WO2018188422A1 - 一种用于超级电容器的蒜皮基活性炭电极材料及制备方法 - Google Patents
一种用于超级电容器的蒜皮基活性炭电极材料及制备方法 Download PDFInfo
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- activated carbon
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 195
- 240000002234 Allium sativum Species 0.000 title claims abstract description 95
- 235000004611 garlic Nutrition 0.000 title claims abstract description 95
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- 238000004519 manufacturing process Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Definitions
- the invention relates to the technical field of super activated carbon materials, in particular to a garlic-based activated carbon electrode material for a supercapacitor and a preparation method thereof.
- Supercapacitors also known as electrochemical capacitors, electric double layer capacitors
- electrochemical capacitors electric double layer capacitors
- the electrode material is the key material that determines the performance index of the supercapacitor.
- Activated carbon as a porous carbon material, has advantages such as large specific surface area, rich pore structure, stable chemical properties, easy repeated use, simple preparation process and low price, in environmental protection, national defense technology, chemical industry, food processing, There are important applications in the fields of medicine and health. China is rich in resources and is a major producer and exporter of activated carbon. With the rapid development of production, the application of activated carbon itself and various composite materials based on activated carbon will be further expanded, and the amount of activated carbon will continue to increase. In particular, the market for super activated carbon for capacitors is in great demand, but domestic production is small, and most rely on imports.
- Biomass is an important raw material for the preparation of activated carbon. It is mainly used in traditional agro-forestry biomass, including straws of various crops, wood, husks, pits, and rice husks. Most of these biomass materials are wastes of agricultural and forestry products, which are low in cost and low in ash content, and have many pores inside. They are easy to enter the activator, have good reaction performance, are favorable for the formation of pore structure, and have high mechanical strength. Excellent materials with broad market prospects.
- the carbon material prepared by the chemical activation method using biomass as a raw material has a high specific surface area, and is an ideal supercapacitor electrode material.
- Chi-Chang Hu et al. used pistachio shells as raw materials to increase their specific surface area by chemical activation, but at a high sweep speed of 300 mv/s, the specific capacitance was only 47 F/g (Electrhimica Acta 52 (2007) 2498-2505).
- the activated carbon prepared by the method has a high specific surface area, its specific capacitance is relatively attenuated at a high current density, and is not suitable for use under high current operating conditions.
- the Chinese patent (Public No. CN102417179A) discloses that the peanut shell is used as a raw material and activated by KOH, and the activated carbon material has a specific surface area of 1227 m 2 /g, which exhibits good stability as a capacitor electrode material.
- biomass such as straw, wood, husk, pit, rice husk and the like are used as raw materials for preparing capacitor electrode activated carbon, and the activation effect by the activator is poor, and the prepared activated carbon material has a small specific surface area. It is difficult to adjust the pore structure and specific surface area of activated carbon.
- one of the objects of the present invention is to provide an application of the garlic skin in the preparation of an activated carbon electrode material for a supercapacitor.
- China is a large agricultural production country in the world, producing a large amount of agricultural waste every year. A large part of these wastes are directly discarded, which affects the beauty of the environment and may even cause environmental pollution. It is also a great waste of resources.
- China has a long history of planting garlic and a large planting area. However, due to traditional habits, most of the garlic is eaten only during the edible process of garlic, and garlic peel is often discarded as a by-product of processing. This has caused a waste of resources.
- the inventors of the present invention have found through research that the garlic skin has a natural pore structure, and at the same time, the garlic skin is rich in minerals, and these minerals can act as a substitute for the activator to activate the activated carbon.
- the super activated carbon is prepared from garlic skin, and the agricultural waste can be utilized in high quality, and the added value of the industrial chain can be expanded, and a high-performance electrode material for super capacitor can be obtained.
- the second object of the present invention is to provide a method for preparing a garlic-based activated carbon electrode material for a super capacitor. It can fully activate the activated carbon, increase the specific surface area of the activated carbon material, and increase the energy density of the supercapacitor.
- a method for preparing a garlic-based activated carbon electrode material for a supercapacitor heating the garlic skin to 550-700 ° C under an inert atmosphere, carbonizing for a period of time to obtain a garlic charcoal material, and then adding the garlic charcoal material to
- the alkali metal hydroxide solution is immersed in a high temperature for a period of time to obtain an impregnated material, and then the impregnated material is heated to 400-450 ° C for low-temperature activation, and after a low-temperature activation for a period of time, heating is continued to 700-850 ° C for high-temperature activation, and after high-temperature activation for a period of time
- the activated material is obtained, and finally the activated material is post-treated to obtain activated carbon.
- the invention firstly prepares activated carbon by using garlic skin, and pyrolyzes the organic matter in the garlic skin by heating to 550-700 ° C carbonization, changes the structural characteristics of the organic matter and the pore characteristics of the garlic skin, and obtains garlic skin with certain pore and mechanical strength.
- the carbonized material is used as an intermediate material.
- the alkali metal hydroxide is used as an activator to etch the garlic charcoal material.
- low temperature activation is carried out at 400 to 450 ° C to form alkali metal carbonate to promote pore development, and on the other hand, 700 to 850 ° C High temperature activation, this temperature is higher than the boiling point of alkali metal, so that the alkali metal forms alkali metal vapor, and the alkali metal vapor will diffuse into different carbon layers to form a new pore structure; the gaseous alkali metal travels between the layers of the crystallites. The opening layer is twisted and deformed to develop new micropores.
- the alkali metal hydroxide is decomposed during the activation process to generate a gas such as CO 2 , which can further promote the activation, greatly increase the specific surface area of the activated carbon, and improve the quality and adsorption performance of the activated carbon.
- a third object of the present invention is to provide an activated carbon prepared by the above production method.
- the activated carbon prepared by the invention has complete activation, and has a specific surface area of up to 2818.22 m 2 /g, which can provide more active sites capable of adsorbing charges, and is beneficial to increase the energy density of the supercapacitor; the pore volume is as high as 1.32 cm 3 /g, The pore size distribution is concentrated within 4 nm, and the pore size distribution and porosity are adjustable within a certain range.
- a fourth object of the present invention is to provide a garlic-based activated carbon electrode material for a supercapacitor which is prepared by using the above activated carbon.
- a fifth object of the present invention is to provide an application of the above activated carbon in a supercapacitor.
- the activated carbon prepared by the present invention can be applied to various electrolyte systems, and provides a fast channel for ions in the electrolyte, so that it has better high current charge and discharge capacity and energy density.
- the activated carbon prepared by the invention has low ash content and good wettability, and the assembled double electrode system double layer supercapacitor has high specific capacitance, small equivalent series resistance, high charge and discharge efficiency, and low
- the time constant, especially at high magnification, has a high energy density and the like.
- Garlic material itself has a rich fiber pipeline.
- the special structure and composition of these natural materials contribute to the formation of short-range ordered carbon structures and hierarchical porous structures, because their plant epidermis is rich in protein, carbohydrates and fiber. Made up of prime. It has been shown that translucent flake plants do lead to the formation of three-dimensional frameworks which have great benefits for improving electrochemical performance.
- biomass materials such as coconut shell, peanut shell and walnut shell, it is more favorable to obtain a larger specific surface area to provide a storage space for electric charge, and the specific surface area of the garlic-based activated carbon is as high as 2800 m 2 /g;
- the garlic-based activated carbon pore size is concentrated in 0.6 ⁇ 1nm, the main role of the capacitor is the ion-accessible micropores, the pore size is 0.5 to 2 nm).
- 3D hierarchical porous structure a large number of micropores provide abundant accumulation space for electrons; mesopores shorten ion diffusion distance, reduce diffusion resistance, and make ions easily penetrate into internal micropores; macropores act as buffer ion storage layers, which are beneficial to ions transmission;
- the present invention provides a garlic-based activated carbon material for supercapacitor and a preparation method thereof, and the carbonization temperature, carbonization time, alkali-carbon ratio, activation temperature and activation time of the activated carbon specific surface area and pore diameter are studied by orthogonal experiment. The effect is to achieve the most suitable pore size (pore size 0.5 ⁇ 2nm) of the most suitable electron channel by pore size regulation, and improve the electrochemical performance;
- the electrode material provided by the invention has low ash content, small series resistance and high conductivity to ensure large rate charge and discharge performance (Fig. 6) and high power density (power density is 3.37WW/kg when the power density is 3307.64W/kg). Good infiltration to promote ion diffusion and increase ion contactable surface area;
- a supercapacitor can be prepared under high current use conditions, and the current density is 0.5 A/g, 1.0 A/g, 2.0 in a two-electrode test system under the condition of a 6 M KOH aqueous electrolyte.
- the specific capacitances at A/g, 3.0 A/g, and 5.0 A/g were 318.67 F/g, 284.53 F/g, 269.33 F/g, 262.51 F/g, and 253.01 F/g, respectively.
- the specific capacitance at a current density of 1.0 A/g reached 462 F/g under the condition of a 6 M KOH aqueous electrolyte.
- the invention has strong professional application, simple design process, low cost, clean and environmental protection, and easy industrialization.
- Figure 1 is a scanning electron micrograph of activated carbon prepared in Example 1;
- Example 2 is a projection electron micrograph of activated carbon prepared in Example 1;
- Figure 3 is a N 2 adsorption of the activated carbon obtained in Example 1;
- Example 4 is a pore size distribution diagram of activated carbon prepared in Example 1;
- Example 5 is a constant current charge and discharge curve of the activated carbon electrode material prepared in Example 1 in a two-electrode test system (at a current density of 0.5 A/g to 3 A/g);
- Example 6 is a constant current charge and discharge curve of the activated carbon electrode material prepared in Example 1 in a three-electrode test system (at a current density of 1 A/g to 10 A/g);
- Example 7 is a cyclic voltammetry curve of the activated carbon electrode material prepared in Example 1 at a scanning rate of 5 mV/s, 50 mV/s, 100 mV/s, and 200 mV/s in a two-electrode test system;
- Example 8 is a cyclic voltammetry curve of the activated carbon electrode material prepared in Example 1 at a scanning rate of 5 mV/s, 20 mV/s, 50 mV/s, and 100 mV/s in a three-electrode test system;
- Fig. 9 is a 5000 cycle performance of the activated carbon electrode prepared in Example 1 (the measurement method is constant current charge and discharge).
- Figure 10 is a Nyquist diagram of the AC impedance test of the activated carbon electrode material prepared in Example 1.
- the low temperature activation described in the present invention means a step of performing activation at 400 to 450 ° C
- the high temperature activation means a step of activation at 700 to 850 ° C.
- the unit "M" means "mol/L”.
- the high temperature impregnation described in the present invention refers to a step of impregnation at a temperature of 80 to 100 °C.
- the present application proposes that the garlic skin is used in the preparation of the activated carbon electrode material of the supercapacitor.
- the inventors of the present invention have found through research that the garlic skin has a natural pore structure, and at the same time, the garlic skin is rich in minerals, and these minerals can act as a substitute for the activator to activate the activated carbon.
- the use of garlic skin as a raw material for the preparation of activated carbon not only solves the problem of high-quality utilization of waste, but also solves the preparation of an environmentally-friendly and energy-saving material with excellent adsorption performance.
- a method for preparing a garlic-based activated carbon electrode material for a supercapacitor wherein the garlic skin is heated to 550-700 ° C under an inert atmosphere, and carbonization is obtained by holding for a period of time.
- the garlic charcoal material is added to the alkali metal hydroxide solution at a high temperature and then immersed for a period of time to obtain an impregnated material, and then the impregnated material is heated to 400-450 ° C for low-temperature activation, and the low-temperature activation is continued for a while.
- the high temperature activation is performed at 700 to 850 ° C, and the activated material is obtained after a high temperature activation for a period of time. Finally, the activated material is post-treated to obtain activated carbon.
- the activated carbon was prepared from garlic skin, and the organic matter in the garlic skin was pyrolyzed by heating to 550-700 °C carbonization, and the structural characteristics of the organic matter and the pore characteristics of the garlic skin were changed to obtain a garlic charcoal material with certain pore and mechanical strength. Intermediate material.
- the alkali metal hydroxide is used as an activator to etch the garlic charcoal material.
- low temperature activation is carried out at 400 to 450 ° C to form alkali metal carbonate to promote pore development, and on the other hand, 700 to 850 ° C High temperature activation, this temperature is higher than the boiling point of alkali metal, so that the alkali metal forms alkali metal vapor, and the alkali metal vapor will diffuse into different carbon layers to form a new pore structure; the gaseous alkali metal travels between the layers of the crystallites. The opening layer is twisted and deformed to develop new micropores.
- the alkali metal hydroxide is decomposed during the activation process to generate a gas such as CO 2 , which can further promote the activation, greatly increase the specific surface area of the activated carbon, and improve the quality and adsorption performance of the activated carbon.
- the garlic skin In order to increase the charring efficiency of the garlic, it is preferred to subject the garlic skin to a carbonization treatment after pretreatment.
- the step of pretreating is: taking the garlic skin, drying it, drying it for the first time, pulverizing, and passing through a 80 mesh sieve. Can further improve the charring efficiency of garlic.
- the drying temperature is 20 to 30 ° C, and the drying temperature is 100 to 110 ° C.
- the heating rate to 550 to 700 ° C is 5 ° C / min, and the holding time is 2 to 5 h. It ensures that the organic matter in the garlic is completely pyrolyzed.
- the above inert atmosphere means one or more of nitrogen, argon and helium.
- the alkali metal hydroxide solution is a saturated solution of an alkali metal hydroxide. It enables the garlic charcoal to be impregnated with more alkali metal hydroxide.
- the alkali metal hydroxide is one or both of potassium hydroxide and sodium hydroxide. Compared with other alkali metal hydroxides, potassium hydroxide and sodium hydroxide are abundant in source and low in cost.
- the mass ratio of the alkali metal hydroxide to the garlic charcoal is from 3.0 to 4.5:1.
- the temperature of the impregnation is 80 ° C and the time of the impregnation is 2 h. At this temperature, the molecular motion property of the alkali metal hydroxide is high, and the alkali metal hydroxide can be quickly entered into the garlic charcoal. 2h can ensure that a sufficient amount of alkali metal hydroxide enters the garlic charcoal.
- the temperature increase rate to 400 to 450 ° C and the temperature rise to 700 to 850 ° C are both 5 ° C / min.
- the time of the low temperature activation is 45 min.
- the high temperature activation time is from 1 to 2.5 h.
- the post-treatment comprises a first water washing, a pickling, a second water washing, a second drying, and grinding.
- the first water washing and the second water washing in the present embodiment are for indicating two different water washing steps, and are not intended to limit the order of the water washing steps.
- the first drying and the second drying in the present embodiment are for indicating two different drying steps, and are not intended to limit the order of the drying steps.
- the temperature of the first water washing and the second water washing are both 80 °C.
- the specific step of the pickling is to wash the pH to 6-7 with an acid solution at 80 °C.
- the pickling employs an acid solution having a concentration of 0.1 M. Preventing the concentration of the acid solution from being too high, destroying the pores of the activated carbon, thereby reducing the specific surface area of the activated carbon.
- the acid solution is one or more of hydrochloric acid, sulfuric acid, and nitric acid.
- the embodiment also provides an activated carbon prepared by the above preparation method.
- the prepared activated carbon is completely activated, and the super activated carbon with a specific surface area of up to 2818.22 m 2 /g can provide more active sites capable of adsorbing charges, which is beneficial to increase the energy density of the supercapacitor; the pore volume is as high as 1.32 cm 3 /g, and the pore size distribution Concentrated within 4 nm, the pore size distribution and porosity are adjustable within a certain range.
- the embodiment also provides a garlic-based activated carbon electrode material for a supercapacitor, which is prepared by using the above activated carbon.
- the embodiment also provides an application of the above activated carbon in a supercapacitor.
- the activated carbon prepared by the present invention can be applied to various electrolyte systems, and provides a fast passage for ions in the electrolyte to have a more excellent high current charge and discharge capacity and energy density.
- the activated carbon prepared by the invention has low ash content and good wettability, and the assembled double electrode system double layer supercapacitor has high specific capacitance, small equivalent series resistance, high charge and discharge efficiency, and low
- the time constant, especially at high magnification, has a high energy density and the like.
- the raw material garlic skin used in the following examples is taken from Jinxiang, Shandong province, in which water accounts for 3.2-3.6 wt%, ash is 4.5-4.9 wt%, organic matter is 91.5-92.3 wt%, and organic matter is mainly cellulose and lignin. .
- the test results are shown in Figures 5 to 7, for example, in a 6M KOH electrolyte, the current density is 0.5 A/g, 1.0 A/g, 2.0 A/g, 3.0 A/g, and 5.0 A/g, respectively. Up to 318.67F/g, 284.53F/g, 269.33F/g, 262.51F/g, 253.01F/g, 5000 times at a current density of 3.0A/g, the constant current charge and discharge capacity retention rate reached 94%, A practical high power, high energy density ideal supercapacitor material.
- the prepared activated carbon was characterized by a specific surface area of 2,542.77 m 2 /g, a pore volume of 0.93 cm 3 /g, and an average pore diameter of 2.17 nm.
- the capacitance value at a current density of 0.5 A/g was measured by a constant current charge and discharge test in a 6 M KOH solution to be 253.70 F/g.
- the methylene blue adsorption value of activated carbon was 39 mL/0.1 g.
- the prepared activated carbon is completely activated and the micropores are developed.
- the specific surface area was 20727.21 m 2 /g, the pore volume was 0.89 cm 3 /g, and the average pore diameter was 2.24 nm.
- a capacitance value of 191.06 F/g at a current density of 0.5 A/g was measured by a constant current charge and discharge test in a 6 M KOH solution.
- the methylene blue adsorption value of the activated carbon was 35 mL/0.1 g.
- the prepared activated carbon was completely activated, and the micropores were developed, and the specific surface area was 1507.59 m 2 /g, the pore diameter was 0.66 cm 3 /g, and the average pore diameter was 2.30 nm.
- the capacitance value at a current density of 0.5 A/g was measured to be 159.30 F/g using a constant current charge and discharge test in a 6 M KOH solution.
- the methylene blue adsorption value of the activated carbon was 22 mL/0.1 g.
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Abstract
Description
Claims (10)
- 蒜皮在制备超级电容器的活性炭电极材料中的应用。
- 一种用于超级电容器的蒜皮基活性炭电极材料的制备方法,其特征是,将蒜皮在惰性气氛下加热至550~700℃,保温一段时间进行炭化获得蒜皮炭化料,再将蒜皮炭化料加入至碱金属氢氧化物溶液中高温浸渍一段时间获得浸渍物料,然后将浸渍物料升温至400~450℃进行低温活化,低温活化一段时间后继续加热至700~850℃进行高温活化,高温活化一段时间后获得活化料,最后将活化料进行后处理即得活性炭。
- 如权利要求2所述的制备方法,其特征是,将蒜皮进行预处理后进行炭化处理;优选的,所述预处理的步骤为,取蒜皮洗净后晾干或第一次烘干,粉碎,过80目筛;进一步优选的,所述晾干的温度为20~30℃,所述烘干的温度为100~110℃。
- 如权利要求2所述的制备方法,其特征是,加热至550~700℃的升温速率为5℃/min,保温时间为2~5h。
- 如权利要求2所述的制备方法,其特征是,所述碱金属氢氧化物溶液为碱金属氢氧化物的饱和溶液;或,碱金属氢氧化物为氢氧化钾、氢氧化钠中的一种或两种;或,碱金属氢氧化物与蒜皮炭化料的质量比为3.0~4.5:1;或,所述浸渍的温度为80℃,所述浸渍的时间为2h。
- 如权利要求2所述的制备方法,其特征是,升温至400~450℃及升温至700~850℃的升温速率均为5℃/min;或,所述低温活化的时间为45min;或,所述高温活化的时间为1~2.5h。
- 如权利要求2所述的制备方法,其特征是,所述后处理依次包括第一次水洗、酸洗、第二次水洗、第二次烘干、研磨;优选的,所述第一次水洗和第二次水洗的温度均为80℃;优选的,所述酸洗的具体步骤为,采用酸溶液在80℃下洗至pH6~7;优选的,所述酸洗采用的酸溶液的浓度为0.1M;优选的,所述酸溶液为盐酸、硫酸、硝酸中的一种或几种。
- 一种权利要求2~7任一所述的制备方法制备的活性炭。
- 一种用于超级电容器的蒜皮基活性炭电极材料,其特征是,采用权利要求8所述的活性炭制备而得。
- 一种权利要求8所述的活性炭在超级电容器中的应用。
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CN108365184A (zh) * | 2018-01-02 | 2018-08-03 | 江苏大学 | 一种锂离子电池用富碳多孔SiOC负极材料及其制备方法 |
CN108516548A (zh) * | 2018-03-06 | 2018-09-11 | 合肥工业大学 | 一种高介孔率活性炭的制备方法及其获得的活性炭 |
CN108493007A (zh) * | 2018-03-13 | 2018-09-04 | 河南工程学院 | 具有高电化学性能的电极片的制备方法 |
CN108557819B (zh) * | 2018-05-30 | 2020-05-15 | 山东大学 | 蒜基废弃物制备多孔炭材料的方法和应用 |
CN110734061B (zh) * | 2018-07-19 | 2021-12-31 | 深圳市环球绿地新材料有限公司 | 一种超容炭、其制备方法和用途 |
CN110697709B (zh) * | 2019-11-13 | 2021-08-06 | 山东大学 | 一种生物质未燃尽炭制备的多孔炭及在超级电容中的应用 |
CN110817867A (zh) * | 2019-12-12 | 2020-02-21 | 山东大学 | 一种蒜皮基超级活性炭的制备方法及其应用 |
CN111268677A (zh) * | 2020-01-20 | 2020-06-12 | 辽宁大学 | 一种新型锂离子电池负极材料碳化葡萄籽的制备方法及应用 |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104051790A (zh) * | 2014-06-06 | 2014-09-17 | 中南大学 | 一种由大蒜或洋葱制备锂电池的方法 |
CN105845937A (zh) * | 2016-05-12 | 2016-08-10 | 陕西科技大学 | 一种原位构筑三维多孔碳骨架/石墨烯复合结构的方法 |
CN105845915A (zh) * | 2016-05-31 | 2016-08-10 | 陕西科技大学 | 一种三维多孔碳骨架/CoO复合结构锂离子电池负极材料的制备方法 |
CN107039193A (zh) * | 2017-04-14 | 2017-08-11 | 山东大学 | 一种用于超级电容器的蒜皮基活性炭电极材料及制备方法 |
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CN101697322B (zh) * | 2009-10-15 | 2011-01-26 | 青岛大学 | 一种多孔碳电极材料的制备方法 |
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CN104051790B (zh) * | 2014-06-06 | 2016-04-13 | 中南大学 | 一种由大蒜和/或洋葱制备锂电池的方法 |
CN105845937A (zh) * | 2016-05-12 | 2016-08-10 | 陕西科技大学 | 一种原位构筑三维多孔碳骨架/石墨烯复合结构的方法 |
CN105845915A (zh) * | 2016-05-31 | 2016-08-10 | 陕西科技大学 | 一种三维多孔碳骨架/CoO复合结构锂离子电池负极材料的制备方法 |
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