CN101704504B - In-situ synthesis method for nano tin dioxide/carbon nano tube composite material - Google Patents
In-situ synthesis method for nano tin dioxide/carbon nano tube composite material Download PDFInfo
- Publication number
- CN101704504B CN101704504B CN2009101547185A CN200910154718A CN101704504B CN 101704504 B CN101704504 B CN 101704504B CN 2009101547185 A CN2009101547185 A CN 2009101547185A CN 200910154718 A CN200910154718 A CN 200910154718A CN 101704504 B CN101704504 B CN 101704504B
- Authority
- CN
- China
- Prior art keywords
- carbon nano
- cnt
- composite material
- nano tube
- tin dioxide
- 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.)
- Expired - Fee Related
Links
Images
Abstract
The invention discloses an in-situ synthesis method for a nano tin dioxide/carbon nano tube composite material, which mainly uses an inorganic tin salt, a carbon nano tube and an alkali source as raw materials. The experimental process mainly comprises the steps of precursor preparation, hydrothermal reaction, precipitate washing and drying and the like. The in-situ synthesis method for the nano tin dioxide/carbon nano tube composite material has the advantages that: a hydrothermal method is adopted to realize the in-situ deposition and the growth of the nano tin dioxide on the surface of the carbon nano tube; the obtained SnO2 nano particles have small and uniform particle size (less than 10nm), are well-crystallized, are uniformly coated on the surface of the carbon nano tube, and are tightly combined with the carbon nano tube; the composite material has potential application prospect in the aspects of a gas sensor material, an anode material of a lithium ion battery and the like. The method has no addition of any surface active agent, has simple and easily-obtained materials, simple process without pollution, short preparation period, mild reaction condition and low cost, and is suitable for large-scale production, so the method is an environment-friendly synthesis method.
Description
Technical field
The present invention relates to a kind of preparation method of nano composite material, especially relate to a kind of method of original position synthesis of nano tin dioxide/carbon nano tube composite material.
Background technology
Existing tin oxide (SnO
2) have natural non-stoichiometry and stable cubic phase rutile structure, because of its good air-sensitive performance has obtained to use widely in gas sensor.SnO
2The air-sensitive response of gas sensitive is a very complex surfaces reaction that on solid gas interface, takes place; The first step that produces the air-sensitive response is the diffusion of object gas and in the absorption on gas sensitive surface, and therefore unobstructed gas diffusion paths, huge specific area and abundant surface-active position are the keys that obtains good air-sensitive performance.In order to improve SnO
2The air-sensitive performance of gas sensitive adopts means such as nanometerization, doping, finishing, wherein nano SnO more
2Gas sensitive and traditional SnO
2Gas sensitive phase specific sensitivity significantly improves, and operating temperature reduces, and has very big advantage in the air-sensitive application facet.CNT has caused that with excellent performance people study interest greatly owing to have particular structure, and the hollow structure of its nanoscale and high-specific surface area are that gas reaction provides a large amount of activity sites, are diffusion, absorption and the nano SnO of gas
2In its surperficial coating advantageous conditions is provided.It is found that SnO recently
2/ carbon nano tube compound material is to NO
2, NH
3, LPG, ethanol etc. show good air-sensitive performance, are expected to the gas sensitive as the high-performance gas sensor.
Have multiple technologies at present both at home and abroad with SnO
2Be deposited on the CNT to obtain the composite of increased functionality: people such as the U.S. Chen of University of Central Florida have realized SnO through sol-gel process
2The preparation of/SWCN composite is based on the sensor and the pure SnO of this composite
2The sensitivity that sensor compares the hydrogen detection has improved three one magnitude (Jianwei Gong, Jianren Sun, Quanfang Chen, Sensors and Actuators B 130 (2008) 829-835); The Xie of Pennsylvania State Univ-Univ Park USA and partner thereof utilize the method for even co-precipitation to prepare SnO
2/ carbon nano tube compound material (Xie J N and Varadan V K, Mater.Chem.Phys.91 (2005) 274-280); The Zettl group in California, USA university Berkeley branch school has reported a kind of preparation SnO
2Chemical treatment under the chemical solution method of/carbon nanotube composite materials, room temperature has realized the SnO of particle diameter less than 6nm
2Nano particle is in the coating (W.Q.Han and A.Zettl, Nano Lett.3 (2003) 681-683) of carbon nano tube surface.The million male groups of thanking of domestic Xiamen University utilize chemical gaseous phase depositing process on multi-walled carbon nano-tubes, to deposit the SnO of controllable size
2Nano particle (Qin Kuang, Song-Fei Li, Zhao-Xiong Xie, et al., Carbon 44 (2006) 1166-1172); High Lian group of Shanghai silicate institute of the Chinese Academy of Sciences utilizes the vapor phase method to realize nano SnO
2Parcel fully (Chinese patent CN 1810650A (publication number)) to CNT; King Tai Hong group of physics institute of the Chinese Academy of Sciences utilizes the method for Zettl to prepare SnO
2The multi-walled carbon nano-tubes that coats, the sensor of producing thus highly sensitive, and have the SnO of ratio
2The resistance (Liang YX, Chen YJ, Wang TH, Appl Phys Lett 85 (2004) 666-668) that nano belt is much lower; The Chen Yujin of Harbin Engineering University also utilizes the method for Zettl to prepare SnO
2/ carbon nano tube compound material, this composite shows outstanding chemical property, can be used as the anode material (Yu-Jin Chen, Chun-Ling Zhu, Xin-Yu Xue, et al., Appl Phys Lett 92 (2008) 223101) of lithium ion battery.
Above-mentioned nano SnO
2The preparation method of/carbon nano tube compound material respectively has pluses and minuses:
1), sol-gel process and sluggish precipitation be simple to operation, but the high-temperature heat treatment in the preparation process (crystallization process) is prone to cause nano SnO
2Growth and hard aggregation, the nano SnO that obtains
2Particle diameter is big (20-100nm);
2), the chemical solution method technology of Zettl is simple, but makes SnO in the preparation process of room temperature
2Crystallization degree lower and with CNT combine a little less than;
3), the film performance of chemical gaseous phase depositing process preparation is good, but equipment needed thereby is complicated, the preparation condition harshness, reaction temperature is very high, cost is higher.
4), the vapor phase method reacts in specific vapor phase agitated reactor, solid-liquid two does not contact mutually in the course of reaction, carry out mass transfer and heat transfer through steam, thereby reaction temperature is lower, gained SnO
2The nano particle crystallization degree is relatively poor.
Summary of the invention
Technical problem to be solved by this invention provides the method for the original position synthesis of nano tin dioxide/carbon nano tube composite material that a kind of technology is simple, reaction condition is gentle, gained SnO
2Nano particle diameter is little and even, and the well-crystallized combines closely with CNT.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of method of original position synthesis of nano tin dioxide/carbon nano tube composite material, and concrete steps are followed successively by:
Step 1 is carried out acidification with CNT, obtains the CNT that the surface has carboxyl or hydroxyl surface functional group behind the washing and drying, and described acid is at least a in red fuming nitric acid (RFNA), the concentrated sulfuric acid;
Step 2 is dissolved into pink salt in deionized water or the absolute ethyl alcohol, is the tin-salt solution of 0.2 ~ 1mol/L through stirring formation Sn ion concentration; Mass ratio (1: 100 ~ 10: 100) according to CNT and pink salt; The CNT that acidification is crossed joins in the mixed solution of deionized water, absolute ethyl alcohol or deionized water and absolute ethyl alcohol; Ultrasonic dispersion 10 ~ 30min forms the suspension of CNT, and described pink salt is a kind of in stannous chloride, stannic chloride or the nitric acid tin;
Step 3 joins the suspension of the CNT of step 2 preparation in the tin-salt solution, continues to stir 10 ~ 40min then, and ultrasonic again 10 ~ 50min forms mixed solution;
Step 4; The alkali source drips of solution is added in the mixed solution of step 3 gained; Until the pH value between 9 ~ 13; And then stir 10 ~ 60min, and forming precursor solution, described alkali source solution is that the aqueous solution or the mass concentration of the potassium hydroxide that concentration is the aqueous solution of the urea of 0.4 ~ 1mol/L, the aqueous solution that concentration is the NaOH of 0.4 ~ 1mol/L, concentration is 0.4 ~ 1mol/L is a kind of in 1 ~ 8% the ammoniacal liquor;
Step 5 is transferred to the precursor solution of step 4 gained in the autoclave, at 100 ~ 200 ℃ of following hydro-thermal reaction 4 ~ 24h, naturally cools to room temperature then, after the filtering supernatant, obtains sediment;
Step 6; Adopt the method for centrifugation or filtration to wash repeatedly with deionized water and absolute ethyl alcohol successively the sediment of step 5 gained; To remove the ion of solubility wherein, the sediment after will washing then obtains nano tin dioxide/carbon nano tube composite material 60 ~ 100 ℃ of oven dry.
Described acidization is at 80 ~ 150 ℃ of 2 ~ 6h that reflux; Described washing is repeatedly washed for the CNT that adopts centrifugation or method of pumping filtration that acidification is crossed, and is neutral until cleaning solution; Described baking temperature is 60 ~ 100 ℃.
Described CNT is a kind of in SWCN or the multi-walled carbon nano-tubes, and the caliber of described SWCN is less than 5nm, and the caliber of described multi-walled carbon nano-tubes is 5 ~ 60nm.
The mass fraction of described red fuming nitric acid (RFNA) is 65 ~ 68%, and the mass fraction of the concentrated sulfuric acid is 95 ~ 98%.
Described stirring is a magnetic agitation, and the stirring intensity when dripping alkali source solution is bigger than other processes.
Hydro-thermal reaction in the step 5 is in thermal and hydric environment, realizes the coating of tin oxide nano particle to CNT through the tin oxide nano particle in the mode of the surface in situ growth of CNT.
Gained tin oxide nano particle size is even, and particle diameter is less than 10nm, and the well-crystallized is evenly distributed in the surface of CNT, combines closely with described CNT.
Compared with prior art, the invention has the advantages that:
1), adopt hydro-thermal method original position in the airtight liquid phase environment of autoclave to synthesize nano tin dioxide/carbon nano tube composite material; Can directly generate crystal through water-heat process; Do not need follow-up high-temperature heat treatment, that has avoided crystal grain in the high-temperature heat treatment process grows up gained SnO
2Nano particle diameter little and even (less than 10nm), the well-crystallized.Through the control hydrothermal condition, can obtain the controlled SnO of particle diameter and pattern
2The composite of nano particle and CNT.
2), introduce electronegative surface functional groups such as carboxyl, hydroxyl on the surface of CNT through acidification; Utilize the electrostatic interaction between electronegative surface functional group and tin ion that the tin ion original position is adsorbed on the surface of CNT, dropping and hydro-thermal reaction through alkali source have realized SnO
2Nano particle the forming core of carbon nano tube surface with grow up gained SnO
2Nano particle is coated on the surface of CNT equably, combines closely with CNT.
3), do not add any surfactant, raw material is simple and easy to, and technology is simply pollution-free, and manufacturing cycle is short, and reaction condition is gentle, and cost is low, suitability for scale production.
Description of drawings
Fig. 1 is the process chart of method of the present invention;
Fig. 2 is the X-ray diffractogram of products therefrom in the practical implementation instance 1 of the present invention;
Fig. 3 is the transmission electron microscope photo of products therefrom in the practical implementation instance 1 of the present invention;
Fig. 4 is the high-resolution-ration transmission electric-lens photo of products therefrom in the practical implementation instance 1 of the present invention.
The specific embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Practical implementation instance 1
Step 1 at 120 ℃ of reflow treatment 5h, spends deionised water repeatedly with the effective red fuming nitric acid (RFNA) of multi-wall carbon nano-tube then, until the pH=7 of cleaning solution, obtains the multi-walled carbon nano-tubes of functionalisation of surfaces again 60 ℃ of oven dry;
Step 2 is with the SnCi of 1.354g
2.2H
2O is dissolved in the 20ml absolute ethyl alcohol, forms Sn through stirring
2+Concentration is the stannous chloride solution of 0.3mol/L; According to the mass ratio (1: 100) of CNT and pink salt, the CNT that acidification is crossed joins ultrasonic dispersion 20min in the 20ml absolute ethyl alcohol, forms the suspension of CNT;
Step 3, the suspension of the CNT of when stirring, step 2 being prepared joins SnCl
2In the solution, continue to stir 20min then, ultrasonic again 10min forms mixed solution;
Step 4 when stirring is that the aqueous solution of the NaOH of 0.4mol/L drops in the described mixed solution of step 3 with concentration, is 10 ~ 11 until pH value, and then stirs 20min, the formation precursor solution;
Step 5 is transferred to the described precursor solution of step 4 in the autoclave, at 160 ℃ of following hydrothermal treatment consists 15h, naturally cools to room temperature then, after the filtering supernatant, obtains sediment;
Step 6 is used deionized water and absolute ethanol washing repeatedly successively with sediment, and to remove the ion of solubility wherein, the 60 ℃ of dry 3h under vacuum condition of the sediment after will washing then obtain nano tin dioxide/carbon nano tube composite material.
Practical implementation instance 2
Step 1, the mixed acid of red fuming nitric acid (RFNA) and the concentrated sulfuric acid that with the effective volume ratio of multi-wall carbon nano-tube is 1: 3 spends deionised water repeatedly then at 120 ℃ of reflow treatment 5h, is neutral until cleaning solution, obtains the multi-walled carbon nano-tubes of functionalisation of surfaces again 60 ℃ of oven dry.
Step 2 is with the SnCl of 1.354g
2.2H
2O is dissolved in the 20ml absolute ethyl alcohol, forms Sn through stirring
2+Concentration is the stannous chloride solution of 0.3mol/L; According to the weight ratio (1: 100) of CNT and pink salt, the CNT that acidification is crossed joins ultrasonic dispersion 20min in the 20ml absolute ethyl alcohol, forms the suspension of CNT;
Step 3, the suspension of the CNT of when stirring, step 2 being prepared joins SnCl
2In the solution, continue to stir 20min then, ultrasonic again 10min forms mixed solution;
Step 4 when stirring is that the aqueous solution of the NaOH of 0.6mol/L drops in the described mixed solution of step 3 with concentration, is 12 until pH value, and then stirs 40min, the formation precursor solution;
Step 5 is transferred to the described precursor solution of step 4 in the autoclave, at 160 ℃ of following hydrothermal treatment consists 15h, naturally cools to room temperature then, after the filtering supernatant, obtains sediment;
Step 6 is used deionized water and absolute ethanol washing repeatedly successively with sediment, and to remove the ion of solubility wherein, the 60 ℃ of dry 3h under vacuum condition of the sediment after will washing then obtain nano tin dioxide/carbon nano tube composite material.
Practical implementation instance 3
Step 1 at 120 ℃ of reflow treatment 5h, spends deionised water repeatedly with the effective red fuming nitric acid (RFNA) of multi-wall carbon nano-tube then, is 7 until the pH of cleaning solution value, obtains the multi-walled carbon nano-tubes of functionalisation of surfaces again 60 ℃ of oven dry.
Step 2 is with the SnCl of 1.354g
2.2H
2O is dissolved in the 20ml absolute ethyl alcohol, forms Sn through stirring
2+Concentration is the stannous chloride solution of 0.3mol/L; According to the weight ratio (5: 100) of CNT and pink salt, the CNT that acidification is crossed joins ultrasonic dispersion 20min in the 20ml absolute ethyl alcohol, forms the suspension of CNT;
Step 3, the suspension of the CNT of when stirring, step 2 being prepared joins SnCl
2In the solution, continue to stir 20min then, ultrasonic again 10min forms mixed solution;
Step 4 when stirring is that 7% ammoniacal liquor drops in the described mixed solution of step 3 with mass concentration, is 12 until pH value, and then stirs 40min, the formation precursor solution;
Step 5 is transferred to the described precursor solution of step 4 in the autoclave, at 180 ℃ of following hydrothermal treatment consists 12h, naturally cools to room temperature then, after the filtering supernatant, obtains sediment;
Step 6 is used deionized water and absolute ethanol washing repeatedly successively with sediment, and to remove the ion of solubility wherein, the 80 ℃ of dry 4h in air of the sediment after will washing then obtain nano tin dioxide/carbon nano tube composite material.
Practical implementation instance 4
Step 1, with SWCN with red fuming nitric acid (RFNA) at 120 ℃ of reflow treatment 5h, spend deionised water then repeatedly, be 7 until the pH of cleaning solution value, obtain the SWCN of functionalisation of surfaces again 60 ℃ of oven dry.
Step 2 is with the SnCl of 3.506g
4.5H
2O is dissolved in the deionized water, forms Sn through stirring
4+Concentration is the tin chloride solution of 0.3mol/L; According to the mass ratio (3: 100) of CNT and pink salt, the CNT that acidification is crossed joins ultrasonic dispersion 20min in the 20ml absolute ethyl alcohol, forms the suspension of CNT;
Step 3, the suspension of the CNT of when stirring, step 2 being prepared joins SnCl
4In the solution, continue to stir 20min then, ultrasonic again 15min forms mixed solution;
Step 4 when stirring is that the aqueous solution of the KOH of 0.5mol/L drops in the described mixed solution of step 3 with concentration, is 11 until pH value, and then stirs 40min, the formation precursor solution;
Step 5 is transferred to the described precursor solution of step 4 in the autoclave, at 180 ℃ of following hydrothermal treatment consists 12h, naturally cools to room temperature then, after the filtering supernatant, obtains sediment;
Step 6 is used deionized water and absolute ethanol washing repeatedly successively with sediment, and to remove the ion of solubility wherein, the 70 ℃ of dry 2h under vacuum condition of the sediment after will washing then obtain nano tin dioxide/carbon nano tube composite material.
A) be the X-ray diffractogram of the CNT after the acidification in the practical implementation instance 1 among Fig. 2; B among Fig. 2) for the X-ray diffractogram of gained nano tin dioxide/carbon nano tube composite material in the practical implementation instance 1, can find out b) in the SnO of the corresponding tetragonal crystal system Rutile structure of each diffraction maximum
2Phase is difficult to pick out the diffraction maximum of CNT, this mainly be since the characteristic diffraction peak of CNT by SnO
2Diffraction maximum cover or the content of CNT less; Fig. 3 can find out that the tin oxide nano particle evenly covers the surface of CNT dispersedly, tin oxide nano particle diameter little and even (being about 5nm) for the transmission electron microscope photo of gained nano tin dioxide/carbon nano tube composite material in the practical implementation instance 1; Fig. 4 can find out that for the high-resolution-ration transmission electric-lens photo of gained nano tin dioxide/carbon nano tube composite material in the practical implementation instance 1 tin oxide nano particle crystal grain is complete, and lattice fringe and crystal grain edge clear show that the tin oxide nano particle crystallization is good.
More than be the description of this invention and non-limiting, based on other embodiment of inventive concept, all among protection scope of the present invention.
Claims (7)
1. the method for an original position synthesis of nano tin dioxide/carbon nano tube composite material is characterized in that concrete steps are followed successively by:
Step 1 is carried out acidification with CNT, obtains the CNT that the surface has carboxyl or hydroxyl surface functional group behind the washing and drying, and described acid is at least a in red fuming nitric acid (RFNA), the concentrated sulfuric acid;
Step 2 is dissolved into pink salt in deionized water or the absolute ethyl alcohol, is the tin-salt solution of 0.2～1mol/L through stirring formation Sn ion concentration; According to the mass ratio of CNT and pink salt 1: 100～10: 100; The CNT that acidification is crossed joins in the mixed solution of deionized water, absolute ethyl alcohol or deionized water and absolute ethyl alcohol; Ultrasonic dispersion 10～30min forms the suspension of CNT, and described pink salt is a kind of in stannous chloride, stannic chloride or the nitric acid tin;
Step 3 joins the suspension of the CNT of step 2 preparation in the tin-salt solution, continues to stir 10～40min then, and ultrasonic again 10～50min forms mixed solution;
Step 4; The alkali source drips of solution is added in the mixed solution of step 3 gained; Until the pH value between 9～13; And then stir 10～60min, and forming precursor solution, described alkali source solution is that the aqueous solution or the mass concentration of the potassium hydroxide that concentration is the aqueous solution of the urea of 0.4～1mol/L, the aqueous solution that concentration is the NaOH of 0.4～1mol/L, concentration is 0.4～1mol/L is a kind of in 1～8% the ammoniacal liquor;
Step 5 is transferred to the precursor solution of step 4 gained in the autoclave, at 100～200 ℃ of following hydro-thermal reaction 4～24h, naturally cools to room temperature then, after the filtering supernatant, obtains sediment;
Step 6; Adopt the method for centrifugation or filtration to wash repeatedly with deionized water and absolute ethyl alcohol successively the sediment of step 5 gained; To remove the ion of solubility wherein, the sediment after will washing then obtains nano tin dioxide/carbon nano tube composite material 60～100 ℃ of oven dry.
2. the method for a kind of original position synthesis of nano tin dioxide/carbon nano tube composite material according to claim 1 is characterized in that: described acidization is at 80～150 ℃ of 2～6h that reflux; Described washing is repeatedly washed for the CNT that adopts centrifugation or method of pumping filtration that acidification is crossed, and is neutral until cleaning solution; Described baking temperature is 60～100 ℃.
3. the method for a kind of original position synthesis of nano tin dioxide/carbon nano tube composite material according to claim 1; It is characterized in that: described CNT is a kind of in SWCN or the multi-walled carbon nano-tubes; The caliber of described SWCN is less than 5nm, and the caliber of described multi-walled carbon nano-tubes is 5～60nm.
4. the method for a kind of original position synthesis of nano tin dioxide/carbon nano tube composite material according to claim 1 is characterized in that: the mass fraction of described red fuming nitric acid (RFNA) is 65 ~ 68%, and the mass fraction of the concentrated sulfuric acid is 95 ~ 98%.
5. the method for a kind of original position synthesis of nano tin dioxide/carbon nano tube composite material according to claim 1 is characterized in that: described stirring is a magnetic agitation, and the stirring intensity when dripping alkali source solution is bigger than other processes.
6. the method for a kind of original position synthesis of nano tin dioxide/carbon nano tube composite material according to claim 1; It is characterized in that: the hydro-thermal reaction in the step 5 is in thermal and hydric environment, realizes the coating of tin oxide nano particle to CNT through the tin oxide nano particle in the mode of the surface in situ growth of CNT.
7. the method for a kind of original position synthesis of nano tin dioxide/carbon nano tube composite material according to claim 6; It is characterized in that: gained tin oxide nano particle size is even; Particle diameter is less than 10nm; The well-crystallized is evenly distributed in the surface of CNT, combines closely with described CNT.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101547185A CN101704504B (en) | 2009-12-03 | 2009-12-03 | In-situ synthesis method for nano tin dioxide/carbon nano tube composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101547185A CN101704504B (en) | 2009-12-03 | 2009-12-03 | In-situ synthesis method for nano tin dioxide/carbon nano tube composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101704504A CN101704504A (en) | 2010-05-12 |
| CN101704504B true CN101704504B (en) | 2012-08-22 |
Family
ID=42374775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101547185A Expired - Fee Related CN101704504B (en) | 2009-12-03 | 2009-12-03 | In-situ synthesis method for nano tin dioxide/carbon nano tube composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101704504B (en) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093890A (en) * | 2010-12-31 | 2011-06-15 | 中华人民共和国辽宁出入境检验检疫局 | Tin dioxide composite nanomaterial for nano cataluminescence sensor and preparation method thereof |
| CN102244235A (en) * | 2011-06-07 | 2011-11-16 | 北京航空航天大学 | Preparation method for ferric oxide coated tin dioxide nanometer polycrystalline microballoon |
| CN102718250A (en) * | 2012-07-03 | 2012-10-10 | 重庆大学 | Method for preparing carbon-material-carrying tin dioxide nanosheet composite material |
| CN103066294B (en) * | 2013-01-28 | 2015-02-04 | 福州大学 | Method for preparing lithium battery material by using plant fibers |
| CN103058173B (en) * | 2013-02-04 | 2014-08-13 | 苏州纳格光电科技有限公司 | Preparation method of nano metal oxide functionalized carbon nanotubes and gas sensor |
| CN106925318B (en) * | 2015-12-31 | 2019-09-24 | 中国石油化工股份有限公司 | One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method |
| CN105789586A (en) * | 2016-03-29 | 2016-07-20 | 陕西科技大学 | SnO2/CNTs (stannic oxide/ carbon nanotubes) composite electrode material for positive electrode of sodium ion battery |
| CN107661770B (en) * | 2016-07-27 | 2020-08-07 | 中国石油化工股份有限公司 | Nanocarbon material forming body, preparation method and application thereof, forming method of nanocarbon material and hydrocarbon dehydrogenation reaction method |
| CN107661764B (en) * | 2016-07-27 | 2020-07-28 | 中国石油化工股份有限公司 | Nanocarbon material forming body, preparation method and application thereof, forming method of nanocarbon material and hydrocarbon dehydrogenation reaction method |
| CN107661765B (en) * | 2016-07-27 | 2020-06-16 | 中国石油化工股份有限公司 | Nanocarbon material forming body, preparation method and application thereof, forming method of nanocarbon material and hydrocarbon dehydrogenation reaction method |
| CN107661759B (en) * | 2016-07-27 | 2020-07-28 | 中国石油化工股份有限公司 | Nanocarbon material forming body, preparation method and application thereof, forming method of nanocarbon material and hydrocarbon dehydrogenation reaction method |
| CN107661761B (en) * | 2016-07-27 | 2020-07-28 | 中国石油化工股份有限公司 | Nanocarbon material forming body, preparation method and application thereof, forming method of nanocarbon material and hydrocarbon dehydrogenation reaction method |
| CN107661763B (en) * | 2016-07-27 | 2020-05-19 | 中国石油化工股份有限公司 | Nanocarbon material forming body, preparation method and application thereof, forming method of nanocarbon material and hydrocarbon dehydrogenation reaction method |
| CN107661766B (en) * | 2016-07-27 | 2020-07-28 | 中国石油化工股份有限公司 | Nanocarbon material forming body, preparation method and application thereof, forming method of nanocarbon material and hydrocarbon dehydrogenation reaction method |
| CN107661762B (en) * | 2016-07-27 | 2020-07-28 | 中国石油化工股份有限公司 | Nanocarbon material forming body, preparation method and application thereof, forming method of nanocarbon material and hydrocarbon dehydrogenation reaction method |
| CN107661769B (en) * | 2016-07-27 | 2020-06-12 | 中国石油化工股份有限公司 | Nanocarbon material forming body, preparation method and application thereof, forming method of nanocarbon material and hydrocarbon dehydrogenation reaction method |
| CN107661760B (en) * | 2016-07-27 | 2020-07-28 | 中国石油化工股份有限公司 | Nanocarbon material forming body, preparation method and application thereof, forming method of nanocarbon material and hydrocarbon dehydrogenation reaction method |
| CN107661767B (en) * | 2016-07-27 | 2020-07-28 | 中国石油化工股份有限公司 | Nanocarbon material forming body, preparation method and application thereof, forming method of nanocarbon material and hydrocarbon dehydrogenation reaction method |
| CN107661768B (en) * | 2016-07-27 | 2020-07-28 | 中国石油化工股份有限公司 | Nanocarbon material forming body, preparation method and application thereof, forming method of nanocarbon material and hydrocarbon dehydrogenation reaction method |
| CN106848279B (en) * | 2017-01-13 | 2019-08-09 | 陕西科技大学 | A kind of liquid phase is from adsorbing SnO2The preparation method and application of/biology carbon composite |
| CN106953079B (en) * | 2017-03-27 | 2019-11-12 | 华中科技大学 | A kind of multilevel structure carbon nano tube/tin dioxide composite material and preparation method |
| CN109068418A (en) * | 2018-06-15 | 2018-12-21 | 盐城工学院 | A kind of SnO2Composite carbon nanometer tube Electric radiant Heating Film and preparation method thereof |
| CN110336035B (en) * | 2019-07-12 | 2021-05-11 | 广东工业大学 | Tin dioxide/aluminum oxide doped carbon composite material and preparation method thereof |
| CN111192997A (en) * | 2020-01-07 | 2020-05-22 | 北京理工大学 | Diaphragm for activated carbon-loaded tin oxide lithium-sulfur battery and preparation method and application thereof |
| CN113809305B (en) * | 2021-09-17 | 2022-12-27 | 青岛科技大学 | Preparation method and device of tin/carbon nanotube composite material |
| CN114639799A (en) * | 2022-03-28 | 2022-06-17 | 广东技术师范大学 | Composite electrode for all-solid-state metal lithium battery and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810650A (en) * | 2006-03-03 | 2006-08-02 | 中国科学院上海硅酸盐研究所 | Composite powder of nanomer tin dioxide particle in-situ coated carbon nanotube and its prepn process |
| CN1850641A (en) * | 2006-05-26 | 2006-10-25 | 上海大学 | Method for preparing carbon nano tube/tin dioxide composite electro catalytic electrode |
| KR100645308B1 (en) * | 2005-10-18 | 2006-11-14 | 한양대학교 산학협력단 | Vertical alignment of carbon nanotubes with the assistance of sonication |
| CN101439855A (en) * | 2008-12-24 | 2009-05-27 | 北京科技大学 | Microwave assisted hydrothermal process for synthesizing nano-SnO2-MWCNTs |
| CN101462045A (en) * | 2007-12-18 | 2009-06-24 | 比亚迪股份有限公司 | Composite material of stannic oxide and carbon, and preparation method thereof |
-
2009
- 2009-12-03 CN CN2009101547185A patent/CN101704504B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100645308B1 (en) * | 2005-10-18 | 2006-11-14 | 한양대학교 산학협력단 | Vertical alignment of carbon nanotubes with the assistance of sonication |
| CN1810650A (en) * | 2006-03-03 | 2006-08-02 | 中国科学院上海硅酸盐研究所 | Composite powder of nanomer tin dioxide particle in-situ coated carbon nanotube and its prepn process |
| CN1850641A (en) * | 2006-05-26 | 2006-10-25 | 上海大学 | Method for preparing carbon nano tube/tin dioxide composite electro catalytic electrode |
| CN101462045A (en) * | 2007-12-18 | 2009-06-24 | 比亚迪股份有限公司 | Composite material of stannic oxide and carbon, and preparation method thereof |
| CN101439855A (en) * | 2008-12-24 | 2009-05-27 | 北京科技大学 | Microwave assisted hydrothermal process for synthesizing nano-SnO2-MWCNTs |
Non-Patent Citations (2)
| Title |
|---|
| 易斌，等.纳米氧化锡修饰碳纳米管的研究.《稀有金属材料与工程》.2008,第37卷(第5期),883-886. * |
| 高晓红,等.碳纳米管/SnO2复合电极的制备及其电催化性能研究.《化学学报》.2007,第65卷(第7期),589-594. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101704504A (en) | 2010-05-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101704504B (en) | In-situ synthesis method for nano tin dioxide/carbon nano tube composite material | |
| CN101857222B (en) | Preparation method of large-area and continuous graphen/zinc oxide composite structure | |
| CN102154695B (en) | Nickel oxide nano rod array material, method for preparing same and application thereof | |
| CN101412505B (en) | Preparation of high-purity tin diselenide nano-plate | |
| CN105502286B (en) | A kind of porous nano NiFe2O4Preparation method | |
| CN101767814B (en) | Multilevel-structure zinc oxide constructed by three dimension units and preparation method thereof | |
| CN104591233B (en) | A kind of bitter earth nano brilliant coating graphite alkene matrix material and preparation method thereof | |
| CN105645459B (en) | A kind of surface modification sea urchin shape ZnO/TiO2Composite and preparation method thereof | |
| CN103253647B (en) | Preparation method for directly growing high density carbon nanotube array on carbon fiber paper base bottom | |
| CN104773762A (en) | NiCo2O4 mesoporous nanotube material grown on carbon fiber cloth and preparation method thereof | |
| CN104815637A (en) | Method for hydrothermal method preparation of graphene-loaded flower-type titanium dioxide composite material | |
| CN102134092B (en) | Simple preparation method of hollow-spherical and flower-shaped indium oxide with secondary structure and application | |
| CN102398902A (en) | Method for preparing carbon nano material by using natural endellite as formwork | |
| CN103771485A (en) | Controllable preparation method for three-dimensional nano self-assembly of copper oxide | |
| CN104108709A (en) | Porous graphene and preparation method thereof | |
| CN107055510A (en) | A kind of preparation method of metal organic complex nanotube and its derivative porous CNT | |
| Xia et al. | Microwave-assisted facile and rapid synthesis of layered metal hydroxide nanosheet arrays towards high-performance aqueous hybrid supercapacitors | |
| CN109665525A (en) | A kind of preparation method of " dumbbell shape " iron nitrogen codope porous carbon | |
| CN102001698B (en) | Preparation method of indium oxide mesoporous nanospheres | |
| Zhao et al. | Metal-organic framework derived nickel‑cobalt layered double hydroxide nanosheets cleverly constructed on interconnected nano-porous carbon for high-performance supercapacitors | |
| CN105110384A (en) | Porous cobaltosic oxide and preparation method thereof | |
| CN105778088B (en) | A kind of graphene/polyaniline nanometer stick array composite and preparation method and application | |
| CN114632536A (en) | NiCo with photocatalytic properties2O4/NiO/g-C3N4Nanotube preparation method and application | |
| CN102651470B (en) | Method for preparing whisker shaped lithium titanate (Li4Ti5O12) by low-temperature solid phase method | |
| Wang et al. | Hydrothermal synthesis of SnO2 nanoflower arrays and their optical properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120822 Termination date: 20151203 |
|
| EXPY | Termination of patent right or utility model |