CN107039193A - A kind of garlic skin matrix activated carbon electrode material and preparation method for ultracapacitor - Google Patents

A kind of garlic skin matrix activated carbon electrode material and preparation method for ultracapacitor Download PDF

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CN107039193A
CN107039193A CN201710243663.XA CN201710243663A CN107039193A CN 107039193 A CN107039193 A CN 107039193A CN 201710243663 A CN201710243663 A CN 201710243663A CN 107039193 A CN107039193 A CN 107039193A
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garlic skin
activated carbon
temperature
time
preparation
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CN107039193B (en
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韩奎华
张晴
王永征
赵建立
李诗杰
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Shandong University
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Shandong University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • H01G11/34Carbon-based characterised by carbonisation or activation of carbon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/12Surface area
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/14Pore volume
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/16Pore diameter
    • C01P2006/17Pore diameter distribution
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/40Electric properties
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

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  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a kind of garlic skin matrix activated carbon electrode material and preparation method for ultracapacitor.Garlic skin is heated to 550~700 DEG C under an inert atmosphere, insulation a period of time carries out charing and obtains garlic skin carbonized material, garlic skin carbonized material is added to alkali hydroxide soln high temperature time of infusion again and obtains dipping material, then dipping material is warming up to 400~450 DEG C of progress low-temperature activations, low-temperature activation continues to be heated to 700~850 DEG C of progress high-temperature activations for a period of time afterwards, high-temperature activation obtains activated material afterwards for a period of time, and activated material progress post processing finally is produced into activated carbon.Activated carbon can be made to activate completely, increase the specific surface area of absorbent charcoal material, improve the energy density of ultracapacitor.

Description

A kind of garlic skin matrix activated carbon electrode material and preparation method for ultracapacitor
Technical field
The present invention relates to super active carbon material technical field, and in particular to a kind of garlic skin base for ultracapacitor is lived Property carbon electrode material and preparation method.
Background technology
Ultracapacitor (also referred to as electrochemical capacitor, double layer capacitor) is one kind between traditional capacitor and battery Between new type of energy storage device, it has high-energy-density, and high power density has extended cycle life, and fast charging and discharging is economic and environment-friendly The advantages of.There is of crucial importance and wide answer in multiple fields such as information technology, electric automobile, Aero-Space and science and techniques of defence Use prospect.Wherein, electrode material is the critical material for determining performance of the supercapacitor index.
Activated carbon, as a kind of porous carbon material, because its specific surface area is big, pore structure abundant, stable chemical performance, easily anti- Multiple use, preparation technology simple flow, it is cheap the advantages of, environmental protection, science and techniques of defence, chemical industry, food processing, There is important application in the fields such as medical and health.China natural resources are enriched, and are production and the big export country of activated carbon.With the fast of production Speed development, the application of various composites of the activated carbon and based on activated carbon in itself will be further expanded, activity The consumption of charcoal also will constantly increase.Especially electric capacity is huge with the super-activated carbon market demand, but domestic production amount very little, portion big absolutely Divide dependence on import.
Biomass is that a kind of important activated carbon prepares raw material, conventional mainly traditional agriculture and forestry biomass, bag Include various crop stalks, timber, shell, fruit stone, rice husk etc..Such biological material is generally agriculture and forestry product discarded object, cost It is cheap and content of ashes is low, it is internal to have many holes again, easily enter activator, reactivity worth is good, is conducive to hole knot The formation of structure, high mechanical strength is the excellent material for preparing activated carbon, with wide market prospects.
At present in the various electrode materials of ultracapacitor, prepared by raw material of biomass by chemical activation method Carbon material has higher specific surface area, is a kind of ideal electrode material for super capacitor.Chi-Chang Hu et al. Its specific surface area is improved by chemical activation as raw material using Fructus Pistaciae Verae shell, but specific capacitance under speed is swept in 300mv/s height Although only 47F/g (Electrhimica Acta52 (2007) 2498-2505), activated carbon prepared by this kind of method has higher Specific surface area, but its specific capacitance value decays relatively serious at higher current densities, is not suitable for the operating condition under high current Under use.
Chinese patent (publication number CN102417179A), which is disclosed, uses peanut shell for raw material, and activation process is carried out with KOH, The specific surface area of gained absorbent charcoal material reaches 1227m2/ g, it shows preferable stability as capacitor electrode material.
But it is above-mentioned in the prior art using straw, timber, shell, fruit stone, the biomass such as rice husk as preparing capacitor The raw material of electrode activity charcoal, the specific surface area that there is the absorbent charcoal material that the activation effect using activator is poor, prepare is smaller, The problems such as being difficult to be adjusted the pore structure and specific surface area of activated carbon.
The content of the invention
In order to overcome the defect of prior art, one of mesh of the invention there is provided garlic skin and prepare the work of ultracapacitor Application in property carbon electrode material.
China is agricultural production big country in the world, and substantial amounts of agricultural wastes are produced every year.It is very big in these discarded objects A part is simply discarded, have impact on environment it is attractive in appearance, the pollution of environment is possibly even caused, while being also the very big wave of resource Take.China is as the original producton location of garlic, and the plantation to garlic is with a long history, and cultivated area is big.However, due to traditional habit, Garlic it is edible during most only selection garlics meats use, Cortex Bulbus Allii is often abandoned as processing byproduct.Cause resource wave Take.The present inventor has found that garlic skin has natural pore structure by studying, while containing abundant mineral in garlic skin Matter, these mineral matters can play certain activation instead of activator, so that activated carbon is activated completely.Garlic skin prepares super Level activated carbon, agricultural wastes high-qualityization can be utilized, both expanded industrial chain added value, a kind of super capacitor can be obtained again Use high performance electrode material.
In order to realize application of the garlic skin in the active carbon electrode material of ultracapacitor is prepared, increase absorbent charcoal material The purposes such as specific surface area, the second object of the present invention is to provide a kind of garlic skin matrix activated carbon electrode material for ultracapacitor Preparation method, activated carbon can be made to activate completely, increase absorbent charcoal material specific surface area, improve ultracapacitor energy Density.
To achieve these goals, the technical scheme of preparation method of the invention is:
A kind of preparation method of garlic skin matrix activated carbon electrode material for ultracapacitor, by garlic skin under an inert atmosphere 550~700 DEG C are heated to, insulation a period of time carries out charing and obtains garlic skin carbonized material, then garlic skin carbonized material is added to alkali gold Belong to hydroxide solution high temperature time of infusion and obtain dipping material, dipping material then is warming up into 400~450 DEG C enters Row low-temperature activation, low-temperature activation continues to be heated to for a period of time 700~850 DEG C of progress high-temperature activations afterwards, during one section of high-temperature activation Between after obtain activated material, finally by activated material progress post processing produce activated carbon.
The present invention, first, activated carbon is prepared using garlic skin, by being heated to 550~700 DEG C of charings to organic in garlic skin Thing is pyrolyzed, and is changed the architectural feature and garlic skin pore character of organic matter, is obtained the garlic with certain hole and mechanical strength Skin carbonized material is used as intermediate material.Secondly, garlic skin carbonized material is etched using alkali metal hydroxide as activator, on the one hand, Low-temperature activation is carried out at 400~450 DEG C, the carbonate of generation alkali metal makes Pore development, on the other hand, 700~850 DEG C of progress High-temperature activation, this temperature is higher than the boiling point of alkali metal, makes alkali metal formation vapour of an alkali metal, and vapour of an alkali metal can diffuse into difference Carbon-coating, form new pore structure;Gaseous alkali metal is walked between the synusia of crystallite, struts its change that is distorted such as direction synusia Shape, develops new micropore.3rd, decompose in alkali metal hydroxide activation process and produce CO2Deng gas, these gases can rise To the progress of further promotion activation, the specific surface area of activated carbon is greatly increased, the quality and adsorptivity of activated carbon is improved Energy.
The third object of the present invention is to provide activated carbon prepared by a kind of above-mentioned preparation method.
Activated carbon activation produced by the present invention is complete, and its specific surface area is up to 2818.22m2/ g, can provide the suction of more multipotency The avtive spot of attached electric charge, is conducive to improving the energy density of ultracapacitor;Its pore volume is up to 1.32cm3/ g, pore-size distribution Concentrate within 4nm, it is adjustable in pore-size distribution and porosity certain limit.
The fourth object of the present invention is to provide a kind of garlic skin matrix activated carbon electrode material for ultracapacitor, using upper Activated carbon is stated to be prepared.
The fifth object of the present invention is to provide a kind of application of above-mentioned activated carbon in ultracapacitor.
First, the activated carbon that prepared by the present invention is applicable to various electrolyte systems, and is provided for the ion in electrolyte Quick passage, makes it have more excellent high current charge-discharge ability and its energy density.Secondly, the activity that prepared by the present invention Charcoal ash are point low, and wellability is good, be assembled into two electrode system double electric layers supercapacitors have higher specific capacitance, less etc. Series resistance, higher efficiency for charge-discharge, and low time constant are imitated, discharge and recharge has higher particularly under high magnification Energy density etc..
Beneficial effects of the present invention are:
1. garlic skin material itself has abundant fiber conduit, with other biological materials such as coconut husk, peanut shell, walnut shell phase Than being more beneficial for obtaining larger specific surface area providing the storage area of electric charge, garlic skin matrix activated carbon specific surface area is up to 2800m2/g;Similarly serving to favor rational hole and pore-size distribution, (garlic skin base is lived to balance the requirement between specific capacitance and high rate performance Property charcoal aperture integrated distribution in 0.6~1nm, what electric capacity was played a major role is the enterable micropore of ion, aperture be 0.5~ 2nm);
2. the invention provides a kind of ultracapacitor garlic skin matrix activated carbon material and preparation method thereof, using orthogonal reality The method of testing have studied carbonization temperature, carbonization time, alkali carbon ratio, activation temperature, soak time to activated carbon specific surface area and aperture Influence, the purpose is to reach the most probable pore size (0.5~2nm of aperture) of most suitable electron channel by aperture control, is carried High electrochemical performance;
3. the electrode material ash content that the present invention is provided is low, series resistance is small, and conductance height ensures high rate charge-discharge Can (such as Fig. 6) and high power density (power density is 3307.64W/kg when energy density is 8.79Wh/kg);Good infiltration Property to promote ion to spread, increase ion accessible surface product;
4. can prepare the ultracapacitor under high current use condition using the activated carbon of the present invention, it is in water system Under electrolyte conditions, current density is 0.5A/g, 1.0A/g, 2.0A/g, 3.0A/g, and the specific capacitance under 5.0A/g is respectively reached 318.67F/g, 284.53F/g, 269.33F/g, 262.51F/g, 253.01F/g.
5. professional application of the present invention is strong, and design technology process is simple, and cost is relatively low, clean environment firendly, it is easy to industry Change and realize.
Brief description of the drawings
The Figure of description for constituting the part of the application is used for providing further understanding of the present application, and the application's shows Meaning property embodiment and its illustrate be used for explain the application, do not constitute the improper restriction to the application.
Fig. 1 is the stereoscan photograph of activated carbon made from embodiment 1;
Fig. 2 is the N of activated carbon made from embodiment 12Adsorption/desorption figure;
Fig. 3 is activated carbon pore size distribution map made from embodiment 1;
Fig. 4 is activated carbon capillary graph of pore diameter distribution made from embodiment 1;
Fig. 5 is the constant current charge-discharge curve under 0.5A/g electric currents of activated carbon electrodes prepared by embodiment 1;
Fig. 6 be embodiment 1 prepare activated carbon electrodes in 5mV/s, 10mV/s, 20mV/s, 50mV/s, 100mV/s's sweeps Retouch the cyclic voltammetry curve under speed;
Fig. 7 is 5000 cycle performances of activated carbon electrodes prepared by embodiment 1 (assay method is constant current charge-discharge).
Embodiment
It is noted that described further below is all exemplary, it is intended to provide further instruction to the application.Unless another Indicate, all technologies used herein and scientific terminology are with usual with the application person of an ordinary skill in the technical field The identical meanings of understanding.
It should be noted that term used herein above is merely to describe embodiment, and be not intended to restricted root According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative It is also intended to include plural form, additionally, it should be understood that, when in this manual using term "comprising" and/or " bag Include " when, it indicates existing characteristics, step, operation, device, component and/or combinations thereof.
Heretofore described low-temperature activation refers to the step of being activated for 400~450 DEG C, and described high-temperature activation Refer to 700~850 DEG C the step of activated.
Unit " M " expression " mol/L " in the present invention.
The step of heretofore described high temperature dipping refers to the dipping that temperature is 80~100 DEG C.
As background technology is introduced, there is that the activation effect using activator is poor, activated carbon is lived in the prior art Change incomplete defect, in order to solve technical problem as above, the activity of ultracapacitor is being prepared present applicant proposes garlic skin Application in carbon electrode material.
The present inventor has found that garlic skin has natural pore structure by studying, while containing what is enriched in garlic skin Mineral matter, these mineral matters can play certain activation instead of activator, so that activated carbon is activated completely.Utilize garlic The raw material that skin is prepared as activated carbon, had both solved the utilization of discarded object high-qualityization, solved that to prepare a kind of absorption property excellent again Environmental protection, energy and material.
There is provided a kind of garlic skin matrix activated carbon electricity for ultracapacitor in a kind of typical embodiment of the present invention The preparation method of pole material, garlic skin is heated under an inert atmosphere 550~700 DEG C, insulation a period of time carries out charing acquisition Garlic skin carbonized material, then garlic skin carbonized material is added into alkali hydroxide soln high temperature time of infusion impregnated Material, is then warming up to 400~450 DEG C of progress low-temperature activations by dipping material, and low-temperature activation continues to be heated to for a period of time afterwards 700~850 DEG C of progress high-temperature activations, high-temperature activation obtains activated material, is finally post-processed activated material i.e. afterwards for a period of time Obtain activated carbon.
First, activated carbon is prepared using garlic skin, the organic matter in garlic skin carried out by being heated to 550~700 DEG C of charings Pyrolysis, changes the architectural feature and garlic skin pore character of organic matter, obtains with certain hole and the charing of the garlic skin of mechanical strength Material is used as intermediate material.Secondly, garlic skin carbonized material is etched using alkali metal hydroxide as activator, on the one hand, 400~ 450 DEG C of progress low-temperature activations, the carbonate of generation alkali metal makes Pore development, on the other hand, 700~850 DEG C of progress high temperature work Change, this temperature is higher than the boiling point of alkali metal, make alkali metal formation vapour of an alkali metal, vapour of an alkali metal can diffuse into different carbon Layer, forms new pore structure;Gaseous alkali metal is walked between the synusia of crystallite, struts its deformation that is distorted such as direction synusia, Develop new micropore.3rd, decompose in alkali metal hydroxide activation process and produce CO2Deng gas, these gases can be played Further promote the progress of activation, greatly increase the specific surface area of activated carbon, improve the quality and absorption property of activated carbon.
In order to which garlic skin charing efficiency will be improved, it is preferred that carry out charing process after garlic skin is pre-processed.
It is further preferred that the step of pretreatment is, takes garlic skin to dry or dry for the first time after cleaning, crush, mistake 80 mesh sieves.Garlic skin charing efficiency can further be improved.
Still more preferably, the temperature dried is 20~30 DEG C, and the temperature of the drying is 100~110 DEG C.
It is preferred that, the heating rate for being heated to 550~700 DEG C is 5 DEG C/min, and soaking time is 2~5h.It ensure that garlic Organic matter in skin is pyrolyzed completely.
Above-mentioned inert atmosphere refers to the one or more in nitrogen, argon gas, helium.
It is preferred that, the alkali hydroxide soln is the saturated solution of alkali metal hydroxide.Garlic skin charcoal can be made Material can impregnate more alkali metal hydroxides.
It is preferred that, alkali metal hydroxide is one or both of potassium hydroxide, sodium hydroxide.Potassium hydroxide, hydrogen-oxygen That changes sodium compares otheralkali metal hydroxide, and abundance, cost is relatively low.
It is preferred that, the mass ratio of alkali metal hydroxide and garlic skin carbonized material is 3.0~4.5:1.
It is preferred that, the temperature of the dipping is 80 DEG C, and the time of the dipping is 2h.Alkali metal hydroxide at this temperature Molecular motion performance it is higher, alkali metal hydroxide can be made to rapidly enter in garlic skin carbonized material.2h ensure that enough Alkali metal hydroxide is entered in garlic skin carbonized material.
It is preferred that, it is 5 DEG C/min to be warming up to 400~450 DEG C and be warming up to 700~850 DEG C of heating rate.
It is preferred that, the time of the low-temperature activation is 45min.
It is preferred that, the time of the high-temperature activation is 1~2.5h.
It is preferred that, the post processing includes washing for the first time, pickling, second of washing, second of drying, grinding successively.
Washing for the first time described in present embodiment, second washing be in order to represent water-washing steps different twice, and Be not configured to limit the precedence of water-washing step.
Drying for the first time described in present embodiment, second drying be in order to represent baking steps different twice, and Be not configured to limit the precedence of baking step.
It is further preferred that the temperature of the first time washing and second of washing is 80 DEG C.
Enter preferred, concretely comprising the following steps for the pickling is washed till pH 6~7 using acid solution at 80 DEG C.
It is further preferred that the concentration for the acid solution that the pickling is used is 0.1M.Prevent acid solutions too high, destroy The hole of activated carbon, so as to reduce the specific surface area of activated carbon.
It is further preferred that the acid solution is the one or more in hydrochloric acid, sulfuric acid, nitric acid.
Present embodiment additionally provides activated carbon prepared by a kind of above-mentioned preparation method.
Obtained activated carbon activation is complete, and specific surface area is up to 2818.22m2/ g super-activated carbon, can be provided more The active sites of energy adsorption charge, are conducive to improving the energy density of ultracapacitor;Pore volume is up to 1.32cm3/ g, pore-size distribution Concentrate within 4nm, it is adjustable in pore-size distribution and porosity certain limit.
Present embodiment additionally provides a kind of garlic skin matrix activated carbon electrode material for ultracapacitor, using above-mentioned work Property charcoal is prepared.
Present embodiment additionally provides a kind of application of above-mentioned activated carbon in ultracapacitor.
First, the activated carbon that prepared by the present invention is applicable to various electrolyte systems, and is provided for the ion in electrolyte Quick passage, makes it have more excellent high current charge-discharge ability and its energy density.Secondly, the activity that prepared by the present invention Charcoal ash are point low, and wellability is good, be assembled into two electrode system double electric layers supercapacitors have higher specific capacitance, less etc. Series resistance, higher efficiency for charge-discharge, and low time constant are imitated, discharge and recharge has higher particularly under high magnification Energy density etc..
In order that the technical scheme of the application can clearly be understood by obtaining those skilled in the art, below with reference to tool The embodiment of body describes the technical scheme of the application in detail with comparative example.
Raw material explanation:The raw material garlic skin used in following examples, is derived from Shandong Jinxiang, wherein moisture account for 3.2~ 3.6wt%, 4.5~4.9wt% of ash content, 91.5~92.3wt% of organic matter, organic matter is mainly cellulose and lignin.
Embodiment 1
Take garlic skin to dry or dry after cleaning, crush, cross 80 mesh sieves, garlic skin powder is made;Garlic skin powder is positioned over tubular type In resistance furnace, 600 DEG C are heated under inert atmosphere (flow is 2L/min), heating rate is 5 DEG C/min, are incubated 2h, cooling To room temperature, garlic skin carbonized material is made;At room temperature, it is 4 according to the mass ratio of KOH solids and garlic skin carbonized material:1, take garlic skin to carbonize Expect 6g, corresponding KOH solids be 24g, saturation KOH solution is thoroughly mixed with garlic skin carbonized material, after put it into air blast Drying box impregnates 2h, material after must impregnating with 80 DEG C of high temperature;Material after dipping is put into Muffle furnace to be activated, from room temperature to rise Warm 5 DEG C/min of speed be warming up to 400 DEG C progress low-temperature activations, be incubated 45min, after be warming up to 800 DEG C with identical heating rate High-temperature activation is carried out, 2.5h is incubated, corundum crucible is taken out, naturally cools to room temperature, produce activated material by activation after terminating;Take out Activated material, is washed with 80 DEG C of distilled water, the rear HCl solution with 0.1M under 80 DEG C of high temperature pickling to neutral pH 6~7, then according to So washed, dried under the conditions of last 105 DEG C with 80 DEG C of distilled water, activated carbon 3.03g is made in grinding.The activated carbon of preparation is entered Row structural characterization, structural characterization result as shown in figures 1-4, can show that prepared activated carbon activation is complete from Fig. 1~4, Micropore is flourishing, specific surface area 2818.22m2/ g, pore volume is 1.32cm3/ g, average pore size 2.62nm.By above-mentioned garlic skin matrix activated carbon By activating substance:Conductive agent:Binding agent=80:10:10 ratio is mixed, and electrode slice is made.Adopted in 6M KOH solutions The test of specific capacitance is carried out under different scanning rates with cyclic voltammetry.Its test result is as shown in Fig. 5~7, for example, in 6M Current density is 0.5A/g, 1.0A/g, 2.0A/g, 3.0A/g in KOH electrolyte, and the specific capacitance under 5.0A/g is respectively reached 318.67F/g, 284.53F/g, 269.33F/g, 262.51F/g, 253.01F/g, 5000 times under 3.0A/g current density Constant current charge-discharge capacitance conservation rate reaches 94%, is the ideal hyper electricity of a kind of high power of practicality, high-energy-density Container material.
Embodiment 2
Take garlic skin to dry or dry after cleaning, crush, cross 80 mesh sieves, garlic skin powder is made;Garlic skin powder is positioned over tubular type In resistance furnace, 600 DEG C are heated under inert atmosphere (flow is 2L/min), heating rate is 5 DEG C/min, are incubated 2h, cooling To room temperature, garlic skin carbonized material is made;At room temperature, it is 3.5 according to the mass ratio of KOH solids and garlic skin carbonized material:1, take garlic skin charcoal Material 6g, corresponding KOH solids be 24g, saturation KOH solution is thoroughly mixed with garlic skin carbonized material, after put it into drum Wind drying box impregnates 2h, material after must impregnating with 80 DEG C of high temperature;Material after dipping is put into Muffle furnace to be activated, from room temperature with 5 DEG C/min of heating rate be warming up to 400 DEG C progress low-temperature activations, be incubated 45min, after be warming up to 850 with identical heating rate DEG C carry out high-temperature activation, be incubated 2h, activation terminate after corundum crucible is taken out, naturally cool to room temperature, produce activated material;Take out Activated material, is washed with 80 DEG C of distilled water, the rear HCl solution with 0.1M under 80 DEG C of high temperature pickling to neutral pH 6~7, then according to So washed, dried under the conditions of last 105 DEG C with 80 DEG C of distilled water, activated carbon 3.91g is made in grinding.The activated carbon of preparation is entered Row structural characterization, specific surface area 2542.77m2/ g, pore volume is 0.93cm3/ g, average pore size 2.17nm.By above-mentioned garlic skin base activity Charcoal presses activating substance:Conductive agent:Binding agent=80:10:10 ratio is mixed, and electrode slice is made.In 6M KOH solutions Constant current charge-discharge is used to measure under 0.5A/g current density capacitance for 253.70F/g.And the methylene of activated carbon Blue adsorptive value is 39mL/0.1g.
Embodiment 3
Take garlic skin to dry or dry after cleaning, crush, cross 80 mesh sieves, garlic skin powder is made;Garlic skin powder is positioned over tubular type In resistance furnace, 600 DEG C are heated under inert atmosphere (flow is 2L/min), heating rate is 5 DEG C/min, are incubated 5h, cooling To room temperature, garlic skin carbonized material is made;At room temperature, it is 4 according to the mass ratio of KOH solids and garlic skin carbonized material:1, take garlic skin to carbonize Expect 6g, corresponding KOH solids be 24g, saturation KOH solution is thoroughly mixed with garlic skin carbonized material, after put it into air blast Drying box impregnates 2h, material after must impregnating with 80 DEG C of high temperature;Material after dipping is put into Muffle furnace to be activated, from room temperature to rise Warm 5 DEG C/min of speed be warming up to 400 DEG C progress low-temperature activations, be incubated 45min, after be warming up to 800 DEG C with identical heating rate High-temperature activation is carried out, 1h is incubated, corundum crucible is taken out, naturally cools to room temperature, produce activated material by activation after terminating;Take out and live Material, is washed with 80 DEG C of distilled water, and pickling is to neutral pH 6~7 under 80 DEG C of high temperature for the rear HCl solution with 0.1M, then still Washed, dried under the conditions of last 105 DEG C with 80 DEG C of distilled water, activated carbon 3.72g is made in grinding.Prepared activated carbon activation Completely, micropore is flourishing.Specific surface area is 2077.21m2/ g, pore volume is 0.89cm3/ g, average pore size is 2.24nm.By above-mentioned garlic Scytoblastema activated carbon presses activating substance:Conductive agent:Binding agent=80:10:10 ratio is mixed, and electrode slice is made.In 6M Constant current charge-discharge is used to measure under 0.5A/g current density capacitance for 191.06F/g in KOH solution.And activity The methylene blue adsorption value of charcoal is 35mL/0.1g.
Embodiment 4
Take garlic skin to dry or dry after cleaning, crush, cross 80 mesh sieves, garlic skin powder is made;Garlic skin powder is positioned over tubular type In resistance furnace, 550 DEG C are heated under inert atmosphere (flow is 2L/min), heating rate is 5 DEG C/min, are incubated 5h, cooling To room temperature, garlic skin carbonized material is made;At room temperature, it is 4.5 according to the mass ratio of KOH solids and garlic skin carbonized material:1, take garlic skin charcoal Material 6g, corresponding KOH solids be 24g, saturation KOH solution is thoroughly mixed with garlic skin carbonized material, after put it into drum Wind drying box impregnates 2h, material after must impregnating with 80 DEG C of high temperature;Material after dipping is put into Muffle furnace to be activated, from room temperature with 5 DEG C/min of heating rate be warming up to 400 DEG C progress low-temperature activations, be incubated 45min, after be warming up to 750 with identical heating rate DEG C carry out high-temperature activation, be incubated 2h, activation terminate after corundum crucible is taken out, naturally cool to room temperature, produce activated material;Take out Activated material, is washed with 80 DEG C of distilled water, the rear HCl solution with 0.1M under 80 DEG C of high temperature pickling to neutral pH 6~7, then according to So washed, dried under the conditions of last 105 DEG C with 80 DEG C of distilled water, activated carbon 4.96g is made in grinding.Prepared activated carbon is lived Change complete, micropore prosperity, specific surface area 1507.59m2/ g, aperture is 0.66cm3/ g, average pore size 2.30nm.By above-mentioned garlic skin Matrix activated carbon presses activating substance:Conductive agent:Binding agent=80:10:10 ratio is mixed, and electrode slice is made.In 6M KOH Constant current charge-discharge is used to measure under 0.5A/g current density capacitance for 159.30F/g in solution.And activated carbon Methylene blue adsorption value be 22mL/0.1g.
Although above-mentioned the embodiment of the present invention is described with reference to accompanying drawing, not to invention protection domain Limitation, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art are not required to Pay various modifications or deform still within the scope of the present invention that creative work can make.

Claims (10)

1. application of the garlic skin in the active carbon electrode material of ultracapacitor is prepared.
2. a kind of preparation method of garlic skin matrix activated carbon electrode material for ultracapacitor, it is characterized in that, by garlic skin lazy Property atmosphere under be heated to 550~700 DEG C, insulation a period of time carries out charing and obtains garlic skin carbonized material, then garlic skin carbonized material is added Enter to alkali hydroxide soln high temperature time of infusion and obtain dipping material, dipping material is then warming up to 400 ~450 DEG C of progress low-temperature activations, low-temperature activation continues to be heated to 700~850 DEG C of progress high-temperature activations for a period of time afterwards, and high temperature is lived Activated material is obtained after changing a period of time, activated material progress post processing is finally produced into activated carbon.
3. preparation method as claimed in claim 2, it is characterized in that, carry out charing process after garlic skin is pre-processed;
It is preferred that, it is to take garlic skin to dry or dry for the first time after cleaning the step of the pretreatment, crushes, cross 80 mesh sieves;
It is further preferred that the temperature dried is 20~30 DEG C, the temperature of the drying is 100~110 DEG C.
4. preparation method as claimed in claim 2, it is characterized in that, the heating rate for being heated to 550~700 DEG C is 5 DEG C/min, Soaking time is 2~5h.
5. preparation method as claimed in claim 2, it is characterized in that, the alkali hydroxide soln is alkali metal hydroxide The saturated solution of thing;
Or, alkali metal hydroxide is one or both of potassium hydroxide, sodium hydroxide;
Or, the mass ratio of alkali metal hydroxide and garlic skin carbonized material is 3.0~4.5:1;
Or, the temperature of the dipping is 80 DEG C, the time of the dipping is 2h.
6. preparation method as claimed in claim 2, it is characterized in that, it is warming up to 400~450 DEG C and is warming up to 700~850 DEG C Heating rate is 5 DEG C/min;
Or, the time of the low-temperature activation is 45min;
Or, the time of the high-temperature activation is 1~2.5h.
7. preparation method as claimed in claim 2, it is characterized in that, the post processing includes washing for the first time, pickling, the successively Secondary washing, second of drying, grinding;
It is preferred that, the temperature of the first time washing and second of washing is 80 DEG C;
It is preferred that, concretely comprising the following steps for the pickling is washed till pH 6~7 using acid solution at 80 DEG C;
It is preferred that, the concentration for the acid solution that the pickling is used is 0.1M;
It is preferred that, the acid solution is the one or more in hydrochloric acid, sulfuric acid, nitric acid.
8. activated carbon prepared by a kind of any described preparation method of claim 2~7.
9. a kind of garlic skin matrix activated carbon electrode material for ultracapacitor, it is characterized in that, using the work described in claim 8 Property charcoal is prepared.
10. a kind of application of the activated carbon described in claim 8 in ultracapacitor.
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108365184A (en) * 2018-01-02 2018-08-03 江苏大学 A kind of lithium ion battery porous SiOC negative materials of rich carbon and preparation method thereof
CN108493007A (en) * 2018-03-13 2018-09-04 河南工程学院 The preparation method of electrode slice with high electrochemical performance
CN108516548A (en) * 2018-03-06 2018-09-11 合肥工业大学 A kind of preparation method of high mesoporous rate activated carbon and its activated carbon of acquisition
CN108557819A (en) * 2018-05-30 2018-09-21 山东大学 Garlic base waste prepares the methods and applications of porous carbon material
WO2018188422A1 (en) * 2017-04-14 2018-10-18 山东大学 Garlic skin-based activated carbon electrode material for use with supercapacitor and preparation method
CN110697709A (en) * 2019-11-13 2020-01-17 山东大学 Porous carbon prepared from biomass unburned carbon and application of porous carbon in super capacitor
CN110734061A (en) * 2018-07-19 2020-01-31 深圳市环球绿地新材料有限公司 super-capacity carbon, preparation method and application thereof
CN110817867A (en) * 2019-12-12 2020-02-21 山东大学 Preparation method and application of garlic skin based super activated carbon
CN111268677A (en) * 2020-01-20 2020-06-12 辽宁大学 Preparation method and application of novel lithium ion battery negative electrode material carbonized grape seed
CN111573671A (en) * 2020-05-08 2020-08-25 福建农林大学 Method for preparing supercapacitor electrode material by using perilla-based activated carbon and application of supercapacitor electrode material
CN111634908A (en) * 2020-04-22 2020-09-08 山东大学 Method for preparing porous carbon by nitrogen and oxygen co-doping porous carbon and L-lysine and application
CN113830766A (en) * 2021-08-20 2021-12-24 华中农业大学 Preparation method of porous activated charcoal for fermentation, activation and oxidation

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101468797A (en) * 2007-12-24 2009-07-01 徐文东 Preparation of super active carbon material
CN101697322A (en) * 2009-10-15 2010-04-21 青岛大学 Method for preparing porous carbon electrode material
CN104051790A (en) * 2014-06-06 2014-09-17 中南大学 Method for preparing lithium battery from garlic or onions
CN105845915A (en) * 2016-05-31 2016-08-10 陕西科技大学 Method for preparing anode material of three-dimensional porous carbon skeleton/CoO composite structured lithium ion battery

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105845937B (en) * 2016-05-12 2018-12-11 陕西科技大学 A kind of method that three-dimensional porous carbon skeleton/graphene composite structure is constructed in original position
CN107039193B (en) * 2017-04-14 2018-10-19 山东大学 A kind of garlic skin matrix activated carbon electrode material and preparation method for ultracapacitor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101468797A (en) * 2007-12-24 2009-07-01 徐文东 Preparation of super active carbon material
CN101697322A (en) * 2009-10-15 2010-04-21 青岛大学 Method for preparing porous carbon electrode material
CN104051790A (en) * 2014-06-06 2014-09-17 中南大学 Method for preparing lithium battery from garlic or onions
CN105845915A (en) * 2016-05-31 2016-08-10 陕西科技大学 Method for preparing anode material of three-dimensional porous carbon skeleton/CoO composite structured lithium ion battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
V. SELVAMANI ET AL.: "Garlic peel derived high capacity hierarchical N-doped porous carbon anode for sodium/lithium ion cell", 《ELECTROCHIMICA ACTA》 *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018188422A1 (en) * 2017-04-14 2018-10-18 山东大学 Garlic skin-based activated carbon electrode material for use with supercapacitor and preparation method
CN108365184A (en) * 2018-01-02 2018-08-03 江苏大学 A kind of lithium ion battery porous SiOC negative materials of rich carbon and preparation method thereof
CN108516548A (en) * 2018-03-06 2018-09-11 合肥工业大学 A kind of preparation method of high mesoporous rate activated carbon and its activated carbon of acquisition
CN108493007A (en) * 2018-03-13 2018-09-04 河南工程学院 The preparation method of electrode slice with high electrochemical performance
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CN110697709A (en) * 2019-11-13 2020-01-17 山东大学 Porous carbon prepared from biomass unburned carbon and application of porous carbon in super capacitor
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