CN106587055A - Biomass-based porous carbon material, preparation method thereof, and application thereof in supercapacitor - Google Patents

Biomass-based porous carbon material, preparation method thereof, and application thereof in supercapacitor Download PDF

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CN106587055A
CN106587055A CN201611010659.0A CN201611010659A CN106587055A CN 106587055 A CN106587055 A CN 106587055A CN 201611010659 A CN201611010659 A CN 201611010659A CN 106587055 A CN106587055 A CN 106587055A
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porous carbon
biomass
carbon materials
rice straw
carbonized
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CN201611010659.0A
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Chinese (zh)
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钟林新
陈泽虹
彭新文
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华南理工大学
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/24Electrodes characterised by structural features, e.g. forms, shapes, surface areas, porosities or dimensions, of the materials making up or comprised in the electrodes; characterised by the structural features of powders or particles used therefor
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their materials
    • H01G11/32Carbon-based, e.g. activated carbon materials
    • H01G11/34Carbon-based, e.g. activated carbon materials characterised by carbonisation or activation of carbon
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their materials
    • H01G11/32Carbon-based, e.g. activated carbon materials
    • H01G11/44Raw materials therefor, e.g. resins or coal
    • 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
    • C01P2006/16Pore diameter
    • 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

Abstract

The invention belongs to the field of material science and energy storage and discloses a biomass-based porous carbon material, a preparation method thereof, and an application thereof in a supercapacitor. The method includes the steps of: 1) drying and crushing rice straws; 2) non-carbonizing or pre-carbonizing the crushed rice straws, uniformly mixing the rice straws with an activator water solution and drying the mixture, or non-carbonizing or pre-carbonizing the crushed rice straws and directly mixing the rice straws with a solid activator uniformly to produce a mixed product; and 3) placing the mixed product in a tube furnace to perform carbonizing activation in an inert gas atmosphere at high temperature; 4) washing the carbonized product in an acid solution and an alkali solution, and washing the carbonized product with deionized water to neutral, and drying the washed product to prepare the biomass-based porous carbon material. The porous carbon material has excellent supercapacitor performance and is simple in preparation method.

Description

A kind of biomass-based porous carbon materials and preparation method and the application in ultracapacitor
Technical field
The invention belongs to material science and energy storage field, and in particular to a kind of life with excellent super capacitor performance Material base porous carbon materials and preparation method thereof and the application in ultracapacitor.
Background technology
Ultracapacitor is a kind of new energy storage device between traditional capacitor and rechargeable battery, due to work( Rate density is high, have extended cycle life, the advantages of charge-discharge velocity is high, the always focus of people's research and development.Electrode material is to determine Determine the topmost part of performance of the supercapacitor, wherein porous active material with carbon element is due to stability height, life-span length, raw material Abundance, the advantages of conduct electricity very well, it has also become the most electrode material of commercial competitiveness.In recent years due to fossil energy Shortage, the development of material with carbon element receives certain restriction.In order to further develop the challenge of material with carbon element and reply energy crisis, Researcher has turned one's attention to the renewable biomass resources rich in carbon.
China is that topmost Rice Cropping is national in the world, and Oryza glutinosa total output accounts for the 1/3 of national total output of grain.Rice Bar as rice production during main garbage, enormous amount.Material with carbon element is prepared by raw material of rice straw, both can overcoming The restriction that stone crisis of resource develops to material with carbon element, can improve the value of rice straw again, reduce and burn the environmental pollution for bringing Problem.Rice straw raw material contains substantial amounts of silicon dioxide, the silicon dioxide existed with its own as native template, using chemical activation Method prepare rice straw base porous carbon materials, and be applied to the preparation of electrode material for super capacitor, it is possible to achieve rice straw The high-valued application of biomass material.
The content of the invention
In order to overcome the shortcoming and defect of prior art, it is an object of the invention to provide a kind of have excellent super capacitor The preparation method of the biomass-based porous carbon materials of performance.
Another object of the present invention is to provide the biomass-based porous carbon materials obtained by above-mentioned preparation method.It is described many Hole material with carbon element has the advantages that with low cost, specific surface area is big, pore-size distribution is reasonable, super capacitor performance is excellent.
It is still another object of the present invention to provide the application of above-mentioned biomass-based porous carbon materials.The biomass-based porous Application of the material with carbon element in ultracapacitor, adsorbing material, catalysis material, particularly for preparing the electrode material of ultracapacitor Material.
The purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of biomass-based porous carbon materials, comprises the steps:
(1) rice straw is dried, crushed;
(2) it is by the rice straw after crushing after not being carbonized or being carbonized in advance, uniform with activator aqueous solution, dry;Or Rice straw after crushing after not being carbonized or being carbonized in advance, is directly mixed homogeneously with solid activating agent, obtains mixed product by person Thing;
(3) mixed product is placed in tube furnace, in atmosphere of inert gases, high temperature cabonization activation;
(4) product after carbonization is washed using acid solution and aqueous slkali, then is washed with deionized to neutrality, will Product after washing is dried, and obtains biomass-based porous carbon materials.
Baking temperature described in step (1), (2) and (4) is 50~100 DEG C, and drying time is 4~24 hours.Further Preferably, baking temperature is 60 DEG C, and drying time is 12 hours.
Pre- carbonization described in step (2) is referred to from room temperature and is warming up to 200~750 with (0.5~20) DEG C/min heating rate DEG C, it is incubated 0~20 hour.It is further preferred that heating rate is 5 DEG C/min, carburizing temperature is 300 DEG C, and temperature retention time is 90 Minute.
Activator described in step (2) is KHCO3、KOH、NaOH、ZnCl2、H3PO4One or more of.Further preferably , the activator is KHCO3One or more of or KOH.
The method that rice straw and solid activating agent directly mix described in step (2) is polishing, and milling time is 5~40 points Clock.
Activator described in step (2) is (0.25~5) with the mass ratio of rice straw:1.It is further preferred that activator with Rice straw mass ratio is 1:1.The activator aqueous solution is referred to and is dissolved activator using water, preferably just dissolved.
Noble gases described in step (3) are nitrogen or argon.
Carbonization-activation described in step (3) is referred to from room temperature and is warming up to 600 with the heating rate of (0.5~20) DEG C/min ~1000 DEG C, and it is incubated 0.2~10 hour.It is further preferred that the process of the carbonization is with 3 DEG C/min of liter from room temperature Warm ramp is to 750 DEG C, and is incubated 2 hours.
Acid solution and aqueous slkali described in step (4) carry out washing and referring to washed with hydrochloric acid, sodium hydroxide successively, Huo Zhexian Use salt acid elution after being washed with sodium hydroxide again.
Acid solution described in step (4) is the H that concentration is 0.05~2M2SO4Or HCl solution;The aqueous slkali is quality Fraction is 20%~25% KOH or NaOH solution.
Under the preparation condition of the present invention, the specific surface area of prepared biomass-based porous carbon materials is 824~ 2064m2/g;In three-electrode system, 1M H are used2SO4Electrolyte carries out electro-chemical test, when electric current density is 0.5A/g, than electricity Hold for 223~357F/g.
The biomass-based porous carbon materials are prepared by said method.
Application of the biomass-based porous carbon materials in ultracapacitor.
The present invention preparation method and the porous carbon materials for preparing, compared with prior art, have the advantage that and Beneficial effect:
(1) with rice straw as carbon source, raw material sources are extensive and cheap, can reduce the cost of manufacture of ultracapacitor, be The higher value application of agricultural wastes provides an effective way.
(2) using native silicon dioxide in rice straw raw material be template, prepare porous carbon materials, conventional template method can be solved Middle template skewness, the problems such as remove difficult, expensive.
(3) present invention prepares porous carbon materials by a step carbonization-activation, and preparation method is simple, and step is few, is capable of achieving big Large-scale production.
(4) rice straw base porous carbon materials specific surface area prepared by the present invention is up to 2064m2/ g, with excellent super electricity Capacitive energy, specific capacitance are up to 357F/g, forthright good again, and after cycle charge-discharge 10000 times, electric capacity retention is up to 99%.
Description of the drawings
Fig. 1 is the SEM figures of porous carbon materials CAC-750-1KOH prepared by embodiment 1, wherein the amplification point of figure a, b Wei 2000 times and 5000 times;
Fig. 2 is porous carbon materials DAC-750-1KHCO prepared by embodiment 63TEM figures, wherein figure a, b is different amplifications Multiple figure;
Fig. 3 is the SEM figures of unactivated material with carbon element DC-750 prepared by comparative example, wherein the amplification of figure a, b is respectively 1000 times and 2000 times;
Fig. 4 is the specific capacitance block diagram of material with carbon element prepared by porous carbon materials prepared by embodiment 1~9 and comparative example.
Specific embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited In this.To this not marked parameter process, can refer to routine techniquess is carried out.
Embodiment 1
A kind of preparation method of biomass-based porous carbon materials, comprises the steps:
(1) rice straw is dried 12 hours in 60 DEG C of baking ovens, crushed;
(2) rice straw after crushing is carried out standby after pre- carbonization, pre- carbonisation is with 5 DEG C/min of speed liters from room temperature Temperature is incubated 90 minutes to 300 DEG C;The KOH of certain mass is added in a reservoir, is added a small amount of water to dissolve KOH, will be carbonized in advance During rice straw afterwards adds container, (mass ratio of KOH and rice straw is 1:1) stir, be dried 12 hours in 60 DEG C of baking ovens;
(3) mixture of above-mentioned dried rice straw and KOH is carried out into carbonization-activation in argon atmosphere, from room temperature with 3 DEG C/min 750 DEG C of target temperature is warming up to, and is incubated 2 hours, obtain carbide;
(4) by carbide 1M salt acid elution 2 times, then washed 4 times with 20% sodium hydroxide of mass fraction, be finally washed to Neutrality, is dried 12 hours in 60 DEG C of baking ovens, obtains the i.e. biomass-based porous carbon materials of rice straw base porous carbon materials.The present embodiment Gained material with carbon element is labeled as CAC-750-1KOH.Fig. 1 (wherein schemes putting for a, b for the SEM figures of porous carbon materials CAC-750-1KOH Big multiple is respectively 2000 times and 5000 times), the rice straw base porous carbon materials for as can be seen from the figure being prepared by this method Surface is uniform-distribution with substantial amounts of hole.Its specific surface area is 1909m2/ g, average pore size are 2.41nm.In three-electrode system In, use 1M H2SO4Electrolyte carry out electro-chemical test, when electric current density is 0.5A/g, specific capacitance is up to 357F/g;Circulation is filled After electric discharge 10000 times, electric capacity retention is 99%;In symmetry electrode system, when power density is 514W/kg, energy density For 40kW/kg.The specific capacitance figure of material with carbon element obtained by the present embodiment is as shown in Figure 4.
Embodiment 2
A kind of preparation method of biomass-based porous carbon materials, comprises the steps:
(1) rice straw is dried 12 hours in 60 DEG C of baking ovens, crushed;
(2) KHCO of certain mass is added in beaker3, a small amount of water is added by KHCO3Rice straw is added beaker by dissolving In (KHCO3Mass ratio with rice straw is 5:1) stir, be dried 12 hours in 60 DEG C of baking ovens;
(3) by above-mentioned dried rice straw and KHCO3Mixture carbonization-activation is carried out in nitrogen atmosphere, from room temperature with 3 DEG C/min are warming up to 1000 DEG C of target temperature, and are incubated 2 hours;
(4) carbide is washed 4 times with 20% sodium hydroxide of mass fraction, then with 1M salt acid elution 2 times, is finally washed to Neutrality, is dried 12 hours in 60 DEG C of baking ovens, obtains the i.e. biomass-based porous carbon materials of rice straw base porous carbon materials.The present embodiment Gained material with carbon element is labeled as DAC-1000-5KHCO3, its specific surface area is 1742m2/ g, aperture are 2.42nm.In three-electrode system In, use 1M H2SO4Electrolyte carries out electro-chemical test, and when electric current density is 0.5A/g, specific capacitance is 280F/g.The present embodiment institute The specific capacitance figure for obtaining material with carbon element is as shown in Figure 4.
Embodiment 3
A kind of preparation method of biomass-based porous carbon materials, comprises the steps:
(1) rice straw is dried 12 hours in 60 DEG C of baking ovens, crushed;
(2) KHCO of certain mass is added in a reservoir3, a small amount of water is added by KHCO3Rice straw is added beaker by dissolving In (KHCO3Mass ratio with rice straw is 1:1) stir, be dried 12 hours in 60 DEG C of baking ovens;
(3) by above-mentioned dried rice straw and KHCO3Mixture carbonization-activation is carried out in argon atmosphere, from room temperature with 3 DEG C/min are warming up to 800 DEG C of target temperature, and are incubated 2 hours;
(4) carbide is washed 4 times with 20% sodium hydroxide of mass fraction, then with 1M salt acid elution 2 times, is finally washed to Neutrality, is dried 12 hours in 60 DEG C of baking ovens, obtains the i.e. biomass-based porous carbon materials of rice straw base porous carbon materials.The present embodiment Gained material with carbon element is labeled as DAC-800-1KHCO3, its specific surface area is up to 2064m2/ g, average pore size are 2.31nm.It is electric three In polar body system, 1M H are used2SO4Electrolyte carries out electro-chemical test, and when electric current density is 0.5A/g, specific capacitance reaches 252F/g.This reality The specific capacitance figure for applying material with carbon element obtained by example is as shown in Figure 4.
Embodiment 4
A kind of preparation method of biomass-based porous carbon materials, comprises the steps:
(1) rice straw is dried 12 hours in 60 DEG C of baking ovens, crushed;
(2) rice straw is carried out standby after pre- carbonization, pre- carbonisation is to be warming up to 750 DEG C with 5 DEG C/min from room temperature, is protected Temperature 90 minutes;The ZnCl of certain mass is added in a reservoir2, a small amount of water is added by ZnCl2Dissolving, by the rice straw after pre- carbonization Add (ZnCl in container2Mass ratio with rice straw is 4:1) stir, be dried 12 hours in 60 DEG C of baking ovens;
(3) by above-mentioned dried rice straw and ZnCl2Mixture carries out carbonization-activation in argon atmosphere, from room temperature with 3 DEG C/min 750 DEG C of target temperature is warming up to, and is incubated 2 hours;
(4) by carbide 1M salt acid elution 2 times, then washed 4 times with 20% sodium hydroxide of mass fraction, be finally washed to Neutrality, is dried 12 hours in 60 DEG C of baking ovens, obtains the i.e. biomass-based porous carbon materials of rice straw base porous carbon materials.The present embodiment Gained material with carbon element is labeled as CAC-750-0.25ZnCl2, its specific surface area is 1269m2/ g, average pore size are 2.41nm.It is electric three In polar body system, 1M H are used2SO4Electrolyte carries out electro-chemical test, and when electric current density is 0.5A/g, specific capacitance reaches 237F/g.This reality The specific capacitance figure for applying material with carbon element obtained by example is as shown in Figure 4.
Embodiment 5
A kind of preparation method of biomass-based porous carbon materials, comprises the steps:
(1) rice straw is dried 12 hours in 60 DEG C of baking ovens, crushed;
(2) rice straw is carried out standby after pre- carbonization, pre- carbonisation is to be warming up to 200 DEG C with 5 DEG C/min from room temperature, is protected Temperature 90 minutes;The NaOH of certain mass is added in beaker, adds a small amount of water to dissolve NaOH, the rice straw after pre- carbonization is added Enter in beaker that (mass ratio of NaOH and rice straw is 1:1) stir, be dried 12 hours in 60 DEG C of baking ovens;
(3) above-mentioned dried rice straw and NaOH mixture are carried out into carbonization-activation in argon atmosphere, from room temperature with 3 DEG C/min 600 DEG C of target temperature is warming up to, and is incubated 2 hours;
(4) by carbide 1M salt acid elution 2 times, then washed 4 times with 20% sodium hydroxide of mass fraction, be finally washed to Neutrality, is dried 12 hours in 60 DEG C of baking ovens, obtains the i.e. biomass-based porous carbon materials of rice straw base porous carbon materials.The present embodiment Gained material with carbon element is labeled as CAC-600-1NaOH, and its specific surface area is 824m2/ g, aperture are 3.12nm.In three-electrode system In, use 1M H2SO4Electrolyte carry out electro-chemical test, when electric current density is 0.5A/g, specific capacitance reaches 223F/g.The present embodiment The specific capacitance figure of gained material with carbon element is as shown in Figure 4.
Embodiment 6
A kind of preparation method of biomass-based porous carbon materials, comprises the steps:
(1) rice straw is dried 12 hours in 60 DEG C of baking ovens, crushed;
(2) KHCO of certain mass is added in beaker3, a small amount of water is added by KHCO3Rice straw is added beaker by dissolving In (KHCO3Mass ratio with rice straw is 1:1) stir, be dried 12 hours in 60 DEG C of baking ovens;
(3) by above-mentioned dried rice straw and KHCO3Mixture carries out carbonization-activation in argon atmosphere, from room temperature with 3 DEG C/min 750 DEG C of target temperature is warming up to, and is incubated 2 hours;
(4) by carbide 1M salt acid elution 2 times, then washed 4 times with 20% sodium hydroxide of mass fraction, be finally washed to Neutrality, is dried 12 hours in 60 DEG C of baking ovens, obtains the i.e. biomass-based porous carbon materials of rice straw base porous carbon materials.The present embodiment Gained material with carbon element is labeled as DAC-750-1KHCO3.(a, b are difference to the TEM figures of the porous carbon materials of the present embodiment as shown in Figure 2 Amplification).Material with carbon element DAC-750-1KHCO as can be seen from Figure 23Containing abundant pore structure, aperture is big to be received to hundreds of Rice, little to several nanometer.According to (b) in Fig. 2 it can also be seen that sample has certain carbonization structure.DAC-750-1KHCO3's Specific surface area is 1495m2/ g, average pore size are 2.29nm.In three-electrode system, 1M H are used2SO4Electrolyte carries out electrochemistry Test, when electric current density is 0.5A/g, specific capacitance is 248F/g;When electric current density is up to 50A/g, specific capacitance is 180F/g, electricity Hold retention up to 73%.The specific capacitance figure of material with carbon element obtained by the present embodiment is as shown in Figure 4.
Embodiment 7
A kind of preparation method of biomass-based porous carbon materials, comprises the steps:
(1) rice straw is dried 12 hours in 60 DEG C of baking ovens, crushed;
(2) H of certain mass is added in mortar3PO4With rice straw (H3PO4Mass ratio with rice straw is 1:1), by two kinds Solid abrasive 20 minutes, mix homogeneously;
(3) by above-mentioned H3PO4Carbonization-activation is carried out in argon atmosphere with rice straw mixture, is risen with 3 DEG C/min from room temperature Temperature is to 750 DEG C of target temperature, and is incubated 2 hours;
(4) carbide is washed 4 times with 20% sodium hydroxide of mass fraction, then with 1M salt acid elution 2 times, is finally washed to Neutrality, is dried 12 hours in 60 DEG C of baking ovens, obtains the i.e. biomass-based porous carbon materials of rice straw base porous carbon materials.The present embodiment Gained material with carbon element is labeled as DAC-750-1H3PO4, its specific surface area is 1344m2/ g, aperture are 2.53nm.In three-electrode system In, use 1M H2SO4Electrolyte carries out electro-chemical test, and when electric current density is 0.5A/g, specific capacitance is 256F/g.The present embodiment institute The specific capacitance figure for obtaining material with carbon element is as shown in Figure 4.
Embodiment 8
A kind of preparation method of biomass-based porous carbon materials, comprises the steps:
(1) rice straw is dried 12 hours in 60 DEG C of baking ovens, crushed;
(2) KOH, KHCO of certain mass are added in mortar3With rice straw (KOH, KHCO3Mass ratio with rice straw is 1:1: 1), by three kinds of solid abrasive mix homogeneously;
(3) by above-mentioned KOH, KHCO3Carbonization-activation is carried out in argon atmosphere with rice straw mixture, from room temperature with 3 DEG C/minute Clock is warming up to 750 DEG C of target temperature, and is incubated 2 hours;
(4) carbide is washed 4 times with 20% sodium hydroxide of mass fraction, then with 1M salt acid elution 2 times, is finally washed to Neutrality, is dried 12 hours in 60 DEG C of baking ovens, obtains the i.e. biomass-based porous carbon materials of rice straw base porous carbon materials.The present embodiment Gained material with carbon element is labeled as DAC-750-1KOH-1KHCO3, its specific surface area is 1834m2/ g, aperture are 2.52nm.In three electrodes In system, 1M H are used2SO4Electrolyte carries out electro-chemical test, and when electric current density is 0.5A/g, specific capacitance is 276F/g.This enforcement The specific capacitance figure of example gained material with carbon element is as shown in Figure 4.
Embodiment 9
A kind of preparation method of biomass-based porous carbon materials, comprises the steps:
(1) rice straw is dried 12 hours in 60 DEG C of baking ovens, crushed;
(2) rice straw is carried out standby after pre- carbonization, pre- carbonisation is to be warming up to 300 DEG C with 5 DEG C/min from room temperature, is protected Temperature 90 minutes;The KHCO of certain mass is added in a reservoir3, a small amount of water is added by KHCO3Dissolving, by the rice straw after pre- carbonization Add (KHCO in container3Mass ratio with rice straw is 1:1) stir, be dried 12 hours in 60 DEG C of baking ovens;
(3) by above-mentioned dried rice straw and KHCO3Mixture carbonization-activation is carried out in argon atmosphere, from room temperature with 3 DEG C/min are warming up to 750 DEG C of target temperature, and are incubated 2 hours;
(4) by carbide 1M salt acid elution 2 times, then washed 4 times with 20% sodium hydroxide of mass fraction, be finally washed to Neutrality, is dried 12 hours in 60 DEG C of baking ovens, obtains the i.e. biomass-based porous carbon materials of rice straw base porous carbon materials.The present embodiment Gained material with carbon element is labeled as CAC-750-1KHCO3.Porous carbon materials CAC-750-1KHCO3Specific surface area be 1269m2/ g, puts down Aperture is 2.41nm.In three-electrode system, 1M H are used2SO4Electrolyte carries out electro-chemical test, and electric current density is 0.5A/g When, specific capacitance reaches 337F/g;When electric current density is up to 50A/g, specific capacitance is 180F/g, and electric capacity retention is up to 73%.This enforcement The specific capacitance figure of example gained material with carbon element is as shown in Figure 4.
Comparative example
A kind of preparation method of material with carbon element, comprises the steps:
Rice straw raw material after crushing is directly carbonized to 750 DEG C on the premise of without activator, carbonization is produced Thing is washed after 4 times with 20% sodium hydroxide, is washed to neutrality, is dried, is obtained material with carbon element and be named as DC-750.The carbon of the present embodiment Material SEM is schemed as shown in figure 3, it can be seen that the sample not activated is based on block structure, being stacked with, not having between bulk There is the pore structure of formation rule.The specific capacitance figure of the material with carbon element of the present embodiment is as shown in Figure 4.The specific surface area of the material with carbon element is 595m2/g;When electric current density is 0.5A/g, specific capacitance is 179F/g, far below the rice straw base porous carbon materials after activation, is such as schemed Shown in 4.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention not by above-described embodiment Limit, other any spirit and the changes, modification, replacement made under principle without departing from the present invention, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (10)

1. a kind of preparation method of biomass-based porous carbon materials, it is characterised in that:Comprise the steps:
(1) rice straw is dried, crushed;
(2) it is by the rice straw after crushing after not being carbonized or being carbonized in advance, uniform with activator aqueous solution, dry;Or will Rice straw after crushing after not being carbonized or being carbonized in advance directly is mixed homogeneously with solid activating agent, obtains mixed product;
(3) mixed product is placed in tube furnace, in atmosphere of inert gases, high temperature cabonization activation;
(4) product after carbonization is washed using acid solution and aqueous slkali, then is washed with deionized to neutrality, will washing Product afterwards is dried, and obtains biomass-based porous carbon materials.
2. the preparation method of biomass-based porous carbon materials according to claim 1, it is characterised in that:
Activator described in step (2) is KHCO3、KOH、NaOH、ZnCl2、H3PO4One or more of;It is pre- described in step (2) Carbonization refers to that being warming up to 200~750 DEG C with the heating rate of (0.5~20) DEG C/min from room temperature is carbonized, insulation 0~20 Hour.
3. the preparation method of biomass-based porous carbon materials according to claim 2, it is characterised in that:The activator is KHCO3One or more of or KOH;
In the pre- carbonization, heating rate is 5 DEG C/min, and carburizing temperature is 300 DEG C, and temperature retention time is 90 minutes.
4. the preparation method of biomass-based porous carbon materials according to claim 1, it is characterised in that:Described in step (3) Carbonization-activation is referred to from room temperature and is warming up to 600~1000 DEG C with the heating rate of (0.5~20) DEG C/min, and is incubated 0.2~10 Hour.
5. the preparation method of biomass-based porous carbon materials according to claim 1, it is characterised in that:Described in step (2) Activator is (0.25~5) with the mass ratio of rice straw:1.
6. the preparation method of biomass-based porous carbon materials according to claim 1, it is characterised in that:Described in step (3) Noble gases are nitrogen or argon;
Acid solution described in step (4) is the H that concentration is 0.05~2M2SO4Or HCl solution;The aqueous slkali is mass fraction KOH or NaOH solution for 20%~25%.
7. the preparation method of biomass-based porous carbon materials according to claim 1, it is characterised in that:Step (4) acid Solution and aqueous slkali carry out washing and referring to washed with hydrochloric acid, sodium hydroxide successively, or hydrochloric acid is used after first being washed with sodium hydroxide Washing;
Baking temperature described in step (1), (2) and (4) is 50~100 DEG C, and drying time is 4~24 hours;Institute in step (2) The method for stating rice straw and the direct mixing of solid activating agent is polishing, and milling time is 5-40 minutes.
8. the biomass-based porous carbon materials that a kind of preparation method by described in any one of claim 1~7 is obtained.
9. biomass-based porous carbon materials according to claim 8, it is characterised in that:The biomass-based porous carbon materials Specific surface area is 824~2064m2/g;In three-electrode system, 1M H are used2SO4Electrolyte carries out electro-chemical test, electric current density For 0.5A/g when, specific capacitance for 223~357F/g.
10. according to any one of claim 8~9 biomass-based porous carbon materials application, it is characterised in that:The biology Application of the matter base porous carbon materials in ultracapacitor.
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CN107311171A (en) * 2017-07-11 2017-11-03 吉林大学 The preparation method and activated carbon of activated carbon
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CN107522200A (en) * 2017-08-16 2017-12-29 华南师范大学 A kind of preparation method and applications of active bio matter carbon material
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CN108948412A (en) * 2018-05-17 2018-12-07 齐鲁工业大学 A kind of siliceous poromeric preparation method for supercapacitor
CN108439402A (en) * 2018-06-06 2018-08-24 山东大学 A kind of ultracapacitor ginger stalk matrix activated carbon and preparation method thereof
CN109019553A (en) * 2018-07-18 2018-12-18 江苏科技大学 It is a kind of with hard template method by the method and its application of cassia tree leaf synthesising biological matter carbon material
CN108928820A (en) * 2018-09-30 2018-12-04 淮阴师范学院 A kind of rice straw based super capacitor active carbon and preparation method thereof
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CN109755040A (en) * 2018-12-06 2019-05-14 桂林理工大学 Utilize the method for sunflower seed shell preparation high pressure water system electrode material for super capacitor
CN109589881A (en) * 2018-12-13 2019-04-09 南京工业大学 A kind of method and application preparing the porous carbon-based aeroge of N doping with leather waste
CN110136992A (en) * 2019-05-24 2019-08-16 南京林业大学 A method of electrode material for super capacitor is prepared using grape
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