CN103779111A - Method for manufacturing electrode materials of super-capacitors by using surplus sludge - Google Patents
Method for manufacturing electrode materials of super-capacitors by using surplus sludge Download PDFInfo
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- CN103779111A CN103779111A CN201410040335.6A CN201410040335A CN103779111A CN 103779111 A CN103779111 A CN 103779111A CN 201410040335 A CN201410040335 A CN 201410040335A CN 103779111 A CN103779111 A CN 103779111A
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a method for manufacturing electrode materials of super-capacitors by using surplus sludge. The method includes the following steps that firstly, the surplus sludge is dried and smashed and passes through a 100-mesh screen, under inert atmosphere, the surplus sludge is calcined for one to three hours at the temperature of 400 DEG C to 900 DEG C, then inorganic substance is removed, drying is performed, and the electrode materials of the super-capacitors are obtained. According to the method, the problem of environmental pollution of the surplus sludge is solved, waste is made to be profitable, the electrode materials of the high-performance super-capacitors are manufactured, the synthetic process is simple, the manufacturing cost is low, and raw materials are abundant.
Description
Technical field
The present invention relates to the technical field of ultracapacitor, particularly a kind of method of utilizing excess sludge to prepare the electrode material of ultracapacitor.
Background technology
Global pollution becoming serious, people's living environment constantly worsens, and how effectively to curb environmental pollution and becomes facing mankind and key subjects urgently to be resolved hurrily.Water pollutant derives from industry and agriculture field, as pollutant sources such as mining site, papermaking, weaving, plating and sanitary sewages.On the one hand, the water pollutant that comprises a large amount of harmful organic pollutions and heavy metal ion can cause serious harm to health; On the other hand, the shortage that it has further aggravated water resources, has a strong impact on industrial and agricultural production and resident's daily life.Microbial degradation method for the most effectual way of sewage disposal at present, by microorganism adsorption, absorption and conversion process, the pollutant in dewatering.But microbial degradation method, in obtaining clean water, has also produced a large amount of Compound Heavy Metals and the excess sludge of organic pollution.Excess sludge how effectively to process these band pollutions becomes scientific research personnel's a urgent need to solve the problem.
On the other hand, along with being on the rise of the energy and problem of environmental pollution, development new forms of energy or improvement energy storage and transform mode cause researcher's interest gradually.Have high power density, the ultracapacitor of long service life and high security is a kind of ideal chose that solves energy conversion and storage problem.Based on charge storage mechanism, ultracapacitor can be divided into double electric layer capacitor and the fake capacitance device based on redox reaction.Electrode material for electric double layer capacitor is mainly take material with carbon element as main.In various fake capacitance equipment material, transition metal oxide and hydroxide are a kind of high performance ultracapacitor active materials.Therefore, carbon and metallic element are the main components of electrode material for super capacitor.
Summary of the invention
In order to overcome the above-mentioned shortcoming and deficiency of prior art, the object of the present invention is to provide a kind of method of utilizing excess sludge to prepare the electrode material of ultracapacitor, synthetic method is simple, and cost is low.
Object of the present invention is achieved through the following technical solutions:
Utilize excess sludge to prepare a method for the electrode material of ultracapacitor, comprise the following steps:
First excess sludge is dried, pulverizes, is crossed 100 mesh sieves, under inert atmosphere, under 400～900 degrees Celsius, calcine 1～3 hour, then remove inorganic matter, after dry, obtain the electrode material of ultracapacitor, the electrode material of the ultracapacitor obtaining, contain porous carbon, element doping porous carbon and metal oxide nanoparticles/porous carbon composite material etc.
Described removal inorganic matter, is specially: adopt acid treatment, remove inorganic matter.
Described removal inorganic matter, is specially: adopt alkali treatment, remove inorganic matter.
Described acid treatment is for adopting hydrofluoric acid to process.
Described alkali treatment is for adopting potassium hydroxide solution to process.
Described excess sludge comprises sanitary sewage excess sludge, paper mill excess sludge, steel plant's excess sludge or Electroplate Factory's mud etc.
The present invention has developed the technology of utilizing excess sludge to prepare electrode material for super capacitor, has both solved the processing problem of excess sludge, has prepared again high-specific surface area, high performance electrode material for super capacitor.Because the chief component of excess sludge is divided into inorganic matter (silica etc.), organic substance (microbial cell etc.) and metal ion (iron ion, copper ion, chromium ion, nickel ion etc.), pass through carbonization treatment, the organic substances such as microbial cell are converted into porous carbon materials, metal ion mixing or load on porous carbon, these two kinds of components are the electrode material that ultracapacitor is good just.Meanwhile, due to the existence of the inorganic matters such as silica, after calcining, material with carbon element can be wrapped in its surface, then, by acid or caustic corrosion processing, removes inorganic template, obtains hierarchical porous structure, is conducive to the diffusion of electrolytic solution for super capacitor.Therefore, utilize excess sludge can obtain porous carbon back or carbon-metal base hybrid supercapacitor electrode material.
Compared with prior art, the present invention has the following advantages and beneficial effect:
1. the invention solves excess sludge problem of environmental pollution, and turn waste into wealth and prepared the electrode material of high-performance super capacitor.
2. the synthetic electrode material of the present invention has high specific area, high ratio electric capacity, good cyclical stability, high power density and energy density.
3. required carbon, nitrogen, phosphorus and the metallic element of the electrode material of of the present invention grade of capacitor, all derives from excess sludge.
4. synthesis technique of the present invention is simple, and preparation cost is low, abundant raw material.
Accompanying drawing explanation
Fig. 1 is the shape appearance figure of the electrode material that obtains by ESEM in embodiment 1.
Fig. 2 is the shape appearance figure of the electrode material that obtains by transmission electron microscope in embodiment 1.
Fig. 3 is the specific area result of the electrode material that obtains by nitrogen adsorption desorption in embodiment 1.
Fig. 4 is the pore-size distribution result of the specific area of the electrode material that obtains by nitrogen adsorption desorption in embodiment 1.
Fig. 5 is the electrode material prepared of embodiment 1, the spectral distribution figure of primary sludge.
Fig. 6 is the capacity measurement result of testing the electrode material of ultracapacitor in embodiment 1 and embodiment 2 by CV.
Fig. 7 is the electrode material of ultracapacitor in the embodiment 1 CV test result figure under different scanning speed.
Fig. 8 is that the electrode material of ultracapacitor in embodiment 1 discharges and recharges the test result figure under speed in difference.
Fig. 9 is the cyclical stability test result figure of the electrode material of ultracapacitor in embodiment 1.
Figure 10 is energy density and the power density diagram of the electrode material of ultracapacitor in embodiment 1.
Figure 11 is the shape appearance figure of the electrode material that obtains by ESEM in embodiment 2.
Figure 12 is the specific area test result of the electrode material that obtains by nitrogen adsorption desorption in embodiment 2.
Figure 13 is the electrode material shape appearance figure obtaining by ESEM in embodiment 3.
Figure 14 is the specific area test result of passing through nitrogen adsorption desorption acquisition electrode material of embodiment 3.
Figure 15 is copper oxidation nanometer particulate load in the embodiment 4 combination electrode transmission electron microscope picture at porous carbon.
Figure 16 is the cyclic voltammetry scan figure of the electrode material of ultracapacitor in embodiment 4.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
10 grams of excess sludge in domestic sewage plants are dried, pulverize, cross 100 mesh sieves, mix with zinc chloride for 1:5 in mass ratio.Then under inert atmosphere, calcine 2 hours for 700 degrees Celsius.Adopt the hydrofluoric acid treatment to remove inorganic matter, then 60 degrees Celsius dry 12 hours, obtain ultracapacitor.As Fig. 1 and Fig. 2, can see unordered porous pattern by ESEM and the synthetic electrode material shape appearance figure of transmission electron microscope observing.The specific area that obtains electrode material by nitrogen adsorption desorption test be 940m2/g(as shown in Figure 3), main bore dia concentrates on 3.8 and 8.6 nanometers (as shown in Figure 4).Test known sample by power spectrum and mainly formed by carbon, oxygen and nitrogen, as shown in Figure 5.
Adopt the electrochemical workstation of three-electrode system, the 1M H2SO4 aqueous solution is electrolyte, Pt line to electrode, reference electrode adopts mercury/mercurous chloride electrode, the glass-carbon electrode of the carbon electrode material of ultracapacitor prepared by load the present embodiment is work electrode, measure ultracapacitor performance, result as shown in Figure 6.The capacitance that obtains ultracapacitor by calculating is 248F/g.
Adopt the electrochemical workstation of three-electrode system, the 1M H2SO4 aqueous solution is electrolyte, Pt line to electrode, reference electrode adopts mercury/mercurous chloride electrode, the glass-carbon electrode of the carbon electrode material of ultracapacitor prepared by load the present embodiment is work electrode, under different scanning speed, measure ultracapacitor performance, result as shown in Figure 7.
Adopt the electrochemical workstation of three-electrode system, the 1M H2SO4 aqueous solution is electrolyte, Pt line to electrode, reference electrode adopts mercury/mercurous chloride electrode, the glass-carbon electrode of the carbon electrode material of ultracapacitor prepared by load the present embodiment is work electrode, under different current densities, measure ultracapacitor performance, result as shown in Figure 8.
Adopt the electrochemical workstation of three-electrode system, the 1M H2SO4 aqueous solution is electrolyte, Pt line to electrode, reference electrode adopts mercury/mercurous chloride electrode, the glass-carbon electrode of the carbon electrode material of ultracapacitor prepared by load the present embodiment is work electrode, measure ultracapacitor stability, as Fig. 9, after circulation 10000 circles, capacitance does not reduce.
Adopt the electrochemical workstation of three-electrode system, the 1M H2SO4 aqueous solution is electrolyte, Pt line to electrode, reference electrode adopts mercury/mercurous chloride electrode, the glass-carbon electrode of the carbon electrode material of ultracapacitor prepared by load the present embodiment is work electrode, energy density and the power density diagram of measuring ultracapacitor as Figure 10, have high energy density 70.6Wh/kg under high power density 160W/kg.
10 grams of excess sludge in domestic sewage plants are dried, pulverize, cross 100 mesh sieves, then, under inert atmosphere, calcine 2 hours for 700 degrees Celsius.Adopt hydrofluoric acid treatment to remove inorganic matter, then 60 degrees Celsius are dried 12 hours, obtain the electrode material of ultracapacitor.By the synthetic electrode material shape appearance figure of scanning electron microscopic observation as shown in figure 11, can see porous pattern.The specific area of testing the electrode material obtaining by nitrogen adsorption desorption is 310m2/g, as shown in figure 12.
The electrochemical workstation that adopts three-electrode system, the 1M H2SO4 aqueous solution is electrolyte, is Pt line to electrode, reference electrode adopts mercury/mercurous chloride electrode, the glass-carbon electrode of the carbon electrode material of ultracapacitor prepared by load the present embodiment is work electrode, measures ultracapacitor performance, as Fig. 6.The capacitance that obtains ultracapacitor prepared by the present embodiment by calculating is 154F/g.
10 grams of paper mill excess sludges are dried, pulverize, cross 100 mesh sieves, and the zinc chloride that is 1:5 with mass ratio mixes.Then under inert atmosphere, calcine 2 hours for 700 degrees Celsius, obtain the electrode material of the ultracapacitor of porous.By the synthetic electrode material shape appearance figure of scanning electron microscopic observation as shown in figure 13, can see porous pattern.The specific area that obtains electrode material by the test of nitrogen adsorption desorption is 132m2/g, as shown in figure 14.
10 grams of excess sludges that are rich in copper are dried, pulverize, cross 100 mesh sieves, then, under inert atmosphere, calcine 2 hours for 600 degrees Celsius.Adopt potassium hydroxide treatment, then 70 degrees Celsius are dried 12 hours, obtain the electrode material of ultracapacitor.By the synthetic electrode material shape appearance figure of transmission electron microscope observing as shown in figure 15, can see that metal oxide nanoparticles loads on porous carbon, be copper oxide nanometer particle/porous carbon combination electrode material.
Adopt the electrochemical workstation of three-electrode system, the 3M KOH aqueous solution is electrolyte, Pt line to electrode, reference electrode adopts silver silver chloride electrode, the glass-carbon electrode of the combination electrode material of ultracapacitor prepared by load the present embodiment is work electrode, measure ultracapacitor performance, result as shown in figure 16.The capacitance that obtains ultracapacitor prepared by the present embodiment by calculating is 443F/g.
Above-described embodiment is preferably execution mode of the present invention; but embodiments of the present invention are not limited by the examples; as; excess sludge can also be steel plant's excess sludge or Electroplate Factory's mud etc.; other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (6)
1. utilize excess sludge to prepare a method for the electrode material of ultracapacitor, it is characterized in that, comprise the following steps:
First excess sludge is dried, pulverizes, crosses 100 mesh sieves, under inert atmosphere, under 400～900 degrees Celsius, calcine 1～3 hour, then remove inorganic matter, after being dried, obtain the electrode material of ultracapacitor.
2. the method for utilizing excess sludge to prepare electrode for super capacitor material according to claim 1, is characterized in that, described removal inorganic matter, is specially: adopt acid treatment, remove inorganic matter.
3. the method for utilizing excess sludge to prepare the electrode material of ultracapacitor according to claim 1, is characterized in that, described removal inorganic matter, is specially: adopt alkali treatment, remove inorganic matter.
4. the method for utilizing excess sludge to prepare the electrode material of ultracapacitor according to claim 2, described acid treatment is for adopting hydrofluoric acid to process.
5. the method for utilizing excess sludge to prepare the electrode material of ultracapacitor according to claim 3, described alkali treatment is for adopting potassium hydroxide to process.
6. the method for utilizing excess sludge to prepare the electrode material of ultracapacitor according to claim 1, is characterized in that, described excess sludge is sanitary sewage excess sludge, paper mill excess sludge, steel plant's excess sludge or Electroplate Factory's mud.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105870465A (en) * | 2016-05-25 | 2016-08-17 | 华南理工大学 | Preparation method of auto-doped carbon catalysis material based on activated sludge domestication |
| CN106024422A (en) * | 2016-05-25 | 2016-10-12 | 华南理工大学 | Method for preparing a capacitive electrode material by using domesticated activated sludge |
| CN106348291A (en) * | 2016-10-13 | 2017-01-25 | 华北电力大学（保定） | Method for preparing active carbon by utilizing urban sludge |
| CN106920966A (en) * | 2017-04-12 | 2017-07-04 | 同济大学 | A kind of carbon-based lithium ion cell negative electrode material and its preparation using sludge as precursor |
| CN108831758A (en) * | 2018-06-12 | 2018-11-16 | 上海电力学院 | A kind of recovery and treatment method of the trade waste of cupric |
| CN110937590A (en) * | 2019-12-19 | 2020-03-31 | 中冶京诚工程技术有限公司 | Preparation method of porous carbon material and prepared porous carbon material |
| CN111646547A (en) * | 2020-05-21 | 2020-09-11 | 中南民族大学 | Preparation method and application of municipal sludge derived carbon material electrode doped with iron and nitrogen |
| CN114773128A (en) * | 2022-04-14 | 2022-07-22 | 昆明理工大学 | Resource utilization method of waste rape leaves |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834008A (en) * | 2006-04-11 | 2006-09-20 | 太原理工大学 | Method of preparing carbon pellets by using heavy oil residue as raw material |
-
2014
- 2014-01-27 CN CN201410040335.6A patent/CN103779111A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834008A (en) * | 2006-04-11 | 2006-09-20 | 太原理工大学 | Method of preparing carbon pellets by using heavy oil residue as raw material |
Non-Patent Citations (4)
| Title |
|---|
| HUANLEI WANG等: "Supercapacitors based on carbons with tuned porosity derived from paper pulp mill sludge biowaste", 《CARBON》 * |
| 朱石清等: "污泥改性活性炭技术及其应用进展", 《中国给水排水》 * |
| 李兰廷等: "含铜活性炭电极材料的制备及电化学性能研究", 《中国矿业大学学报》 * |
| 黄利华: "剩余污泥制备活性炭及其应用研究", 《环境工程学报》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105870465A (en) * | 2016-05-25 | 2016-08-17 | 华南理工大学 | Preparation method of auto-doped carbon catalysis material based on activated sludge domestication |
| CN106024422A (en) * | 2016-05-25 | 2016-10-12 | 华南理工大学 | Method for preparing a capacitive electrode material by using domesticated activated sludge |
| CN105870465B (en) * | 2016-05-25 | 2019-01-29 | 华南理工大学 | A kind of preparation method of the auto-dope carbon catalysis material based on activated sludge acclimatization |
| CN106348291A (en) * | 2016-10-13 | 2017-01-25 | 华北电力大学（保定） | Method for preparing active carbon by utilizing urban sludge |
| CN106920966A (en) * | 2017-04-12 | 2017-07-04 | 同济大学 | A kind of carbon-based lithium ion cell negative electrode material and its preparation using sludge as precursor |
| CN106920966B (en) * | 2017-04-12 | 2019-10-01 | 同济大学 | A kind of carbon-based lithium ion cell negative electrode material and its preparation using sludge as precursor |
| CN108831758A (en) * | 2018-06-12 | 2018-11-16 | 上海电力学院 | A kind of recovery and treatment method of the trade waste of cupric |
| CN110937590A (en) * | 2019-12-19 | 2020-03-31 | 中冶京诚工程技术有限公司 | Preparation method of porous carbon material and prepared porous carbon material |
| CN111646547A (en) * | 2020-05-21 | 2020-09-11 | 中南民族大学 | Preparation method and application of municipal sludge derived carbon material electrode doped with iron and nitrogen |
| CN114773128A (en) * | 2022-04-14 | 2022-07-22 | 昆明理工大学 | Resource utilization method of waste rape leaves |
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Application publication date: 20140507 |