CN1407569A - Use of activated carbon nano-tube - Google Patents
Use of activated carbon nano-tube Download PDFInfo
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- CN1407569A CN1407569A CN01128835A CN01128835A CN1407569A CN 1407569 A CN1407569 A CN 1407569A CN 01128835 A CN01128835 A CN 01128835A CN 01128835 A CN01128835 A CN 01128835A CN 1407569 A CN1407569 A CN 1407569A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/13—Energy storage using capacitors
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Abstract
A use of activated carbon nano tubes relates to an electrode material of electrochemical capacitors. These capacitors do not only have high working voltage, good repeatability and large current density of charge of discharge but also higher capacitance.
Description
The invention belongs to field of functional materials, relate to the purposes of activated carbon nano-tube, particularly activated carbon nano-tube as the electric chemical super capacitor electrode material.
Electric chemical super capacitor is that a kind of energy is quick, the energy device of high current charge-discharge.No matter in actual life, still in high-tech area, it all is the indispensable part of modern science and technology product.Particularly in recent years, it causes people's great attention gradually with the big capacity of its uniqueness, big electric current fast charging and discharging and the high characteristics such as life-span that recycle.Its application also is expanded gradually, particularly environmentally friendly vehicle---the appearance of electric automobile, and powerful ultracapacitor has shown its unprecedented application prospect especially.When automobile starting and climbing, provide big electric current fast; When automobile normal running, boost battery charge; When braking automobile, the big electric current that quick store automobiles produces.Can reduce the restriction of electric automobile like this, prolong the useful life of storage battery greatly, improve the practicality of electric automobile the storage battery heavy-current discharge.In view of the importance of electric chemical super capacitor, each western developed country is one after another with its key strategy research and development project as country.The European Economic Community in 1996 have formulated the development plan (Development of Supercapacitors for ElectricVehicles) of electric automobile super capacitor.USDOE has also formulated (comprising US military) project of corresponding development electric chemical super capacitor, its recent (1998-2003) target will reach the specific power of 500W/Kg, later target in 2003 is the specific power that will reach 1500W/Kg, and following useful life is more than 10000 times.
Carbon nano-tube is that doctor lijima by Japanese NEC Corporation found first in 1991 and formal the proposition.Saying of image, it is meant that five-membered ring, hexatomic ring or the heptatomic ring (mainly being hexatomic ring) be made up of carbon atom connect together, composition is to the same writing board shape of paper, one or more layers the hollow, caliber that forms of curling then tubular material of (100nm-0.4nm) in nanometer range.Difference according to its number of plies of curling can be divided into Single Walled Carbon Nanotube and multi-walled carbon nano-tubes.Its length is from several microns to several millimeters.This have very the structure of high length-diameter ratio and can regard one-dimentional structure as fully, and have complete crystallization.
Carbon nano-tube has characteristics such as metal or semi-conductive conductivity, wideband electromagnetic ripple absorbability, intensity height, excellent adsorption, can be widely used in fields such as energy technology, life science, Aero-Space.As to utilize its intensity be 100 times of steel, and weight is not as good as 1/10 characteristics of steel, as the novel enhanced material; Utilize it to the absorption of electromagnetic wave effect, as stealth material; Utilize its satisfactory electrical conductivity and than bigger serface, as novel hydrogen storage material, catalyst carrier material and battery, electrode material for super capacitor etc.
Because degree of crystallinity height, good conductivity, the pore size of carbon nano-tube concentrate on certain narrow range, are a kind of desirable electric chemical super capacitor electrode materials.But the carbon nano-tube that can prepare in enormous quantities is a multi-walled carbon nano-tubes at present, and its specific area generally is not very big (about 50-410m
2/ g).With regard to bibliographical information, generally about 30F/g of capacity (organic electrolyte) and 100F/g (water electrolysis liquid) when multi-walled carbon nano-tubes is used as the electric chemical super capacitor electrode material, its specific power can reach 8KW/Kg, and is very attractive.
The objective of the invention is to utilize the activation multi-walled carbon nano-tubes to make the electric chemical super capacitor electrode material, utilize high-specific surface area and carbon nano-tube special advantages after its activation, make high performance electric chemical super capacitor (capacity height, have extended cycle life, operating voltage height, power output height).
The activation multi-walled carbon nano-tubes that the present invention uses is according to relevant patent (application number: the activation multi-walled carbon nano-tubes that 01108645.9) makes.This activated carbon nano-tube has sealing two ends and all is opened, on the tube wall of carbon nano-tube nano-pore is arranged, the outer wall partial oxidation of carbon nano-tube, originally be removed or part is removed attached to the graphitized carbon on the carbon nano-tube, the degree of graphitization of carbon nano-tube is low, the specific area of carbon nano-tube is big, the characteristics that the hollow tubular structure of carbon nano-tube itself is not destroyed.
Embodiment: with the Co-Ni composite oxides is catalyst, and the multi-walled carbon nano-tubes (MCNT1) about the 20nm that makes with chemical vapour deposition technique is a benchmark, on this basis, is activator with KOH, the N of 240ml/min
2Protection, 800 ℃ of activation 1 hour, make three kinds of different activation degrees activation multi-walled carbon nano-tubes (MCNT2, MCNT3, MCNT4).Carbon nano-tube before and after handling is used its apparent structure of transmission electron microscope observation respectively, uses N
2Absorption BET method surveys its specific area and the BJH method is calculated its pore volume.Activated carbon nano-tube is made bonding agent with 10wt% Kynoar (PVDF), and 10wt% acetylene black is made conductive agent, makes disk shape electrode, serves as the positive and negative electrode of electric chemical super capacitor, in the argon gas glove box, with the LiClO of 1.0mol/l
4(ethyl carbonate+diethyl carbonate, 50/50, v/v) make electrolyte, be assembled into button-shaped simulation electric chemical super capacitor.With the constant current is 5mA/g, and the scope of discharging and recharging is that the charge and discharge mode of 0-3V is tested its electrochemical behavior at the DC-5 cell tester.The reversible capacity of different carbon nano-tube is with the parameter of its discharge curve, and by formula (I * t)/V calculates that (wherein, C represents the electrochemistry capacitance of material to C=; The electric current that the I representative is constant; T represents discharge time; The voltage range of V representative discharge).It the results are shown in Table 1, table 2, Fig. 1, Fig. 2, Fig. 3.
Table 1 is gained activation multi-walled carbon nano-tubes and does not activate the specific area (using the BET method) of multi-walled carbon nano-tubes and the experimental result of pore volume (using the BJH method).S wherein
BET: specific area; V
Tot: total pore volume; V
Mi: the micropore pore volume; V
Me: mesopore volume; R
Mean: porose mean radius.Show as can be known thus, along with the increase of KOH/CNTs ratio, the specific area of resulting activated carbon nano-tube also increases gradually.When ratio increased to 4: 1, specific area increased to original nearly 3 times.Simultaneously total pore volume, mesopore volume and micropore pore volume constantly increases, but that the micropore pore volume is contributed all the time is very little, and porose mean radius all the time greater than 2nm.
Table 2 is electrochemistry capacitance (organic liquor) experimental results of four samples.Along with the increase of specific area, the capacity of activated carbon nano-tube increases gradually as seen from table.When the ratio of KOH/CNTs was 4, the organic liquor capacity reached 50F/g, was 2 times of preceding carbon nano-tube (MCNT1) capacity of activation.And the electrochemistry capacitance of carbon nano-tube in organic solution of bibliographical information generally is about 30F/g at present.
Transmission electron microscope picture (amplifying 100,000 times) when Fig. 1 is multi-walled carbon nano-tubes activation preceding (MCNT1), Fig. 2 are the transmission electron microscope pictures (amplifying 200,000 times) of activation back carbon nano-tube (MCNT2).Thus two figure more as can be known, the hollow structure of carbon nano-tube does not destroy, just carbon nano-tube obviously shorten and the tube wall of carbon nano-tube like smoothless before the activation, this is because of the cause of nano-pore is arranged on it.Fig. 3 is the constant temperature adsorption curve (N of carbon nano-tube (MCNT1, MCNT2, MCNT3, MCNT4) before and after the activation
2, 77K absorption).Figure because multi-walled carbon nano-tubes activates the increase of back specific area, improves its adsorption capacity to N2 as can be known greatly thus.
Table 1 Sample KOH/CNTs SBET V
tot V
mi V
me R
mean
ratio(w/w) (m
2/g) (cm
3/g) (cm
3/g) (cm
3/g) (nm)
MCNT1 0∶1 194.1 0.66 0.016 0.644 7.32
MCNT2 2∶1 365.8 0.65 0.038 0.612 5.33
MCNT3 4∶1 510.5 0.91 0.139 0.771 4.08
MCNT4 6∶1 509.8 1.12 0.106 1.014 4.71
Table 2
Sample C(F/g)
MCNT1 25
MCNT2 36
MCNT3 50
MCNT4 42
Claims (8)
1. the purposes of an activated carbon nano-tube is characterized in that doing with the multi-walled carbon nano-tubes of activation the electrode material of electric chemical super capacitor.
2. purposes according to claim 1 is characterized in that the multi-walled carbon nano-tubes after the activated processing, has the specific area bigger than original multi-walled carbon nano-tubes, can be original specific area 1-10 doubly, can reach 100-4000m
2/ g.
3. purposes according to claim 2, after it is characterized in that the activated processing of multi-walled carbon nano-tubes, sealing two ends all is opened, on the tube wall of carbon nano-tube nano-pore is arranged, the outer wall partial oxidation of carbon nano-tube, originally be removed attached to the graphitized carbon on the carbon nano-tube or part is removed, the degree of graphitization of carbon nano-tube reduces.
4. purposes according to claim 2, it is characterized in that the activated processing of multi-walled carbon nano-tubes after, the hollow tubular structure of carbon nano-tube itself still is retained.
5. purposes according to claim 2, the operating voltage that it is characterized in that single activated carbon nano-tube electric chemical super capacitor is 0-4.0V.
6. purposes according to claim 2, the electrolyte that it is characterized in that the activated carbon nano-tube electric chemical super capacitor is organic electrolyte, solute is LiClO
4, TEABF
4(tetraethyl ammonium tetrafluoroborate), LiBF
4, LiPF
6, concentration is between 0.2-1.0mol/l.
7. purposes according to claim 2, the electrolyte that it is characterized in that the activated carbon nano-tube electric chemical super capacitor is H
2SO
4, NaOH, Na
2CO
3Aqueous electrolyte, concentration is between 5-70wt%.
8. purposes according to claim 2, the charging and discharging currents density that it is characterized in that the activated carbon nano-tube electric chemical super capacitor is 0.1mA/g-1000A/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01128835A CN1407569A (en) | 2001-09-11 | 2001-09-11 | Use of activated carbon nano-tube |
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| CN01128835A CN1407569A (en) | 2001-09-11 | 2001-09-11 | Use of activated carbon nano-tube |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102214515A (en) * | 2011-03-22 | 2011-10-12 | 浙江大学 | Method for manufacturing activated carbon/carbon nanotube composite electrode for super capacitor |
| CN113441110A (en) * | 2021-08-13 | 2021-09-28 | 成都中科普瑞净化设备有限公司 | Method for preparing adsorbent for adsorbing and separating carbon monoxide |
-
2001
- 2001-09-11 CN CN01128835A patent/CN1407569A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102214515A (en) * | 2011-03-22 | 2011-10-12 | 浙江大学 | Method for manufacturing activated carbon/carbon nanotube composite electrode for super capacitor |
| CN113441110A (en) * | 2021-08-13 | 2021-09-28 | 成都中科普瑞净化设备有限公司 | Method for preparing adsorbent for adsorbing and separating carbon monoxide |
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