CN115410834A - Method for preparing lignin-based super-capacity carbon through catalytic activation - Google Patents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H01G11/44—Raw materials therefor, e.g. resins or coal
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- 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
Abstract
The invention discloses a method for preparing lignin-based super-capacity carbon by catalytic activation, which comprises the steps of adding a certain proportion of resin and a catalyst into a lignin raw material, carrying out pretreatment, ball milling, activation, post-treatment and the like, and realizing in-situ regulation and control of the pore diameter of the super-capacity carbon by using low-temperature crosslinking and high-temperature catalytic activation to obtain the super-capacity carbon with reasonable pore diameter structure and excellent performance. The invention realizes the alkali-free preparation of the super-capacity carbon, realizes the greening environmental protection and resource utilization cyclic cyclization in the super-capacity carbon preparation process, greatly expands the application field of lignin and improves the added value of the lignin; meanwhile, the preparation method of the super-capacity carbon is simplified, has the characteristics of simple method and low cost, and meets the requirement of large-scale industrial production of the super-capacity carbon.
Description
Technical Field
The invention belongs to the field of electrode materials for supercapacitors, and particularly relates to a method for preparing lignin-based super-capacity carbon through catalytic activation.
Background
As a novel energy storage device between a conventional capacitor and a battery, a super capacitor is highly regarded for its advantages of fast charging and discharging rate, high power density, and ultra-long cycle life.
Common electrolytic materials for supercapacitors include four types of electrode materials, such as metal oxides, activated carbon, conductive polymers, and composite materials. Among various electrode materials, activated carbon has advantages such as a large specific surface area, a developed pore structure, stable physicochemical properties, and good economical efficiency, and thus has become a mainstream commercial electrode material for supercapacitors.
The electrode material used for the super capacitor is mainly microporous, has a reasonable pore structure and a high specific surface area, and the specific surface area is generally controlled to be 1600-2400m 2 (ii) in terms of/g. The micropores in the activated carbon mainly provide a large specific surface area to accommodate a large amount of electrolyte ions to form an electrical double layer at the electrode/electrolyte interface, providing a larger specific capacity, and the macropores and mesopores provide transport channels for the electrolyte ions, improving rate capability, so that a suitable pore size structure is very critical for the electrolytic material. The pore size structure is not only relevant to the activation process, but also closely relevant to the precursor.
The lignin is a three-dimensional polymer compound containing various active functional groups as one of the precursor materials, and is a compound mainly formed by connecting phenylpropane structural units through carbon-carbon bonds and ether bonds. Lignins are receiving attention due to their characteristics of wide sources, reproducibility, low price, and the like. Meanwhile, due to the unique three-dimensional structure, the three-dimensional structure characteristics of the carbon fiber can be maintained after treatment, so that the carbon fiber can be applied to the field of super-capacity activated carbon. CN 109336085A takes sodium lignosulfonate as a raw material and boric acid as a template agent to prepare the lignin-based carbon nanosheet, and the method has the characteristics of simple steps, greenness, sustainability, low cost and controllable morphology, but the used template agent has the problem of high price. Patents CN 113979433A, CN 104576077A, CN 105948042B, etc. respectively provide applications of lignin in the field of supercapacitors, the used lignin-based super-capacity carbon is obtained by activating with alkaline substances (KOH or NaOH), although some problems of lignin application in the field of supercapacitors are solved, the method using alkaline substances (KOH and NaOH) is easy to generate waste liquid after activation, which causes environmental pollution and requires higher treatment cost, and meanwhile, the process flow is longer, the application of alkali is easy to corrode equipment, and the requirement of equipment service life is shortened. CN 114162819A discloses an economical and environment-friendly preparation method of lignin-based hierarchical structure porous carbon, which obtains lignin-based hierarchical structure porous carbon material by mixing, carbonizing and activating lignin and copper chloride.
At present, although the provided method obtains good lignin-based activated carbon, the method has the defects of complex flow and environmental pollution.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made keeping in mind the above problems 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-capacity 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-capacity carbon by catalytic activation comprises the following steps,
crushing lignin to be less than 75 micrometers, putting the lignin into a tubular furnace, introducing oxidizing gas with the flow rate of 5-80L/H, and carrying out oxidation treatment for 1-4 hours to obtain a treated first product;
mixing the first product, resin and a catalyst, and then carrying out ball milling to obtain an activated precursor;
the activated precursor is placed into a tube furnace, the temperature is raised to 800-1100 ℃ under the inert atmosphere, and the inert gas is converted into CO 2 Gas is filled and the temperature is kept for 1 to 6 hours;
after the heat preservation is finished, under the condition of final temperature, the activated gas is changed into inert atmosphere, and H is introduced at the same time 2 Keeping the temperature for 1 to 5 hours to obtain an activated product;
and (3) washing the activated product with deionized water, and drying to obtain the lignin-based super-capacity carbon.
As a preferable scheme of the method for preparing the lignin-based super-capacity carbon by catalytic activation, the method comprises the following steps: the specific surface area of the lignin-based super-capacity carbon is 1482 to 2170m 2 The total pore volume is 0.7347-1.2139 cm 3 The average pore diameter is 1.9825-2.2367 nm.
As a preferable scheme of the method for preparing the lignin-based super-capacity carbon by catalytic activation, the method comprises the following steps: the carbon content of the lignin is 50.3-61.7%.
As a preferable scheme of the method for preparing the lignin-based super-capacity carbon by catalytic activation, the method comprises the following steps: the oxidizing gas comprises air and O 2 And ozone.
As a preferable scheme of the method for preparing the lignin-based super-capacity carbon by catalytic activation, the method comprises the following steps: the first product contains 4-39% of oxygen-containing functional groups.
As a preferable scheme of the method for preparing the lignin-based super-capacity carbon by catalytic activation, the method comprises the following steps: the resin is cured phenolic resin or waste phenolic resin, the coking value of the resin is 55-60%, and the ash content is less than 0.3%.
As a preferable scheme of the method for preparing the lignin-based super-capacity carbon by catalytic activation,wherein: the mass ratio of the first product to the resin is 1:0.2 to 1, the catalyst is CaCl 2 And one or more of KCl and NaCl, wherein 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 the lignin-based super-capacity carbon by catalytic activation, the method comprises the following steps: the ball milling treatment time is 2-6 h, and the D50 of the treated ball grinding material is 30 mu m.
As a preferable scheme of the method for preparing the lignin-based super-capacity carbon by catalytic activation, the method comprises the following steps: placing the activated precursor into a tube furnace, and heating to 800-1100 ℃ under 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 H is introduced at the same time 2 Wherein the volume percentage of the hydrogen in the inert gas is 5-30%, and the inert atmosphere is nitrogen or argon.
As a preferable scheme of the method for preparing the lignin-based super-capacity carbon by catalytic activation, the method comprises the following steps: the final temperature condition is that 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 and high-temperature catalytic activation are 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 alkali-free preparation of the super-capacity carbon, realizes the green environmental protection and resource utilization cyclic cyclization in the super-capacity carbon preparation process, greatly expands the application field of lignin and improves the added value of the lignin;
the preparation method of the super-capacity carbon simplifies the preparation process 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 needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a lignin-based super-capacity carbon adsorption isotherm of example 1 of the present invention;
FIG. 3 is a graph of the pore size distribution of lignin-based super-capacity carbon according to example 1 of the present invention;
FIG. 4 is a SEM of lignin-based super-compatible carbon according to example 1 of the present invention;
FIG. 5 is a charging and discharging curve of lignin-based super capacity carbon of example 1 of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as specifically described herein, and it will be appreciated by those skilled in the art that the present invention may be practiced without departing from the spirit and scope of the present invention and that the present invention is not limited by the specific embodiments disclosed below.
Furthermore, the references herein to "one embodiment" or "an embodiment" refer to a particular feature, structure, or characteristic that may be included in at least one implementation of the present 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.
The phenolic resin (2-8 ℃, drying, sealing and storing, liquid, manufacturer Michelin, solid content-70%) of the invention is a common commercial product, and the product is placed at normal temperature for two weeks to be cured to obtain cured phenolic resin; other raw materials are all common commercial products.
Example 1:
s1, pretreatment: crushing lignin to 50 μm, placing in a tube furnace, and introducing O at a certain flow rate 2 (flow rate of80L/h) for 4h, obtaining a treated first product with 39% oxygen-containing functional groups;
s2, ball milling: mixing the first product, cured phenolic resin and CaCl 2 Adding the mixture into a ball ink tank according to a certain proportion for ball milling, wherein the specific proportion is as follows: the mass ratio of the lignin to the resin is as follows: 1:1, the amount of catalyst added is 30% of the total mass of lignin and resin. After ball milling for 6h, an activated precursor is obtained, the D50 of which is 15 mu m.
S3, activation: the activated precursor was placed in a tube furnace and heated to 950 ℃ under inert atmosphere to convert the inert gas (nitrogen 99.999%) to CO 2 Gas is kept for 6 hours, after the heat preservation is finished, the activated gas is changed into nitrogen/argon atmosphere under the condition of final temperature, and H is introduced at the same time 2 And the temperature is kept for 3h 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%;
s4, post-processing: and cleaning the activated product by using deionized water, and drying to obtain the lignin-based activated carbon. Evaporating the washed washing liquid, returning the evaporated residual catalyst to the ball milling process, and condensing the evaporated liquid for washing the lignin-based active carbon.
The super-capacity carbon is obtained through the steps, and the pore structure is characterized in that: specific surface area 2170m 2 Perg, total pore volume 1.2139cm 3 G, average pore diameter 2.2367nm. The electrode plate is mixed with adhesive PTFE and conductive agent SuperP according to the proportion of 8. Under the condition of current density of 1A/g, the specific capacity of the obtained lignin-based super-capacity carbon is 330.3F/g.
The process flow diagram of the present invention, see FIG. 1; the lignin-based super-capacity carbon adsorption isotherm of the present example 1 is shown in fig. 2, and the lignin-based super-capacity carbon pore size distribution curve is shown in fig. 3; the lignin-based super-capacity carbon SEM of this example is shown in fig. 4; the charging and discharging curves of the lignin-based super-capacity carbon in the embodiment 1 are shown in figure 5; it can be seen that the in-situ regulation and control of the pore diameter of the super-capacity carbon is realized by utilizing low-temperature crosslinking and 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 μm, placing in a tubular furnace, introducing O2 (flow rate is 60L/h) with a certain flow rate for oxidation treatment for 1h to obtain a treated first product with oxygen-containing functional groups of 23%;
s2, ball milling: mixing the first product, cured phenolic resin and CaCl 2 Adding the mixture into a ball ink tank according to a certain proportion for ball milling, wherein the specific proportion is as follows: the mass ratio of the lignin to the resin is as follows: 1, 0.6, wherein the addition amount of the catalyst is 20 percent of the total mass of the lignin and the resin. After ball milling for 4h, an activated precursor is obtained, the D50 of which is 21 μm.
S3, activation: the activated precursor was placed in a tube furnace and heated to 1000 ℃ under inert atmosphere to convert the inert gas (nitrogen 99.999%) to CO 2 Gas is kept for 4 hours, after the heat preservation is finished, the activated gas is changed into nitrogen/argon atmosphere under the condition of final temperature, and H is introduced at the same time 2 Thermal insulation 2h, H 2 Accounting for 20 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 0.6 percent;
s4, post-processing: and cleaning the activated product by using deionized water, and drying to obtain the lignin-based activated carbon. Evaporating the washed washing liquid, returning the evaporated residual catalyst to the ball milling process, and condensing the evaporated liquid for 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 diameter 2.0701nm. The electrode plate is mixed with adhesive PTFE and conductive agent SuperP according to the proportion of 8. Under the condition of current density of 1A/g, the specific capacity of the obtained lignin-based super-capacity carbon is 318.4F/g.
Example 3:
s1, pretreatment: crushing lignin to 50 μm, placing in a tube furnace, and introducing O at a certain flow rate 2 (flow rate 30L/h) for 2h, obtaining a first treated productThe oxygen-containing functional group is 15%;
s2, ball milling: mixing the first product, cured phenolic resin and CaCl 2 Adding the mixture into a ball ink tank according to a certain proportion for ball milling, wherein the specific proportion is as follows: the mass ratio of the lignin to the resin is as follows: 1, 0.4, wherein the addition amount of the catalyst is 10 percent of the total mass of the lignin and the resin. After ball milling for 2h, an activated precursor is obtained, the D50 of which is 30 mu m.
S3, activation: the activated precursor was placed in a tube furnace and heated to 1000 ℃ under inert atmosphere to convert the inert gas (nitrogen 99.999%) to CO 2 Gas is kept for 2 hours, after the heat preservation is finished, the activated gas is changed into nitrogen/argon atmosphere under the condition of final temperature, and H is introduced at the same time 2 Thermal insulation 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-processing: and cleaning the activated product by using deionized water, and drying to obtain the lignin-based activated carbon. Evaporating the washed washing liquid, returning the evaporated residual catalyst to the ball milling process, and condensing the evaporated liquid for washing the lignin-based active carbon.
The super-capacity carbon is obtained through 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 diameter 2.0013nm. Mixing the electrode plate with a binder PTFE and a conductive agent SuperP according to the ratio of 8. Under the condition of current density of 1A/g, the specific capacity of the obtained lignin-based super-capacity carbon is 306.1F/g.
Example 4:
s1, pretreatment: crushing lignin to 50 μm, placing in a tube furnace, and introducing O at a certain flow rate 2 Carrying out oxidation treatment (with the flow rate of 5L/h) for 4h to obtain a treated first product, wherein the oxygen-containing functional group of the treated first product is 4%;
s2, ball milling: mixing the first product, cured phenolic resin and CaCl 2 Adding the mixture into a ball ink tank according to a certain proportion for ball milling, wherein the specific proportion is as follows: the mass ratio of the lignin to the resin is as follows: 12 percent of the total mass of the lignin and the resin. After ball milling for 3h, an activated precursor is obtained, the D50 of which is 24 μm.
S3, activation: the activated precursor was placed in a tube furnace and heated to 950 ℃ under inert atmosphere to convert the inert gas (nitrogen 99.999%) to CO 2 Gas is kept for 3 hours, after the heat preservation is finished, the activated gas is changed into nitrogen/argon atmosphere under the condition of final temperature, and H is introduced at the same time 2 Keeping warm for 4h 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-processing: and (4) cleaning the activated product by using deionized water, and drying to obtain the lignin-based activated carbon. Evaporating the washed washing liquid, returning the evaporated residual catalyst to the ball milling process, and condensing the evaporated liquid for washing the lignin-based active carbon.
The super-capacity carbon is obtained through 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 diameter 1.9825nm. The electrode plate is mixed with adhesive PTFE and conductive agent SuperP according to the proportion of 8. Under the condition of current density of 1A/g, the specific capacity of the obtained lignin-based super-capacity carbon is 294.7F/g.
Example 5:
the ball milling parameters of different S2 balls are controlled under the conditions of the example 1, the other conditions are the same as the example 1, and the specific conditions and results are shown in the table 1.
TABLE 1
It can be seen that the specific capacity of the super-capacity carbon is the best when the D50 is 21 μm.
Example 6:
compared with example 1, the difference is in the S3 activation step, and other conditions are the same as example 1: (CO not introduced) 2 Gas)
S3, activation: placing the activated precursorHeating to 950 deg.C in inert atmosphere in a tubular furnace, maintaining the temperature of inert gas (nitrogen gas 99.999%) for 6 hr, converting the activated gas into nitrogen/argon atmosphere at final temperature, and introducing H 2 And the temperature is kept for 3h 2 Accounting for 30 percent of the volume of the mixed gas.
Example 7:
compared to example 1, the difference is that the S3 activation step: (general formula II) 2 Gas)
S3, activation: the activated precursor was placed in a tube furnace and heated to 950 ℃ under inert atmosphere to convert the inert gas nitrogen (99.999%) to CO 2 Carrying out gas insulation for 6h, converting the activated gas into nitrogen/argon atmosphere under the final temperature condition after the heat insulation is finished, and carrying out heat insulation for 3h;
the other conditions were the same as in example 1.
Example 8:
compared to example 1, the difference is that the S3 activation step: (CO-free) 2 And H 2 Gas)
S3, activation: placing the activated precursor into a tubular furnace, heating to 950 ℃ under an inert atmosphere, keeping the temperature of the inert gas nitrogen (99.999%) for 6 hours, converting the activated gas into a nitrogen/argon atmosphere under a final temperature condition after the heat preservation is finished, and keeping the temperature for 3 hours;
the other conditions were the same as in example 1.
Example 9:
compared to example 1, the difference is that the S3 activation step:
s3, activation: the activated precursor was placed in a tube furnace and heated to 950 ℃ under inert atmosphere to convert the inert gas nitrogen (99.999%) to CO 2 Gas is kept for 6 hours, after the heat preservation is finished, the activated gas is changed into nitrogen/argon atmosphere under the condition of final temperature, and H is introduced at the same time 2 And the temperature is kept for 3h 2 Accounting for 20 percent of the volume of the mixed gas;
the other conditions were the same as in example 1.
Example 10:
compared to example 1, the difference is that the S3 activation step:
s3, activation: the activated precursor was placed in a tube furnace and heated to 950 ℃ under inert atmosphere to convert the inert gas nitrogen (99.999%) to CO 2 Gas is kept for 6 hours, after the heat preservation is finished, the activated gas is changed into nitrogen/argon atmosphere under the condition of final temperature, and H is introduced at the same time 2 And the temperature is kept for 3h 2 Accounting for 40 percent of the volume of the mixed gas;
the other conditions were the same as in example 1.
The super-capacity carbon prepared in the embodiments 6 to 10, the binder PTFE and the conductive agent SuperP are mixed according to the ratio of 8.
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-capacity carbon, which utilizes low-temperature surface oxidation modification to form a stable lignin-based activated carbon precursor structure, realizes dispersion homogenization of a catalyst in the precursor by ball milling with the precursor, and further uses CO 2 The method has the advantages that the method is used for activating a medium, pore forming and hole expanding are carried out on a lignin-based precursor, low-cost and environment-friendly preparation of lignin-based activated carbon is realized, the preparation method of the super-capacity carbon simplifies the preparation process 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; meanwhile, the super-capacity carbon with good pore size distribution and good electrochemical performance can be obtained; reduces the environmental pollution and eliminates the potential safety hazard caused by potassium vapor in the preparation process of the traditional method.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A method for preparing lignin-based super-capacity carbon by catalytic activation is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
crushing lignin to be less than 75 micrometers, putting the lignin into a tubular furnace, introducing oxidizing gas with the flow rate of 5-80L/H, and carrying out oxidation treatment for 1-4 hours to obtain a treated first product;
mixing the first product, resin and a catalyst, and then carrying out ball milling to obtain an activated precursor;
placing an activated precursor into a tubeIn a furnace, the temperature is raised to 800-1100 ℃ under inert atmosphere, and inert gas is converted into CO 2 Gas is filled and the temperature is kept for 1 to 6 hours;
after the heat preservation is finished, under the condition of final temperature, the activated gas is changed into inert atmosphere, and H is introduced at the same time 2 Keeping the temperature for 1-5 h to obtain an activated product;
and (3) washing the activated product with deionized water, and drying to obtain the lignin-based super-capacity carbon.
2. The method for preparing lignin-based super-capacity carbon by catalytic activation according to claim 1, wherein: the specific surface area of the lignin-based super-capacity carbon is 1482 to 2170m 2 The total pore volume is 0.7347-1.2139 cm 3 The average pore diameter is 1.9825-2.2367 nm.
3. The method for preparing lignin-based super-capacity carbon by catalytic activation according to claim 1 or 2, wherein: the carbon content of the lignin is 50.3-61.7%.
4. The method for preparing lignin-based super-capacity charcoal by catalytic activation according to claim 3, wherein: the oxidizing gas comprises air and O 2 And ozone.
5. The method for preparing lignin-based super-capacity carbon by catalytic activation according to claim 4, wherein: the first product has 4-39% of oxygen-containing functional groups.
6. The method for preparing lignin-based super-capacity carbon by catalytic activation according to any one of claims 1, 2, 4 or 5, wherein: the resin is cured phenolic resin or waste phenolic resin, the coking value of the resin is 55-60%, and the ash content is less than 0.3%.
7. The method for preparing lignin-based super-capacity carbon by catalytic activation according to claim 6, wherein: the mass ratio of the first product to the resin is 1:0.2 to 1, the catalyst is CaCl 2 KCl or NaCl, the catalyst accounts for 2-45% of the total mass of the first product and the resin.
8. The method for preparing lignin-based super-capacity carbon by catalytic activation according to claim 7, wherein: the ball milling treatment time is 2-6 h, and the D50 of the treated ball grinding material is 30 mu m.
9. The method for preparing lignin-based super-capacity carbon by catalytic activation according to claim 8, wherein: placing the activated precursor into a tube furnace, and heating to 800-1100 ℃ under 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 H is introduced at the same time 2 Wherein the volume percentage of the hydrogen in the inert gas is 5-30%, and the inert atmosphere is nitrogen or argon.
10. The method for preparing lignin-based super-capacity charcoal by catalytic activation according to claim 8, wherein: the final temperature condition is that the final temperature is 800-1100 ℃.
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| CN116854068A (en) * | 2023-06-14 | 2023-10-10 | 常州大学 | Method for preparing super-capacity carbon by low-temperature crosslinking of lignin composite tar |
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| 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 |
| CN116854068A (en) * | 2023-06-14 | 2023-10-10 | 常州大学 | Method for preparing super-capacity carbon by low-temperature crosslinking of lignin composite tar |
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