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CN102633252A - Method for producing porous carbon for super capacitor by utilizing lignosulfonate - Google Patents

Method for producing porous carbon for super capacitor by utilizing lignosulfonate Download PDF

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Publication number
CN102633252A
CN102633252A CN2012101268865A CN201210126886A CN102633252A CN 102633252 A CN102633252 A CN 102633252A CN 2012101268865 A CN2012101268865 A CN 2012101268865A CN 201210126886 A CN201210126886 A CN 201210126886A CN 102633252 A CN102633252 A CN 102633252A
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China
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porous carbon
carbon material
ultracapacitor
sulfonated lignin
electrode
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CN2012101268865A
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陈祥迎
周青青
杨保俊
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Hefei University of Technology
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Hefei University of Technology
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Abstract

The invention discloses a method for producing porous carbon for a super capacitor by utilizing a lignosulfonate. The method is characterized by comprising the following steps of: putting calcium lignosulphonate or magnesium lignosulphonate in nitrogen or argon atmosphere and keeping at 600-800 DEG C for 1-4 hours; after cooling to the room temperature, soaking calcium lignosulphonate or magnesium lignosulphonate in diluted hydrochloric acid or diluted nitric acid having a mass concentration of 10-30%, carrying out ultrasonic dispersion to even distribution and then stirring for not less than 6 hours; next, performing suction filtering and water washing until the eluate is neutral, and then drying, thereby obtaining porous carbon material suitable for manufacturing the super capacitor. The preparation method disclosed by the invention is simple and convenient for operation; and the obtained porous carbon material can be used for preparing the super capacitor which is capable of showing excellent capacitance characteristics.

Description

A kind of sulfonated lignin that utilize prepare the method for ultracapacitor with porous charcoal
Technical field
The invention belongs to porous carbon preparation method for material technical field, be specifically related to be the method for feedstock production ultracapacitor with porous carbon material with sulfonated lignin.
Background technology
In recent years, along with the miniaturized day by day of electronics, electricinstallation and the continuous development of electromobile industry, power supply has caused people's extensive concern day by day with the ultracapacitor of memory candidate device in support.Ultracapacitor has characteristics such as electrical capacity is big, leakage current is little, discharge and recharge simple, specific power is high and have extended cycle life as a kind of novel energy-storing device.It can provide the specific energy higher 20~200 times than electrolytic condenser, than high specific power and the cycle life more than 10 times of lithium cell.In order to develop the ultracapacitor of excellent performance, people are successively developed and have been used many different electrode materialss, mainly concentrate on carbon-based electrode material, metal oxide electrode material and three types of electrode materialss of conductive polymer electrodes material.Wherein raw material of wood-charcoal material, excellent performance cheap and easy to get and coming into one's own, and successful commercialization with it.
In carbon material; Porous carbon material, absorbent charcoal material, NACF, charcoal aerosol and carbon nanotube etc. can be as electrode materialss; Wherein porous carbon material becomes the maximum and best electrode materials of prospect of research in this field because of having big specific surface area and less internal resistance.
It is that precursor prepares the method for ultracapacitor with porous carbon material with the metallic organic framework compound that Chinese patent CN 101604580B discloses a kind of.But the preparation more complicated of metallic organic framework compound, expensive raw material price and originate limited.
" functional materials " (2010 supplementary issue II (41) volume, 353) and " Chinese Journal of Inorganic Chemistry " (2011,27 (2), 219; Zhou Jin et al.New Carbon Materials, 2010,25 (2), 370; Zhou Jin et al.Carbon, 2010,48 (10), 2765]) having introduced a kind of is the method that feedstock production is used for the porous carbon material of ultracapacitor with the Citrate trianion.Citrate trianion is medically having been widely used, but price is more expensive.And sulfonated lignin are sub products of sulphite process papermaking wood pulp, with sulphite papermaking wood pulp waste liquor through add concentrate after, with precipitation agents such as lime, calcium chloride, monobasic lead acetates, pass through technology such as deposition, separation, oven dry and make.If can be raw material with sulfonated lignin, be to reclamation of waste materials, can prepare the electrode materials of excellent property again simultaneously, thereby have more wide application prospect.But do not see that before sulfonated lignin are used as carbon source, do not see with sulfonated lignin the report of the method aspect that is the feedstock production porous carbon material that is used for ultracapacitor so far.
Summary of the invention
The objective of the invention is to propose a kind of sulfonated lignin that utilize and prepare the method for ultracapacitor, adopt direct pyrolytic method, can be used for preparing the raw material range of the porous carbon material of ultracapacitor with expansion with porous charcoal.
The present invention utilizes sulfonated lignin for feedstock production is used for the method for the porous carbon material of ultracapacitor, it is characterized in that: place inert atmosphere to keep 1-4 hour in 600-800 ℃ sulfonated lignin, be cooled to room temperature after; Be immersed in the diluted acid; Take ultra-sonic dispersion to being evenly distributed, restir is no less than 6 hours, carries out suction filtration then; It is neutral washing to elutant, is drying to obtain to can be used for making the porous carbon material that ultracapacitor is used.
Said sulfonated lignin can adopt calcium lignin sulphonate or magnesium lignosulfonate.
Said inert atmosphere can adopt nitrogen or argon gas.
It is Hydrogen chloride or the rare nitric acid of 10-30% that said diluted acid can adopt mass concentration.
Can find out that from field emission scanning electron microscope (FESEM) picture the material that adopts the inventive method to prepare has vesicular structure.With this porous carbon material grind into powder; Cross 180 mesh sieves; In porous charcoal: graphite: 80: 15: 5 ratio of the mass ratio of ptfe emulsion, add a spot of absolute ethyl alcohol and mix, evenly spread upon on the nickel system electrode that suppresses by 1cm * 1cm size; 100 ℃ of following vacuum-dryings 24 hours, with Hg/Hg 2Cl 2Electrode is formed three-electrode system with platinum electrode as counter electrode as reference electrode, in the KOH of 6mol/L aqueous electrolyte liquid, carries out the test of chemical property.Charging and discharging curve demonstrates that typical triangle is symmetrically distributed and linear change in time all, and the voltage that electrical condenser in its charge and discharge process is described is linear change in time, has good capacitance characteristic.All cyclic voltammetry curves are comparatively the rectangle of rule, do not have the redox peak, explain that its capacity is mainly from the electric double layer capacitance of porous carbon electrode and electrolyte interface.Can find out from cyclic voltammetry curve and charging and discharging curve, adopt the porous carbon material of the inventive method preparation to can be used as super capacitor material.
Compared with present technology, beneficial effect of the present invention is embodied in:
The present invention is the porous carbon material that feedstock production is used for ultracapacitor first with sulfonated lignin, and the structure of the structure of sulfonated lignin and metallic organic framework compound, Citrate trianion has more different, thereby has enlarged the raw material of preparation porous carbon material.Itself just has porous road, high-specific surface area the metallic organic framework compound, and Hydrocerol A and Citrate trianion are the raw materials of common preparation porous carbon material, and adopt sulfonated lignin not appear in the newspapers so far as the raw material of preparation porous carbon material at home and abroad.Preparing method of the present invention is simple, and is easy and simple to handle, and the porous charcoal that makes is used for ultracapacitor and shows good capacitance characteristic.
Description of drawings
Fig. 1 is later sample (a) and washing X-ray diffraction (XRD) the spectrogram comparison of (b) afterwards before washing of pyrolysis lignin calcium sulphonate in the embodiment of the invention 1.
Fig. 2 is field emission scanning electron microscope (FESEM) figure of the porous carbon material that makes among the embodiment 1.
Fig. 3 is assembled into the constant current charge-discharge graphic representation of three-electrode system in the KOH of 6mol/L solution for the porous carbon material that makes among the embodiment 1 as electrode materials.
Fig. 4 is for the porous carbon electrode made with the porous carbon material that makes in the various embodiments of the present invention with Hg/Hg 2Cl 2Electrode as reference electrode, with platinum electrode as the cyclic voltammetry curve figure of three-electrode system in the KOH of 6mol/L solution that counter electrode was assembled into.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is further specified.
Embodiment 1:
Utilizing calcium lignin sulphonate to prepare ultracapacitor in the present embodiment operates with porous carbon material according to the following steps:
(1) utilize calcium lignin sulphonate to be the feedstock production porous charcoal
Commercial calcium lignin sulphonate is directly placed tube furnace; In nitrogen atmosphere, be warming up to 800 ℃ with 5 ℃/min temperature rise rate from room temperature, constant temperature 2h reduces to room temperature then; With the gained sample with the Hydrogen chloride ultrasonic cleaning of mass concentration 20% 4 minutes; Restir reaction 7 hours, the suction filtration after washing is to neutral, and 120 ℃ are drying to obtain finished product.
Fig. 1 is the XRD spectra of the later sample of pyrolysis lignin calcium sulphonate (a) and washing back (b) before washing in the present embodiment.Contain charcoal acid calcium (CaCO in the sample before the washing 3), sulfurated lime compositions such as (CaS), the symbol * that marks among the figure represents charcoal acid calcium, # represents sulfurated lime, represents impurity substances.Can explain that from this XRD spectra decomposition has taken place calcium lignin sulphonate the above-mentioned experimentation of present embodiment; And the composition of washing back sample is mainly porous charcoal.
Fig. 2 can see that for the FESEM figure of the product material that makes in the present embodiment material sample for preparing in the present embodiment has vesicular structure.
(2) preparation porous carbon electrode and carry out the test of chemical property
With the above-mentioned porous charcoal grind into powder for preparing; Cross 180 mesh sieves; In porous charcoal: graphite: 80: 15: 5 ratio of the mass ratio of ptfe emulsion, add after a small amount of absolute ethyl alcohol mixes, evenly spread upon and suppress on the nickel system electrode surface that is of a size of 1cm * 1cm; 100 ℃ of vacuum-dryings 24 hours, form porous carbon electrode; With Hg/Hg 2Cl 2Electrode is as reference electrode, as counter electrode, forms three-electrode system with the porous carbon electrode for preparing in the present embodiment with platinum electrode, in concentration is the KOH aqueous electrolyte liquid of 6mol/L, carries out the test of chemical property.
Fig. 3 is for to make the constant current charge-discharge graphic representation of three-electrode system in the KOH of 6mol/L solution that is assembled into behind the porous carbon electrode with the porous carbon material for preparing in the present embodiment.This charging and discharging curve demonstrates that typical triangle is symmetrically distributed and linear change in time all, and the voltage that electrical condenser in its charge and discharge process is described is linear change in time, has good capacitance characteristic.
Fig. 4 has provided porous carbon electrode that the porous carbon material that adopts the inventive method to make makes and with Hg/Hg 2Cl 2Electrode as reference electrode, with platinum electrode as the cyclic voltammetry curve figure of three-electrode system in the KOH of 6mol/L solution that counter electrode was assembled into.Curve A wherein 1-A 2Be the porous carbon material cyclic voltammetry curve for preparing in the present embodiment, there is not the redox peak in the rectangle that it presents comparatively rule, explains that its capacity is mainly from the electric double layer capacitance of porous carbon electrode and electrolyte interface.
Embodiment 2:
Utilizing sulfonated lignin to prepare ultracapacitor in the present embodiment operates with porous charcoal according to the following steps:
Commercial calcium lignin sulphonate is directly placed tube furnace; In argon gas atmosphere, be warming up to 700 ℃ with 5 ℃/min temperature rise rate from room temperature, constant temperature 3h reduces to room temperature then; With the gained sample with rare nitric acid ultrasonic cleaning of mass concentration 10% 4 minutes; Restir reaction 6 hours, the suction filtration after washing is drying to obtain finished product to neutral.
Adopt with embodiment 1 in same mode the porous carbon material for preparing in the present embodiment made porous carbon electrode carry out electro-chemical test.Curve B among Fig. 4 1-B 2Cyclic voltammetry curve figure for the porous carbon electrode for preparing in the present embodiment.There is not the redox peak in the rectangle that it presents comparatively rule, explains that its capacity is mainly from the electric double layer capacitance of porous carbon electrode and electrolyte interface.
Embodiment 3:
Commercial magnesium lignosulfonate is directly placed tube furnace; In nitrogen atmosphere, be warming up to 800 ℃ with 5 ℃/min temperature rise rate from room temperature, constant temperature 1h reduces to room temperature then; With the gained sample with rare nitric acid ultrasonic cleaning of mass concentration 25% 4 minutes; Restir reaction 7 hours, the suction filtration after washing is drying to obtain finished product to neutral.
Adopt with embodiment 1 in same mode the porous carbon material for preparing in the present embodiment made porous carbon electrode carry out electro-chemical test.Curve C among Fig. 4 1-C 2Cyclic voltammetry curve figure for the porous carbon electrode for preparing in the present embodiment.There is not the redox peak in the rectangle that it presents comparatively rule, explains that its capacity is mainly from the electric double layer capacitance of porous carbon electrode and electrolyte interface.
Embodiment 4:
Commercial magnesium lignosulfonate is directly placed tube furnace; In nitrogen atmosphere, be warming up to 600 ℃ with 5 ℃/min temperature rise rate from room temperature, constant temperature 4h reduces to room temperature then; It is 30% Hydrogen chloride ultrasonic cleaning 4 minutes that the gained sample is used mass concentration; Restir reaction 8 hours, the suction filtration after washing is drying to obtain finished product to neutral.
Adopt with embodiment 1 in identical mode the porous carbon material for preparing in the present embodiment made porous carbon electrode carry out electro-chemical test.Curve D among Fig. 4 1-D 2Cyclic voltammetry curve figure for the porous carbon material for preparing in the present embodiment.
All cyclic voltammetry curves all are comparatively the rectangle of rule among above-mentioned each embodiment, do not have the redox peak, explain that its capacity is mainly from the electric double layer capacitance of porous carbon electrode and electrolyte interface.Explain that thus the porous carbon material that adopts the inventive method to prepare can be applied to prepare ultracapacitor.
By on can know that preparation method of the present invention is simple, and is easy and simple to handle; Prepared porous carbon material can be used for preparing ultracapacitor, shows good capacitance characteristic.

Claims (4)

1. one kind is utilized sulfonated lignin for feedstock production is used for the method for the porous carbon material of ultracapacitor, it is characterized in that: place inert atmosphere to keep 1-4 hour in 600-800 ℃ sulfonated lignin, be cooled to room temperature after; Be immersed in the diluted acid; Take ultra-sonic dispersion to being evenly distributed, restir is no less than 6 hours, carries out suction filtration then; It is neutral washing to elutant, is drying to obtain to can be used for making the porous carbon material that ultracapacitor is used.
2. utilize sulfonated lignin for feedstock production is used for the method for the porous carbon material of ultracapacitor according to claim 1, be characterised in that said sulfonated lignin adopt calcium lignin sulphonate or magnesium lignosulfonate.
3. utilize sulfonated lignin for feedstock production is used for the method for the porous carbon material of ultracapacitor according to claim 1, be characterised in that said inert atmosphere adopts nitrogen or argon gas.
4. utilize sulfonated lignin for feedstock production is used for the method for the porous carbon material of ultracapacitor according to claim 1, be characterised in that it is Hydrogen chloride or the rare nitric acid of 10-30% that said diluted acid adopts mass concentration.
CN2012101268865A 2012-04-26 2012-04-26 Method for producing porous carbon for super capacitor by utilizing lignosulfonate Pending CN102633252A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103253651A (en) * 2013-05-23 2013-08-21 广西大学 Lignin-based porous carbon material and preparation method thereof
CN104190355A (en) * 2014-07-09 2014-12-10 常州合肥工业大学研究院 Method for preparing porous carbon material and treatment method for treating oil-containing sewage
CN106542513A (en) * 2016-09-12 2017-03-29 广东工业大学 Mesoporous macropore porous carbon of a kind of S doping high specific surface micro-pore and its preparation method and application
CN106564876A (en) * 2016-10-24 2017-04-19 宁波工程学院 Lignin-based flower-shaped carbon nano-material and preparation method and application thereof
CN109231205A (en) * 2018-09-18 2019-01-18 中国东方电气集团有限公司 A kind of activated carbon for super capacitors and preparation method thereof that sulfosalt surfactant is modified
CN115346801A (en) * 2022-08-15 2022-11-15 广东工业大学 Lignin-derived porous carbon for supercapacitor and preparation method and application thereof
CN116040628A (en) * 2022-12-23 2023-05-02 中国人民解放军军事科学院防化研究院 Method for rapidly preparing highly graphitized porous carbon

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Publication number Priority date Publication date Assignee Title
CN101092239A (en) * 2007-06-25 2007-12-26 高凤仙 Method for preparing super active carbon based on hickory with coal being adulterated
CN101910060A (en) * 2007-12-03 2010-12-08 独立行政法人产业技术综合研究所 Carbon microparticle produced from raw material lignin, and process for production thereof
CN101966990A (en) * 2010-11-15 2011-02-09 西北农林科技大学 Method for preparing activated carbon from kernel of common macrocarpium fruit
CN102071267A (en) * 2010-12-15 2011-05-25 广东石油化工学院 Method for coproducing xylose, white carbon black and active carbon from rice hulls

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101092239A (en) * 2007-06-25 2007-12-26 高凤仙 Method for preparing super active carbon based on hickory with coal being adulterated
CN101910060A (en) * 2007-12-03 2010-12-08 独立行政法人产业技术综合研究所 Carbon microparticle produced from raw material lignin, and process for production thereof
CN101966990A (en) * 2010-11-15 2011-02-09 西北农林科技大学 Method for preparing activated carbon from kernel of common macrocarpium fruit
CN102071267A (en) * 2010-12-15 2011-05-25 广东石油化工学院 Method for coproducing xylose, white carbon black and active carbon from rice hulls

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103253651A (en) * 2013-05-23 2013-08-21 广西大学 Lignin-based porous carbon material and preparation method thereof
CN104190355A (en) * 2014-07-09 2014-12-10 常州合肥工业大学研究院 Method for preparing porous carbon material and treatment method for treating oil-containing sewage
CN104190355B (en) * 2014-07-09 2016-08-24 常州合肥工业大学研究院 The preparation method of porous carbon material and for processing the processing method of oil-polluted water
CN106542513A (en) * 2016-09-12 2017-03-29 广东工业大学 Mesoporous macropore porous carbon of a kind of S doping high specific surface micro-pore and its preparation method and application
CN106564876A (en) * 2016-10-24 2017-04-19 宁波工程学院 Lignin-based flower-shaped carbon nano-material and preparation method and application thereof
CN106564876B (en) * 2016-10-24 2019-02-01 宁波工程学院 A kind of flower-shaped carbon nanomaterial of lignin-base and its preparation method and application
CN109231205A (en) * 2018-09-18 2019-01-18 中国东方电气集团有限公司 A kind of activated carbon for super capacitors and preparation method thereof that sulfosalt surfactant is modified
CN109231205B (en) * 2018-09-18 2021-11-05 中国东方电气集团有限公司 Sulfonate surfactant modified activated carbon for supercapacitor and preparation method thereof
CN115346801A (en) * 2022-08-15 2022-11-15 广东工业大学 Lignin-derived porous carbon for supercapacitor and preparation method and application thereof
CN116040628A (en) * 2022-12-23 2023-05-02 中国人民解放军军事科学院防化研究院 Method for rapidly preparing highly graphitized porous carbon

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Application publication date: 20120815