CN109422263B - Cellulose porous activated carbon and preparation method and application thereof - Google Patents

Cellulose porous activated carbon and preparation method and application thereof Download PDF

Info

Publication number
CN109422263B
CN109422263B CN201710718213.1A CN201710718213A CN109422263B CN 109422263 B CN109422263 B CN 109422263B CN 201710718213 A CN201710718213 A CN 201710718213A CN 109422263 B CN109422263 B CN 109422263B
Authority
CN
China
Prior art keywords
cellulose
potassium hydroxide
activated carbon
porous activated
activating agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710718213.1A
Other languages
Chinese (zh)
Other versions
CN109422263A (en
Inventor
吴敏
黄勇
张云秀
孟秋华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Technical Institute of Physics and Chemistry of CAS
Original Assignee
Technical Institute of Physics and Chemistry of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Technical Institute of Physics and Chemistry of CAS filed Critical Technical Institute of Physics and Chemistry of CAS
Priority to CN201710718213.1A priority Critical patent/CN109422263B/en
Publication of CN109422263A publication Critical patent/CN109422263A/en
Application granted granted Critical
Publication of CN109422263B publication Critical patent/CN109422263B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/40—Fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • 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
    • C01P2006/16—Pore diameter
    • 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

Landscapes

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

Abstract

The invention relates to cellulose-based porous activated carbon and a preparation method and application thereof, wherein the method comprises the following steps: 1) mixing natural cellulose with an aqueous solution of an activating agent, fully grinding the mixture to obtain a fiber jelly, and freeze-drying the fiber jelly to obtain a solid mixture of the cellulose and the activating agent; 2) and (2) putting the solid mixture prepared in the step 1) into an inert gas or nitrogen environment, and carbonizing at 500-1000 ℃ for 0.5-4 h to obtain the carbon nano tube. The invention also discloses application of the cellulose-based porous activated carbon in a supercapacitor electrode material. The method is simple to operate, and the use amount of the raw materials and the activating agent can be strictly controlled. The prepared porous activated carbon has extremely high specific surface area and can be widely applied to electrode materials of supercapacitors.

Description

Cellulose porous activated carbon and preparation method and application thereof
Technical Field
The invention relates to the technical field of natural polymer materials, in particular to cellulose-based porous activated carbon and a preparation method and application thereof.
Background
The electrode material is used as a key part influencing the electric energy storage capacity (namely capacitance) of the super capacitor, and the research on the raw materials and the preparation method is particularly important for the characteristics of large specific surface area, good cycle characteristics and the like. Porous carbon materials have received much attention from researchers because of their advantages of availability, adjustable microstructure, and large specific surface area.
In recent years, many porous carbon materials have been studied including graphene, carbon nanotubes, biomass carbonized materials, and the like. Graphene and carbon nanotubes have good electrical conductivity and large specific surface area, but the preparation method is complex and expensive, which restricts the application of the graphene and carbon nanotubes. The biomass carbonized material has attracted the interest of many researchers with low price and abundant reserves, especially the biomass carbonized material obtained by chemical activation. The method is a main mode for preparing the electrode material of the super capacitor because the chemical activation is mild and simple, the yield is high, the pore size distribution of the obtained carbon material is clear and the specific surface area is high.
In the process of preparing the carbon material, the activation methods generally adopted are a soaking method and a hydrothermal method, and the amount of the activating agent entering the material is not uniform, and the reaction conditions are not precise, so that the prepared materials have certain difference.
Disclosure of Invention
The invention aims to provide a preparation method of cellulose-based porous activated carbon. The invention adopts a grinding mode to fully mix the natural cellulose raw material and the aqueous solution of the activating agent; not only simplifies the preparation method, but also effectively controls the reaction conditions and the use amount of the activating agent.
The method comprises the following steps:
1) mixing natural cellulose with an aqueous solution of an activating agent, fully grinding the mixture to obtain a fiber jelly, and freeze-drying the fiber jelly to obtain a solid mixture of the cellulose and the activating agent;
2) and (2) putting the solid mixture prepared in the step 1) into an inert gas or nitrogen environment, and carbonizing at 500-1000 ℃ for 0.5-4 h to obtain the carbon nano tube.
The adopted natural cellulose has a macroscopic shape of fiber, particles or pulp; the mass percentage of cellulose in the natural cellulose is not less than 90%; the natural cellulose employed in the present invention is not limited in kind; preferably one or more of wood, cotton, hemp, crop straw or crop fruit.
The mode of purifying cellulose in the present invention is a conventional purification mode.
The activating agent is selected from one or more of potassium hydroxide, phosphoric acid or zinc chloride;
the mass ratio of the natural cellulose to the activating agent is 1: 0.2-2, and preferably 1: 0.6-1.6.
The weight percentage of the activating agent in the activating agent aqueous solution is 1 wt% -10 wt%, and preferably 3wt% -8 wt%.
When the activator of the present invention is an aqueous solution of potassium hydroxide, freeze drying removes the water leaving a solid potassium hydroxide and creating pores. In the carbonization process, at high temperature, potassium hydroxide reacts with carbon, and then the pore is formed by decomposition and gasification, so that the porous carbon material with large specific surface can be obtained.
In order to realize the full mixing of the natural cellulose and the potassium hydroxide aqueous solution, the grinding mode is adopted; further adopting a ball milling mode to fully and uniformly mix the raw materials with the aqueous solution of the activating agent; wherein, the grinding ball is made of one or more of zirconium dioxide, agate and steel ball; and/or the ball-to-feed ratio is 3-4: 1; and/or the ball milling time is 2-12 hours; and/or the rotating speed is 200-400 rpm.
The invention further adopts freeze drying after fully mixing. The temperature of the freeze drying is-60 ℃ to-100 ℃. Conventional drying causes shrinkage of the material without the structure of the sample being destroyed during freeze drying because the solid components are supported by the ice in their place. As the ice sublimes, voids remain in the dry residue, which preserves the chemical structural integrity of the product and creates voids.
The invention further provides that the step 2) is specifically as follows: and (2) putting the solid mixture prepared in the step 1) into an inert gas or nitrogen environment, and carbonizing at 600-800 ℃ for 0.8-1.2 h to obtain the porous activated carbon.
As a preferred embodiment of the present invention, there is provided a method for producing a cellulose-based porous activated carbon, comprising the steps of:
1) mixing natural cellulose with 3-8 wt% of potassium hydroxide aqueous solution, ball-milling uniformly to obtain a fiber jelly, and freeze-drying at the temperature of-80 ℃ to obtain a solid mixture of the cellulose and the potassium hydroxide;
the mass ratio of the natural cellulose to the potassium hydroxide is 1: 0.6-1.6;
the mass percentage of cellulose in the natural cellulose is not less than 90%;
2) and (2) putting the solid mixture prepared in the step 1) into an inert gas or nitrogen environment, and carbonizing at 600-800 ℃ for 0.8-1.2 h to obtain the carbon nano tube.
A second object of the present invention is to provide a cellulose-based porous activated carbon produced by any of the above-described methods.
The cellulose-based porous activated carbon has a specific surface area of 500m2/g～1000m2/g。
The third purpose of the invention is to provide the application of the cellulose-based porous activated carbon in the electrode material of the super capacitor;
the application specifically comprises the following steps: when the porous activated carbon is used as an electrode, a potassium hydroxide solution is used as an electrolyte.
Preferably, when the porous activated carbon is used as an electrode, a KOH solution with the concentration of 6mol/L is used as an electrolyte. The electrolyte has the advantages of high conductivity, low internal resistance, small ionic radius of the electrolyte, easy entry into micropores, full infiltration with the micropores, full utilization of the surface area of an electrode material and the like.
The invention has at least the following beneficial effects:
1. the invention adopts a ball milling mode to mix raw materials and an activating agent in one step, so that the raw materials and the activating agent are fully mixed; the method is simple to operate, and the use amount of the raw materials and the activating agent can be strictly controlled.
2. The fiber-based porous activated carbon prepared by the method has large specific surface area up to 1000m2(ii)/g, and is almost all microporous; as an electrode material of a super capacitor, the mass specific capacitance of a two-electrode system can reach 300F/g at the highest under the current density of 1A/g, and the super capacitor has good cycle stability. The renewable, environment-friendly and low-cost cellulose is used as the active carbon precursor, and a new idea is provided for preparing the electrode material of the super capacitor through mixing and activation by a ball milling process.
Drawings
FIG. 1 is an SEM image of porous activated carbon prepared in example 1;
FIG. 2 is a nitrogen adsorption/desorption curve and a pore diameter distribution curve of porous activated carbon prepared in example 2;
FIG. 3 is a constant current charge and discharge diagram of porous activated carbon prepared in example 2;
FIG. 4 is a cyclic voltammogram of the porous activated carbon prepared in example 2;
FIG. 5 is an AC impedance spectrum of porous activated carbon prepared in example 2.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
A method of making cellulose-based porous activated carbon, the method comprising the steps of:
(1) adding 1g of cotton pulp cellulose and 1.6g of potassium hydroxide into 18.4g of water, and mixing to obtain a mixture; wherein 1.6g of potassium hydroxide is added into 18.4g of water, and the concentration of the prepared potassium hydroxide solution is 8 wt%;
(2) preparing the mixture into cellulose gum by ball milling; wherein the ball milling tank and the grinding balls are made of zirconium dioxide, and the ball material ratio is 3.5: 1; ball milling is carried out for 10 hours at the rotating speed of 300 rpm;
(3) freeze-drying the cellulose gum at-80 deg.C to obtain solid mixture of cellulose and potassium hydroxide;
(4) and (2) activating the solid mixture of carbonized cellulose and potassium hydroxide under the condition of nitrogen, wherein the carbonization temperature is 600 ℃, and the carbonization time is 1h, so as to obtain the cellulose-based porous activated carbon.
As shown in the SEM image of the porous carbon material of fig. 1, it is apparent from the figure that the material is indeed porous structure. The specific surface area of the obtained active carbon can reach 678 m through nitrogen adsorption and desorption experiment detection2(ii) in terms of/g. As an electrode material of a super capacitor, the mass specific capacitance of a two-electrode system can reach 180F/g under the current density of 1A/g.
Example 2
A method of making cellulose-based porous activated carbon, the method comprising the steps of:
(1) adding 1g of cotton pulp cellulose and 1g of potassium hydroxide into 19g of water, and mixing to obtain a mixture; wherein 1g of potassium hydroxide is added into 19g of water, and the concentration of the prepared potassium hydroxide solution is 5 wt%;
(2) preparing the mixture into cellulose gum by ball milling; wherein the ball milling tank and the grinding balls are made of zirconium dioxide, and the ball material ratio is 3.5: 1; ball milling is carried out for 10 hours at the rotating speed of 300 rpm;
(3) freeze-drying the cellulose gum at-80 deg.C to obtain solid mixture of cellulose and potassium hydroxide;
(4) and (2) activating the solid mixture of carbonized cellulose and potassium hydroxide under the condition of nitrogen, wherein the carbonization temperature is 600 ℃, and the carbonization time is 1h, so as to obtain the cellulose-based porous activated carbon.
SEM test proves that the material is really porous. FIG. 2 shows the nitrogen adsorption/desorption curve and the pore size distribution curve of example 2, and the specific surface area of the obtained material is 1057m2(ii) in terms of/g. Fig. 3, fig. 4 and fig. 5 show the results of bipolar electrochemical performance tests of the activated carbon as an electrode material. The cyclic voltammetry curve of the porous carbon material is in a better rectangle-like shape, which shows the ideal double-layer capacitance characteristic, and the capacitance value and the internal resistance are obtained by constant current charge and discharge test and alternating current impedance test, the capacitance value reaches 290F/g, and the migration internal resistance is smaller and is only 0.90 omega.
Example 3
A method of making cellulose-based porous activated carbon, the method comprising the steps of:
(1) adding 1g of cotton pulp cellulose and 0.6g of potassium hydroxide into 19.4g of water, and mixing to obtain a mixture, wherein 0.6g of potassium hydroxide is added into 19.4g of water, and the concentration of the obtained potassium hydroxide solution is 3 wt%;
(2) preparing the mixture into cellulose gum by ball milling; wherein the ball milling tank and the grinding balls are made of zirconium dioxide, and the ball material ratio is 3.5: 1; ball milling is carried out for 10 hours at the rotating speed of 300 rpm;
(3) freeze-drying the cellulose gum at-80 deg.C to obtain solid mixture of cellulose and potassium hydroxide;
(4) and (2) activating the solid mixture of carbonized cellulose and potassium hydroxide under the condition of nitrogen, wherein the carbonization temperature is 600 ℃, and the carbonization time is 1h, so as to obtain the cellulose-based porous activated carbon.
SEM test proves that the material is really porous. The specific surface area of the obtained active carbon can reach 960m through the detection of a nitrogen adsorption and desorption experiment2(ii) in terms of/g. As an electrode material of a super capacitor, the mass specific capacitance of a two-electrode system can reach 194F/g under the current density of 1A/g.
Example 4
A method of making cellulose-based porous activated carbon, the method comprising the steps of:
(1) adding 1g of cotton pulp cellulose and 0.8g of potassium hydroxide into 19.2g of water, and mixing to obtain a mixture, wherein 0.8g of potassium hydroxide is added into 19.2g of water, and the concentration of the obtained potassium hydroxide solution is 4 wt%;
(2) preparing the mixture into cellulose gum by ball milling; wherein the ball milling tank and the balls are made of zirconium dioxide, the ball-material ratio is 3.5:1, and the ball milling is carried out for 10 hours at the rotating speed of 300 rpm;
(3) freeze-drying the cellulose gum at-80 deg.C to obtain solid mixture of cellulose and potassium hydroxide;
(4) and (2) activating the solid mixture of carbonized cellulose and potassium hydroxide under the condition of nitrogen, wherein the carbonization temperature is 600 ℃, and the carbonization time is 1h, so as to obtain the cellulose-based porous activated carbon. SEM test proves that the material is really porous.
The specific surface area of the obtained active carbon can reach 842m through the detection of a nitrogen adsorption and desorption experiment2(ii) in terms of/g. As an electrode material of a super capacitor, the mass specific capacitance of a two-electrode system can reach 178F/g under the current density of 1A/g.
Example 5
A method of making cellulose-based porous activated carbon, the method comprising the steps of:
(1) adding 1g of cotton pulp cellulose and 1.2g of potassium hydroxide into 18.8g of water, and mixing to obtain a mixture, wherein 1.2g of potassium hydroxide is added into 18.8g of water, and the concentration of the obtained potassium hydroxide solution is 6 wt%;
(2) preparing the mixture into cellulose gum by ball milling; wherein the ball milling tank and the balls are made of zirconium dioxide, the ball-material ratio is 3.5:1, and the ball milling is carried out for 10 hours at the rotating speed of 300 rpm;
(3) freeze-drying the cellulose gum at-80 deg.C to obtain solid mixture of cellulose and potassium hydroxide;
(4) and (2) activating the solid mixture of carbonized cellulose and potassium hydroxide under the condition of nitrogen, wherein the carbonization temperature is 600 ℃, and the carbonization time is 1h, so as to obtain the cellulose-based porous activated carbon.
SEM test proves that the material is really porous. The specific surface area of the obtained active carbon can reach 898m through the detection of a nitrogen adsorption and desorption experiment2(ii) in terms of/g. As an electrode material of a super capacitor, the mass specific capacitance of a two-electrode system can reach 152F/g under the current density of 1A/g.
Example 6
A method of making cellulose-based porous activated carbon, the method comprising the steps of:
(1) adding 1g of cotton pulp cellulose and 1.4g of potassium hydroxide into 18.6g of water, and mixing to obtain a mixture, wherein 1.4g of potassium hydroxide is added into 18.6g of water, and the concentration of the obtained potassium hydroxide solution is 7 wt%;
(2) preparing the mixture into cellulose colloid by ball milling, wherein the ball milling tank and balls are made of zirconium dioxide with a ball-to-material ratio of 3.5:1, and the ball milling is carried out for 10 hours at a rotating speed of 300 rpm;
(3) freeze-drying the cellulose gum at-80 deg.C to obtain solid mixture of cellulose and potassium hydroxide;
(4) and (2) activating the solid mixture of carbonized cellulose and potassium hydroxide under the condition of nitrogen, wherein the carbonization temperature is 600 ℃, and the carbonization time is 1h, so as to obtain the cellulose-based porous activated carbon.
SEM test proves that the material is really porous. The specific surface area of the obtained active carbon can reach 906m through the detection of a nitrogen adsorption and desorption experiment2(ii) in terms of/g. As an electrode material of a super capacitor, the mass specific capacitance of a two-electrode system can reach 143F/g under the current density of 1A/g.
Example 7
A method of making cellulose-based porous activated carbon, the method comprising the steps of:
(1) adding 1g of cotton pulp cellulose and 1g of potassium hydroxide into 19g of water, and mixing to obtain a mixture, wherein 1g of potassium hydroxide is added into 19g of water, and the concentration of the prepared potassium hydroxide solution is 5 wt%;
(2) preparing the mixture into cellulose colloid by ball milling, wherein the ball milling tank and balls are made of zirconium dioxide with a ball-to-material ratio of 3.5:1, and the ball milling is carried out for 10 hours at a rotating speed of 300 rpm;
(3) freeze-drying the cellulose gum at-80 deg.C to obtain solid mixture of cellulose and potassium hydroxide;
(4) and (2) activating the solid mixture of carbonized cellulose and potassium hydroxide under the condition of nitrogen, wherein the carbonization temperature is 700 ℃, and the carbonization time is 1h, so as to obtain the cellulose-based porous activated carbon.
SEM test proves that the material is really porous. The specific surface area of the obtained active carbon can reach 663m through the detection of a nitrogen adsorption and desorption experiment2(ii) in terms of/g. As an electrode material of a super capacitor, the mass specific capacitance of a two-electrode system can reach 120F/g under the current density of 1A/g.
Example 8
A method of making cellulose-based porous activated carbon, the method comprising the steps of:
(1) adding 1g of cotton pulp cellulose and 1g of potassium hydroxide into 19g of water, and mixing to obtain a mixture, wherein 1g of potassium hydroxide is added into 19g of water, and the concentration of the prepared potassium hydroxide solution is 5 wt%;
(2) preparing the mixture into cellulose colloid by ball milling, wherein the ball milling tank and balls are made of zirconium dioxide with a ball-to-material ratio of 3.5:1, and the ball milling is carried out for 10 hours at a rotating speed of 300 rpm;
(3) freeze-drying the cellulose gum at-80 deg.C to obtain solid mixture of cellulose and potassium hydroxide;
(4) and (2) activating the solid mixture of carbonized cellulose and potassium hydroxide under the condition of nitrogen, wherein the carbonization temperature is 800 ℃, and the carbonization time is 1h, so as to obtain the cellulose-based porous activated carbon.
SEM test proves that the material is really porous. The specific surface area of the obtained active carbon can reach 510m through the detection of a nitrogen adsorption and desorption experiment2(ii) in terms of/g. As an electrode material of a super capacitor, the mass specific capacitance of a two-electrode system can reach 103F/g under the current density of 1A/g.
Example 9
A method of making cellulose-based porous activated carbon, the method comprising the steps of:
(1) adding 1g of corncob cellulose and 1g of potassium hydroxide into 19g of water, and mixing to obtain a mixture, wherein 1g of potassium hydroxide is added into 19g of water, and the concentration of the prepared potassium hydroxide solution is 5 wt%;
(2) preparing the mixture into cellulose colloid by ball milling, wherein the ball milling tank and balls are made of zirconium dioxide with a ball-to-material ratio of 3.5:1, and the ball milling is carried out for 10 hours at a rotating speed of 300 rpm;
(3) freeze-drying the cellulose gum at-80 deg.C to obtain solid mixture of cellulose and potassium hydroxide;
(4) and (2) activating the solid mixture of carbonized cellulose and potassium hydroxide under the condition of nitrogen, wherein the carbonization temperature is 600 ℃, and the carbonization time is 1h, so as to obtain the cellulose-based porous activated carbon.
SEM test proves that the material is really porous. The specific surface area of the obtained active carbon can reach 910m through the detection of a nitrogen adsorption and desorption experiment2(ii) in terms of/g. As an electrode material of a super capacitor, the mass specific capacitance of a two-electrode system can reach 274F/g under the current density of 1A/g.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (12)

1. A method of making a cellulose-based porous activated carbon, comprising the steps of:
1) mixing natural cellulose with an aqueous solution of an activating agent, fully grinding the mixture to obtain a fiber jelly, and freeze-drying the fiber jelly to obtain a solid mixture of the cellulose and the activating agent; the activating agent is selected from one or more of potassium hydroxide, phosphoric acid or zinc chloride; the mass ratio of the natural cellulose to the activating agent is 1: 0.6-1.6; the weight percentage of the activating agent in the activating agent aqueous solution is 3-8 wt%;
the grinding is carried out in a ball milling mode; wherein, the grinding ball is made of one or more of zirconium dioxide, agate and steel ball; the ball-material ratio is 3-4: 1; the ball milling time is 2-12 hours, and the rotating speed is 200-400 rpm;
2) and (2) putting the solid mixture prepared in the step 1) into an inert gas or nitrogen environment, and carbonizing at 500-1000 ℃ for 0.5-4 h to obtain the carbon nano tube.
2. The method according to claim 1, wherein the mass percentage of cellulose in the natural cellulose is not less than 90%.
3. The method of claim 2, wherein the natural cellulose is purified from one or more of wood, cotton, hemp, crop straw, or crop fruit.
4. The method according to any one of claims 1 to 3, wherein the temperature of the freeze drying is from-60 ℃ to-100 ℃.
5. The method according to any one of claims 1 to 3, wherein the step 2) is specifically: and (2) putting the solid mixture prepared in the step 1) into an inert gas or nitrogen environment, and carbonizing at 600-800 ℃ for 0.8-1.2 h to obtain the carbon nano tube.
6. The method according to claim 4, wherein the step 2) is specifically: and (2) putting the solid mixture prepared in the step 1) into an inert gas or nitrogen environment, and carbonizing at 600-800 ℃ for 0.8-1.2 h to obtain the carbon nano tube.
7. Method according to claim 1, characterized in that it comprises the following steps:
1) mixing natural cellulose with 3-8 wt% of potassium hydroxide aqueous solution, ball-milling uniformly to obtain a fiber jelly, and freeze-drying at the temperature of-80 ℃ to obtain a solid mixture of the cellulose and the potassium hydroxide;
the mass ratio of the natural cellulose to the potassium hydroxide is 1: 0.6-1.6;
the mass percentage of cellulose in the natural cellulose is not less than 90%;
2) and (2) putting the solid mixture prepared in the step 1) into an inert gas or nitrogen environment, and carbonizing at 600-800 ℃ for 0.8-1.2 h to obtain the carbon nano tube.
8. A cellulose-based porous activated carbon prepared by the method of any one of claims 1 to 7.
9. The cellulose-based porous activated carbon as claimed in claim 8, which has a specific surface area of 500m2/g~1000m2/g。
10. Use of a porous activated carbon as claimed in claim 8 or 9 in supercapacitor electrode materials.
11. The application according to claim 10, characterized in that it is specifically: the potassium hydroxide solution is used as the electrolyte.
12. Use according to claim 11, characterized in that a 6mol/L potassium hydroxide solution is used as electrolyte.
CN201710718213.1A 2017-08-21 2017-08-21 Cellulose porous activated carbon and preparation method and application thereof Active CN109422263B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710718213.1A CN109422263B (en) 2017-08-21 2017-08-21 Cellulose porous activated carbon and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710718213.1A CN109422263B (en) 2017-08-21 2017-08-21 Cellulose porous activated carbon and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN109422263A CN109422263A (en) 2019-03-05
CN109422263B true CN109422263B (en) 2021-10-26

Family

ID=65498027

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710718213.1A Active CN109422263B (en) 2017-08-21 2017-08-21 Cellulose porous activated carbon and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN109422263B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110422914A (en) * 2019-08-02 2019-11-08 重庆大学 A kind of charcoal base capacitance electrode material and the capacitive electrode using its preparation
CN113683088A (en) * 2021-07-27 2021-11-23 西安交通大学 Cellulose-based three-dimensional porous carbon material and preparation method and application thereof
CN114392719A (en) * 2021-12-31 2022-04-26 合肥工业大学 Method for preparing carbon-based magnetic activated carbon and prepared carbon-based magnetic activated carbon
CN115677716A (en) * 2022-09-09 2023-02-03 华北电力大学 High-value utilization method of cotton processing waste
CN115818641A (en) * 2023-01-05 2023-03-21 西南科技大学 Porous biochar based on feijoa insoluble dietary fiber and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8555896B2 (en) * 2007-12-19 2013-10-15 Philip Morris Usa Inc. Activated carbon from microcrystalline cellulose
CN104307470A (en) * 2014-09-30 2015-01-28 天津理工大学 Preparation method of cellulose fiber-based active carbon fibers with high adsorption capacity as well as product and application of cellulose fiber-based active carbon fibers with high adsorption capacity
CN105133091A (en) * 2014-05-28 2015-12-09 吴光平 Preparation method of plant active carbon fiber column
CN105384162A (en) * 2015-12-04 2016-03-09 华南理工大学 Corncob-based porous carbon material, and preparation method and application thereof
CN106587055A (en) * 2016-11-17 2017-04-26 华南理工大学 Biomass-based porous carbon material, preparation method thereof, and application thereof in supercapacitor
CN106809834A (en) * 2017-04-13 2017-06-09 合肥工业大学 A kind of method that vacuum freeze drying prepares activated carbon from activated sludge

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8555896B2 (en) * 2007-12-19 2013-10-15 Philip Morris Usa Inc. Activated carbon from microcrystalline cellulose
CN105133091A (en) * 2014-05-28 2015-12-09 吴光平 Preparation method of plant active carbon fiber column
CN104307470A (en) * 2014-09-30 2015-01-28 天津理工大学 Preparation method of cellulose fiber-based active carbon fibers with high adsorption capacity as well as product and application of cellulose fiber-based active carbon fibers with high adsorption capacity
CN105384162A (en) * 2015-12-04 2016-03-09 华南理工大学 Corncob-based porous carbon material, and preparation method and application thereof
CN106587055A (en) * 2016-11-17 2017-04-26 华南理工大学 Biomass-based porous carbon material, preparation method thereof, and application thereof in supercapacitor
CN106809834A (en) * 2017-04-13 2017-06-09 合肥工业大学 A kind of method that vacuum freeze drying prepares activated carbon from activated sludge

Also Published As

Publication number Publication date
CN109422263A (en) 2019-03-05

Similar Documents

Publication Publication Date Title
CN109422263B (en) Cellulose porous activated carbon and preparation method and application thereof
Wang et al. Nitrogen-doped biomass-based hierarchical porous carbon with large mesoporous volume for application in energy storage
Elaiyappillai et al. Low cost activated carbon derived from Cucumis melo fruit peel for electrochemical supercapacitor application
Tang et al. Research advances in biomass-derived nanostructured carbons and their composite materials for electrochemical energy technologies
Wu et al. Carbon nanotubes grown on the inner wall of carbonized wood tracheids for high-performance supercapacitors
Wang et al. 3-dimensional interconnected framework of N-doped porous carbon based on sugarcane bagasse for application in supercapacitors and lithium ion batteries
Wei et al. Synthesis of porous carbons from coal tar pitch for high-performance supercapacitors
Luo et al. A review on biomass-derived activated carbon as electrode materials for energy storage supercapacitors
Ruiz-Montoya et al. Recent progress in and prospects for supercapacitor materials based on metal oxide or hydroxide/biomass-derived carbon composites
CN111320172B (en) Directional synthesis method and application of biomass activated carbon-based electrode material containing micropore-mesoporous pore canal
Zhao et al. Efficient synthesis of nitrogen and oxygen co-doped hierarchical porous carbons derived from soybean meal for high-performance supercapacitors
CN111453726A (en) Nitrogen-doped porous carbon material and preparation method and application thereof
Li et al. Fatsia japonica-derived hierarchical porous carbon for supercapacitors with high energy density and long cycle life
JP2010517918A (en) Composite material containing biopolymer carbide and carbon nanotubes
Yan et al. Nitrogen-doped oxygen-rich activated carbon derived from Longan shell for supercapacitors
CN112265990A (en) Preparation method and application of furfural residue porous activated carbon material
Kang et al. Hierarchically Porous Carbons Derived from Cotton Stalks for High‐Performance Supercapacitors
CN109637843A (en) A method of supercapacitor is prepared by electrode material of celery
CN114506838B (en) Three-dimensional conductive network reinforced nickel-doped carbon aerogel material and preparation method and application thereof
Li et al. A new synthesis of O/N-doped porous carbon material for supercapacitors
Kang et al. Multifunctional N and O co-doped 3D carbon aerogel as a monolithic electrode for either enzyme immobilization, oxygen reduction and showing supercapacitance
Kang et al. Bifunctional N-doped hierarchical porous carbon nanosheets derived from heterologously-expressed spidroin for supercapacitors and oxygen reduction reaction
Wang et al. Regenerated bamboo-derived cellulose fibers/RGO-based composite for high-performance supercapacitor electrodes
CN113979434A (en) Biomass-based carbon electrode material and preparation method and application thereof
Qi et al. Self-assembled nano Co-Ni pompon structured hierarchical porous carbon and the excellent electrochemical capacity

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant