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 PDF

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WO2018188422A1
WO2018188422A1 PCT/CN2018/077494 CN2018077494W WO2018188422A1 WO 2018188422 A1 WO2018188422 A1 WO 2018188422A1 CN 2018077494 W CN2018077494 W CN 2018077494W WO 2018188422 A1 WO2018188422 A1 WO 2018188422A1
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activated carbon
garlic
temperature
activation
garlic skin
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French (fr)
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韩奎华
张晴
王永征
赵建立
李诗杰
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山东大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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.

Abstract

本发明公开了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。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。能够使活性炭完全活化，增加活性炭材料的比表面积，提高超级电容器的能量密度。

Description

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 技术领域
本发明涉及超级活性炭材料技术领域，具体涉及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。
背景技术
超级电容器(也称为电化学电容器，双电层电容器)是一种介于传统电容器和电池之间的新型储能器件，它具有高能量密度，高功率密度，循环寿命长，快速充放电，经济环保等优点。在信息技术、电动汽车、航空航天和国防科技等多个领域具有极其重要和广阔的应用前景。其中，电极材料是决定超级电容器性能指标的关键材料。
活性炭，作为一种多孔炭材料，因其比表面积大、孔结构丰富、化学性能稳定、易反复使用、制备工艺流程简便、价格低廉等优点，在环境保护、国防科技、化学工业、食品加工、医药卫生等领域有着重要应用。我国资源丰富,是活性炭的生产和出口大国。伴随生产的快速发展，活性炭本身以及以活性炭为基础的各种复合材料的应用将得到进一步扩展,活性炭的用量也将不断增长。尤其电容用超级活性炭市场需求巨大，但国内生产量很小，绝大部分依赖进口。
生物质是一种重要的活性炭制备原材料，常用的主要是传统的农林业生物质，包括各种农作物秸杆，木材、果壳、果核、稻壳等。此类生物质材料多为农林产品废弃物，成本低廉且灰分含量低，内部又有许多孔隙，容易使活化剂进入，反应性能良好，有利于孔隙结构的形成，机械强度高，是制备活性炭的优良材料，具有广阔的市场前景。
目前在超级电容器的各种电极材料中，以生物质为原料通过化学活化方法制备的碳材料具有较高的比表面积，是一种较为理想的超级电容器电极材料。Chi-Chang Hu等人采用开心果壳作为原料通过化学活化提高其比表面积，但是在300mv/s的高扫速下比电容仅有47F/g(Electrhimica Acta52(2007)2498-2505)，该种方法制备的活性炭虽然有较高的比表面积，但是其比电容值在高电流密度下衰减相对严重，不适合在大电流下操作条件下使用。
中国专利(公开号CN102417179A)公开了采用花生壳为原料，用KOH进行活化处理，所得活性炭材料的比表面积达到1227m 2/g，其作为电容器电极材料表现出较好的稳定性。
然而上述现有技术中采用秸杆、木材、果壳、果核、稻壳等生物质作为制备电容器电极活性炭的原料，存在利用活化剂的活化效果较差、制备的活性炭材料的比表面积较小、 难以对活性炭的孔隙结构和比表面积进行调整等问题。
发明内容
为了克服现有技术的缺陷，本发明的目之一是提供了蒜皮在制备超级电容器的活性炭电极材料中的应用。
我国是世界上的农业生产大国,每年产生大量的农业废弃物。这些废弃物中很大一部分被直接丢弃，影响了环境的美观、甚至可能造成环境的污染，同时也是资源的极大浪费。我国作为大蒜的原产地，对大蒜的种植历史悠久，种植面积大。然而，由于传统习惯，在大蒜的食用过程中多数仅选择蒜肉食用，大蒜皮作为加工副产物常被抛弃。造成了资源浪费。本发明的发明人通过研究发现蒜皮具有天然的孔隙结构，同时蒜皮中含有丰富的矿物质，这些矿物质可代替活化剂起到一定的活化作用，从而使得活性炭完全活化。蒜皮制备超级活性炭，可以将农业废弃物高质化利用，既拓展产业链附加值，又可以获得一种超级电容用高性能电极材料。
为了实现蒜皮在制备超级电容器的活性炭电极材料中的应用、增加活性炭材料的比表面积等目的，本发明的目的之二是提供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，能够使活性炭完全活化，增加活性炭材料的比表面积，提高超级电容器的能量密度。
为了实现上述目的，本发明的制备方法的技术方案为：
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，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。
本发明，首先，采用蒜皮制备活性炭，通过加热至550～700℃炭化对蒜皮中的有机物进行热解，改变有机物的结构特征和蒜皮孔隙特征，得到具有一定孔隙和机械强度的蒜皮炭化料作为中间物料。其次，使用碱金属氢氧化物作为活化剂刻蚀蒜皮炭化料，一方面，在400～450℃进行低温活化，生成碱金属的碳酸盐使孔隙发展，另一方面，700～850℃进行高温活化，此温度高于碱金属的沸点，使碱金属形成碱金属蒸汽，碱金属蒸汽会扩散入不同的碳层，形成新的孔结构；气态碱金属在微晶的层片间穿行，撑开方向层片等其发生扭曲变形，开发出新的微孔。第三，碱金属氢氧化物活化过程中分解产生CO 2等气体，这些气体能起到进一步促进活化作用的进行，大大增加活性炭的比表面积，提高活性炭的质量和吸附性能。
本发明的目的之三是提供一种上述制备方法制备的活性炭。
本发明制得的活性炭活化完全，其比表面积高达2818.22m 2/g，可以提供更多能吸附电荷的活性位点，有利于提高超级电容器的能量密度；其孔容高达1.32cm 3/g，孔径分布集中在4nm以内，孔径分布和孔隙率一定范围内可调。
本发明的目的之四是提供一种用于超级电容器的蒜皮基活性炭电极材料，采用上述活性炭制备而得。
本发明的目的之五是提供一种上述活性炭在超级电容器中的应用。
首先，本发明制备的活性炭可适用于各种电解液体系，且为电解液中的离子提供快速的通道，使其具有更优良的大电流充放电能力及其能量密度。其次，本发明制备的活性炭灰分低，浸润性好，组装成得二电极体系双电层超级电容器具有较高的比电容、较小的等效串联电阻、较高的充放电效率，以及低的时间常数，特别是在高倍率下充放电具有较高的能量密度等。
本发明的有益效果为：
1.蒜皮材料自身有丰富的纤维管道，这些天然材料的特殊结构和组成有助于短程有序的碳结构和层次多孔结构形成，因为它们的植物表皮是由丰富的蛋白质，碳水化合物和纤维素构成的。已经证明，半透明薄片植物确实导致了三维框架的形成，这种结构对提高电化学性能有很大的好处。(添加)与其它生物质材料如椰壳、花生壳、核桃壳相比，更有利于得到较大的比表面积来提供电荷的储存空间，蒜皮基活性炭比表面积高达2800m 2/g；
2.同样利于合理的孔及孔径分布来平衡比电容与倍率性能之间的要求(蒜皮基活性炭孔径集中分布在0.6～1nm，对电容起主要作用的是离子可进入的微孔，孔径为0.5～2nm)。3D层次多孔结构：大量微孔为电子提供了丰富的累积空间；中孔缩短了离子扩散距离，降低了扩散阻力，使得离子易于渗入内部微孔；大孔作为缓冲离子的存储层，有利于离子传输；
3.本发明提供了一种超级电容器用蒜皮基活性炭材料及其制备方法，采用正交实验法研究了炭化温度、炭化时间、碱碳比、活化温度、活化时间对活性炭比表面积和孔径的影响，其目的是可以通过孔径调控达到最合适电子通道的最可几孔径(孔径0.5～2nm)，提高电化学性能；
4.本发明提供的电极材料灰分低，串联电阻小，导电率高来确保大倍率充放电性能(如图6)和高功率密度(能量密度为8.79Wh/kg时功率密度为3307.64W/kg)；良好的浸润性以促进离子扩散，增加离子可接触表面积；
5.采用本发明的活性炭能够制备出在大电流使用条件下的超级电容器，其在两电极测试***中，6M KOH水系电解液条件下，电流密度为0.5A/g，1.0A/g，2.0A/g，3.0A/g，5.0A/g时的比电容分别达到318.67F/g，284.53F/g，269.33F/g，262.51F/g,253.01F/g。其在三电极测试***中，6M KOH水系电解液条件下，电流密度为1.0A/g时的比电容达到462F/g。
6.本发明专业应用性强，并且设计工艺过程简单，成本较低、清洁环保，易于产业化实现。
附图说明
构成本申请的一部分的说明书附图用来提供对本申请的进一步理解，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的不当限定。
图1是实施例1制得的活性炭的扫描电镜照片；
图2是实施例1制得的活性炭的投射电镜照片；
图3是实施例1制得的活性炭的N 2吸附脱附图；
图4是实施例1制得的活性炭孔径分布图；
图5是实施例1制备的活性炭电极材料在两电极测试***中(0.5A/g-3A/g电流密度下)恒电流充放电曲线；
图6是实施例1制备的活性炭电极材料在三电极测试***中(1A/g-10A/g电流密度下)恒电流充放电曲线；
图7是实施例1制备的活性炭电极材料在两电极测试***中在5mV/s，50mV/s，100mV/s，200mV/s的扫描速率下的循环伏安曲线；
图8是实施例1制备的活性炭电极材料在三电极测试***中在5mV/s，20mV/s，50mV/s，100mV/s的扫描速率下的循环伏安曲线；
图9是实施例1制备的活性炭电极的5000次循环性能(测定方法为恒电流充放电)。
图10是实施例1制备的活性炭电极材料交流阻抗测试的奈奎斯特图。
具体实施方式
应该指出，以下详细说明都是例示性的，旨在对本申请提供进一步的说明。除非另有指明，本文使用的所有技术和科学术语具有与本申请所属技术领域的普通技术人员通常理解的相同含义。
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本申请的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包 括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。
本发明中所述的低温活化是指在400～450℃进行活化的步骤，而所述的高温活化是指700～850℃进行活化的步骤。
本发明中单位“M”表示“mol/L”。
本发明中所述的高温浸渍是指温度为80～100℃的浸渍的步骤。
正如背景技术所介绍的，现有技术中存在利用活化剂的活化效果较差、活性炭活化不完全的缺陷，为了解决如上的技术问题，本申请提出了蒜皮在制备超级电容器的活性炭电极材料中的应用。
本发明的发明人通过研究发现蒜皮具有天然的孔隙结构，同时蒜皮中含有丰富的矿物质，这些矿物质可代替活化剂起到一定的活化作用，从而使得活性炭完全活化。利用蒜皮作为活性炭制备的原材料，既解决废弃物高质化利用，又解决制备一种吸附性能优异的环保、能源材料。
本发明的一种典型的实施方式中，提供了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，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后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。
首先，采用蒜皮制备活性炭，通过加热至550～700℃炭化对蒜皮中的有机物进行热解，改变有机物的结构特征和蒜皮孔隙特征，得到具有一定孔隙和机械强度的蒜皮炭化料作为中间物料。其次，使用碱金属氢氧化物作为活化剂刻蚀蒜皮炭化料，一方面，在400～450℃进行低温活化，生成碱金属的碳酸盐使孔隙发展，另一方面，700～850℃进行高温活化，此温度高于碱金属的沸点，使碱金属形成碱金属蒸汽，碱金属蒸汽会扩散入不同的碳层，形成新的孔结构；气态碱金属在微晶的层片间穿行，撑开方向层片等其发生扭曲变形，开发出新的微孔。第三，碱金属氢氧化物活化过程中分解产生CO 2等气体，这些气体能起到进一步促进活化作用的进行，大大增加活性炭的比表面积，提高活性炭的质量和吸附性能。
为了将提高蒜皮炭化效率，优选的，将蒜皮进行预处理后进行炭化处理。
进一步优选的，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。能够进一步提高蒜皮炭化效率。
更进一步优选的，所述晾干的温度为20～30℃，所述烘干的温度为100～110℃。
优选的，加热至550～700℃的升温速率为5℃/min，保温时间为2～5h。能够保证蒜皮中 的有机物完全热解。
上述惰性气氛是指氮气、氩气、氦气中的一种或几种。
优选的，所述碱金属氢氧化物溶液为碱金属氢氧化物的饱和溶液。能够使蒜皮炭化料能够浸渍更多的碱金属氢氧化物。
优选的，碱金属氢氧化物为氢氧化钾、氢氧化钠中的一种或两种。氢氧化钾、氢氧化钠的相比其他碱金属氢氧化物，来源丰富，成本较低。
优选的，碱金属氢氧化物与蒜皮炭化料的质量比为3.0～4.5:1。
优选的，所述浸渍的温度为80℃，所述浸渍的时间为2h。该温度下碱金属氢氧化物的分子运动性能较高，能够使碱金属氢氧化物快速进入蒜皮炭化料中。2h能够保证足量的碱金属氢氧化物进入到蒜皮炭化料中。
优选的，升温至400～450℃及升温至700～850℃的升温速率均为5℃/min。
优选的，所述低温活化的时间为45min。
优选的，所述高温活化的时间为1～2.5h。
优选的，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。
本实施方式中所述第一次水洗、第二次水洗是为了表示两次不同的水洗步骤，并不是为了限定水洗步骤的先后次序。
本实施方式中所述第一次烘干、第二次烘干是为了表示两次不同的烘干步骤，并不是为了限定烘干步骤的先后次序。
进一步优选的，所述第一次水洗和第二次水洗的温度均为80℃。
进一下优选的，所述酸洗的具体步骤为，采用酸溶液在80℃下洗至pH 6～7。
进一步优选的，所述酸洗采用的酸溶液的浓度为0.1M。防止酸溶液浓度过高，破坏活性炭的孔隙，从而降低活性炭的比表面积。
进一步优选的，所述酸溶液为盐酸、硫酸、硝酸中的一种或几种。
本实施方式还提供了一种上述制备方法制备的活性炭。
制得的活性炭活化完全，比表面积高达2818.22m 2/g的超级活性炭，可以提供更多能吸附电荷的活性位，有利于提高超级电容器的能量密度；孔容高达1.32cm 3/g，孔径分布集中在4nm以内，孔径分布和孔隙率一定范围内可调。
本实施方式还提供了一种用于超级电容器的蒜皮基活性炭电极材料，采用上述活性炭制备而得。
本实施方式还提供了一种上述活性炭在超级电容器中的应用。
首先，本发明制备的活性炭可适用于各种电解液体系，且为电解液中的离子提供快速 的通道，使其具有更优良的大电流充放电能力及其能量密度。其次，本发明制备的活性炭灰分低，浸润性好，组装成得二电极体系双电层超级电容器具有较高的比电容、较小的等效串联电阻、较高的充放电效率，以及低的时间常数，特别是在高倍率下充放电具有较高的能量密度等。
为了使得本领域技术人员能够更加清楚地了解本申请的技术方案，以下将结合具体的实施例与对比例详细说明本申请的技术方案。
原料说明：以下实施例中采用的原料蒜皮，取自山东金乡，其中水分占3.2～3.6wt％，灰分4.5～4.9wt％，有机质91.5～92.3wt％，有机质主要为纤维素和木质素。
实施例1
取蒜皮洗净后晾干或烘干，粉碎，过80目筛，制得蒜皮粉末；将蒜皮粉放置于管式电阻炉中，在惰性气氛(流量为2L/min)下加热至600℃，升温速率为5℃/min，保温2h，冷却至室温，制得蒜皮炭化料；室温下，按照KOH固体与蒜皮炭化料的质量比为4:1，取蒜皮炭化料6g，对应的KOH固体为24g，将饱和KOH溶液与蒜皮炭化料充分搅拌混合，后将其放入鼓风干燥箱以80℃高温浸渍2h，得浸渍后物料；将浸渍后物料放入马弗炉进行活化，从室温以升温速率5℃/min升温至400℃进行低温活化，保温45min，后以相同的升温速率升温至800℃进行高温活化，保温2.5h，活化结束后将刚玉坩埚取出，自然冷却至室温，即得活化料；取出活化料，用80℃蒸馏水水洗，后用0.1M的HCl溶液在80℃高温下酸洗至中性pH 6～7，随后依然用80℃蒸馏水水洗，最后105℃条件下烘干，研磨，制得活性炭3.03g。对制备的活性炭进行结构表征，结构表征结果如图1～4所示，从图1～4中能够表明所制备的活性炭活化完全，微孔发达，比表面积2818.22m 2/g，孔容为1.32cm 3/g，平均孔径2.62nm。将上述蒜皮基活性炭按活化物质：导电剂：粘结剂＝80：10：10的比例进行混合，制成电极片。在6M KOH溶液中采用循环伏安法在不同扫描速率下进行比电容的测试。其测试结果如图5～7所示，例如，在6M KOH电解质中电流密度为0.5A/g，1.0A/g，2.0A/g，3.0A/g，5.0A/g下的比电容分别达到318.67F/g，284.53F/g，269.33F/g，262.51F/g，253.01F/g，5000次在3.0A/g的电流密度下恒电流充放电电容量保持率达到94％，是一种实用性的高功率、高能量密度的理想超级电容器材料。
实施例2
取蒜皮洗净后晾干或烘干，粉碎，过80目筛，制得蒜皮粉末；将蒜皮粉放置于管式电阻炉中，在惰性气氛(流量为2L/min)下加热至600℃，升温速率为5℃/min，保温2h，冷却至室温，制得蒜皮炭化料；室温下，按照KOH固体与蒜皮炭化料的质量比为3.5:1，取蒜皮炭化料6g，对应的KOH固体为24g，将饱和KOH溶液与蒜皮炭化料充分搅拌混合， 后将其放入鼓风干燥箱以80℃高温浸渍2h，得浸渍后物料；将浸渍后物料放入马弗炉进行活化，从室温以升温速率5℃/min升温至400℃进行低温活化，保温45min，后以相同的升温速率升温至850℃进行高温活化，保温2h，活化结束后将刚玉坩埚取出，自然冷却至室温，即得活化料；取出活化料，用80℃蒸馏水水洗，后用0.1M的HCl溶液在80℃高温下酸洗至中性pH6～7，随后依然用80℃蒸馏水水洗，最后105℃条件下烘干，研磨，制得活性炭3.91g。对制备的活性炭进行结构表征，比表面积2542.77m 2/g，孔容为0.93cm 3/g，平均孔径2.17nm。将上述蒜皮基活性炭按活化物质：导电剂：粘结剂＝80：10：10的比例进行混合，制成电极片。在6M KOH溶液中采用恒电流充放电测试测得0.5A/g的电流密度下电容值为253.70F/g。且活性炭的亚甲基蓝吸附值为39mL/0.1g。
实施例3
取蒜皮洗净后晾干或烘干，粉碎，过80目筛，制得蒜皮粉末；将蒜皮粉放置于管式电阻炉中，在惰性气氛(流量为2L/min)下加热至600℃，升温速率为5℃/min，保温5h，冷却至室温，制得蒜皮炭化料；室温下，按照KOH固体与蒜皮炭化料的质量比为4:1，取蒜皮炭化料6g，对应的KOH固体为24g，将饱和KOH溶液与蒜皮炭化料充分搅拌混合，后将其放入鼓风干燥箱以80℃高温浸渍2h，得浸渍后物料；将浸渍后物料放入马弗炉进行活化，从室温以升温速率5℃/min升温至400℃进行低温活化，保温45min，后以相同的升温速率升温至800℃进行高温活化，保温1h，活化结束后将刚玉坩埚取出，自然冷却至室温，即得活化料；取出活化料，用80℃蒸馏水水洗，后用0.1M的HCl溶液在80℃高温下酸洗至中性pH6～7，随后依然用80℃蒸馏水水洗，最后105℃条件下烘干，研磨，制得活性炭3.72g。所制备的活性炭活化完全，微孔发达。比表面积为2077.21m 2/g，孔容为0.89cm 3/g，平均孔径为2.24nm。将上述蒜皮基活性炭按活化物质：导电剂：粘结剂＝80：10：10的比例进行混合，制成电极片。在6M KOH溶液中采用恒电流充放电测试测得在0.5A/g的电流密度下电容值为191.06F/g。且活性炭的亚甲基蓝吸附值为35mL/0.1g。
实施例4
取蒜皮洗净后晾干或烘干，粉碎，过80目筛，制得蒜皮粉末；将蒜皮粉放置于管式电阻炉中，在惰性气氛(流量为2L/min)下加热至550℃，升温速率为5℃/min，保温5h，冷却至室温，制得蒜皮炭化料；室温下，按照KOH固体与蒜皮炭化料的质量比为4.5:1，取蒜皮炭化料6g，对应的KOH固体为24g，将饱和KOH溶液与蒜皮炭化料充分搅拌混合，后将其放入鼓风干燥箱以80℃高温浸渍2h，得浸渍后物料；将浸渍后物料放入马弗炉进行活化，从室温以升温速率5℃/min升温至400℃进行低温活化，保温45min，后以相同的升温速率升温至750℃进行高温活化，保温2h，活化结束后将刚玉坩埚取出，自然冷却至室温，即得 活化料；取出活化料，用80℃蒸馏水水洗，后用0.1M的HCl溶液在80℃高温下酸洗至中性pH6～7，随后依然用80℃蒸馏水水洗，最后105℃条件下烘干，研磨，制得活性炭4.96g。所制备的活性炭活化完全，微孔发达，比表面积1507.59m 2/g，孔径为0.66cm 3/g，平均孔径2.30nm。将上述蒜皮基活性炭按活化物质：导电剂：粘结剂＝80：10：10的比例进行混合，制成电极片。在6M KOH溶液中采用恒电流充放电测试测得在0.5A/g的电流密度下电容值为159.30F/g。且活性炭的亚甲基蓝吸附值为22mL/0.1g。
上述虽然结合附图对本发明的具体实施方式进行了描述，但并非对发明保护范围的限制，所属领域技术人员应该明白，在本发明的技术方案的基础上，本领域技术人员不需要付出创造性劳动即可做出的各种修改或变形仍在本发明的保护范围内。

Claims (10)

  1. 蒜皮在制备超级电容器的活性炭电极材料中的应用。
  2. 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。
  3. 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℃。
  4. 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。
  5. 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。
  6. 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。
  7. 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。
  8. 一种权利要求2～7任一所述的制备方法制备的活性炭。
  9. 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。
  10. 一种权利要求8所述的活性炭在超级电容器中的应用。
PCT/CN2018/077494 2017-04-14 2018-02-28 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 WO2018188422A1 (zh)

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