CN101777652B - Production method of active carbon of direct carbon conversion fuel cell - Google Patents
Production method of active carbon of direct carbon conversion fuel cell Download PDFInfo
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- CN101777652B CN101777652B CN201010018317XA CN201010018317A CN101777652B CN 101777652 B CN101777652 B CN 101777652B CN 201010018317X A CN201010018317X A CN 201010018317XA CN 201010018317 A CN201010018317 A CN 201010018317A CN 101777652 B CN101777652 B CN 101777652B
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Abstract
The invention discloses a production method of active carbon of a direct carbon conversion fuel cell, which mainly comprises the steps of: producing carbonization material by taking biomass such as oak scobs or bamboo chip, and the like as raw material; taking K2CO3 or and the mixture of K2CO3 and KOH as a activating agent; activating the carbonization material under the carbonization temperatureof 750-1000 DEG C and the atmosphere of nitrogen to obtain the active carbon; loading active carbon by means of Ni with additive to improve the electric conduction performance of the active carbon; and leaching with acid solution to increase the type and the content of the oxygen-containing functional group on the surface of the active carbon and reduce the ash content of the active carbon. The specific surface area of the treated active carbon can be reach 1967 m<2>/g; the volume resistivity can be reduced at 1654 mu omega.m; the type and the content of the oxygen-containing functional groupare increased; the ash content is greatly reduced; and the specific surface area, the electric conduction performance, the ash content and the combination property of the surface oxygen-containing functional group are better adapted to the requirement of direct carbon fuel cell to fuel, compared with the raw materials of the existing direct carbon fuel cell such as black lead, active carbon, petroleum coke and the like.
Description
Technical field
The present invention is a kind of preparation method of direct conversion carbon consuming cell active carbon, relates to fuel cell and active carbon field.
Background technology
Fuel cell is a kind of chemical energy in the fuel to be converted into the device of electric energy, and its generating efficiency is high, few, the CO of pollutant discharge amount
2Discharge capacity can reduce 40～60%, noise low (＜60dB); Modular construction; Varying duty rate high (20～120%); Both but centrally connected power supply also was fit to decentralized power supply; Floor space is little.Therefore, fuel cell be known as after water power, thermoelectricity and nuclear power the 4th generation TRT.Directly carbon consuming cell (DCFC) is as a kind of high-temperature fuel cell, and it directly uses solid carbon to act as a fuel, and compares with hydrogen oxygen fuel cell, has more following advantage: the theoretical efficiency of battery is near 100%; The source of solid carbon fuel is wide; The energy density of fuel is high.
Basically all use graphite, active carbon, carbon black, biomass coke etc. as anode in the DCFC experimental study both at home and abroad at present.Graphite has good electric conductivity, and content of ashes is zero, but reactivity is lower; Active carbon is a kind of porous carbonaceous material with flourishing pore structure and bigger serface that utilizes biological organic substance preparation; Have high specific surface area, flourishing, the internal structure of porosity; Have high reaction activity and high, but ash content is higher, and electric conductivity is relatively poor.Choose suitable biomass material, produce active carbon, pass through HNO again through the carbonization-activation operating mode
3Solution impregnation increases the activated carbon surface oxygen-containing functional group simultaneously and reduces ash content; With the nickel acetate is that additive carries out the Ni load with enhanced activity charcoal electric conductivity, thereby the specific area that obtains being suitable for direct carbon consuming cell is big, content of ashes is low, conduct electricity very well and the active carbon of oxygen-containing functional group is rich on the surface.With the fuel of the active carbon after handling, can improve the performance of battery as DCFC.
Summary of the invention
Technical problem: the present invention is intended to overcome the deficiency of existing DCFC anode carbon fuel, propose a kind of specific area big, conduct electricity very well, content of ashes is low and the surperficial preparation method that is rich in the direct carbon conversion fuel cell active carbon of oxygen-containing functional group.
Technical scheme: for solving the problems of the technologies described above, it is raw material that the present invention adopts biomass such as oak sawdust and bamboo chip, and charing 0.5～1.5h makes carbonized material under 350～450 ℃ of temperature; With strong base-weak acid salt or highly basic and strong base weak acid salt mixture is activator, under different activation temperatures, alkali charcoal ratio and soak time, obtains best active carbon; Use nickel acetate to carry out active carbon Ni load then and carry out the electric conductivity modification; Last HNO at variable concentrations
3Middle dipping carries out surface modification and ash disposal.
The preparation method of the direct carbon consuming cell fuel carbon of the present invention comprises the steps:
The first step, carbonized material preparation: adopt oak sawdust or the bamboo chip raw material as preparation high-activity biological matter powdered carbon, raw material are charing 0.5～1.5h time under 350～450 ℃ of carbonization temperatures, makes the complete charing of raw material,
Second step; Active carbon is produced: select strong base-weak acid salt or highly basic and strong base weak acid salt mixture as activator; Activator is 0.5～5 with the ratio of carbonized material, adds distilled water and mixes, and at room temperature floods 12～24h; 100～140 ℃ temperature, the nitrogen flow of 100～200ml/min is dry down then; Dry good mixture carries out activation in the condition held of nitrogen protection in reactor, activation temperature is at 750～1000 ℃, and soak time is at 30～150min, and activation is cooled to room temperature after finishing; At last, with active carbon use distilled water repeatedly cleaning and filtering be neutrality until filtrating, 100～140 ℃ temperature under the nitrogen flow of 100～200ml/min after the drying, is collected, subsequent use;
In the 3rd step, active carbon Ni load: use additive that active carbon is carried out the Ni load to improve its electric conductivity, according to 1～5% load Ni with respect to active carbon weight, adding distilled water is to mixture and stir drying under nitrogen protection; Dry good raw material joins in the reactor, is 5～20 ℃/min at heating rate, be heated under 100～200ml/min nitrogen flow after temperature is 800～1000 ℃, and behind insulation 30～150min, natural cooling;
The 4th step, activated carbon surface modification and ash disposal: active carbon is flooded 8～24h in 60～100 ℃ of acid solutions, clean to neutral with distilled water then, subsequent use after intensive drying under 100～140 ℃ of nitrogen protections.
Described activator is K
2CO
3Or KOH and K
2CO
3Mixture, improve the active carbon specific area.
Described additive is a nickel acetate, improves the electric conductivity of active carbon.
Hydrochloric acid and nitric acid mixed solution that activated carbon surface modification and ash disposal were adopted 1: 1 carry out, and it is active to improve activated carbon surface, reduce the active carbon dust burdening.
Beneficial effect: according to above-mentioned preparation method of active carbon, can produce specific area big, conduct electricity very well, surface oxygen functional group is abundant and the low active carbon of content of ashes.Bigger serface can increase the contact area of carbon fuel reaction, increases the reaction chance; Electric conductivity helps the transmission of anode electronics in carbon fuel preferably, reduces the anode ohmic polarization; The activated energy barrier that functional group can reduce anode reaction is rich on the surface, promotes reaction; The low life-span that can prolong direct carbon consuming cell of content of ashes.
Embodiment
For effect of the present invention better is described, embodiment is listed below.
Embodiment 1:
(1) KOH and K
2CO
3By 1: 1 preparation composite activating agent, take by weighing composite activating agent and oak carbonized material at 4: 1 by mass ratio then, add distilled water and mix, at room temperature flood 12h, 120 ℃ temperature, the nitrogen of 150ml/min is dry down then.Dry good mixture the nitrogen current held in reactor, carry out activation, activation temperature is 800 ℃, soak time is 60min, activation is cooled to room temperature after finishing.At last, with active carbon use distilled water repeatedly cleaning and filtering be neutrality until filtrating, after drying under 120 ℃ of nitrogen protections, collect, subsequent use.
(2), add distilled water to mixture and stir drying under nitrogen protection according to 2% load Ni with respect to active carbon weight.Dry good raw material joins in the reactor, is 5 ℃/min at heating rate, and nitrogen flow is to be heated under the 100ml/min after temperature is 900 ℃, behind the insulation 120min, and natural cooling.
(3) employing of the active carbon after activation concentration is the HNO of 4mol/l
3Middle dipping 12h, dipping temperature is 80 ℃, cleans to neutral with distilled water then, is collecting behind the dry 2h under 120 ℃ of nitrogen protections.
The active carbon specific area that obtains is 1855m
2.g
-1, pore volume is 0.941m
3.g
-1, specific insulation has dropped to 4490 μ Ω .m by 31130 μ Ω .m after the Ni load, and ash content drops to 8.21% by 21.17%, and Fig. 2 (1) is seen in the variation of surface oxygen functional group.
Embodiment 2:
(1) KOH and K
2CO
3By 1: 1 preparation composite activating agent, take by weighing composite activating agent and oak carbonized material at 3: 1 by mass ratio then, add distilled water and mix, at room temperature flood 12h, 120 ℃ temperature, the nitrogen of 150ml/min is dry down then.Dry good mixture the nitrogen current held in reactor, carry out activation, activation temperature is 800 ℃, soak time is 60min, activation is cooled to room temperature after finishing.At last, with active carbon use distilled water repeatedly cleaning and filtering be neutrality until filtrating, after drying under 120 ℃ of nitrogen protections, collect, subsequent use.
(2), add distilled water to mixture and stir drying under nitrogen protection according to 2% load Ni with respect to active carbon weight.Dry good raw material joins in the reactor, is 5 ℃/min at heating rate, and nitrogen flow is to be heated under the 100ml/min after temperature is 900 ℃, behind the insulation 120min, and natural cooling.
(3) employing of the active carbon after activation concentration is the HNO of 4mol/l
3Middle dipping 12h, dipping temperature is 80 ℃, cleans to neutral with distilled water then, is collecting behind the dry 2h under 120 ℃ of nitrogen protections.
The active carbon specific area that obtains is 1967m
2.g
-1, pore volume is 0.976m
3.g
-1, specific insulation has dropped to 8130 μ Ω .m by 75301 μ Ω .m after the Ni load, and ash content drops to 6.19% by 10.34%, and accompanying drawing 2 (2) is seen in the variation of surface oxygen functional group.
Embodiment 3:
(1) takes by weighing K at 1: 1 by mass ratio
2CO
3With the oak carbonized material, add distilled water and mix, at room temperature flood 12h, 120 ℃ temperature, the nitrogen of 150ml/min is dry down then.Dry good mixture the nitrogen current held in reactor, carry out activation, activation temperature is 900 ℃, soak time is 120min, activation is cooled to room temperature after finishing.At last, with active carbon use distilled water repeatedly cleaning and filtering be neutrality until filtrating, after drying under 120 ℃ of nitrogen protections, collect, subsequent use.
(2), add distilled water to mixture and stir drying under nitrogen protection according to 5% load Ni with respect to active carbon weight.Dry good raw material joins in the reactor, is 5 ℃/min at heating rate, and nitrogen flow is to be heated under the 100ml/min after temperature is 900 ℃, behind the insulation 120min, and natural cooling.
(3) employing of the active carbon after activation concentration is the HNO of 4mol/l
3Middle dipping 12h, dipping temperature is 80 ℃, cleans to neutral with distilled water then, is collecting behind the dry 2h under 120 ℃ of nitrogen protections.
The active carbon specific area that obtains is 1240m
2.g
-1, pore volume is 0.768m
3.g
-1, specific insulation has dropped to 1654 μ Ω .m by 3414 μ Ω .m after the Ni load, and ash content drops to 3.65% by 11.82%, and Fig. 2 (3) is seen in the variation of surface oxygen functional group.
Embodiment 4:
(1) KOH and K
2CO
3By 1: 2 preparation composite activating agent, take by weighing composite activating agent and oak carbonized material at 3: 1 by mass ratio then, add distilled water and mix, at room temperature flood 12h, 120 ℃ temperature, the nitrogen of 150ml/min is dry down then.Dry good mixture the nitrogen current held in reactor, carry out activation, activation temperature is 800 ℃, soak time is 90min, activation is cooled to room temperature after finishing.At last, with active carbon use distilled water repeatedly cleaning and filtering be neutrality until filtrating, after drying under 120 ℃ of nitrogen protections, collect, subsequent use.
(2), add distilled water to mixture and stir drying under nitrogen protection according to 2% load Ni with respect to active carbon weight.Dry good raw material joins in the reactor, is 5 ℃/min at heating rate, and nitrogen flow is to be heated under the 100ml/min after temperature is 900 ℃, behind the insulation 120min, and natural cooling.
(3) employing of the active carbon after activation concentration is the HNO of 4mol/l
3Middle dipping 12h, dipping temperature is 80 ℃, cleans to neutral with distilled water then, is collecting behind the dry 2h under 120 ℃ of nitrogen protections.
The active carbon specific area that obtains is 1806m
2.g
-1, pore volume is 0.934m
3.g
-1, specific insulation has dropped to 7473 μ Ω .m by 64590 μ Ω .m after the Ni load, and ash content drops to 7.40% by 17.04%, and Fig. 2 (4) is seen in the variation of surface oxygen functional group.
Embodiment 5:
(1) takes by weighing K at 1: 1 by mass ratio
2CO
3With the oak carbonized material, add distilled water and mix, at room temperature flood 12h, 120 ℃ temperature, the nitrogen of 150ml/min is dry down then.Dry good mixture the nitrogen current held in reactor, carry out activation, activation temperature is 950 ℃, soak time is 150min, activation is cooled to room temperature after finishing.At last, with active carbon use distilled water repeatedly cleaning and filtering be neutrality until filtrating, after drying under 120 ℃ of nitrogen protections, collect, subsequent use.
(2), add distilled water to mixture and stir drying under nitrogen protection according to 5% load Ni with respect to active carbon weight.Dry good raw material joins in the reactor, is 5 ℃/min at heating rate, and nitrogen flow is to be heated under the 100ml/min after temperature is 900 ℃, behind the insulation 120min, and natural cooling.
(3) employing of the active carbon after activation concentration is the HNO of 2mol/l
3Middle dipping 12h, dipping temperature is 80 ℃, cleans to neutral with distilled water then, is collecting behind the dry 2h under 120 ℃ of nitrogen protections.
The active carbon specific area that obtains is 1179m
2.g
-1, pore volume is 0.721m
3.g
-1, specific insulation has dropped to 1809 μ Ω .m by 3414 μ Ω .m after the Ni load, and ash content drops to 3.65% by 11.82%, and Fig. 2 (5) is seen in the variation of surface oxygen functional group.
Claims (3)
1. the preparation method of a direct carbon conversion fuel cell active carbon is characterized in that the method comprising the steps of as follows:
The first step, carbonized material preparation: adopt oak sawdust or the bamboo chip raw material as preparation high-activity biological matter powdered carbon, raw material are charing 0.5～1.5h time under 350～450 ℃ of carbonization temperatures, makes the complete charing of raw material,
Second step; Active carbon is produced: select strong base-weak acid salt or highly basic and strong base weak acid salt mixture as activator; Activator is 0.5～5 with the ratio of carbonized material, adds distilled water and mixes, and at room temperature floods 12～24h; 100～140 ℃ temperature, the nitrogen flow of 100～200ml/min is dry down then; Dry good mixture carries out activation in the condition held of nitrogen protection in reactor, activation temperature is at 750～1000 ℃, and soak time is at 30～150min, and activation is cooled to room temperature after finishing; At last, with active carbon use distilled water repeatedly cleaning and filtering be neutrality until filtrating, 100～140 ℃ temperature under the nitrogen flow of 100～200ml/min after the drying, is collected, subsequent use;
In the 3rd step, active carbon Ni load: use additive that active carbon is carried out the Ni load to improve its electric conductivity, according to 1～5% load Ni with respect to active carbon weight, adding distilled water is to mixture and stir drying under nitrogen protection; Dry good raw material joins in the reactor, is 5～20 ℃/min at heating rate, be heated under 100～200ml/min nitrogen flow after temperature is 800～1000 ℃, and behind insulation 30～150min, natural cooling;
The 4th step, activated carbon surface modification and ash disposal: active carbon is flooded 8～24h in 60～100 ℃ of acid solutions, clean to neutral with distilled water then, subsequent use after intensive drying under 100～140 ℃ of nitrogen protections;
Described additive is a nickel acetate.
2. the preparation method of direct carbon conversion fuel cell active carbon according to claim 1 is characterized in that described activator is K
2CO
3Or KOH and K
2CO
3Mixture, improve the active carbon specific area.
3. the preparation method of direct carbon conversion fuel cell active carbon according to claim 1 is characterized in that hydrochloric acid and nitric acid mixed solution that activated carbon surface modification and ash disposal were adopted 1: 1 carry out, and it is active to improve activated carbon surface, reduces the active carbon dust burdening.
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| CN101979316A (en) * | 2010-11-02 | 2011-02-23 | 上海大学 | Method for preparing active carbon material by using waste and old polyethylene glycol terephthalate |
| US9533281B2 (en) * | 2013-03-14 | 2017-01-03 | University Of North Texas | Porositization process of carbon or carbonaceous materials |
| CN103408011B (en) * | 2013-07-25 | 2015-11-11 | 浙江工业大学 | A kind of preparation method of Sargassum horneri matrix activated carbon |
| CN106430187A (en) * | 2016-09-20 | 2017-02-22 | 湖南南方搏云新材料股份有限公司 | Method of using uncured carbon felt leftover material for preparing supercapacitor electrode activated carbon |
| CN106430189A (en) * | 2016-10-26 | 2017-02-22 | 山西新华化工有限责任公司 | Preparation method of efficient water purifying activated carbon |
| CN107623105A (en) * | 2017-10-09 | 2018-01-23 | 江西理工大学 | A kind of preparation method of lithium ion battery GND and conductive agent material |
| CN108640112A (en) * | 2018-03-08 | 2018-10-12 | 哈尔滨工程大学 | A kind of preparation method of high activity active fruit shell carbon anode fuel for indirect carbon consuming cell |
| CN108609600B (en) * | 2018-05-17 | 2020-04-10 | 深圳市贝可家环境健康科技有限公司 | Novel three-dimensional carbon material and preparation method and application thereof |
| CN111755704B (en) * | 2019-03-27 | 2021-10-08 | 中南大学 | Preparation method of porous carbon cathode lithium air battery |
| CN110562977A (en) * | 2019-09-29 | 2019-12-13 | 上海应用技术大学 | Preparation method of biomass charcoal material with high specific surface area and toluene adsorption effect |
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| CN101140999A (en) * | 2006-09-26 | 2008-03-12 | 朱志刚 | Direct carbon fuel battery |
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| CN101140999A (en) * | 2006-09-26 | 2008-03-12 | 朱志刚 | Direct carbon fuel battery |
Non-Patent Citations (3)
| Title |
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| JP特开2001-122608A 2001.05.08 |
| JP特开2007-119342A 2007.05.17 |
| 李晨等.直接碳燃料电池技术研究进展分析.《热能动力工程》.2007,第22卷(第1期),1-5. * |
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