CN115410834B - Method for preparing lignin-based super-carbon by catalytic activation - Google Patents

Method for preparing lignin-based super-carbon by catalytic activation Download PDF

Info

Publication number
CN115410834B
CN115410834B CN202211114679.8A CN202211114679A CN115410834B CN 115410834 B CN115410834 B CN 115410834B CN 202211114679 A CN202211114679 A CN 202211114679A CN 115410834 B CN115410834 B CN 115410834B
Authority
CN
China
Prior art keywords
carbon
lignin
based super
super
steps
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
CN202211114679.8A
Other languages
Chinese (zh)
Other versions
CN115410834A (en
Inventor
雷廷宙
董莉莉
任素霞
杨延涛
刘鹏
孙堂磊
李艳玲
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.)
Changzhou University
Original Assignee
Changzhou University
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 Changzhou University filed Critical Changzhou University
Priority to CN202211114679.8A priority Critical patent/CN115410834B/en
Publication of CN115410834A publication Critical patent/CN115410834A/en
Application granted granted Critical
Publication of CN115410834B publication Critical patent/CN115410834B/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
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—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
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • 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)

Abstract

The invention discloses a method for preparing lignin-based super-capacity carbon by catalytic activation, which comprises the steps of adding resin and catalyst in a certain proportion into lignin raw materials, and carrying out pretreatment, ball milling, activation and post-treatment. The invention realizes the non-alkalization preparation of the super-carbon, the green environmental protection and the recycling of the resource utilization in the super-carbon preparation process, greatly expands the application field of lignin and improves the added value thereof; meanwhile, the preparation process of the preparation method of the super-capacity carbon is simplified, the method is simple and low in cost, and the requirement of large-scale industrial production of the super-capacity carbon is met.

Description

Method for preparing lignin-based super-carbon by catalytic activation
Technical Field
The invention belongs to the field of electrode materials for super capacitors, and particularly relates to a method for preparing lignin-based super carbon by catalytic activation.
Background
Super capacitor is a new energy storage device between traditional capacitor and battery, and is highly valued because of its advantages of fast charge and discharge rate, high power density, long cycle life, etc.
The common electrolytic materials of the super capacitor comprise four electrode materials of metal oxide, active carbon, conductive polymer and composite material. Among various electrode materials, active carbon has the advantages of large specific surface area, developed pore structure, stable physical and chemical properties, good economy and the like, and becomes the electrode material for the mainstream commercial use of super capacitors.
The electrode material used by the super capacitor is usually based on micropores, has reasonable pore structure and high heightThe specific surface area of (2) is generally controlled to 1600-2400m 2 And/g. Micropores in the activated carbon mainly provide a larger specific surface area to accommodate a large amount of electrolyte ions to form an electric double layer at an electrode/electrolyte interface, a larger specific capacity is provided, macropores and mesopores provide transport channels for electrolyte ions, and rate performance is improved, so that a proper pore size structure is very critical for an electrolytic material. While pore size structure is not only related to the activation process but also closely related to the precursor.
Lignin is a three-dimensional high molecular compound containing a plurality of active functional groups as one of precursor materials, and is mainly a compound formed by connecting phenylpropane structural units through carbon-carbon bonds and ether bonds. Lignin is attracting attention because of its wide source, renewable and low price. Meanwhile, because of the unique three-dimensional structure, the three-dimensional structure characteristics of the activated carbon can be maintained after treatment, so that the activated carbon can be applied to the field of super-capacity activated carbon. CN 109336085A takes sodium lignin sulfonate as a raw material and boric acid as a template agent to prepare lignin-based carbon nano-sheets, and the method has the characteristics of simple steps, green and sustainable properties, low cost and controllable morphology, but the template agent has the problem of high price. The application of lignin in the field of super capacitors is provided in the patents of CN 113979433A, CN 104576077A, CN 105948042B and the like, the lignin-based super carbon is obtained by activating alkaline substances (KOH or NaOH), although the problems of the application of lignin in the field of super capacitors are solved, waste liquid is easy to generate after the activation by adopting an alkaline substance (KOH and NaOH), the environmental pollution is caused, the higher treatment cost is required, the process flow is longer, the equipment is easy to be corroded by the application of alkali, and the service life requirement of the equipment is shortened. CN 114162819A discloses a preparation method of an economic and environment-friendly lignin-based multi-stage structure porous carbon, which is to obtain the lignin-based multi-stage structure porous carbon material by mixing lignin and cupric chloride, carbonizing and activating.
At present, although the provided method obtains good lignin-based activated carbon, the method has the defects of complex flow and environmental protection.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description summary and in the title of the application, to avoid obscuring the purpose of this section, the description summary and the title of the invention, which should not be used to limit the scope of the invention.
The present invention has been made in view of the above and/or problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a method for preparing lignin-based super-carbon by catalytic activation.
In order to solve the technical problems, the invention provides the following technical scheme: a method for preparing lignin-based super-carbon by catalytic activation comprises,
crushing lignin to less than 75 mu m, putting the crushed lignin into a tube furnace, introducing oxidizing gas with the flow rate of 5-80L/H, and oxidizing for 1-4H to obtain a treated first product;
mixing the first product, resin and catalyst, and then performing ball milling to obtain an activated precursor;
placing the activated precursor into a tube furnace, heating to 800-1100 ℃ under inert atmosphere, and converting the inert gas into CO 2 Gas, and preserving heat for 1-6 h;
after the heat preservation is finished, under the final temperature condition, the activated gas is converted into inert atmosphere, and H is introduced at the same time 2 Preserving heat for 1-5 h to obtain an activated product;
and (3) cleaning the activated product by deionized water, and drying to obtain the lignin-based super-carbon.
As a preferable scheme of the method for preparing lignin-based super-carbon by catalytic activation, the invention comprises the following steps: the lignin-based super carbon has a specific surface area of 1482-2170 m 2 Per gram, total pore volume of 0.7347～1.2139cm 3 And/g, the average pore diameter is 1.9825-2.2367 nm.
As a preferable scheme of the method for preparing lignin-based super-carbon by catalytic activation, the invention comprises the following steps: the carbon content of the lignin is 50.3-61.7%.
As a preferable scheme of the method for preparing lignin-based super-carbon by catalytic activation, the invention comprises the following steps: the oxidizing gas comprises air, O 2 And ozone.
As a preferable scheme of the method for preparing lignin-based super-carbon by catalytic activation, the invention comprises the following steps: the first product has an oxygen-containing functional group of 4 to 39 percent.
As a preferable scheme of the method for preparing lignin-based super-carbon by catalytic activation, the invention comprises the following steps: the resin is cured phenolic resin or waste phenolic resin, the coking value of the resin is 55-60%, and ash content is below 0.3%.
As a preferable scheme of the method for preparing lignin-based super-carbon by catalytic activation, the invention comprises the following steps: the mass ratio of the first product to the resin is 1:0.2 to 1 percent, wherein the catalyst is CaCl 2 One or more of KCl and NaCl, and the catalyst accounts for 2-45% of the total mass of the first product and the resin.
As a preferable scheme of the method for preparing lignin-based super-carbon by catalytic activation, the invention comprises the following steps: the ball milling treatment time is 2-6 h, and the D50 of the ball grinding material after the ball milling treatment is 30 mu m.
As a preferable scheme of the method for preparing lignin-based super-carbon by catalytic activation, the invention comprises the following steps: placing the activated precursor into a tube furnace, and heating to 800-1100 ℃ under an inert atmosphere, wherein the inert atmosphere is nitrogen or argon, and the gas flow is 20-80L/h; the activated gas is converted into inert atmosphere and simultaneously H is introduced 2 Wherein, the hydrogen accounts for 5-30% of the volume of the inert gas, and the inert atmosphere is nitrogen or argon.
As a preferable scheme of the method for preparing lignin-based super-carbon by catalytic activation, the invention comprises the following steps: the final temperature is 800-1100 ℃.
The invention has the beneficial effects that:
according to the invention, lignin is used as a raw material, and low-temperature crosslinking high-temperature catalytic activation is adopted to realize in-situ regulation and control of the pore diameter of the super-capacity carbon, so that the super-capacity carbon with reasonable pore diameter structure and excellent performance is obtained;
the invention realizes the non-alkalization preparation of the super-carbon, the green environmental protection and the recycling of the resource utilization in the super-carbon preparation process, greatly expands the application field of lignin and improves the added value thereof;
the preparation method of the super-capacity carbon simplifies the preparation flow of the super-capacity carbon, has the characteristics of simple method and low cost, and meets the requirement of large-scale industrial production of the super-capacity carbon.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a lignin-based super-carbon adsorption isotherm of example 1 of the present invention;
FIG. 3 is a graph of the pore size distribution of lignin-based super-carbon of example 1 of the present invention;
FIG. 4 is a SEM of lignin-based super carbon of example 1 of the present invention;
FIG. 5 is a charge and discharge curve of lignin-based super-carbon according to example 1 of the present invention.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
In the invention, phenolic resin (2-8 ℃, drying, sealing and preserving, liquid, mizurine of manufacturer, solid content-70%) is a common commercial product, and the cured phenolic resin is obtained after two weeks of curing at normal temperature; the other raw materials are all common commercial products.
Example 1:
s1, pretreatment: crushing lignin to 50 μm, placing into a tube furnace, introducing O with certain flow rate 2 (flow 80L/h) oxidation treatment for 4h to obtain a treated first product with an oxygen-containing functional group of 39%;
s2 ball milling: the first product, the cured phenolic resin and CaCl 2 Adding the materials into a ball ink tank according to a certain proportion for ball milling, wherein the specific proportion is as follows: the mass ratio of lignin to resin is as follows: the addition amount of the catalyst is 30% of the total mass of lignin and resin in a ratio of 1:1. After a ball milling time of 6 hours, an activated precursor was obtained, which had a D50 of 15. Mu.m.
S3, activating: the activated precursor is placed in a tube furnace, heated to 950 ℃ under an inert atmosphere, and the inert gas (nitrogen 99.999%) is converted into CO 2 Gas is kept for 6 hours, after the heat preservation is finished, the activated gas is converted into nitrogen/argon atmosphere under the final temperature condition, and H is introduced at the same time 2 Preserving heat for 3h, H 2 Accounting for 30 percent of the volume of the mixed gas. After the heat preservation is finished, an activated product is obtained, and the oxygen content of the activated product is 0.3 percent;
s4, post-treatment: and (3) cleaning the activated product with deionized water, and drying to obtain the lignin-based activated carbon. Evaporating the washed washing liquid, returning the evaporated catalyst to the ball milling process, condensing the evaporated liquid and washing the lignin-based active carbon.
The super-capacity carbon is obtained after the steps, and the pore structure is characterized in that: specific surface area 2170m 2 Per g, total pore volume 1.2139cm 3 /g, average pore size 2.2367nm. The electrode plate is mixed with a bonding agent PTFE and a conductive agent SuperP according to the proportion of 8:1:1 to prepare the electrode plate, and the electrochemical performance under a three-electrode system is tested in a KOH aqueous solution with the concentration of 6 mol. Under the condition of current density of 1A/g, the specific capacity of the obtained lignin-based super Rong Tan is 330.3F/g.
The process flow diagram of the invention is shown in FIG. 1; lignin-based super-carbon adsorption isotherms of this example 1, see fig. 2, lignin-based super-carbon pore size distribution curves, see fig. 3; the lignin-based super carbon SEM of this example, see fig. 4; the charge-discharge curve of lignin-based super-carbon in this example 1 is shown in fig. 5; it can be seen that the in-situ regulation and control of the pore diameter of the super-capacity carbon are realized by utilizing low-temperature crosslinking high-temperature catalytic activation, and the super-capacity carbon with reasonable pore diameter structure and excellent performance is obtained.
Example 2:
s1, pretreatment: crushing lignin to 50 mu m, putting the lignin into a tube furnace, introducing O2 with a certain flow (the flow is 60L/h) for oxidation treatment for 1h to obtain a treated first product, wherein the oxygen-containing functional group of the first product is 23%;
s2 ball milling: the first product, the cured phenolic resin and CaCl 2 Adding the materials into a ball ink tank according to a certain proportion for ball milling, wherein the specific proportion is as follows: the mass ratio of lignin to resin is as follows: 1:0.6, the addition amount of the catalyst is 20% of the total mass of lignin and resin. After a ball milling time of 4 hours, an activated precursor was obtained, which had a D50 of 21. Mu.m.
S3, activating: the activated precursor is placed in a tube furnace, heated to 1000 ℃ under an inert atmosphere, and the inert gas (nitrogen 99.999%) is converted into CO 2 Gas is kept for 4 hours, after the heat preservation is finished, the activated gas is converted into nitrogen/argon atmosphere under the final temperature condition, and H is introduced at the same time 2 Preserving heat for 2h, H 2 Accounting for 20 percent of the volume of the mixed gas. Activation is obtained after the heat preservation is finishedA product having an oxygen content of 0.6%;
s4, post-treatment: and (3) cleaning the activated product with deionized water, and drying to obtain the lignin-based activated carbon. Evaporating the washed washing liquid, returning the evaporated catalyst to the ball milling process, condensing the evaporated liquid and washing the lignin-based active carbon.
The super-capacity carbon is obtained after the steps, and the pore structure is characterized in that: specific surface area 1919m 2 Per g, total pore volume 0.9932cm 3 /g, average pore size 2.0701nm. The electrode plate is mixed with a bonding agent PTFE and a conductive agent SuperP according to the proportion of 8:1:1 to prepare the electrode plate, and the electrochemical performance under a three-electrode system is tested in a KOH aqueous solution with the concentration of 6 mol. Under the condition of current density of 1A/g, the specific capacity of the obtained lignin-based super Rong Tan is 318.4F/g.
Example 3:
s1, pretreatment: crushing lignin to 50 μm, placing into a tube furnace, introducing O with certain flow rate 2 (flow rate is 30L/h) to perform oxidation treatment for 2h to obtain a treated first product, wherein the oxygen-containing functional group of the first product is 15%;
s2 ball milling: the first product, the cured phenolic resin and CaCl 2 Adding the materials into a ball ink tank according to a certain proportion for ball milling, wherein the specific proportion is as follows: the mass ratio of lignin to resin is as follows: 1:0.4, and the addition amount of the catalyst is 10 percent of the total mass of lignin and resin. After a ball milling time of 2 hours, an activated precursor was obtained, which had a D50 of 30. Mu.m.
S3, activating: the activated precursor is placed in a tube furnace, heated to 1000 ℃ under an inert atmosphere, and the inert gas (nitrogen 99.999%) is converted into CO 2 Gas is kept for 2H, after the heat preservation is finished, the activated gas is converted into nitrogen/argon atmosphere under the final temperature condition, and H is introduced at the same time 2 Preserving heat for 1h, H 2 Accounting for 5 percent of the volume of the mixed gas. After the heat preservation is finished, an activated product is obtained, and the oxygen content of the activated product is 0.8%;
s4, post-treatment: and (3) cleaning the activated product with deionized water, and drying to obtain the lignin-based activated carbon. Evaporating the washed washing liquid, returning the evaporated catalyst to the ball milling process, condensing the evaporated liquid and washing the lignin-based active carbon.
The super-capacity carbon is obtained after the steps, and the pore structure is characterized in that: specific surface area 1612m 2 Per g, total pore volume 0.9017cm 3 /g, average pore size 2.0013nm. The electrode plate is mixed with a bonding agent PTFE and a conductive agent SuperP according to the proportion of 8:1:1 to prepare the electrode plate, and the electrochemical performance under a three-electrode system is tested in a KOH aqueous solution with the concentration of 6 mol. Under the condition of current density of 1A/g, the specific capacity of the obtained lignin-based super Rong Tan is 306.1F/g.
Example 4:
s1, pretreatment: crushing lignin to 50 μm, placing into a tube furnace, introducing O with certain flow rate 2 (flow rate is 5L/h) to perform oxidation treatment for 4h to obtain a treated first product, wherein the oxygen-containing functional group of the first product is 4%;
s2 ball milling: the first product, the cured phenolic resin and CaCl 2 Adding the materials into a ball ink tank according to a certain proportion for ball milling, wherein the specific proportion is as follows: the mass ratio of lignin to resin is as follows: 1:0.2, the addition amount of the catalyst is 2% of the total mass of lignin and resin. After 3 hours of ball milling, an activated precursor was obtained, which had a D50 of 24. Mu.m.
S3, activating: the activated precursor is placed in a tube furnace, heated to 950 ℃ under an inert atmosphere, and the inert gas (nitrogen 99.999%) is converted into CO 2 Gas is kept for 3 hours, after the heat preservation is finished, the activated gas is converted into nitrogen/argon atmosphere under the final temperature condition, and H is introduced at the same time 2 Preserving heat for 4h, H 2 Accounting for 10 percent of the volume of the mixed gas. After the heat preservation is finished, an activated product is obtained, and the oxygen content of the activated product is 0.7%;
s4, post-treatment: and (3) cleaning the activated product with deionized water, and drying to obtain the lignin-based activated carbon. Evaporating the washed washing liquid, returning the evaporated catalyst to the ball milling process, condensing the evaporated liquid and washing the lignin-based active carbon.
The super-capacity carbon is obtained after the steps, and the pore structure is characterized in that: specific surface area 1482m 2 Per g, total pore volume 0.7347cm 3 /g, average pore size 1.9825nm. It is combined with adhesive PTFE. The conductive agent SuperP is mixed according to the proportion of 8:1:1 to prepare a pole piece, and the electrochemical performance of the three-electrode system is tested in a KOH aqueous solution with the concentration of 6 mol. The specific capacity of the obtained lignin-based super Rong Tan is 294.7F/g under the condition of the current density of 1A/g.
Example 5:
the parameters of the different S2 ball mills were controlled under the conditions of example 1, and the other conditions were the same as in example 1, and the specific conditions and results are shown in Table 1.
TABLE 1
Figure BDA0003844939190000071
It can be seen that the specific capacity of super carbon is optimal at 21 μm for D50.
Example 6:
in comparison with example 1, the difference is the S3 activation step, otherwise the conditions are the same as in example 1: (CO is not introduced 2 Gas (es)
S3, activating: placing the activated precursor into a tube furnace, heating to 950 ℃ under inert atmosphere, preserving the temperature of inert gas (nitrogen 99.999%) for 6 hours, converting the activated gas into nitrogen/argon atmosphere under final temperature after the heat preservation is finished, and simultaneously introducing H 2 Preserving heat for 3h, H 2 Accounting for 30 percent of the volume of the mixed gas.
Example 7:
the difference compared to example 1 is the S3 activation step: (general No. H) 2 Gas (es)
S3, activating: the activated precursor is placed in a tube furnace, heated to 950 ℃ under an inert atmosphere, and the inert gas nitrogen (99.999%) is converted into CO 2 Gas is kept warm for 6 hours, after the heat preservation is finished, the activated gas is converted into nitrogen/argon atmosphere under the final temperature condition, and the heat preservation is carried out for 3 hours;
other conditions were the same as in example 1.
Example 8:
the difference compared to example 1 is the S3 activation step: (without CO) 2 And H 2 Gas (es)
S3, activating: placing the activated precursor into a tube furnace, heating to 950 ℃ under inert atmosphere, keeping the temperature of inert gas nitrogen (99.999%), keeping the temperature for 6 hours, and after the heat preservation is finished, converting the activated gas into nitrogen/argon atmosphere under the final temperature condition, and keeping the temperature for 3 hours;
other conditions were the same as in example 1.
Example 9:
the difference compared to example 1 is the S3 activation step:
s3, activating: the activated precursor is placed in a tube furnace, heated to 950 ℃ under an inert atmosphere, and the inert gas nitrogen (99.999%) is converted into CO 2 Gas is kept for 6 hours, after the heat preservation is finished, the activated gas is converted into nitrogen/argon atmosphere under the final temperature condition, and H is introduced at the same time 2 Preserving heat for 3h, H 2 Accounting for 20 percent of the volume of the mixed gas;
other conditions were the same as in example 1.
Example 10:
the difference compared to example 1 is the S3 activation step:
s3, activating: the activated precursor is placed in a tube furnace, heated to 950 ℃ under an inert atmosphere, and the inert gas nitrogen (99.999%) is converted into CO 2 Gas is kept for 6 hours, after the heat preservation is finished, the activated gas is converted into nitrogen/argon atmosphere under the final temperature condition, and H is introduced at the same time 2 Preserving heat for 3h, H 2 Accounting for 40 percent of the volume of the mixed gas;
other conditions were the same as in example 1.
The super-capacity carbon prepared in examples 6 to 10, a bonding agent PTFE and a conductive agent SuperP are mixed according to the ratio of 8:1:1 to prepare a pole piece, the electrochemical performance of a three-electrode system is tested in a KOH aqueous solution with the concentration of 6mol, and the specific capacity of the obtained lignin-based super-capacity carbon is shown in Table 2 under the condition of the current density of 1A/g.
TABLE 2
Example 6 Example 7 Example 8 Example 9 Example 10
Specific capacity (F/g) 60.4 236.9 80.7 306.7 320.1
The invention provides a preparation method of lignin-based super-carbon, which utilizes low-temperature surface oxidation modification to form a stable lignin-based active carbon precursor structure, uses the precursor to realize dispersion homogenization of a catalyst in the precursor by ball milling, and uses CO further 2 In order to activate the medium, pore-forming and reaming are carried out on the lignin-based precursor, so that the low-cost and environment-friendly preparation of the lignin-based activated carbon is realized, the preparation method of the super-capacity carbon simplifies the preparation flow of the super-capacity carbon, has the characteristics of simple method and low cost, meets the requirement of large-scale industrial production of the super-capacity carbon, and at present, the main flow super-capacity carbon preparation method adopts a KOH activation method, and compared with the prior art, the preparation method of the super-capacity carbon has the advantages that the super-capacity carbon preparation process is free from alkalization, the equipment corrosion is reduced, and the preparation cost of the super-capacity carbon is greatly reduced; meanwhile, super-capacity carbon with good pore size distribution and good electrochemical performance can be obtained; the environmental pollution is reduced, and the environmental pollution is also reduced,eliminates the potential safety hazard caused by potassium steam in the preparation process of the traditional method.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.

Claims (10)

1. A method for preparing lignin-based super-carbon by catalytic activation is characterized by comprising the following steps: comprising the steps of (a) a step of,
crushing lignin to less than 75 mu m, putting the lignin into a tube furnace, introducing oxidizing gas with the flow of 5-80L/H, and oxidizing for 1-4 hours to obtain a treated first product;
mixing the first product, resin and catalyst, and then performing ball milling to obtain an activated precursor;
placing the activated precursor into a tube furnace, heating to 800-1100 ℃ in an inert atmosphere, and converting the inert gas into CO 2 Gas, and preserving heat for 1-6 hours;
after the heat preservation is finished, under the final temperature condition, the activated gas is converted into inert atmosphere, and H is introduced at the same time 2 Preserving heat for 1-5 h to obtain an activated product;
washing the activated product with deionized water, and drying to obtain lignin-based super-carbon;
wherein the resin is cured phenolic resin or waste phenolic resin, and the catalyst is CaCl 2 One or more of KCl or NaCl.
2. The method for preparing lignin-based super-carbon by catalytic activation according to claim 1, wherein the method comprises the steps of: the lignin-based super carbon has a specific surface area of 1482-2170 m 2 The total pore volume per gram is 0.7347-1.2139 cm and the average pore diameter is 1.9825-2.2367 nm.
3. The method for preparing lignin-based super carbon by catalytic activation according to claim 1 or 2, wherein: the carbon content of the lignin is 50.3-61.7%.
4. A method for preparing lignin-based super-carbon according to claim 3 wherein the method comprises the steps of: the oxidizing gas comprises air, O 2 And ozone.
5. The method for preparing lignin-based super-carbon by catalytic activation according to claim 4, wherein the method comprises the following steps: the first product has an oxygen-containing functional group of 4-39%.
6. The method for preparing lignin-based super carbon according to any one of claims 1, 2, 4 or 5 wherein the method comprises the steps of: the coking value of the resin is 55-60%, and ash content is below 0.3%.
7. The method for preparing lignin-based super-carbon according to claim 6 wherein the method comprises the steps of: the mass ratio of the first product to the resin is 1: 0.2-1% of catalyst accounting for 2-45% of the total mass of the first product and the resin.
8. The method for preparing lignin-based super-carbon according to claim 7 wherein the method comprises the steps of: the ball milling treatment time is 2-6 hours, and the D50 of the ball grinding material after the ball milling treatment is 30 mu m.
9. The method for preparing lignin-based super-carbon according to claim 8 wherein the method comprises the steps of: placing the activated precursor into a tube furnace, and heating to 800-1100 ℃ under an inert atmosphere, wherein the inert atmosphere is nitrogen or argon, and the gas flow is 20-80L/h; the activated gas is converted into inert atmosphere and simultaneously H is introduced 2 Wherein, the hydrogen accounts for 5-30% of the volume of the inert gas, and the inert atmosphere is nitrogen or argon.
10. The method for preparing lignin-based super-carbon according to claim 8 wherein the method comprises the steps of: the final temperature is 800-1100 ℃.
CN202211114679.8A 2022-09-14 2022-09-14 Method for preparing lignin-based super-carbon by catalytic activation Active CN115410834B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211114679.8A CN115410834B (en) 2022-09-14 2022-09-14 Method for preparing lignin-based super-carbon by catalytic activation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211114679.8A CN115410834B (en) 2022-09-14 2022-09-14 Method for preparing lignin-based super-carbon by catalytic activation

Publications (2)

Publication Number Publication Date
CN115410834A CN115410834A (en) 2022-11-29
CN115410834B true CN115410834B (en) 2023-05-05

Family

ID=84164905

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211114679.8A Active CN115410834B (en) 2022-09-14 2022-09-14 Method for preparing lignin-based super-carbon by catalytic activation

Country Status (1)

Country Link
CN (1) CN115410834B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116190686B (en) * 2023-03-21 2024-03-26 常州大学 Preparation method and application of in-situ activated furfural residue and nitrogen-sulfur co-doped porous carbon catalyst
CN116854068B (en) * 2023-06-14 2024-07-23 常州大学 Method for preparing super-capacity carbon by low-temperature crosslinking of lignin composite tar

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105518814A (en) * 2013-09-20 2016-04-20 爱恩株式会社 Activated carbon for use in electrode of power-storage device, and method for producing same
CN111747406A (en) * 2020-07-06 2020-10-09 南京林业大学 Processing technology for improving specific surface area of activated carbon through baking pretreatment

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107500291B (en) * 2017-07-10 2019-10-18 吉林大学 A kind of preparation method of lignin-base phenolic resin capacitance carbon
CN112225216A (en) * 2020-09-03 2021-01-15 华南理工大学 Medium-micropore lignin-based activated carbon and preparation method thereof
EP4294758A1 (en) * 2021-02-17 2023-12-27 CarbonIP Technologies Inc. Sweeping gas process for production of activated carbon-based electrode materials
CN113800496A (en) * 2021-08-06 2021-12-17 深圳市德方纳米科技股份有限公司 Hard carbon material and preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105518814A (en) * 2013-09-20 2016-04-20 爱恩株式会社 Activated carbon for use in electrode of power-storage device, and method for producing same
CN111747406A (en) * 2020-07-06 2020-10-09 南京林业大学 Processing technology for improving specific surface area of activated carbon through baking pretreatment

Also Published As

Publication number Publication date
CN115410834A (en) 2022-11-29

Similar Documents

Publication Publication Date Title
CN115410834B (en) Method for preparing lignin-based super-carbon by catalytic activation
CN108483442B (en) Preparation method of nitrogen-doped carbon electrode material with high mesoporous rate
WO2020103635A1 (en) Lignin porous carbon nano sheet, preparation method therefor, and application thereof in super capacitor electrode material
CN108529587B (en) Preparation method and application of phosphorus-doped biomass graded porous carbon material
CN106848312B (en) A kind of modified porous graphene, modified porous graphene negative electricity pole piece and preparation method thereof
CN111204755B (en) Preparation method and application of biomass porous carbon material
CN104817082A (en) Method for preparing nitrogen-enriched porous carbon material for supercapacitor by taking lignite as raw material
CN107244664B (en) Preparation method and application of graphene-like structure carbon electrode material
CN113135568A (en) Nitrogen-doped porous carbon material and preparation method and application thereof
CN109368640B (en) Method for preparing graded porous carbon material by using hair base
CN109775710B (en) Preparation method of nitrogen-doped porous carbon material and application of nitrogen-doped porous carbon material in supercapacitor
CN105384169A (en) Preparation method of active carbon for preparing super capacitor electrode
CN113161161B (en) Nano carbon material composite resin hard carbon electrode material and preparation method and application thereof
CN112479205A (en) Narrow-pore bamboo sheath activated carbon and preparation method thereof
CN112599363A (en) SnO (stannic oxide)2Modified N, P co-doped porous carbon supercapacitor material
CN115094440B (en) Preparation method of cobalt/ferroferric oxide/carbon nano tube/C porous microsphere hydrogen production catalyst
CN110255537A (en) A kind of preparation method of the three-dimensional porous graphene of high-ratio surface boron atom doping
CN110407208A (en) A kind of preparation method of mesoporous graphene-based charcoal-aero gel
CN112811419B (en) Low-cost preparation process of carbon aerogel and carbon aerogel
CN110482546B (en) Energy-storage activated carbon and preparation method thereof
CN110862077B (en) Preparation method of hierarchical porous carbon material rich in mesopores for supercapacitor
CN110143582B (en) Preparation method and application of oxygen-containing porous carbon aerogel
CN111261877B (en) Supported hollow sphere carbon material, preparation method thereof and application thereof in electrocatalysis
CN109659149B (en) Graphene activated carbon composite material and preparation method and application thereof
CN112429714A (en) Preparation process of modified super-capacitor carbon

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