CN102157732A - Titanium dioxide/carbon composite nanotube and preparation and application thereof - Google Patents
Titanium dioxide/carbon composite nanotube and preparation and application thereof Download PDFInfo
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- CN102157732A CN102157732A CN2011100718278A CN201110071827A CN102157732A CN 102157732 A CN102157732 A CN 102157732A CN 2011100718278 A CN2011100718278 A CN 2011100718278A CN 201110071827 A CN201110071827 A CN 201110071827A CN 102157732 A CN102157732 A CN 102157732A
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Abstract
The invention relates to a titanium dioxide/carbon composite nanotube and preparation thereof as well as application of the titanium dioxide/carbon composite nanotube as a cathode material of a lithium ion battery, belonging to the field of chemical power sources. The titanium dioxide/carbon composite nanotube is in a tubular structure and formed by compositing anatase-phase titanium dioxide and carbon. The composite nanotube product disclosed by the invention has a uniform shape, a good tubular structure, high specific surface area and good dispersity. The preparation method has the advantages of simpleness, easiness of operation, low reaction temperature, low energy consumption, low cost and easiness of obtaining raw materials, no pollution, high productivity and easiness of realizing large-scale production; the obtained composite nanotube product as the cathode material of the lithium ion battery has good cycle stability and high-rate performance; in addition, the titanium dioxide/carbon composite nanotube is expected to be used in the fields of supercapacitors, dye sensitized solar cells, pollutant adsorption, and the like.
Description
Technical field
The invention belongs to field of chemical power source, particularly a kind of titanium dioxide/carbon composite nano pipe and preparation thereof and as the application of lithium ion battery negative material.
Background technology
At present, the lithium ion battery negative material of commercial usefulness is a material with carbon element, and there is certain shortcoming in it, such as, Li dendrite takes place and separates out, thereby cause safety problem near the current potential of lithium metal in the current potential of carbon easily in charge and discharge process.Anatase phase titanium dioxide has remarkable advantages as lithium ion battery negative material: change in volume is very little in charge and discharge process, good cycle, and at 1.7V(vs, Li
+/ Li) locate to occur platform, to compare with the material with carbon element of commodity, titanium dioxide has better security performance.But the conductivity of titanium dioxide is relatively poor, has influenced the high rate capability of material, has restricted its application.At present, the method for the high rate capability of raising titanium dioxide has the preparation nano-sized materials to shorten lithium ion diffusion length, the equal approach of bulk phase-doped, surperficial coated with conductive.
Titanate radical nanopipe is since 1998 report, people have adopted several different methods to attempt having prepared this tubular structure material, and its performance has been carried out deep research.Discover, the titanate radical nanopipe poor heat stability, when calcining heat was higher than 300 ℃, its crystal structure transition was an anatase, its tubulose pattern is destroyed simultaneously, becomes particle or corynebacterium structure.And,, improve its conductivity simultaneously at its coated with carbon if can prepare anatase phase titanium dioxide with tubular structure, will be expected to obtain to possess the lithium cell cathode material of good high rate performance.
Summary of the invention
The object of the present invention is to provide a kind of titanium dioxide/carbon composite nano pipe, the relatively poor defective of conductivity of titanium dioxide when overcoming as lithium ion battery negative material.
The technical solution used in the present invention is as follows:
A kind of titanium dioxide/carbon composite nano pipe, described composite nano tube are tubular structure, are made of anatase phase titanium dioxide and carbon.
Described composite nano tube bore is 3-10nm.
The mass content of carbon preferably is controlled to be 1-10% in the described composite nano tube.Carbon content in the product can be regulated by the amount of regulating the carbon containing organic compound, preferably is controlled at 1-10% when using in lithium ion battery negative material.If when other different applications are used, can carry out the adjustment of carbon content accordingly.
The present invention also further provides the preparation method of a kind of described titanium dioxide/carbon composite nano pipe: titanate radical nanopipe is mixed fully reaction with the solution of dissolved organic matter, drying, grinding afterwards evenly, in inert atmosphere, calcine, promptly get described titanium dioxide/carbon composite nano pipe.
Described dissolved organic matter is glucose, sucrose, soluble starch, fructose, tartaric acid, citric acid, benzoic acid or melamine.Be that described dissolved organic matter can be selected solubility carbon containing organic compound, also can be and contain other heteroatomic carbon containing organic compounds.The solvent of the solution of dissolved organic matter is water or ethanol.
Used carbon source solubility carbon containing organic compound, with it in the water-soluble or ethanol equal solvent time, realize mixing of carbon containing solution of organic compound and titanate radical nanopipe, to be the carbon containing solution of organic compound mix the back with titanate radical nanopipe to the amount of general solubilizer that to become muddy be the best.
Described titanate radical nanopipe is after sodium titanate nanotubes soaks in strong acid and washs to pH is the titanate radical nanopipe of 4-9.
Baking temperature is a room temperature to 200 ℃, is not less than 30min drying time, generally is no more than 2d.
Calcining heat is 300-500 ℃, and the time is 1-6h.
Adopt cheap carbon source among the present invention, it is dissolved in the suitable solvent forms homogeneous solution, then titanate radical nanopipe is placed solution, mix, and drying composite, in inert atmosphere, calcine afterwards, get final product titanium dioxide/carbon composite nano pipe.
Described composite nano tube has good tubular-shaped structures, high specific area, and size is even, good dispersion.
Described titanium dioxide/carbon composite nano pipe has good application as lithium ion battery negative material, has excellent chemical property.
Because the tubular structure material that obtained is made of anatase titania and carbon simultaneously, so material has the character of titanium dioxide and carbon simultaneously, therefore also can be used for fields such as ultracapacitor, sensitization solar battery, organic pollution adsorbent.
The present invention has following advantage with respect to prior art:
Composite nano tube product pattern of the present invention is even, has good tubular-shaped structures, high specific area, good dispersion.The preparation method is simple, and reaction temperature is low, and energy consumption is low, and raw material is cheap and easy to get, and is pollution-free, and the productive rate height is accomplished scale production easily; The product that obtains has improved conductivity, charge-discharge performance, cycle performance, the high rate performance of titania nanotube lithium ion battery negative material.
Description of drawings
The XRD figure of the blank sample anatase titania nanotube that Fig. 1 obtains at 400 ℃ of calcinings of inert atmosphere 4h for embodiment 1,2,3,4 and titanate radical nanopipe;
Fig. 2 is the XRD figure of embodiment 2,5,6;
Fig. 3 is the HRTEM figure of embodiment 2;
Fig. 4 is the HRTEM figure of embodiment 5;
Fig. 5 is the HRTEM figure of embodiment 6;
Fig. 6 is embodiment 1,2,3,4 and inert atmosphere 400
oThe high rate performance figure of blank sample anatase titania nanotube under different multiplying that C calcining 4h obtains;
Fig. 7 is embodiment 1,2,3,4 and inert atmosphere 400
oThe cycle performance figure of blank sample anatase titania nanotube under 5C that C calcining 4h obtains;
Fig. 8 is the high rate performance figure of embodiment 2,5,6 under different multiplying;
Fig. 9 is an inert atmosphere 400
oBlank sample anatase titania nanotube preceding 5 charging and discharging curve figure under 0.2C that C calcining 4h obtains;
Figure 10 is embodiment 2 preceding 5 charging and discharging curve figure under 0.2C.
Embodiment
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment 1
With glucose is carbon source, and glucose is dissolved in an amount of distilled water, according to C: TiO
2It is even that=2: 98 mass ratio adds a certain amount of titanate radical nanopipe mixed grinding, becomes muddy, and 60 ℃ of dry 5h grind evenly again, and mixture is warming up to 400 ℃ and calcines, reaction time 4h in inert atmosphere.Promptly get titanium dioxide/carbon composite nano pipe.
As carbon source, glucose is dissolved in an amount of distilled water with glucose, is (C: TiO according to Cwt%=5%
2=5: 95) a certain amount of titanate radical nanopipe mixed grinding of adding is even, becomes muddy, and 60 ℃ of dry 8h grind evenly again, and mixture is warming up to 400 ℃ and calcines, reaction time 4h in inert atmosphere.Promptly get titanium dioxide/carbon composite nano pipe.
Embodiment 3
As carbon source, glucose is dissolved in an amount of distilled water with glucose, is (C: TiO according to Cwt%=7.5%
2=7.5: 92.5) a certain amount of titanate radical nanopipe mixed grinding of adding is even, becomes muddy, and 60 ℃ of dry 10h grind evenly again, and mixture is warming up to 400 ℃ and calcines, reaction time 4h in inert atmosphere.Promptly get titanium dioxide/carbon composite nano pipe.
As carbon source, glucose is dissolved in an amount of distilled water with glucose, is (C: TiO according to Cwt%=10%
2=10: 90) a certain amount of titanate radical nanopipe mixed grinding of adding is even, becomes muddy, and 120 ℃ of dry 5h grind evenly again, and mixture is warming up to 400 ℃ and calcines, reaction time 4h in inert atmosphere.Promptly get titanium dioxide/carbon composite nano pipe.
As carbon source, glucose is dissolved in an amount of distilled water with glucose, is (C: TiO according to Cwt%=5%
2=5: 95) a certain amount of titanate radical nanopipe mixed grinding of adding is even, becomes muddy, and 120 ℃ of dry 6h grind evenly again, and mixture is warming up to 300 ℃ and calcines, reaction time 4h in inert atmosphere.Promptly get titanium dioxide/carbon composite nano pipe.
As carbon source, glucose is dissolved in an amount of distilled water with glucose, is (C: TiO according to Cwt%=5%
2=5: 95) a certain amount of titanate radical nanopipe mixed grinding of adding is even, becomes muddy, and 120 ℃ of dry 7h grind evenly again, and mixture is warming up to 500 ℃ and calcines, reaction time 4h in inert atmosphere.Promptly get titanium dioxide/carbon composite nano pipe.
Prepared material is carried out chemical property---the constant current charge-discharge test:
Carry out the composition of the test battery electrode diaphragm of electro-chemical test: anodal diaphragm is anatase titania nanotube or titanium dioxide/carbon composite nano pipe as active material (when the laboratory tests, be to be assembled into half-cell), active material: conductive agent acetylene black: the mass ratio of binding agent Kynoar (PVDF)=80: 10: 10.After grinding half an hour, add an amount of N-methyl pyrrolidone (NMP) and become muddy, behind the magnetic agitation 12h, be coated on the Copper Foil in the closed container, 120 ℃ are dried by the fire general 6h then, make the disk of diameter 15mm.
The simulated battery process of assembling test: packaged battery carries out in the argon atmospher glove box, and lithium metal is made negative pole, and electrolyte adopts 1mol/L LiPF
6EC: DMC (1:1) mixed liquor, barrier film adopt Celgard 2400.Specific discharge capacity under 0.2C, 0.5C, 1C, 2C, 5C different multiplying can find out that by comparing titanium dioxide/carbon composite nano pipe is than blank sample TiO as can be seen from Figure 6
2The performance of nanotube is all good, and the performance of the titanium dioxide in the time of 400 ℃/carbon composite nano pipe (5%) is best.Blank sample TiO
2Nanotube, with the increase of multiplying power, the specific capacity decay is serious, and after 0.2C discharged and recharged 5 times, specific discharge capacity was 178.2mAh/g, and after 5C discharged and recharged 5 times, specific discharge capacity was 58.1mAh/g; Titanium dioxide/carbon composite nano pipe (5%), after 0.2C discharged and recharged 5 times, specific discharge capacity was 220.3mAh/g, after 5C discharged and recharged 5 times, specific discharge capacity was 144.3mAh/g.Under 5C, the cyclicity of the titanium dioxide in the time of 400 ℃/carbon composite nano pipe (5%) is also fine as can be seen from Figure 7.Titanium dioxide under the 5C/carbon composite nano pipe (5%), 50 times circulation back specific capacity still remains on 146.6mAh/g, and blank sample TiO
2Nanotube, specific capacity are then at 60mAh/g.
Claims (10)
1. titanium dioxide/carbon composite nano pipe is characterized in that, described composite nano tube is a tubular structure, is made of anatase phase titanium dioxide and carbon.
2. titanium dioxide as claimed in claim 1/carbon composite nano pipe is characterized in that, described composite nano tube bore is 3-10nm.
3. titanium dioxide as claimed in claim 1/carbon composite nano pipe is characterized in that, the mass content of carbon is 1-10% in the described composite nano tube.
4. as the described titanium dioxide of one of claim 1-3/carbon composite nano pipe, it is characterized in that, obtain by laxative remedy: titanate radical nanopipe is mixed fully reaction with the solution of dissolved organic matter, drying, grinding afterwards evenly, in inert atmosphere, calcine, promptly get described titanium dioxide/carbon composite nano pipe.
5. the preparation method of the described titanium dioxide of claim 1/carbon composite nano pipe, it is characterized in that, titanate radical nanopipe is mixed fully reaction with the solution of dissolved organic matter, drying, grinding afterwards evenly, in inert atmosphere, calcine, promptly get described titanium dioxide/carbon composite nano pipe.
6. the preparation method of titanium dioxide as claimed in claim 5/carbon composite nano pipe is characterized in that, the mass content of carbon is 1-10% in the described composite nano tube.
7. the preparation method of titanium dioxide as claimed in claim 6/carbon composite nano pipe is characterized in that, calcining heat is 300-500 ℃, and the time is 1-6h.
8. the preparation method of titanium dioxide as claimed in claim 6/carbon composite nano pipe is characterized in that, described dissolved organic matter is glucose, sucrose, soluble starch, fructose, tartaric acid, citric acid, benzoic acid or melamine; The solvent of the solution of dissolved organic matter is water or ethanol.
9. the preparation method of titanium dioxide as claimed in claim 6/carbon composite nano pipe is characterized in that, baking temperature is a room temperature to 200 ℃, is not less than 30min drying time.
10. the described titanium dioxide of claim 1/carbon composite nano pipe is as the application of lithium ion battery negative material.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105047860A (en) * | 2014-12-19 | 2015-11-11 | 上海杉杉科技有限公司 | Battery cathode TiO2/intermediate-phase microsphere composite material and preparation method thereof |
| CN105036072A (en) * | 2015-05-22 | 2015-11-11 | 武汉理工大学 | Method for improving conductivity of modified titanium dioxide nanotube |
| CN105406042A (en) * | 2015-11-16 | 2016-03-16 | 中国海洋大学 | Preparation method for carbon-coated super-long titanium dioxide nanotube negative electrode material of lithium ion battery |
| CN106311285A (en) * | 2015-07-01 | 2017-01-11 | 中国石化扬子石油化工有限公司 | SO42-/TiO2-C nanotube, and preparation method and application thereof |
| CN106340625A (en) * | 2016-09-29 | 2017-01-18 | 湘潭大学 | Preparation method of titanous self-doped titanium dioxide/carbon composite cathode material |
| CN106552617A (en) * | 2015-09-28 | 2017-04-05 | 中国石化扬子石油化工有限公司 | A kind of Pd/TiO2- C nano pipe catalyst and preparation method thereof |
| CN112694121A (en) * | 2020-12-30 | 2021-04-23 | 程承 | Porous carbon microsphere in-situ composite nano TiO2Preparation method and application of |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101071853A (en) * | 2007-06-01 | 2007-11-14 | 河南大学 | Nano lithium titanate for Negative electrode material of cell or electrochemical vessel, and its and titanium dioxide composite preparing method |
| CN101302036A (en) * | 2008-07-03 | 2008-11-12 | 南开大学 | Preparation of doped titanium dioxide nano-tube |
-
2011
- 2011-03-24 CN CN2011100718278A patent/CN102157732A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101071853A (en) * | 2007-06-01 | 2007-11-14 | 河南大学 | Nano lithium titanate for Negative electrode material of cell or electrochemical vessel, and its and titanium dioxide composite preparing method |
| CN101302036A (en) * | 2008-07-03 | 2008-11-12 | 南开大学 | Preparation of doped titanium dioxide nano-tube |
Non-Patent Citations (2)
| Title |
|---|
| SANG-JUN PARK，ET AL.: "Synthesis of carbon-coated TiO2 nanotubes for high-power lithium-ion batteries", 《JOURNAL OF POWER SOURCES》 * |
| 沈晶晶等: "介孔TiO2的水热法制备及其光催化性能", 《物理化学学报》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105047860A (en) * | 2014-12-19 | 2015-11-11 | 上海杉杉科技有限公司 | Battery cathode TiO2/intermediate-phase microsphere composite material and preparation method thereof |
| CN105047860B (en) * | 2014-12-19 | 2019-08-06 | 上海杉杉科技有限公司 | Battery cathode titanium dioxide carbonaceous mesophase spherules composite material and preparation method |
| CN105036072A (en) * | 2015-05-22 | 2015-11-11 | 武汉理工大学 | Method for improving conductivity of modified titanium dioxide nanotube |
| CN105036072B (en) * | 2015-05-22 | 2017-03-22 | 武汉理工大学 | Method for improving conductivity of modified titanium dioxide nanotube |
| CN106311285A (en) * | 2015-07-01 | 2017-01-11 | 中国石化扬子石油化工有限公司 | SO42-/TiO2-C nanotube, and preparation method and application thereof |
| CN106311285B (en) * | 2015-07-01 | 2019-06-25 | 中国石化扬子石油化工有限公司 | A kind of SO42-/TiO2-C nano pipe, preparation method and applications |
| CN106552617A (en) * | 2015-09-28 | 2017-04-05 | 中国石化扬子石油化工有限公司 | A kind of Pd/TiO2- C nano pipe catalyst and preparation method thereof |
| CN106552617B (en) * | 2015-09-28 | 2019-09-06 | 中国石化扬子石油化工有限公司 | A kind of Pd/TiO2C nano pipe catalyst and preparation method thereof |
| CN105406042A (en) * | 2015-11-16 | 2016-03-16 | 中国海洋大学 | Preparation method for carbon-coated super-long titanium dioxide nanotube negative electrode material of lithium ion battery |
| CN106340625A (en) * | 2016-09-29 | 2017-01-18 | 湘潭大学 | Preparation method of titanous self-doped titanium dioxide/carbon composite cathode material |
| CN112694121A (en) * | 2020-12-30 | 2021-04-23 | 程承 | Porous carbon microsphere in-situ composite nano TiO2Preparation method and application of |
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Application publication date: 20110817 |