CN116854068A - Method for preparing super-capacity carbon by low-temperature crosslinking of lignin composite tar - Google Patents
Method for preparing super-capacity carbon by low-temperature crosslinking of lignin composite tar Download PDFInfo
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- 229920005610 lignin Polymers 0.000 title claims abstract description 79
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 77
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000004132 cross linking Methods 0.000 title claims abstract description 29
- 239000003990 capacitor Substances 0.000 claims abstract description 16
- 230000003213 activating effect Effects 0.000 claims abstract description 9
- 239000002028 Biomass Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000011269 tar Substances 0.000 claims description 47
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 26
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 12
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 11
- 239000012190 activator Substances 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 238000001994 activation Methods 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000004939 coking Methods 0.000 claims description 5
- 238000000265 homogenisation Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical group [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 239000011279 mineral tar Substances 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 19
- 239000011148 porous material Substances 0.000 abstract description 18
- 238000002360 preparation method Methods 0.000 abstract description 13
- 239000003575 carbonaceous material Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 4
- 239000011707 mineral Substances 0.000 abstract description 4
- 239000007833 carbon precursor Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 9
- 239000007772 electrode material Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 240000003826 Eichhornia crassipes Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- 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 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
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
Abstract
The application discloses a method for preparing super-capacity carbon by low-temperature crosslinking of lignin composite tar, which belongs to the technical field of porous carbon material preparation, and adopts lignin and tar as raw materials to prepare a lignin and tar composite super-capacity carbon precursor by a low-temperature crosslinking method, so that the characteristics of biomass and mineral materials are fully utilized, the reasonable regulation and control of the pore diameter of the super-capacity carbon are realized by a method of combining volatile and an activating agent, the super-capacity carbon with a three-dimensional network structure is formed, and the super-capacity carbon has good electrochemical performance when applied to super-capacitors, and meets the application requirements of the super-capacitors.
Description
Technical Field
The application belongs to the technical field of porous carbon material preparation, and particularly relates to a method for preparing super-capacity carbon by low-temperature crosslinking of lignin composite tar.
Background
As a novel energy storage device between the traditional capacitor and the rechargeable battery, the super capacitor has the characteristics of high charging and discharging speed, high power density, long service life, wide working temperature range, low maintenance cost and the like, and is widely applied to various fields of energy storage and wind power. The electrode material serves as the core of the supercapacitor, determining the final electrochemical performance of the device. Electrode materials used in supercapacitors have heretofore mainly included four types of carbon materials, metal oxides/hydroxides, conductive polymers, and composite materials. Among all electrode materials, active carbon has the characteristics of high surface area and developed pore volume, good thermal stability, chemical stability, mechanical stability, excellent conductivity and the like, and becomes the electrode material with the most successful commercialization of super capacitors.
The performance of commercial activated carbon is affected by a plurality of factors, and mainly comprises precursor materials, pore size distribution, pore size, specific surface area, conductivity and the like. However, the activated carbon material still has the problems of high cost, uneven pore structure distribution, unstable quality and the like. At present, research on activated carbon for super capacitor is focused on utilizing various activation processes to regulate and optimize pore diameter structure, specific surface area and the like of the activated carbon so as to obtain the activated carbon with stable performance.
Lignin, which is a more widespread material in biomass materials, is the second most abundant biomass resource next to cellulose. The material consists of basic monomers of a phenylpropane-based structure, is a typical natural macromolecular compound with heterogeneous structure, and has the advantages of rich content, biodegradability, low cost, environmental friendliness and the like. With lignin productionIncreasing, how to achieve high value-added utilization of lignin has become a focus of industry attention. Particularly, the development of various functional carbon materials (especially super-capacity carbon with high added value) by taking lignin as a raw material becomes an approach for industry attempt. CN 106744793B provides a method for preparing porous carbon of polyacrylic acid grafted lignin, which comprises grafting polyacrylic acid onto lignin, controlling the pore space of active carbon by controlling the surface functional group of precursor and the volume steric hindrance of lignin in polymeric gel, and carbonizing the polyacrylic acid grafted lignin composite material to prepare porous carbon electrode material with low cost, high specific surface area and continuous inside. However, the method provided by the patent adopts polyacrylic acid as a grafting reagent, so that the problem of economic application exists, and meanwhile, the preparation of super-capacity carbon by adopting a gel method can lead to lower tap density of the material and influence the volume specific capacity of the super-capacitor. CN 110980727A provides a preparation method of active foam carbon for super capacitor electrode material, which takes lignin as raw material to prepare lignin resin, and prepares super capacitor material through profiling, dipping silver nitrate and high-temperature carbonization, the active foam carbon prepared by the technology has high porosity and uniform aperture, and the specific surface area is up to 18000cm 2 ·g -1 The conductivity reaches 2660S cm -1 The high added value application of the water hyacinth material is realized. The method for improving the super-capacity carbon by adopting the silver nitrate has the economic problem of large-scale application, and meanwhile, the specific surface area of the material is too large, so that the volume specific capacity of the super-capacity carbon is seriously influenced when the material is applied to the super-capacity carbon. In addition, lignin is directly used for preparing the carbon material with high added value, and the economic problem exists due to the low yield.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the application and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description of the application and in the title of the application, which may not be used to limit the scope of the application.
The present application has been made in view of the above and/or problems occurring in the prior art.
Therefore, the application aims to overcome the defects in the prior art and provide a method for preparing super carbon by low-temperature crosslinking of lignin composite tar.
In order to solve the technical problems, the application provides the following technical scheme: comprising the steps of (a) a step of,
pretreatment: crushing lignin to below 100 mu m, dissolving the lignin in an organic solvent, adding tar into the organic solvent for homogenization treatment, adding trioxymethylene and p-toluenesulfonic acid into the organic solvent for reaction until the organic solvent is evaporated, and obtaining a first product with a coking value of 69% -82%;
dipping treatment: crushing the first product, dissolving the crushed first product in a fluoride solution for homogenization treatment to realize full mixing and soaking of the first product and the fluoride solution, and sequentially drying and carbonizing to obtain a second product;
washing: the second product is fully washed by deionized water, fluoride in the second product is removed, and the second product with high purity is obtained and is marked as a third product; the fluoride and water are obtained by distillation treatment of washing water, and the fluoride and water are returned to the dipping treatment step to realize recycling;
and (3) activating treatment: crushing the third product to below 100 meshes, mixing with an activating agent, heating to a first temperature under an inert atmosphere, and preserving heat for 1-3 h; after the heat preservation is finished, the temperature is increased to a second temperature, and the heat preservation is carried out for 1 to 6 hours; obtaining a fourth product after the second heat preservation is finished;
and (3) sequentially carrying out water washing, acid washing and water washing treatment on the fourth product to obtain the lignin-based super-carbon.
As a preferable scheme of the method for preparing the super carbon by low-temperature crosslinking of the lignin composite tar, the application comprises the following steps: the pretreatment, wherein tar is biomass tar or mineral tar, and the adding proportion is 5% -32% of lignin.
As a preferable scheme of the method for preparing the super carbon by low-temperature crosslinking of the lignin composite tar, the application comprises the following steps: the pretreatment, wherein the addition ratio of the trioxymethylene is 2-13%, the addition ratio of the p-toluenesulfonic acid is 1-8%, and the addition ratio is the ratio of the total mass of lignin and tar.
As a preferable scheme of the method for preparing the super carbon by low-temperature crosslinking of the lignin composite tar, the application comprises the following steps: in the pretreatment, the reaction temperature of the reaction after adding trioxymethylene and p-toluenesulfonic acid is 90-180 ℃ and the reaction time is 80-160 min.
As a preferable scheme of the method for preparing the super carbon by low-temperature crosslinking of the lignin composite tar, the application comprises the following steps: the dipping treatment is carried out, wherein the fluoride is sodium fluoride or potassium fluoride, and the concentration of the fluoride in the fluoride solution is 0.5% -7.4%.
As a preferable scheme of the method for preparing the super carbon by low-temperature crosslinking of the lignin composite tar, the application comprises the following steps: the temperature of the carbonization is 500-580 ℃.
As a preferable scheme of the method for preparing the super carbon by low-temperature crosslinking of the lignin composite tar, the application comprises the following steps: in the activation treatment, the activator is KOH or NaOH, and the mass ratio of the activator to the third product is 1: (2.5-4).
As a preferable scheme of the method for preparing the super carbon by low-temperature crosslinking of the lignin composite tar, the application comprises the following steps: the activation treatment, wherein the first temperature is 450-550 ℃, the heat preservation time at the temperature is 2-3 h, the second temperature is 700-900 ℃, and the heat preservation time at the temperature is 2-4 h.
The application further aims to overcome the defects in the prior art and provide the super-capacity carbon prepared by low-temperature crosslinking of the lignin composite tar, wherein the super-capacity carbon has a three-dimensional network structure.
It is still another object of the present application to overcome the deficiencies in the prior art and to provide an application of super carbon prepared by low temperature crosslinking of lignin composite tar, which can be used in the preparation of super capacitors.
The application has the beneficial effects that:
(1) According to the application, lignin and tar are used as raw materials, a lignin and tar composite super-capacity carbon precursor is prepared by a low-temperature crosslinking method, the characteristics of biomass and mineral materials are fully utilized, reasonable regulation and control of the pore diameter of the super-capacity carbon are realized by a method of combining volatile and activating agents, and the super-capacity carbon with a three-dimensional network structure is formed.
(2) By adopting the low-temperature crosslinking and fluoride catalysis methods, the yield of lignin is greatly improved, the application of lignin is expanded, and the high added value application of lignin and tar is realized.
(3) The active carbon for the super capacitor prepared by the method has a reasonable pore diameter structure and good electrochemical performance, and meets the application requirement of the super capacitor.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, 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 application, 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 an SEM image of lignin-based super-carbon of example 1 of the present application;
FIG. 2 is a graph showing pore size distribution of lignin-based super-carbon according to example 1 of the present application;
FIG. 3 is an adsorption isotherm plot of lignin-based super-carbon of example 1 of the present application;
FIG. 4 is a CV plot of lignin-based super-carbon of example 1 of the present application;
FIG. 5 is a graph of charge and discharge of lignin-based super-carbon according to example 1 of the present application;
FIG. 6 is an EIS impedance spectrum of lignin-based super-capacitor carbon of example 1 of the present application;
Detailed Description
In order that the above-recited objects, features and advantages of the present application will become more apparent, a more particular description of the application 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 application, but the present application may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present application 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 application. 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 lignin used in the application is enzymolysis lignin or alkali lignin, the ash content of the lignin is 0.52% -1.56%, and the carbon content is 41.3-60.2%;
the tar used in the application is biomass tar or mineral substance for oiling, the coking value of the tar is 10% -56%, the dynamic viscosity is 147MPa x s-8650 MPa x s, and the adding proportion is 5% -32%;
the activator used in the application is KOH or NaOH, and the purity is more than 98.5%;
the other raw materials are all commonly and commercially available unless specified.
The method for testing the super carbon capacity performance in the application comprises the following steps:
preparing a pole piece according to the proportion of Super carbon, adhesive PTFE and conductive agent Super P of 8:1:1 to form a three-electrode system, and testing the electrochemical performance of the three-electrode system in a KOH aqueous solution with the concentration of 6 mol.
Example 1
The embodiment provides a method for preparing super carbon by low-temperature crosslinking of lignin composite tar, which specifically comprises the following steps:
s1, pretreatment:
crushing lignin to below 100 mu m, dissolving the lignin in N, N-dimethylformamide DMF, adding 24% of tar into the DMF, homogenizing the tar to obtain a tar coking value of 48%, adding trioxymethylene which is 6% of the total mass of the lignin and the tar into the DMF, reacting the mixture for 30min at 120 ℃, and reacting until an organic solvent is evaporated to obtain a first product with a coking value of 76%;
s2, dipping treatment:
crushing the first product, dissolving the crushed first product in fluoride solution with the concentration of 3%, carrying out homogenization treatment by mechanical stirring to fully mix and impregnate the first product and the fluoride solution, drying, and carrying out carbonization treatment at 550 ℃ under inert atmosphere to obtain a second product;
s3, washing:
the second product is fully washed by deionized water, fluoride in the second product is removed, and the second product with high purity is obtained and is marked as a third product; wherein, the washing water is distilled to obtain fluoride and water, and the step S2 is returned to realize recycling;
s4, activating treatment:
crushing the third product to below 100 meshes, mixing the crushed third product with an activating agent KOH in a ratio of 4:1, heating to a first temperature of 550 ℃ under an inert atmosphere, preserving heat for 3 hours, heating to a second temperature of 850 ℃ after the heat preservation is finished, preserving heat for 3 hours, and obtaining a fourth product after the heat preservation is finished;
and (3) sequentially carrying out water washing, acid washing and water washing treatment on the fourth product to obtain the lignin-based super-carbon.
The pore structure characteristics of the super-capacity carbon prepared by the embodiment are measured as follows: specific surface area 1873m 2 Per g, total pore volume 1.3116cm 3 Per gram, micropore volume 1.1411cm 3 /g, average pore size 2.0682nm.
Fig. 1 is an SEM image of lignin-based super-carbon in this example, and it can be seen from fig. 1 that the super-carbon prepared by the method has a porous structure and a microstructure of stacked structures.
Fig. 2 is a pore size distribution graph, fig. 3 is an adsorption isotherm graph of super-capacity carbon, and as can be seen from fig. 2 and 3, the adsorption isotherm of super-capacity carbon prepared by the method belongs to a mixed type of type I and type IV of typical adsorption and desorption, and has larger adsorption capacity when the relative pressure is smaller (P/P0 < 0.1), and a phenomenon of rapid increase is shown, which indicates that the porous carbon material prepared by the method has a rich micropore structure, the adsorption capacity increase becomes gentle as the relative pressure continues to increase, and a hysteresis loop appears when the relative pressure is larger (P/P0 > 0.4), and the porous carbon material has a certain proportion of mesopores.
Fig. 4 is a cyclic voltammogram thereof, from which it can be seen that the cyclic voltammogram of the material is shaped approximately rectangular, indicating that the material has typical double layer capacitive characteristics.
Fig. 5 is a charge-discharge graph thereof, from which it can be seen that the charge-discharge curve of the material presents an approximate isosceles triangle, indicating that the material has typical capacitive characteristics.
Fig. 6 is an EIS impedance spectrum thereof, and it can be seen from the figure that the material has a very small internal resistance of 0.46 Ω.
The specific capacity of the super-capacity carbon prepared in the embodiment under the condition of the current density of 1A/g is tested to be 313F/g.
Example 2
The difference between this example and example 1 is that the amount of tar added in the pretreatment in step S1 was adjusted to 0%, 2%, 5%, 10%, 20%, 24%, 32%, 35%, 40%, and the other preparation processes were the same as in example 1, to obtain lignin-based super-carbon.
The relative characterization parameters and performances of the lignin-based super-carbon prepared by different tar adding ratios in the embodiment are measured, and the results are shown in Table 1.
TABLE 1 preparation of super-capacity charcoal at different Tar addition ratios
As can be seen from table 1, as the tar addition ratio increases, the specific surface area, the total pore volume, the micropore volume, and the specific capacity show a tendency of increasing and then decreasing, and the specific capacity is highest at 24%.
Example 3
The difference between this example and example 1 is that the lignin-based super-carbon of this example was produced by adjusting the addition ratio of trioxymethylene in the dipping treatment of step S1 to 1%, 2%, 6%, 10%, 13%, 15%, 20%, respectively, and the other preparation processes were the same as in example 1.
TABLE 2 preparation of super carbon contrast at different addition ratios of trioxymethylene
Trioxymethylene functions as a crosslinking agent in the present application. As can be seen from table 2, as the addition ratio of the trioxymethylene increases, the composite degree of the material increases, and the activation effectiveness of the alkali is reduced under the condition of the same alkali content, so that the specific surface area, the total pore volume, the micropore volume and the specific capacity all show the trend of increasing firstly and then reducing, and especially reach the maximum at 6%.
Example 4
The difference between this example and example 1 is that the lignin-based super-carbon of this example was produced by adjusting the addition ratio of p-toluenesulfonic acid in the impregnation treatment of step S1 to 0%, 0.5%, 1%, 4%, 6%, 8%, 10%, 15%, respectively, and the other preparation processes were the same as in example 1.
TABLE 3 preparation of super carbon contrast at different addition ratios of p-toluenesulfonic acid
The p-toluenesulfonic acid acts as a catalyst in the application, and the increased content can improve the crosslinking degree of lignin and tar. It can be seen from table 3 that as the content of p-toluenesulfonic acid increases, the specific capacity of activated carbon reaches a maximum at 4%.
Example 5
The difference between this example and example 1 is that the concentration of the fluoride in the impregnation treatment in step S2 was adjusted to 0%, 0.5%, 3%, 6%, 7.2%, 8%, 10%, and the other preparation processes were the same as in example 1, to obtain lignin-based super-carbon.
TABLE 4 preparation of super carbon contrast at different fluoride concentrations
As can be seen from Table 4, the electrochemical performance is best when the fluoride content is 0.5% -7.4% along with the increase of the fluoride content, the specific capacity of the activated carbon of the application is more than 290F/g,
comparative example 1
The present comparative example is different from example 1 in that the lignin-based super-carbon of the present comparative example is produced by adjusting the kind of the activator in the activation treatment of step S4 to NaOH, znCl or not adding the activator.
The characterization parameters and properties of the lignin-based super-carbon prepared in this comparative example were measured, and the results are shown in Table 5.
TABLE 5 comparative effect of activators on super carbon
As can be seen from table 5, the performance of the super carbon made with KOH as the activator is significantly better than the poor activator or the alternative with other types of activators.
In conclusion, lignin and tar are used as raw materials, a lignin and tar composite super-capacity carbon precursor is prepared through a low-temperature crosslinking method, characteristics of biomass and mineral materials are fully utilized, reasonable regulation and control of pore diameters of super-capacity carbon are realized through a method of combining volatile and activating agents, and the super-capacity carbon with a three-dimensional network structure is formed.
By adopting the low-temperature crosslinking and fluoride catalysis methods, the yield of lignin is greatly improved, the application of lignin is expanded, and the high added value application of lignin and tar is realized. The active carbon for the super capacitor prepared by the method has a reasonable pore diameter structure and good electrochemical performance, and meets the application requirement of the super capacitor.
It should be noted that the above embodiments are only for illustrating the technical solution of the present application and not for limiting the same, and although the present application 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 application may be modified or substituted without departing from the spirit and scope of the technical solution of the present application, which is intended to be covered in the scope of the claims of the present application.
Claims (10)
1. A method for preparing super-capacity carbon by low-temperature crosslinking of lignin composite tar is characterized by comprising the following steps: comprising the steps of (a) a step of,
pretreatment: crushing lignin to below 100 mu m, dissolving the lignin in an organic solvent, adding tar into the organic solvent for homogenization treatment, adding trioxymethylene and p-toluenesulfonic acid into the organic solvent for reaction until the organic solvent is evaporated, and obtaining a first product with a coking value of 69% -82%;
dipping treatment: crushing the first product, dissolving the crushed first product in a fluoride solution for homogenization treatment to realize full mixing and soaking of the first product and the fluoride solution, and sequentially drying and carbonizing to obtain a second product;
washing: the second product is fully washed by deionized water, fluoride in the second product is removed, and the second product with high purity is obtained and is marked as a third product; the fluoride and water are obtained by distillation treatment of washing water, and the fluoride and water are returned to the step of dipping treatment, so that recycling is realized;
and (3) activating treatment: crushing the third product to below 100 meshes, mixing with an activating agent, heating to a first temperature under an inert atmosphere, and preserving heat for 1-3 h; after the heat preservation is finished, the temperature is increased to a second temperature, and the heat preservation is carried out for 1 to 6 hours; obtaining a fourth product after the second heat preservation is finished;
and (3) sequentially carrying out water washing, acid washing and water washing treatment on the fourth product to obtain the lignin-based super-carbon.
2. The method for preparing super carbon by low-temperature crosslinking of lignin composite tar according to claim 1, which is characterized by comprising the following steps: the pretreatment, wherein tar is biomass tar or mineral tar, and the adding proportion is 5% -32% of lignin.
3. The method for preparing super carbon by low-temperature crosslinking of lignin composite tar according to claim 1 or 2, which is characterized in that: the pretreatment, wherein the addition ratio of the trioxymethylene is 2-13%, the addition ratio of the p-toluenesulfonic acid is 1-8%, and the addition ratio is the ratio of the total mass of lignin and tar.
4. The method for preparing super carbon by low-temperature crosslinking of lignin composite tar according to claim 1 or 3, which is characterized in that: in the pretreatment, the reaction temperature of the reaction after adding trioxymethylene and p-toluenesulfonic acid is 90-180 ℃ and the reaction time is 80-160 min.
5. The method for preparing super carbon by low-temperature crosslinking of lignin composite tar according to claim 1, which is characterized by comprising the following steps: the dipping treatment is carried out, wherein the fluoride is sodium fluoride or potassium fluoride, and the concentration of the fluoride in the fluoride solution is 0.5% -7.4%.
6. The method for preparing super carbon by low-temperature crosslinking of lignin composite tar according to claim 1 or 5, which is characterized in that: the temperature of the carbonization is 500-580 ℃.
7. The method for preparing super carbon by low-temperature crosslinking of lignin composite tar according to claim 1, which is characterized by comprising the following steps: in the activation treatment, the activator is KOH or NaOH, and the mass ratio of the activator to the third product is 1: (2.5-4).
8. The method for preparing super carbon by low-temperature crosslinking of lignin composite tar according to claim 1 or 7, which is characterized in that: the activation treatment, wherein the first temperature is 450-550 ℃, the heat preservation time at the temperature is 2-3 h, the second temperature is 700-900 ℃, and the heat preservation time at the temperature is 2-4 h.
9. The super carbon prepared by the method of any one of claims 1 to 8, wherein: the super-capacity carbon has a three-dimensional network structure.
10. The use of the super carbon of claim 9 in the manufacture of a super capacitor.
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| CN115410834A (en) * | 2022-09-14 | 2022-11-29 | 常州大学 | Method for preparing lignin-based super-capacity carbon through catalytic activation |
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| CN115410834A (en) * | 2022-09-14 | 2022-11-29 | 常州大学 | Method for preparing lignin-based super-capacity carbon through catalytic activation |
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