CN104843783A - Preparation method of amorphous titanium dioxide for lithium titanate - Google Patents
Preparation method of amorphous titanium dioxide for lithium titanate Download PDFInfo
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- CN104843783A CN104843783A CN201510260474.4A CN201510260474A CN104843783A CN 104843783 A CN104843783 A CN 104843783A CN 201510260474 A CN201510260474 A CN 201510260474A CN 104843783 A CN104843783 A CN 104843783A
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- titanium dioxide
- lithium titanate
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Abstract
The invention belongs to the technical field of preparation of titanium dioxide and particularly relates to a preparation method of amorphous titanium dioxide for lithium titanate. The preparation method of amorphous titanium dioxide for lithium titanate comprises the following steps: hydrolyzing titanium sulfate, exchanging ions and deeply removing impurities of hydrolyzed product, drying and depolymerizing slurry to prepare the amorphous titanium dioxide for lithium titanate. The preparation method of amorphous titanium dioxide for lithium titanate is liable to implement and low in production cost. By virtue of the method, similarly spherical particles can be prepared; the ideal effect of washing and removing the impurities of the particles can be achieved; the particles are extremely low in content of included impurities; the processing of subsequent lithium titanate battery materials is greatly facilitated. The final product prepared by the method is free of secondary aggregation and excellent in dispersion state, and can be easily used in the downstream industry.
Description
Technical field
The invention belongs to titanium dioxide preparing technical field, be specifically related to the preparation method of a kind of lithium titanate with unformed titanium dioxide.
Background technology
Along with the development of novel energy and green industry, due to " zero strain " of lithium titanate, improve cycle performance and the work-ing life of electrode, so the development of novel battery lithium titanate material is day by day wide.A kind of important materials titanium dioxide as lithium titanate battery material can't meet the demands at present, hinders the development of lithium titanate battery.At present, the domestic main employing sulfuric acid process of titanium dioxide is produced, and the external main chlorination process that adopts is produced.The titanium dioxide that these two kinds of production technique are produced is mainly used in the industries such as coating, papermaking, plastics, ink, as a kind of mineral dye, its composition is the crystalline structure of anatase titanium dioxide or rutile-type, and, for meeting the requirement of pigment performance, all to carry out adding Ficus caricaL, as aluminium, silicon, potassium, phosphorus etc., the content of its titanium dioxide between 85.0-98.0%, and contains other impurity elements, therefore, these titanium dioxide all can not meet the requirement of lithium titanate battery titanium dioxide.
Summary of the invention
The object of this invention is to provide the preparation method of a kind of lithium titanate with unformed titanium dioxide, scientific and reasonable, simple, low production cost.
The lithium titanate of the present invention preparation method of unformed titanium dioxide, step is as follows:
(1) hydrolysis of titanium sulfate
Put into hydrolytic decomposition pot after the titanium sulfate solution of 50-80 DEG C being joined the deionized water for stirring of 60-80 DEG C to be hydrolyzed;
(2) ion-exchange of hydrolysate and deep impurity-removing
Add sal volatile in product after hydrolysis, put into material storage tank leave standstill after, by the feed liquid deionized water centrifuge washing obtained;
(3) oven dry of slurry and depolymerization
Be mixed into paste after adding TMP in material after washing, put into baking oven dry, crushed after being dried, to break up, to obtain final product.
The concentration of the titanium sulfate solution described in step (1) is 60-120g/L, in titanium dioxide.
The volume ratio of the titanium sulfate solution described in step (1) and deionized water is 1-3:2-6.
Churning time described in step (1) is 20-30min, and stirring velocity is that 10-30 turns/min.
The mass concentration of the sal volatile described in step (2) is 5-8%.
The add-on of the sal volatile described in step (2) is the 8-10% of the product quality after hydrolysis, and the product after hydrolysis is in titanium dioxide.
Time of repose described in step (2) is 12-20 hour.
The mass concentration of the TMP described in step (3) is 3-6%.
The add-on of the TMP described in step (3) is the 0.6-1.2% of the quality of material after washing, and the material after washing is in titanium dioxide.
Drying temperature described in step (3) is 130-150 DEG C, and time of drying is 10-15 hour.
The lithium titanate of the present invention preparation method of unformed titanium dioxide, concrete steps are as follows:
(1) hydrolysis of titanium sulfate
To be warmed up to the titanium sulfate solution of 50-80 DEG C, evenly join in the deionized water being warmed up to 60-80 DEG C, stir 20-30min, material is put into hydrolytic decomposition pot.Titanium sulfate solution (with titanium dioxide metering) concentration controls in the scope of 60-120g/L; The temperature of titanium sulfate solution controls within 50-80 DEG C; Described titanium sulfate solution and the volume ratio of deionized water control in the scope of 1-3:2-6.Whole process adopts the mixing of stirring and carrying out material, and stirring velocity controls to turn/min at 10-30.
(2) ion-exchange of hydrolysate and deep impurity-removing
Metatitanic acid particle after hydrolysis is tiny, in order to further ion depth removal of impurities, add the sal volatile of 5-8% mass concentration, add-on is the 8-10% of product (with the titanium dioxide metering) quality after hydrolysis, metatitanic acid is put into material storage tank and is left standstill after 12-20 hour after being hydrolyzed together, feed liquid is put into the whizzer having completed filter cloth, slowly open whizzer, rotating speed turns/min at 5-15, after material dries, divide the deionized water adding volume of material 3 times for three times, divide and add washing 3 times, remove the foreign ion be mingled with, the temperature of deionized water controls in the scope of 40-60 DEG C.
(3) oven dry of slurry and depolymerization
Material after washing is put into stainless steel pallet, add the TMP of the 3-6% mass concentration configured, add-on is the 0.6-1.2% of material (with the titanium dioxide metering) quality after washing, Homogeneous phase mixing becomes paste, put into baking oven, its temperature is made to remain in the scope of 130-150 DEG C, dry 10-15 hour.Dried material is put into stirrer or vibration mill is pulverized, then the material after pulverizing is put into coffee mill and break up, obtain the unformed titanium dioxide being suitable for lithium titanate.
The invention provides the preparation method of a kind of lithium titanate with unformed titanium dioxide, this titanium dioxide had both been different from the titanium dioxide of anatase titanium dioxide, neither the titanium dioxide of rutile-type, but a kind of unbodied titanium dioxide.Be conducive to using metallic lithium and unbodied titanium dioxide to prepare the lithium titanate battery material with spinel structure.
The present invention compared with prior art, has following beneficial effect:
The present invention is easy to implement, low production cost.Can prepare particle form by the present invention and be similar to spherical granule-morphology, the impurity washing of particle and removal ideal, the foreign matter content be mingled with is extremely low, more useful to the processing of follow-up lithium titanate battery material.The finished product obtained by the present invention can not produce secondary agglomeration, and dispersion state is good, is easy to use in downstream industry.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
Get the titanium sulfate solution of 1000ml, concentration is 60g/L, is warmed up to the titanium sulfate of 50 DEG C, and evenly join and be warmed up in the 2000ml deionized water of 60 DEG C, stirring velocity controls at 10 turns/min.After stirring 20min, material is put into hydrolytic decomposition pot, in hydrolytic decomposition pot, adds the sal volatile 120ml of 5% mass concentration in advance, be hydrolyzed together after metatitanic acid put into material storage tank leave standstill after 12 hours, feed liquid is put into the whizzer having completed filter cloth, slowly open whizzer, rotating speed at 5 turns/min, until material dry after, divide the deionized water adding volume of material 3 times for three times, divide and add washing 3 times, remove the foreign ion be mingled with, the temperature of deionized water controls at 40 DEG C.Material after washing is put into stainless steel pallet, add the TMP of 3% mass concentration configured, add-on is 0.6% of material (with the titanium dioxide metering) quality after washing, Homogeneous phase mixing becomes paste, put into baking oven, its temperature is made to remain on 130 DEG C, dry 10 hours.Dried material is put into stirrer or vibration mill is pulverized, then the material after pulverizing is put into coffee mill and break up, obtain the unformed titanium dioxide being suitable for lithium titanate.
Embodiment 2
Get the titanium sulfate solution of 1000ml, concentration is 60g/L, is warmed up to the titanium sulfate of 60 DEG C, and evenly join and be warmed up in the 2000ml deionized water of 70 DEG C, stirring velocity controls at 20 turns/min.After stirring 30min, material is put into hydrolytic decomposition pot, in hydrolytic decomposition pot, adds the sal volatile 120ml of 8% mass concentration in advance, be hydrolyzed together after metatitanic acid put into material storage tank leave standstill after 15 hours, feed liquid is put into the whizzer having completed filter cloth, slowly open whizzer, rotating speed at 8 turns/min, until material dry after, divide the deionized water adding volume of material 3 times for three times, divide and add washing 3 times, remove the foreign ion be mingled with, the temperature of deionized water controls at 40 DEG C.Material after washing is put into stainless steel pallet, add the TMP of 3% mass concentration configured, add-on is 1.2% of material (with the titanium dioxide metering) quality after washing, Homogeneous phase mixing becomes paste, put into baking oven, its temperature is made to remain on 140 DEG C, dry 15 hours.Dried material is put into stirrer or vibration mill is pulverized, then the material after pulverizing is put into coffee mill and break up, obtain the unformed titanium dioxide being suitable for lithium titanate.
Embodiment 3
Get the titanium sulfate solution of 1000ml, concentration is 60g/L, is warmed up to the titanium sulfate of 70 DEG C, and evenly join and be warmed up in the 2000ml deionized water of 80 DEG C, stirring velocity controls at 20 turns/min.After stirring 30min, material is put into hydrolytic decomposition pot, in hydrolytic decomposition pot, adds the sal volatile 120ml of 7% mass concentration in advance, be hydrolyzed together after metatitanic acid put into material storage tank leave standstill after 12 hours, feed liquid is put into the whizzer having completed filter cloth, slowly open whizzer, rotating speed at 8 turns/min, until material dry after, divide the deionized water adding volume of material 3 times for three times, divide and add washing 3 times, remove the foreign ion be mingled with, the temperature of deionized water controls at 40 DEG C.Material after washing is put into stainless steel pallet, add the TMP of 3% mass concentration configured, add-on is 0.6% of material (with the titanium dioxide metering) quality after washing, Homogeneous phase mixing becomes paste, put into baking oven, its temperature is made to remain on 150 DEG C, dry 10 hours.Dried material is put into stirrer or vibration mill is pulverized, then the material after pulverizing is put into coffee mill and break up, obtain the unformed titanium dioxide being suitable for lithium titanate.
Embodiment 4
Get the titanium sulfate solution of 1000ml, concentration is 60g/L, is warmed up to the titanium sulfate of 80 DEG C, and evenly join and be warmed up in the 2000ml deionized water of 80 DEG C, stirring velocity controls at 30 turns/min.After stirring 30min, material is put into hydrolytic decomposition pot, in hydrolytic decomposition pot, adds the sal volatile 120ml of 8% mass concentration in advance, be hydrolyzed together after metatitanic acid put into material storage tank leave standstill after 20 hours, feed liquid is put into the whizzer having completed filter cloth, slowly open whizzer, rotating speed at 8 turns/min, until material dry after, divide the deionized water adding volume of material 3 times for three times, divide and add washing 3 times, remove the foreign ion be mingled with, the temperature of deionized water controls at 40 DEG C.Material after washing is put into stainless steel pallet, add the TMP of 3% mass concentration configured, add-on is 0.6% of material (with the titanium dioxide metering) quality after washing, Homogeneous phase mixing becomes paste, put into baking oven, its temperature is made to remain on 150 DEG C, dry 10 hours.Dried material is put into stirrer or vibration mill is pulverized, then the material after pulverizing is put into coffee mill and break up, obtain the unformed titanium dioxide being suitable for lithium titanate.
Claims (10)
1. a lithium titanate preparation method for unformed titanium dioxide, is characterized in that step is as follows:
(1) hydrolysis of titanium sulfate
Put into hydrolytic decomposition pot after the titanium sulfate solution of 50-80 DEG C being joined the deionized water for stirring of 60-80 DEG C to be hydrolyzed;
(2) ion-exchange of hydrolysate and deep impurity-removing
Add sal volatile in product after hydrolysis, put into material storage tank leave standstill after, by the feed liquid deionized water centrifuge washing obtained;
(3) oven dry of slurry and depolymerization
Be mixed into paste after adding TMP in material after washing, put into baking oven dry, crushed after being dried, to break up, to obtain final product.
2. the lithium titanate according to claim 1 preparation method of unformed titanium dioxide, is characterized in that the concentration of the titanium sulfate solution described in step (1) is 60-120g/L, in titanium dioxide.
3. the lithium titanate according to claim 1 preparation method of unformed titanium dioxide, is characterized in that the volume ratio of the titanium sulfate solution described in step (1) and deionized water is 1-3:2-6.
4. the lithium titanate according to claim 1 preparation method of unformed titanium dioxide, is characterized in that the churning time described in step (1) is 20-30min, and stirring velocity is that 10-30 turns/min.
5. the lithium titanate according to claim 1 preparation method of unformed titanium dioxide, is characterized in that the mass concentration of the sal volatile described in step (2) is 5-8%.
6. the lithium titanate according to claim 1 preparation method of unformed titanium dioxide, it is characterized in that the add-on of the sal volatile described in step (2) is the 8-10% of the product quality after hydrolysis, the product after hydrolysis is in titanium dioxide.
7. the lithium titanate according to claim 1 preparation method of unformed titanium dioxide, is characterized in that the time of repose described in step (2) is 12-20 hour.
8. the lithium titanate according to claim 1 preparation method of unformed titanium dioxide, is characterized in that the mass concentration of the TMP described in step (3) is 3-6%.
9. the lithium titanate according to claim 1 preparation method of unformed titanium dioxide, it is characterized in that the add-on of the TMP described in step (3) is the 0.6-1.2% of the quality of material after washing, the material after washing is in titanium dioxide.
10. the lithium titanate according to claim 1 preparation method of unformed titanium dioxide, it is characterized in that the drying temperature described in step (3) is 130-150 DEG C, time of drying is 10-15 hour.
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Citations (4)
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|---|---|---|---|---|
| CN101190800A (en) * | 2006-11-30 | 2008-06-04 | 中国科学院过程工程研究所 | Method for preparing rutile-type titanium dioxide by hydrothermal method |
| CN101555038A (en) * | 2009-04-28 | 2009-10-14 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing titanium pigment by hydrolysis |
| US20110003684A1 (en) * | 2004-11-16 | 2011-01-06 | Walid Abdelhemld Daoud | Method for making single-phase anatase titanium oxide |
| KR20110063157A (en) * | 2009-12-04 | 2011-06-10 | (주) 빛과환경 | Manufacturing method of titanium oxide improved whiteness |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110003684A1 (en) * | 2004-11-16 | 2011-01-06 | Walid Abdelhemld Daoud | Method for making single-phase anatase titanium oxide |
| CN101190800A (en) * | 2006-11-30 | 2008-06-04 | 中国科学院过程工程研究所 | Method for preparing rutile-type titanium dioxide by hydrothermal method |
| CN101555038A (en) * | 2009-04-28 | 2009-10-14 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing titanium pigment by hydrolysis |
| KR20110063157A (en) * | 2009-12-04 | 2011-06-10 | (주) 빛과환경 | Manufacturing method of titanium oxide improved whiteness |
Non-Patent Citations (2)
| Title |
|---|
| 季宝允: ""纳米 TiO2的制备和掺杂及其在异构化反应中的应用"", 《中国优秀硕士学位论文全文数据库》 * |
| 邹建新等: "《钒钛产品生产工艺与设备》", 31 January 2014, 化学工业出版社 * |
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Denomination of invention: Preparation method of amorphous titanium dioxide for lithium titanate Effective date of registration: 20230803 Granted publication date: 20161026 Pledgee: China Construction Bank Corporation Zibo Boshan sub branch Pledgor: SHANDONG DOGUIDE GROUP Co.,Ltd. Registration number: Y2023980050752 |
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