CN101944396A - Method for preparing porous mold charcoal/metal oxide composite material for super capacitor electrode - Google Patents
Method for preparing porous mold charcoal/metal oxide composite material for super capacitor electrode Download PDFInfo
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- CN101944396A CN101944396A CN2010102413551A CN201010241355A CN101944396A CN 101944396 A CN101944396 A CN 101944396A CN 2010102413551 A CN2010102413551 A CN 2010102413551A CN 201010241355 A CN201010241355 A CN 201010241355A CN 101944396 A CN101944396 A CN 101944396A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention provides a method for preparing a porous mold charcoal/metal oxide composite material for a super capacitor electrode. The method comprises the following steps: preparing the porous mold charcoal by adopting a wood block direct carbonizing method; and preparing a porous mold charcoal/metal oxide composite material by adopting an electromechanical deposition method and a chemical deposition method. The porous mold charcoal has wide sources, simple preparation process and porous structure, has very high specific capacity after the porous mold charcoal is compounded with the metal oxide and hydroxide; and the composite material has simple preparation process, and is suitable for large-scale production application. The electrode can be directly made of the prepared composite material without adding graphite, polymer adhesive and other additives, so that the conductivity of the electrode can be improved, the output specific capacity of the capacitor can be remarkably improved. The method has remarkable effect in improving the specific volume of the composite material.
Description
Technical field
The present invention relates to be used for the preparation method of the composite material of electrode of super capacitor.
Background technology
Ultracapacitor is a kind of novel energy-storing device between battery and traditional capacitor that occurs in recent years, but because of it has that specific power is big, the light weight fast charging and discharging, have extended cycle life, serviceability temperature wide ranges and pollute plurality of advantages such as little and be subjected to extensive concern.Ultracapacitor mainly is divided into electric double layer type ultracapacitor and oxidation-reduction type ultracapacitor.Mainly by the surface area decision of material, its theoretical capacity is directly proportional with the specific area of electrode material the specific capacity of electric double layer type ultracapacitor.Mainly be to do electrode material by employing active carbon or carbon nano-tube at present, its specific capacity can reach 200F/g.With pure active carbon or carbon nano-tube ultracapacitor as electrode, though the material with carbon element specific area is higher, but it is poor in the water solution system wettability, its low specific capacity problem become restriction its as electrode material for super capacitor and the extensive bottleneck factor of using.The forming charcoal electrode material has bigger specific area, and it is compound to can be used as carrier and metal oxide and hydroxide, is prepared into combination electrode material and uses.Artificial synthetic porous, shaped carbon preparation technology is still quite complicated, and cost is higher, is unfavorable for large-scale industrial production and practical application but so far.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who is used for the porous, shaped charcoal/metal oxide composite of electrode of super capacitor.
The present invention is the preparation method who is used for the porous, shaped charcoal/metal oxide composite of electrode of super capacitor, the steps include: to adopt the wooden unit direct carborization to prepare porous, shaped charcoal, adopt electrochemical deposition method and chemical deposition to prepare porous, shaped charcoal/metal oxide composite then, its concrete steps are:
(1) wooden unit being cut into length respectively is the cuboid of 2cm, 1cm, 0.3cm;
(2) above-mentioned wood particle is transferred in the crucible, and places tube furnace;
(3) utilize vacuum pump that the air in the quartz ampoule is extracted out, make and press in it less than 10Pa;
(4) in vacuum-pumping tube, feed inertia N
2To normal pressure, be 70～80mL/s with mass flowmenter control gaseous flow then;
(5) heating rate with 3 ℃/min begins to be warming up to 900 ℃ of pipe Nei Wenduda, and is incubated 6 hours, makes the wooden unit carbonization, promptly obtains porous, shaped charcoal;
(6) be substrate with prepared porous, shaped charcoal, the hydroxide porous film of electrodeposit metals in the transition metal nitrate solution of 0.05～0.3mol/L is prepared moulding charcoal/metal hydroxides combination electrode material; Adopt chemical deposition in the nitrate solution or metal chloride solutions of 0.2～2.0mol/L transition metal, dropping concentration is 5%～20% ammoniacal liquor, prepares moulding charcoal/metal hydroxides combination electrode material in 2～6 hours in 30 ℃～80 ℃ depositions;
Porous, shaped charcoal/metal hydroxides the combination electrode material that (7) will prepare can make moulding charcoal/metal oxide composite electrode material in 6 hours in 250～450 ℃ of heating in baking oven.
Porous, shaped charcoal source is abundant, and preparation technology is simple and have a loose structure, have very high specific capacity after itself and metal oxide and hydroxide are compound, and the preparation technology of composite material is simple, is suitable for large-scale production and application.The composite material of the present invention's preparation can directly be made electrode, do not need to add additives such as graphite and polymeric binder, improved the conductivity of electrode, capacitor output specific capacity obviously improves, and this method has the effect of highly significant on the specific volume that improves composite material.
Embodiment
The present invention is the preparation method who is used for the porous, shaped charcoal/metal oxide composite of electrode of super capacitor, the steps include: to adopt the wooden unit direct carborization to prepare porous, shaped charcoal, adopt electrochemical deposition method and chemical deposition to prepare porous, shaped charcoal/metal oxide composite then, its concrete steps are:
(1) wooden unit being cut into length respectively is the cuboid of 2cm, 1cm, 0.3cm;
(2) above-mentioned wood particle is transferred in the crucible, and places tube furnace;
(3) utilize vacuum pump that the air in the quartz ampoule is extracted out, make and press in it less than 10Pa;
(4) in vacuum-pumping tube, feed inertia N
2To normal pressure, be 70～80mL/s with mass flowmenter control gaseous flow then;
(5) heating rate with 3 ℃/min begins to be warming up to 900 ℃ of pipe Nei Wenduda, and is incubated 6 hours, makes the wooden unit carbonization, promptly obtains porous, shaped charcoal;
(6) be substrate with prepared porous, shaped charcoal, the hydroxide porous film of electrodeposit metals in the transition metal nitrate solution of 0.05～0.3mol/L is prepared moulding charcoal/metal hydroxides combination electrode material; Adopt chemical deposition in the nitrate solution or metal chloride solutions of 0.2～2.0mol/L transition metal, dropping concentration is 5%～20% ammoniacal liquor, prepares moulding charcoal/metal hydroxides combination electrode material in 2～6 hours in 30 ℃～80 ℃ depositions;
Porous, shaped charcoal/metal hydroxides the combination electrode material that (7) will prepare can make moulding charcoal/metal oxide composite electrode material in 6 hours in 250～450 ℃ of heating in baking oven.
Be embodiment more specifically below:
Embodiment 1: the preparation of porous, shaped charcoal
(1) wooden unit being cut into length respectively is the rectangular-shaped of 2cm, 1cm, 0.3cm;
(2) above-mentioned wood particle is transferred in the crucible, and places tube furnace;
(3) utilize vacuum pump that the air in the quartz ampoule is extracted out, make and press in it less than 10Pa;
(4) in vacuum-pumping tube, feed inertia N
2To normal pressure, be 70～80mL/s with mass flowmenter control gaseous flow then;
(5) heating rate with 3 ℃/min begins to be warming up to 900 ℃ of pipe Nei Wenduda, and is incubated 6 hours, makes the wooden unit carbonization, promptly obtains porous, shaped charcoal.
Embodiment 2: the preparation of porous, shaped charcoal/cobalt hydroxide composite material
Execution mode one: adopt the standard three-electrode system, the Pt electrode is to electrode, and saturated calomel electrode is a reference electrode, and the porous, shaped charcoal that is prepared by embodiment 1 is a matrix, electro-deposition cobalt hydroxide in the 0.1mol/L cobalt nitrate solution, quality control is at 0.8mg/cm
2Deposition finishes the back with deionized water immersion 30 minutes, places 40 ℃ of oven dryings to get final product in 12 hours.The active material quality can be calculated by Faraday's law.
Execution mode two: in the cobalt nitrate solution of porous, shaped charcoal with embodiment 1 preparation with copper wire stuck-at-.0mol/L, in 60 ℃ drip 10% ammoniacal liquor to pH be 12, and keep stirring 3 hours, rinse well with deionized water and get final product.The quality of cobalt hydroxide can be obtained by the of poor quality of electrode before and after the deposition.
Embodiment 3: the preparation of porous, shaped charcoal base nickel hydroxide composite material
Execution mode one: adopt the standard three-electrode system, the Pt electrode is to electrode, and saturated calomel electrode is a reference electrode, and the porous, shaped charcoal that is prepared by embodiment 1 is a matrix, electro-deposition nickel hydroxide in the 0.1mol/L nickel nitrate solution, and quality control is at 1mg/cm
2Deposition finishes the back with deionized water immersion 30 minutes, places 40 ℃ of oven dryings to get final product in 12 hours.
Execution mode two: in the nickel nitrate solution of porous, shaped charcoal with copper wire stuck-at-.0mol/L with embodiment 1 preparation, dripping 10% to pH in 60 ℃ is 12, and keeps stirring 3 hours, rinses well with deionized water to get final product.The quality of nickel hydroxide can be obtained by the of poor quality of electrode before and after the deposition.
Embodiment 4: the preparation of porous, shaped charcoal/cobalt oxide composite material
Porous, shaped charcoal/cobalt hydroxide the composite material of embodiment 2 preparations is placed 250 ℃ of baking ovens 6 hours, can prepare porous, shaped charcoal/cobalt oxide combination electrode material.
Embodiment 5: the preparation of porous, shaped charcoal/nickel oxide composite material
Porous, shaped charcoal/nickel hydroxide the composite material of embodiment 3 preparations is placed 300 ℃ of baking ovens 6 hours, can prepare porous, shaped charcoal base nickel oxide combination electrode material.
Embodiment 6: the preparation of porous, shaped charcoal base manganese dioxide composite material
Employing standard three-electrode system, Pt electrode are to electrode, and saturated calomel electrode is a reference electrode, and the porous, shaped charcoal that is prepared by embodiment 1 is a matrix, electro-deposition manganese dioxide in 0.1mol/L manganese acetate solution, and quality control is at 1.1mg/cm
2Deposition finishes the back with deionized water immersion 30 minutes, places 40 ℃ of oven dryings to get final product in 12 hours.
Claims (5)
1. the preparation method who is used for the porous, shaped charcoal/metal oxide composite of electrode of super capacitor, the steps include: to adopt the wooden unit direct carborization to prepare porous, shaped charcoal, adopt electrochemical deposition method and chemical deposition to prepare porous, shaped charcoal/metal oxide composite then, its concrete steps are:
(1) wooden unit being cut into length respectively is the cuboid of 2cm, 1cm, 0.3cm;
(2) above-mentioned wood particle is transferred in the crucible, and places tube furnace;
(3) utilize vacuum pump that the air in the quartz ampoule is extracted out, make and press in it less than 10Pa;
(4) feeding inertia N2 to normal pressure in vacuum-pumping tube, is 70～80mL/s with mass flowmenter control gaseous flow then;
(5) heating rate with 3 ℃/min begins to be warming up to 900 ℃ of pipe Nei Wenduda, and is incubated 6 hours, makes the wooden unit carbonization, promptly obtains porous, shaped charcoal;
(6) be substrate with prepared porous, shaped charcoal, the hydroxide porous film of electrodeposit metals in the transition metal nitrate solution of 0.05～0.3mol/L is prepared moulding charcoal/metal hydroxides combination electrode material; Adopt chemical deposition in the nitrate solution or metal chloride solutions of 0.2～2.0mol/L transition metal, dropping concentration is 5%～20% ammoniacal liquor, prepares moulding charcoal/metal hydroxides combination electrode material in 2～6 hours in 30 ℃～80 ℃ depositions;
Porous, shaped charcoal/metal hydroxides the combination electrode material that (7) will prepare can make moulding charcoal/metal oxide composite electrode material in 6 hours in 250～450 ℃ of heating in baking oven.
2. the porous, shaped charcoal/metal oxide composite that is used for electrode of super capacitor according to claim 1 is characterized in that: described wooden unit is a pine, perhaps cypress, perhaps Chinese toon wood, perhaps apricot wood, perhaps poplar, perhaps ash, perhaps Chinese parasol tree tree.
3. the moulding charcoal/metal oxide composite that is used for electrode of super capacitor according to claim 1 is characterized in that: described substrate is the porous charcoal of moulding.
4. the preparation method who is used for the porous, shaped charcoal/metal oxide composite of electrode of super capacitor according to claim 1, it is characterized in that: complex method comprises chemically composited method and electro-deposition complex method, described electro-deposition method is permanent electromotive force sedimentation, perhaps galvanostatic deposition method, perhaps pulsed deposition method, perhaps cyclic voltammetric sedimentation.
5. the preparation method who is used for the porous, shaped charcoal/metal oxide composite of electrode of super capacitor according to claim 1 is characterized in that: described transition metal is a nickel, perhaps cobalt, perhaps manganese, perhaps above-mentioned several combination.
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| CN2010102413551A CN101944396B (en) | 2010-07-29 | 2010-07-29 | Method for preparing porous mold charcoal/metal oxide composite material for super capacitor electrode |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102709058A (en) * | 2012-07-01 | 2012-10-03 | 吉林大学 | Method for preparing manganese dioxide-nickel hydroxide composite electrode materials of super capacitors |
| CN103451699A (en) * | 2013-09-17 | 2013-12-18 | 东华大学 | Method for preparing Mn0.12Co0.94Ni0.51O2 ultrathin nanosheet super capacitor material |
| CN103578774A (en) * | 2013-11-15 | 2014-02-12 | 东华大学 | Preparation method for electrode of supercapacitor |
| CN110379646A (en) * | 2019-07-25 | 2019-10-25 | 中南林业科技大学 | A kind of preparation method based on two selenizing molybdenums/charcoal Asymmetric Supercapacitor |
| US10601032B2 (en) | 2016-04-28 | 2020-03-24 | National Chiao Tung University | Composite electrode material |
| CN111470548A (en) * | 2020-04-13 | 2020-07-31 | 山东鲁北国际新材料研究院有限公司 | Binary transition metal oxide-charcoal composite material and preparation method thereof |
| CN112362713A (en) * | 2020-11-24 | 2021-02-12 | 吉林大学 | Sensitive electrode material for direct electrochemical detection of ammonia nitrogen in water and preparation method thereof |
| CN113087086A (en) * | 2021-03-26 | 2021-07-09 | 成都工业学院 | Carbon plate electrode based on waste pine residue and preparation method thereof |
| CN113300568A (en) * | 2021-04-08 | 2021-08-24 | 杭州未名信科科技有限公司 | Electroosmosis pump system, method for manufacturing functional electrode of electroosmosis pump system and fluid conveying method |
| CN113314349A (en) * | 2021-06-24 | 2021-08-27 | 北华大学 | Polyacrylonitrile/wood-based derived carbon porous material and preparation and application thereof |
Families Citing this family (1)
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| CN104923138B (en) * | 2015-05-20 | 2017-04-12 | 北京化工大学 | Device and method for preparing Ni-Co-O composite super-capacitor material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050169829A1 (en) * | 2004-02-03 | 2005-08-04 | Sheng Dai | Robust carbon monolith having hierarchical porosity |
| CN101454243A (en) * | 2006-05-31 | 2009-06-10 | 促进科学E.V.麦克斯-普朗克公司 | Porous carbon electrode with conductive polymer coating |
-
2010
- 2010-07-29 CN CN2010102413551A patent/CN101944396B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050169829A1 (en) * | 2004-02-03 | 2005-08-04 | Sheng Dai | Robust carbon monolith having hierarchical porosity |
| CN101454243A (en) * | 2006-05-31 | 2009-06-10 | 促进科学E.V.麦克斯-普朗克公司 | Porous carbon electrode with conductive polymer coating |
Non-Patent Citations (3)
| Title |
|---|
| 《Advanced Materials》 20031231 Lu，A.H.，Schuth F Synthesis of ordered mesoporous carbon with bimodal pore system and high pore volume 1602 1－5 , 2 * |
| 《Journal of Physical Chemistry B》 19991231 Ryoo；R.S.H.Joo Synthesis of highly ordered carbon molecular sieves via template-mediated structural transformations 7743-7746 1－5 , 2 * |
| 《Journal of Physical Chemistry B》 20001231 Kruk，M.，Ryoo，R Characterization of ordered mesopor-ous carbons synthesized using MCM-48 silicas as templates 7960-7968 1－5 , 2 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102709058B (en) * | 2012-07-01 | 2015-05-13 | 吉林大学 | Method for preparing manganese dioxide-nickel hydroxide composite electrode materials of super capacitors |
| CN102709058A (en) * | 2012-07-01 | 2012-10-03 | 吉林大学 | Method for preparing manganese dioxide-nickel hydroxide composite electrode materials of super capacitors |
| CN103451699A (en) * | 2013-09-17 | 2013-12-18 | 东华大学 | Method for preparing Mn0.12Co0.94Ni0.51O2 ultrathin nanosheet super capacitor material |
| CN103451699B (en) * | 2013-09-17 | 2016-09-07 | 东华大学 | A kind of Mn0.12co0.94ni0.51o2the preparation method of ultrathin nanometer sheet super capacitor material |
| CN103578774A (en) * | 2013-11-15 | 2014-02-12 | 东华大学 | Preparation method for electrode of supercapacitor |
| CN103578774B (en) * | 2013-11-15 | 2016-08-17 | 东华大学 | A kind of preparation method of electrode of super capacitor |
| US10601032B2 (en) | 2016-04-28 | 2020-03-24 | National Chiao Tung University | Composite electrode material |
| CN110379646A (en) * | 2019-07-25 | 2019-10-25 | 中南林业科技大学 | A kind of preparation method based on two selenizing molybdenums/charcoal Asymmetric Supercapacitor |
| CN111470548A (en) * | 2020-04-13 | 2020-07-31 | 山东鲁北国际新材料研究院有限公司 | Binary transition metal oxide-charcoal composite material and preparation method thereof |
| CN112362713A (en) * | 2020-11-24 | 2021-02-12 | 吉林大学 | Sensitive electrode material for direct electrochemical detection of ammonia nitrogen in water and preparation method thereof |
| CN112362713B (en) * | 2020-11-24 | 2021-12-07 | 吉林大学 | Sensitive electrode material for direct electrochemical detection of ammonia nitrogen in water and preparation method thereof |
| CN113087086A (en) * | 2021-03-26 | 2021-07-09 | 成都工业学院 | Carbon plate electrode based on waste pine residue and preparation method thereof |
| CN113300568A (en) * | 2021-04-08 | 2021-08-24 | 杭州未名信科科技有限公司 | Electroosmosis pump system, method for manufacturing functional electrode of electroosmosis pump system and fluid conveying method |
| CN113314349A (en) * | 2021-06-24 | 2021-08-27 | 北华大学 | Polyacrylonitrile/wood-based derived carbon porous material and preparation and application thereof |
| CN113314349B (en) * | 2021-06-24 | 2022-07-15 | 北华大学 | Polyacrylonitrile/wood-based derived carbon porous material and preparation and application thereof |
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