北京化大天瑞纳米材料技术有限公司 | Method of producing rutile type nano titanium dioxide and obtained nano titanium dioxide using said method |
| CN1172993C (en) * | 2002-02-09 | 2004-10-27 | 中国科学院上海硅酸盐研究所 | Process for preparing rutile phase nano titanium dioxide |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1248550A (en) * | 1999-05-12 | 2000-03-29 | 中国科学院上海硅酸盐研究所 | Process for preparing titanic schorl phase titanium dioxide nanometer crystal under room temp. |
| KR100420275B1 (en) * | 2001-04-06 | 2004-03-02 | (주)아해 | Preparation of TiO2 fine powder from titanium tetrachloride with inorganic acid |
| CN1172993C (en) * | 2002-02-09 | 2004-10-27 | 中国科学院上海硅酸盐研究所 | Process for preparing rutile phase nano titanium dioxide |
| CN1172856C (en) * | 2002-03-01 | 2004-10-27 | 北京化大天瑞纳米材料技术有限公司 | Method of producing rutile type nano titanium dioxide and obtained nano titanium dioxide using said method |
Non-Patent Citations (4)
| Title |
|---|
| 四氯化钛强迫水解制备金红石型纳米二氧化钛 方晓明，农云军，杨卓如，陈焕钦，无机盐工业，第35卷第6期 2003 * |
| 用TiCl4制备纳米TiO2的研究状况 杜剑桥，王兰武，钛工业进展，第22卷第2期 2005 * |
| 金红石相TiO2纳米粉的水热合成 李燕，安徽建筑工业学院学报，第5卷第3期 1997 * |
| 金红石相TiO2纳米粉的水热合成 李燕，安徽建筑工业学院学报，第5卷第3期 1997;四氯化钛强迫水解制备金红石型纳米二氧化钛 方晓明，农云军，杨卓如，陈焕钦，无机盐工业，第35卷第6期 2003;用TiCl4制备纳米TiO2的研究状况 杜剑桥，王兰武，钛工业进展，第22卷第2期 2005 * |
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