CN103964499A - Preparation method for carbon-coated nano-titanium dioxide electrode material - Google Patents
Preparation method for carbon-coated nano-titanium dioxide electrode material Download PDFInfo
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- CN103964499A CN103964499A CN201410185902.7A CN201410185902A CN103964499A CN 103964499 A CN103964499 A CN 103964499A CN 201410185902 A CN201410185902 A CN 201410185902A CN 103964499 A CN103964499 A CN 103964499A
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Abstract
The invention relates to a preparation method for carbon-coated nano-titanium dioxide electrode material for a lithium-ion battery. The preparation method comprises the following steps: using titanium sulfate as a titanium source, and glucose or sucrose as a carbon source, weighing the titanium sulfate and the carbon source in a certain mass ratio, and respectively dissolving the titanium sulfate and the carbon source in deionized water; adding the aqueous solution of the carbon source into the aqueous solution of the titanium sulfate, stirring uniformly, and transferring to a hydrothermal reaction kettle; keeping temperature for a certain time, cooling, washing a resultant, filtering, and drying; under the protection of an argon atmosphere, calcinating at high temperature to obtain the carbon-coated nano-titanium dioxide electrode material. According to the preparation method for the carbon-coated nano-titanium dioxide electrode material, selected raw materials are low in cost; the prepared carbon-coated nano-titanium dioxide electrode material has excellent charge-discharge cycle performance, so that requirements on the electrode material of the lithium-ion battery can be met; the preparation method is simple in process and easy in industrial production.
Description
Technical field
The present invention relates to a kind of method of utilizing hydrothermal method to prepare carbon cladding titanium dioxide nano electrode materials, belong to electrochemical energy Material Field.
Background technology
Titanium dioxide TiO
2as lithium ion battery negative material have that theoretical specific capacity is high, good cycle and cheap good characteristic, there is boundless application prospect.But titanium dioxide belongs to semi-conductor, electronic conductivity is lower, and therefore its high theoretical specific capacity is difficult to be not fully exerted, thereby has limited the application of titanium dioxide.
For head it off, conventional method is to prepare titania nanotube (Min Gyu Choi, et al, Journal of Power Sources, 195 (2010) 8289-8296), mesoporous TiO 2 (Hun-Gi Jung, etal, Electrochemistry Communications, 11 (2009) 756-759), nano wire (Zunxian Yang, et al, Electrochemistry Communications, 13 (2011) 46-49), F
-(the Journal of Physical Chemistry C such as the titanium dioxide of doping, 113 (2009) 21258-21263) and prepare the coated titanium dioxide of carbon (a kind of preparation method of titanium dioxide/carbon composite lithium ion battery electrode materials, publication No.: CN102769123A) etc. by solvent thermal process.The titanium dioxide of above-mentioned different shapes and structure all shows good chemical property, but above-mentioned preparation method and technique are all more loaded down with trivial details and manufacturing cost is higher.
Summary of the invention
The present invention aims to provide a kind of method of utilizing hydrothermal method and high temperature sintering to prepare carbon cladding titanium dioxide nano electrode materials, has with low cost, simple process and be easy to industrialization to transform the feature of producing.
A method of preparing above-mentioned carbon cladding titanium dioxide nano electrode materials, comprises following processing step:
(1) get titanium sulfate and carbon source according to certain mass score another name, the mass ratio of titanium sulfate and carbon source is 1:0.2-1:1.5.Titanium sulfate and carbon source are dissolved in respectively in a certain amount of deionized water, after fully stirring, carbon source solution are joined in titanium sulfate aqueous solution, and be uniformly mixed.
(2) above-mentioned mixing solutions is moved in hydrothermal reaction kettle, at 140-200 DEG C of heating and thermal insulation 3-6 hour, naturally cool to subsequently room temperature.
(3) above-mentioned reaction product is used to alcohol and deionized water repetitive scrubbing, filtration dry, then dried product is moved in high temperature sintering furnace, in inert atmosphere, at 600-800 DEG C of roasting 2-4 hour, naturally cool to room temperature.
In above-mentioned reaction, carbon source adopts glucose or sucrose.Reaction principle is that titanium sulfate hydrolysis generates metatitanic acid colloid:
Ti(SO
4)
2+H
2O→TiO(OH)
2+H
++SO
4 2-。
In the water-heat process of 140-200 DEG C, metatitanic acid dehydration generates nano titanium oxide TiO
2particle, meanwhile, glucose or sucrose dehydrating condensation are also coated on titanium dioxide granule surface.In the high-temperature calcination process under protection of inert gas, the coating layer carbonization of titanium dioxide surface, forms the coated titanium dioxide nanostructured electrode material of carbon.
Compared with prior art, the present invention possesses following advantage:
1. the selected abundant raw material of the present invention, cheap.The carbon cladding titanium dioxide nano electrode materials size uniform of preparing and there is good charge-discharge performance.
2. preparation method's condition of the present invention is moderate, and technical process is simple, is easy to suitability for industrialized production.
Brief description of the drawings
Fig. 1 (a) and (b) be respectively X-ray diffractogram (XRD) and the stereoscan photograph of 4 hours carbon cladding titanium dioxides of 600 DEG C of carbonizations.(c) be the charge-discharge performance curve of carbon cladding titanium dioxide under 0.2C condition.
Fig. 2 (a) and (b) be respectively XRD figure spectrum and the stereoscan photograph of 4 hours carbon cladding titanium dioxides of 650 DEG C of carbonizations.(c) be the charge-discharge performance curve of carbon cladding titanium dioxide under 0.2C condition.
Fig. 3 (a) and (b) be respectively XRD figure spectrum and the stereoscan photograph of 4 hours carbon cladding titanium dioxides of 700 DEG C of carbonizations.(c) be the charge-discharge performance curve of carbon cladding titanium dioxide under 0.2C condition.
Fig. 4 (a) and (b) be respectively XRD figure spectrum and the stereoscan photograph of 2 hours carbon cladding titanium dioxides of 800 DEG C of carbonizations.(c) be the charge-discharge performance curve of carbon cladding titanium dioxide under 0.2C condition.
Embodiment
embodiment 1
Be that 1:0.2 takes respectively titanium sulfate and glucose according to the mass ratio of titanium sulfate and glucose, be dissolved in respectively in deionized water, after being uniformly mixed, D/W is joined in titanium sulfate aqueous solution, move into hydrothermal reaction kettle, 140 DEG C of insulations 6 hours.After naturally cooling to room temperature, product is used to deionized water and alcohol repetitive scrubbing, filtration and is dried.Dried product is moved in process furnace, and under argon shield atmosphere, 600 DEG C are incubated carbonization 4 hours, naturally cool to room temperature.
The product that 140 DEG C of hydro-thermals are obtained for 6 hours is after dry, in air, calcine 4 hours in 600 DEG C, make the coating complete oxidation volatilization of titanium dioxide surface, the mass loss before and after calcining by measurement is known, and the ratio that the coating of titanium dioxide surface accounts for total mass is 10.8%.Fig. 1 (a) and (b) be respectively X-ray diffractogram (XRD) and the stereoscan photograph of 4 hours products of 600 DEG C of carbonizations.XRD figure shows that product is anatase titanium dioxide.Because carbon is non-crystalline state, so there is no the diffraction peak of amorphous carbon in XRD figure.Stereoscan photograph shows, the coated titanium dioxide of these carbon is nano level, and particle size is very even.Carbon cladding titanium dioxide is assembled in lithium ion experimental cell, and using lithium sheet as to electrode, its chemical property is as shown in Fig. 1 (c).Under 0.2C condition, the specific discharge capacity of circulation reaches 311.5mAh g first
-1, and cycle performance is relatively stable.
embodiment 2
Be that 1:0.5 takes respectively titanium sulfate and glucose according to the mass ratio of titanium sulfate and glucose, be dissolved in respectively in deionized water, after being uniformly mixed, D/W is joined in titanium sulfate aqueous solution, move into hydrothermal reaction kettle, 160 DEG C of insulations 5 hours.After naturally cooling to room temperature, product is used to deionized water and alcohol repetitive scrubbing, filtration and is dried.Dried product is moved in process furnace, and under argon shield atmosphere, 650 DEG C are incubated carbonization 4 hours, naturally cool to room temperature.
The product that 160 DEG C of hydro-thermals are obtained for 5 hours is after dry, in air, calcine 4 hours in 600 DEG C, make the coating complete oxidation volatilization of titanium dioxide surface, the mass loss before and after calcining by measurement is known, and the ratio that the coating of titanium dioxide surface accounts for total mass is 17.0%.Fig. 2 (a) and (b) be respectively X-ray diffractogram (XRD) and the stereoscan photograph of 4 hours products of 650 DEG C of carbonizations.XRD figure shows that product is anatase titanium dioxide.Carbon is non-crystalline state, so there is no the diffraction peak of amorphous carbon in XRD figure.Stereoscan photograph shows, the coated titanium dioxide of these carbon reaches nano level, and particle size is very even.Carbon cladding titanium dioxide is assembled in lithium ion experimental cell, and using lithium sheet as to electrode, its chemical property is as shown in Fig. 2 (c).Under 0.2C condition, the specific discharge capacity of circulation reaches 397.4mAh g first
-1, and cycle performance is relatively stable.
embodiment 3
Be that 1:1.2 takes respectively titanium sulfate and glucose according to the mass ratio of titanium sulfate and glucose, be dissolved in respectively in deionized water, after being uniformly mixed, D/W is joined in titanium sulfate aqueous solution, move into hydrothermal reaction kettle, 180 DEG C of insulations 4 hours.After naturally cooling to room temperature, product is used to deionized water and alcohol repetitive scrubbing, filtration and is dried.Dried product is moved in process furnace, and under argon shield atmosphere, 700 DEG C are incubated carbonization 4 hours, naturally cool to room temperature.
The product that 180 DEG C of hydro-thermals are obtained for 4 hours is after dry, in air, calcine 4 hours in 600 DEG C, make the coating complete oxidation volatilization of titanium dioxide surface, the mass loss before and after calcining by measurement is known, and the ratio that the coating of titanium dioxide surface accounts for total mass is 21.4%.Fig. 3 (a) and (b) be respectively X-ray diffractogram (XRD) and the stereoscan photograph of 4 hours products of 700 DEG C of carbonizations.XRD figure shows that product is anatase titanium dioxide.Stereoscan photograph shows, the coated titanium dioxide of these carbon reaches nano level, and particle size is very even.Carbon cladding titanium dioxide is assembled in lithium ion experimental cell, and using lithium sheet as to electrode, its chemical property is as shown in Fig. 3 (c).Under 0.2C condition, the specific discharge capacity of circulation reaches 572.1mAh g first
-1, and cycle performance is relatively stable.
embodiment 4
Be that 1:1.5 takes respectively titanium sulfate and glucose according to the mass ratio of titanium sulfate and glucose, be dissolved in respectively in deionized water, after being uniformly mixed, D/W is joined in titanium sulfate aqueous solution, move into hydrothermal reaction kettle, 200 DEG C of insulations 2 hours.After naturally cooling to room temperature, product is used to deionized water and alcohol repetitive scrubbing, filtration and is dried.Dried product is moved in process furnace, and under argon shield atmosphere, 800 DEG C are incubated carbonization 2 hours, naturally cool to room temperature.
The product that 200 DEG C of hydro-thermals are obtained for 2 hours is after dry, in air, calcine 4 hours in 600 DEG C, make the coating complete oxidation volatilization of titanium dioxide surface, the mass loss before and after calcining by measurement is known, and the ratio that the coating of titanium dioxide surface accounts for total mass is 33.1%.Fig. 4 (a) and (b) be respectively X-ray diffractogram (XRD) and the stereoscan photograph of 2 hours products of 800 DEG C of carbonizations.XRD figure shows that product is anatase titanium dioxide.Stereoscan photograph shows, the coated titanium dioxide of these carbon reaches nano level, and particle size is very even.Carbon cladding titanium dioxide is assembled in lithium ion experimental cell, and using lithium sheet as to electrode, its chemical property is as shown in Fig. 4 (c).Under 0.2C condition, the specific discharge capacity of circulation reaches 475.5mAh g first
-1, and cycle performance is relatively stable.
Claims (2)
1. the preparation method of a carbon cladding titanium dioxide nano electrode materials, it is characterized in that preparation process comprises the following steps: (1) selects titanium sulfate as titanium source, glucose or sucrose are as carbon source, take titanium sulfate and carbon source according to certain mass ratio, then under agitation condition, titanium sulfate and carbon source are dissolved in respectively in deionized water; (2) the carbon source aqueous solution is joined in titanium sulfate aqueous solution, after stirring, move into hydrothermal reaction kettle, at 140-200 DEG C of heating and thermal insulation 3-6 hour, naturally cool to subsequently room temperature; (3) hydro-thermal reaction product is used to alcohol and deionized water repetitive scrubbing, filtration dry, then dried product is moved in high temperature sintering furnace, in argon gas atmosphere, in 600-800 DEG C of sintering 2-4 hour, naturally cool to subsequently room temperature.
2. the preparation method of a kind of carbon cladding titanium dioxide nano electrode materials as claimed in claim 1, is characterized in that: described titanium sulfate and the mass ratio of carbon source are 1:0.2-1:1.5.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104282887A (en) * | 2014-10-14 | 2015-01-14 | 江苏华东锂电技术研究院有限公司 | Carbon coating method for electrode active material of lithium ion battery |
| CN104616910A (en) * | 2015-01-09 | 2015-05-13 | 东南大学 | Carbon-coating titanium based nano array material and preparation method and application thereof |
| CN106902818A (en) * | 2017-01-19 | 2017-06-30 | 湖北大学 | TiO2The preparation method of C load Ru novel composite catalysts and its application in catalysis benzoic acid hydrogenation reaction |
| CN108899549A (en) * | 2018-07-14 | 2018-11-27 | 西南大学 | Carbon coating TiO in situ2(B) preparation method and application of negative electrode material |
| CN109509882A (en) * | 2018-07-25 | 2019-03-22 | 国网新疆电力有限公司电力科学研究院 | High-multiplying-power battery nano bar-shape titanium dioxide cathode material and preparation method thereof |
| CN109626421A (en) * | 2018-12-06 | 2019-04-16 | 浙江离火新材料科技有限公司 | The preparation method for the titanium dioxide nanoparticle that organic film coats completely |
| CN110803712A (en) * | 2019-07-09 | 2020-02-18 | 华东理工大学 | Preparation method and application of ovoid carbon-coated single-crystal titanium dioxide microspheres |
| CN111943259A (en) * | 2020-08-24 | 2020-11-17 | 合肥工业大学 | Carbon-coated mesoporous dual-phase titanium dioxide and preparation method and energy storage application thereof |
| CN112705183A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst for preparing diphenyl carbonate and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102769123A (en) * | 2011-05-03 | 2012-11-07 | 北京化工大学 | Preparation method of titanium dioxide/carbon composite lithium battery electrode material |
-
2014
- 2014-05-05 CN CN201410185902.7A patent/CN103964499A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102769123A (en) * | 2011-05-03 | 2012-11-07 | 北京化工大学 | Preparation method of titanium dioxide/carbon composite lithium battery electrode material |
Non-Patent Citations (4)
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104282887A (en) * | 2014-10-14 | 2015-01-14 | 江苏华东锂电技术研究院有限公司 | Carbon coating method for electrode active material of lithium ion battery |
| CN104616910A (en) * | 2015-01-09 | 2015-05-13 | 东南大学 | Carbon-coating titanium based nano array material and preparation method and application thereof |
| CN106902818A (en) * | 2017-01-19 | 2017-06-30 | 湖北大学 | TiO2The preparation method of C load Ru novel composite catalysts and its application in catalysis benzoic acid hydrogenation reaction |
| CN106902818B (en) * | 2017-01-19 | 2019-12-03 | 湖北大学 | The preparation method and its application in catalysis benzoic acid hydrogenation reaction that TiO2-C loads Ru composite catalyst |
| CN108899549A (en) * | 2018-07-14 | 2018-11-27 | 西南大学 | Carbon coating TiO in situ2(B) preparation method and application of negative electrode material |
| CN109509882A (en) * | 2018-07-25 | 2019-03-22 | 国网新疆电力有限公司电力科学研究院 | High-multiplying-power battery nano bar-shape titanium dioxide cathode material and preparation method thereof |
| CN109626421A (en) * | 2018-12-06 | 2019-04-16 | 浙江离火新材料科技有限公司 | The preparation method for the titanium dioxide nanoparticle that organic film coats completely |
| CN110803712A (en) * | 2019-07-09 | 2020-02-18 | 华东理工大学 | Preparation method and application of ovoid carbon-coated single-crystal titanium dioxide microspheres |
| CN112705183A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst for preparing diphenyl carbonate and preparation method and application thereof |
| CN111943259A (en) * | 2020-08-24 | 2020-11-17 | 合肥工业大学 | Carbon-coated mesoporous dual-phase titanium dioxide and preparation method and energy storage application thereof |
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Application publication date: 20140806 |