CN110015660B - Silver-doped lignin porous carbon nanosheet, preparation method thereof and application thereof in supercapacitor electrode material - Google Patents
Silver-doped lignin porous carbon nanosheet, preparation method thereof and application thereof in supercapacitor electrode material Download PDFInfo
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Abstract
The invention belongs to the technical field of biomass carbon materials, and discloses a silver-doped lignin porous carbon nanosheet, a preparation method thereof and application thereof in a supercapacitor electrode material. According to the preparation method, the silver/lignin/oxalate compound is prepared by carrying out layer-by-layer self-assembly on sulfonated lignin, silver salt and oxalate in a selective solvent, and the silver-doped lignin porous carbon nanosheet is obtained by carbonization and acid washing. The silver-doped lignin porous carbon nanosheet prepared by the method provided by the invention has a specific surface area of 200-1000 m2A specific surface area of the micropores is 100 to 300m2A mesoporous specific surface area of 100 to 700m2A pore diameter of 0.5 to 20nm and a pore volume of 0.5 to 1.5cm3(ii)/g; the super-capacitor electrode material has excellent conductivity, and can be applied to the super-capacitor electrode material, so that the specific capacitance and the rate capability of the super-capacitor electrode material are greatly improved.
Description
Technical Field
The invention belongs to the technical field of biomass carbon materials, and particularly relates to a silver-doped lignin porous carbon nanosheet, a preparation method thereof and application thereof in a supercapacitor electrode material.
Background
The increasing exhaustion of traditional fossil energy and the increasing severity of environmental pollution issues have raised new requirements for the development and utilization of new green energy. Electrochemical energy storage devices play a very important role in the field of developing green sustainable energy storage and conversion technologies. As a novel energy storage device between a traditional physical capacitor and a secondary battery, a super capacitor draws wide attention in the fields of portable electronic equipment, electric automobiles and the like due to the advantages of high power density, rapid charge and discharge, long cycle service life, wide applicable temperature range and the like. The electrode material of the super capacitor is a key factor influencing the performance of the super capacitor, and mainly comprises three main categories of carbon materials, metal oxides and conductive polymers. Among them, carbon materials have been widely studied for their advantages of large specific surface area, controllable pore structure, excellent conductivity, stable chemical properties, and the like. Among many carbon materials, graphene has very high theoretical specific surface area and electrical conductivity and is considered as the most potential electrode material for a supercapacitor, however, graphene is not easy to prepare on a large scale, and the industrial application of graphene is greatly limited. Therefore, the porous carbon material which has high specific surface area and good conductivity and is easy to prepare on a large scale is urgently needed to be developed for the research of the electrode material of the super capacitor.
Lignin is the second largest organic high-molecular polymer in natural plants, and is the only renewable aromatic polymer, and the worldwide annual output is up to 1500 hundred million tons. The lignin is a high molecular polymer taking a phenylpropane monomer as a hydrophobic framework, has wide sources and low cost, has the carbon element content as high as 60 percent, and is an ideal carbon material precursor. The lignin is mainly found in industry: is derived from lignosulfonate with good water solubility in acid pulping waste liquid, alkali lignin in alkali pulping and papermaking industry and enzymatic hydrolysis lignin in biorefinery industry.
The lignosulfonate has good water solubility, can be directly carbonized at high temperature to prepare porous carbon, and for example, in Chinese patent CN 102633525, lignosulfonate from acid pulping waste liquid is used as a carbon source, and is directly carbonized at high temperature in an inert atmosphere to prepare a porous carbon material. Pang et al prepared lignin porous Carbon (Green Chemistry,2017,19(16):3916-3926) by pyrolyzing sodium lignin sulfonate at high temperature in one step, and also prepared lignin porous Carbon spheres (Carbon,2018,132:280-293) by pre-oxidizing the sodium lignin sulfonate directly, however, the prepared porous Carbon material has smaller specific surface area, and the pore channel structure is not rich enough and has poor conductivity, which results in lower specific capacitance. The carbon material prepared by directly carbonizing the alkali lignin has smaller specific surface area and specific capacitance lower than 50F/g, and cannot meet the requirements of electrode materials of supercapacitors (ChemUSChem, 2015,8(3): 428-432).
In order to increase the specific surface area and adjust the pore channel structure, a chemical activation method and a template method are adopted when preparing the lignin porous carbon. The chemical activation method mainly utilizes strong corrosive reagents (KOH, ZnCl) under high-temperature conditions2Etc.) to obtain porous carbon having a predominant pore distribution. For example, Chinese patent CN 1061855920A prepares the porous carbon material by carbonizing at high temperature and activating alkali lignin in KOH-containing alkaline papermaking black liquor. ZnCl in Zhangguan2As an activating agent of alkali lignin, is prepared by high-temperature carbonizationPrimary activated carbon (forestry machines and woodworking equipment, 2017,45(02): 35-39). A large number of researches show that the lignin porous carbon with high specific surface area can be prepared by a chemical activation method, but the microstructure still shows a serious aggregation phenomenon and has an excessive random microporous structure, so that the transmission resistance of an electrolyte solution in the electrolyte solution is increased, and the electrochemical performance of the electrolyte solution is difficult to improve. In addition, the high-temperature carbonization process has serious pollution, great damage to equipment and low product yield.
The template method mainly utilizes a template agent (SiO)2，Al2O3Oxides such as ZnO) can realize the precise regulation and control of the aperture of the porous carbon material. For example, in chinese patent CN 106744793a, a three-dimensional lignin porous carbon material is prepared by using a double-template method with the alkali lignin, which is roughly purified in the papermaking black liquor, as a carbon precursor. Chinese patent CN 106744789 a uses lignin extracted from black liquor by acid precipitation method as carbon precursor, and dissolves it in ethanol solution, and mixes it with zinc salt for hydrothermal treatment, and uses zinc oxide generated by hydrothermal treatment of zinc salt as template, and then high-temperature carbonization to obtain spherical porous carbon. The literature (Shijin, C-ZnO composite material prepared by lignin and photocatalytic performance research thereof, northeast forestry university 2015.) adds ethanol dropwise into a mixed solution of zinc acetate and sodium lignosulfonate, adjusts the pH of the solution to be alkaline to generate sodium lignosulfonate/Zn (OH)2And (3) precipitating the compound, carbonizing the compound in inert gas to obtain the lignin carbon/zinc oxide compound and applying the lignin carbon/zinc oxide compound to the field of photocatalysts. The porous carbon material with concentrated pore size distribution can be prepared by the template method, but the pore structure distribution of the prepared porous carbon is relatively single, the preparation process is relatively complex, and the cost is relatively high.
The lignin porous carbon prepared by the chemical activation method and the template method has higher specific surface area, but still has the problem of poor conductivity. The conductivity of the lignin porous carbon can be improved by doping elements such as N, S, B and the like or doping a conductivity enhancer, Zhang and the like take bioethanol lignin as a carbon precursor, and the nitrogen-doped interconnected hierarchical porous carbon with high conductivity is prepared by hydrothermal carbonization, the method is long in time consumption, and the nitrogen content of a product is difficult to regulate and control (ACS applied materials & interfaces,2016,8(22): 13918-. According to the literature (Zhang Wu, research on biomass-based nitrogen-doped coke and porous carbon electrode materials, Hunan university, 2017), sodium lignosulfonate is used as a carbon source, graphene is used as a conductive reinforcing agent, p-phenylenediamine is used as a nitrogen source, and the porous coke material with high conductivity is prepared through one-step low-temperature pyrolysis.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention mainly aims to provide a preparation method of a silver-doped lignin porous carbon nanosheet.
According to the method, oxalate is used as an activating agent, silver is used as a conductive reinforcing agent, and water-soluble sulfonated lignin is used as a carbon precursor and a dispersing agent to prepare the silver-doped lignin porous carbon nanosheet.
According to the method, water-soluble sulfonated lignin is used as a carbon precursor, a weakly corrosive oxalate is used as an activating agent, silver is used as a conductive reinforcing agent, a silver/lignin/oxalate compound which is uniformly dispersed is prepared by layer-by-layer self-assembly in a selective solvent, and then the compound is carbonized to prepare the silver-doped lignin porous carbon nanosheet. In the preparation process, sulfonic groups in the sulfonated lignin can highly disperse the precursor solution and the activating agent, phenolic hydroxyl groups and carboxyl groups can reduce silver ions into silver simple substances, lignin and activating agent molecules can realize horizontal compounding in the layer-by-layer self-assembly process, the activation carbonization effect is improved, the porosity of a carbonized product is further improved, and the activated carbonization effect and the specific capacitance and the rate capability of a supercapacitor are improved by applying the activated carbonization effect and the specific capacitance and the rate capability of the supercapacitor.
The invention also aims to provide the silver-doped lignin porous carbon nanosheet prepared by the method.
The invention further aims to provide application of the silver-doped lignin porous carbon nanosheet in the electrode material of the supercapacitor.
The purpose of the invention is realized by the following scheme:
a preparation method of a silver-doped lignin porous carbon nanosheet is characterized by carrying out layer-by-layer self-assembly on sulfonated lignin, a silver salt and oxalate in a selective solvent to prepare a layer-by-layer self-assembled silver/lignin/oxalate compound, and carbonizing and pickling the compound to obtain the silver-doped lignin porous carbon nanosheet.
The weight ratio of the sulfonated lignin, the silver salt and the oxalate is preferably 100: (5-10): (50-150).
The selective solvent is a water/ethanol combined solvent.
The layer-by-layer self-assembly refers to that the silver/lignin/oxalate compound is assembled for many times by taking dispersion liquid obtained by dispersing sulfonated lignin, silver salt and oxalate in water as matrix solution to obtain the layer-by-layer self-assembled silver/lignin/oxalate compound.
The dispersion is preferably carried out by heating, stirring and dispersing, and more preferably is carried out by heating and stirring at 50-80 ℃ for 20-40 min.
The silver/lignin/oxalate compound is obtained by adding ethanol into a matrix solution for precipitation and separation.
And the assembly refers to adding the silver/lignin/oxalate compound into the matrix solution, uniformly stirring, adding ethanol, and separating out to obtain the assembled silver/lignin/oxalate compound.
The multi-assembling refers to repeating the assembling steps for multiple times. Adding the assembled silver/lignin/oxalate compound into a matrix solution, uniformly stirring, adding ethanol, separating out and separating to obtain a secondary assembled silver/lignin/oxalate compound, and repeating for multiple times; preferably, the repetition is 6 to 10 times, and more preferably 6 times.
The total mass concentration of the sulfonated lignin, the silver salt and the oxalate in the matrix solution is preferably 2-10%.
In the method of the present invention, the volume ratio of the matrix solution to ethanol is preferably 1:1 for each taking.
In the method, the uniform stirring is preferably carried out for 10-30 min.
In the method, the carbonization refers to carbonization for 2-4 hours at 550-850 ℃.
The carbonization is preferably carried out under an inert atmosphere.
And the acid washing refers to washing the carbonized product in 0.5-2 mol/L acid liquor for 1-3 h, and then washing, filtering and drying.
The acid solution can be hydrochloric acid or sulfuric acid.
The drying may include one of drying methods such as air drying, vacuum drying, freeze drying, infrared drying, etc., and preferably freeze drying.
In the method, the sulfonated lignin can be at least one of sodium lignosulfonate, calcium lignosulfonate and magnesium lignosulfonate in red liquor of acid pulping, sulfonated products of alkali lignin in black liquor of alkaline pulping and sulfonated products of enzymatic hydrolysis lignin in a biorefinery industrial process.
The silver salt preferably includes at least one of silver nitrate, silver fluoride and silver perchlorate.
The oxalate preferably includes at least one of zinc oxalate, calcium oxalate, magnesium oxalate, ferrous oxalate and cobalt oxalate.
The preparation method specifically comprises the following steps:
(1) dispersing sulfonated lignin, silver salt and oxalate in water to obtain a matrix solution;
(2) taking the matrix solution of the volume part A, adding the ethanol of the volume part B while stirring, standing and separating to obtain a silver/lignin/oxalate compound;
(3) taking the same A volume part of matrix solution, adding the silver/lignin/oxalate compound obtained in the step (2) into the matrix solution, uniformly stirring, adding the same B volume part of ethanol, standing and separating to obtain an assembled silver/lignin/oxalate compound;
(4) repeating the step (3) for multiple times to obtain a layer-by-layer self-assembled silver/lignin/oxalate compound;
(5) and (3) placing the silver/lignin/oxalate compound which is self-assembled layer by layer in an inert atmosphere, carbonizing at 550-850 ℃ for 2-4 h, and pickling to obtain the silver-doped lignin porous carbon nanosheet.
The preparation process according to the invention is described in more detail below:
(1) weighing sulfonated lignin, silver salt and oxalate, adding into water, heating and stirring uniformly to prepare dispersion liquid;
dispersing oxalate solid powder by using sulfonic acid groups of sulfonated lignin, reducing silver ions into silver simple substances by using phenolic hydroxyl groups and carboxyl groups of the sulfonated lignin to prepare uniformly dispersed dispersion liquid, and promoting the reduction of the silver ions by heating. The dispersion liquid of the sulfonated lignin, the silver and the oxalate is preferably prepared to have the mass concentration of 2-10%, and if the mass concentration of the dispersion liquid is lower than 2%, the yield of the subsequent silver/lignin/oxalate compound is lower; if the mass concentration of the dispersion is more than 10%, the lignin and oxalate tend to self-agglomerate.
(2) Taking a certain volume of the dispersion liquid, adding a certain volume of ethanol, standing, and separating out precipitate to obtain a silver/lignin/oxalate compound;
the method comprises the steps of utilizing sulfonated lignin with good water solubility and insolubility in ethanol, self-assembling in selective solvent ethanol-water, and preparing a silver/lignin/oxalate compound with uniform composition through the interaction force between metal cations of oxalate and pi bonds of lignin molecules.
(3) Taking a certain volume of the dispersion liquid prepared in the step (1), adding the silver/lignin/oxalate compound prepared in the step (2), uniformly stirring, adding a certain volume of ethanol, standing, and separating out a precipitate to obtain a silver/lignin/oxalate compound;
in the step, the volumes of the taken dispersion liquid and the added ethanol are the same as those in the step (2), the silver/lignin/oxalate compound needs to be stirred after being added, and if the silver/lignin/oxalate compound is not stirred uniformly, the silver/lignin/oxalate compound which is uniformly compounded is difficult to form in the subsequent layer-by-layer self-assembly process.
(4) Repeating the step (3) for N times, and separating precipitates to obtain a layer-by-layer self-assembly composite silver/lignin/oxalate compound;
in the step, N is preferably 6-10 times, and more preferably 6 times by repeating the step (3). If the self-assembly times are less than 6, the yield of the formed layer-by-layer self-assembly silver/lignin/oxalate compound after carbonization is low; if the self-assembly frequency is more than 10, the preparation process takes long time, and the production efficiency is influenced.
(5) Placing the silver/lignin/oxalate compound prepared in the step (4) in an inert atmosphere, carbonizing at 550-850 ℃ for 2-4 h to obtain a silver-doped lignin carbon/metal oxide compound, soaking the product in 0.5-2 mol/L acid liquor, washing for 2-4 h, washing with water, filtering and drying to obtain a silver-doped lignin porous carbon nanosheet;
the inert atmosphere in this step may be nitrogen or other inert gases such as argon. The carbonization temperature is required to be 550-850 ℃, and the carbonization time is 2-4 h. If the carbonization temperature or time is insufficient, the carbonization effect of lignin is poor, while if the carbonization temperature or time is too high, the carbonization is excessive, the yield of the product is low, and the energy consumption is large.
The silver-doped lignin porous carbon nanosheet prepared by the method provided by the invention has the specific surface area ranging from 200m to 1000m2The specific surface area of the micropores ranges from 100 m to 300m2The mesoporous specific surface area ranges from 100 m to 700m2A pore diameter of 0.5 to 20nm and a pore volume of 0.5 to 1.5cm3(ii) in terms of/g. The method can be applied to the electrode material of the super capacitor.
The method is based on the solubility difference of sulfonated lignin in water and an organic solvent and the good dispersibility of sulfonated lignin to oxalate, utilizes the interaction force between metal cations of oxalate and pi bonds of lignin molecules in a selective solvent, simultaneously utilizes phenolic hydroxyl groups and carboxyl groups of lignin to reduce silver ions, and prepares the silver/lignin/oxalate compound with uniform composition through a layer-by-layer self-assembly process. And then carbonizing the compound, and pickling to remove the metal oxide nanoparticles between the lignin carbon layers to prepare the silver-doped lignin porous carbon nanosheet. Oxalate has double functions of activation and template in the carbonization process, and silver can enhance heat conduction and the electrical conductivity of the product. Firstly, the gas generated in the thermal decomposition process of oxalate has the function of activating and pore-forming the lignin, thereby being beneficial to forming a microporous structure and simultaneously having the stripping effect to prevent the condensation polymerization of the lignin in the carbonization process. And secondly, metal oxide nanoparticles generated by oxalate pyrolysis can be used as a template to play a role in etching and supporting a lignin carbon sheet frame, so that a carbon nanosheet structure containing rich mesopores can be formed. Finally, silver has high thermal conductivity and high electrical conductivity, and can improve the carbonization effect and enhance the electrical conductivity of the porous carbon nanosheet. The silver-doped porous carbon nanosheet structure has excellent conductivity, can provide a channel for rapid transmission and diffusion of electrolyte ions between the transverse direction and the longitudinal direction of a lamella, and greatly improves the specific capacitance and the rate capability of the electrode material of the supercapacitor.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) compared with the lignin porous carbon prepared by the traditional chemical activation method and the template method, the silver-doped lignin porous carbon nanosheet prepared by the invention has a reasonable pore structure, rich pore size distribution and a more regular two-dimensional carbon nanosheet structure, and simultaneously, the silver doping also enhances the conductivity of the lignin porous carbon nanosheet. The composite material is applied to a supercapacitor electrode material, can provide a good channel for rapid diffusion and transmission of electrolyte ions in an electrochemical process, shows higher specific capacitance and excellent rate capability, and has good potential application value.
(2) In the preparation process of the silver-doped lignin porous carbon nanosheet, the water-soluble sulfonated lignin is used as a carbon precursor and a dispersing agent, the weak-corrosive oxalate is used as an activating agent, the silver is used as a conductive reinforcing agent, the raw materials are wide in source, cheap and easy to obtain, the preparation process is simple and environment-friendly, the corrosion degree on equipment is low, the large-scale preparation is easy to realize, and the high added value utilization of the lignin is realized.
Drawings
Fig. 1 is a scanning electron microscope image of a silver-doped lignin porous carbon nanosheet prepared in example 1 of the present invention.
Fig. 2 is a transmission electron microscope image of the silver-doped lignin porous carbon nanosheet prepared in example 1 of the present invention.
Fig. 3 is a nitrogen adsorption and desorption curve diagram and a pore size distribution diagram of the silver-doped lignin porous carbon nanosheet prepared in example 1 of the present invention.
Fig. 4 is a cyclic voltammetry graph of silver-doped lignin porous carbon nanosheets prepared in example 1 of the present invention.
Fig. 5 is a constant-direct-current charging and discharging curve diagram of the silver-doped lignin porous carbon nanosheet prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The materials referred to in the following examples are commercially available. The using amount of each component is calculated by mass volume portion, g/mL.
Example 1
Weighing 5 parts by mass of sodium lignosulfonate, 0.25 part by mass of silver nitrate and 5 parts by mass of zinc oxalate solid powder, adding the mixture into 500 parts by volume of water, and heating and stirring the mixture for 30min at 50 ℃ to prepare stable dispersion A. Taking 50 parts by volume of the dispersion liquid A, adding 50 parts by volume of ethanol under the stirring state, standing, and separating out precipitate to obtain the silver/lignin/zinc oxalate compound. And adding 50 parts by volume of the dispersion liquid A into the prepared silver/lignin/zinc oxalate compound, stirring for 20min, adding 50 parts by volume of ethanol, standing, and separating out the silver/lignin/zinc oxalate compound. Repeating the operation for 6 times, and separating the precipitate to obtain the silver/lignin/zinc oxalate compound compounded by layer self assembly.
Placing the silver/lignin/zinc oxalate compound compounded by layer-by-layer self-assembly in an inert atmosphere, carbonizing at 650 ℃ for 3 hours to obtain a silver-doped lignin carbon/zinc oxide compound, soaking the product in 1mol/L hydrochloric acid for washing for 2 hours, and then washing, filtering and freeze-drying to obtain the silver-doped lignin porous carbon nanosheet.
Example 2
Weighing 5 parts by mass of magnesium lignosulfonate, 0.25 part by mass of silver fluoride and 7.5 parts by mass of magnesium oxalate solid powder, adding the solid powder into 500 parts by volume of water, and heating and stirring the mixture for 30min at 50 ℃ to prepare stable dispersion liquid A. Taking 50 parts by volume of the dispersion liquid A, adding 50 parts by volume of ethanol under the stirring state, standing, and separating out precipitate to obtain the silver/lignin/magnesium oxalate compound. And adding 50 parts by volume of the dispersion liquid A into the prepared silver/lignin/magnesium oxalate compound, stirring for 20min, adding 50 parts by volume of ethanol, standing, and separating out the silver/lignin/magnesium oxalate compound. Repeating the operation for 8 times, and separating the precipitate to obtain the silver/lignin/magnesium oxalate compound compounded by layer self assembly.
Placing the silver/lignin/magnesium oxalate compound compounded by layer-by-layer self-assembly in an inert atmosphere, carbonizing at 750 ℃ for 2 hours to obtain a silver-doped lignin carbon/magnesium oxide compound, soaking the product in 2mol/L hydrochloric acid for washing for 2 hours, and then washing, filtering and freeze-drying to obtain the silver-doped lignin porous carbon nanosheet.
Example 3
Weighing 10 parts by mass of calcium lignosulphonate, 0.5 part by mass of silver nitrate and 5 parts by mass of calcium oxalate solid powder, adding the solid powder into 500 parts by volume of water, and heating and stirring the mixture for 30min at 50 ℃ to prepare stable dispersion A. Taking 50 parts by volume of dispersion liquid of calcium lignosulfonate, silver and calcium oxalate, adding 50 parts by volume of ethanol under the stirring state, standing, and separating out precipitate to obtain the silver/lignin/calcium oxalate compound. And adding 50 parts by volume of the dispersion liquid A into the prepared silver/lignin/calcium oxalate compound, stirring for 20min, adding 50 parts by volume of ethanol, standing, and separating out the silver/lignin/calcium oxalate compound. Repeating the operation for 6 times, and separating the precipitate to obtain the silver/lignin/calcium oxalate compound compounded by layer self assembly.
Placing the silver/lignin/calcium oxalate compound compounded by layer-by-layer self-assembly in an inert atmosphere, carbonizing at 550 ℃ for 4 hours to obtain a silver-doped lignin carbon/calcium oxide compound, soaking the product in 0.5mol/L hydrochloric acid for washing for 4 hours, and then washing, filtering and freeze-drying to obtain the silver-doped lignin porous carbon nanosheet.
Example 4
Weighing 10 parts by mass of sulfonated alkali lignin, 0.5 part by mass of silver perchlorate and 10 parts by mass of zinc oxalate solid powder, adding the materials into 500 parts by volume of water, and heating and stirring the materials at 50 ℃ for 30min to prepare stable dispersion A. Taking 50 parts by volume of dispersion liquid of sulfonated alkali lignin, silver and zinc oxalate, adding 50 parts by volume of ethanol under the stirring state, standing, and separating out precipitate to obtain the silver/lignin/zinc oxalate compound. And adding 50 parts by volume of the dispersion liquid A into the prepared silver/lignin/zinc oxalate compound, stirring for 20min, adding 50 parts by volume of ethanol, standing, and separating out the silver/lignin/zinc oxalate compound. Repeating the operation for 8 times, and separating the precipitate to obtain the silver/lignin/zinc oxalate compound compounded by layer self assembly.
Placing the silver/lignin/zinc oxalate compound compounded by layer-by-layer self-assembly in an inert atmosphere, carbonizing at 850 ℃ for 2 hours to obtain a silver-doped lignin carbon/zinc oxide compound, soaking the product in 2mol/L hydrochloric acid for washing for 3 hours, and then washing, filtering and freeze-drying to obtain the silver-doped lignin porous carbon nanosheet.
Example 5
Weighing 5 parts by mass of sulfonated enzymatic hydrolysis lignin, 0.25 part by mass of silver nitrate and 5 parts by mass of cobalt oxalate solid powder, adding the materials into 500 parts by volume of water, and heating and stirring the materials for 30min at 50 ℃ to prepare stable dispersion A. And taking 50 parts by volume of the dispersion liquid A, adding 50 parts by volume of ethanol under the stirring state, standing, and separating out a precipitate to obtain the silver/lignin/cobalt oxalate compound. And adding 50 parts by volume of the dispersion liquid A into the prepared silver/lignin/cobalt oxalate compound, stirring for 20min, adding 50 parts by volume of ethanol, standing, and separating out the silver/lignin/cobalt oxalate compound. Repeating the operation for 7 times, and separating the precipitate to obtain the silver/lignin/cobalt oxalate compound which is compounded by layer-by-layer self-assembly.
Placing the layer-by-layer self-assembled and compounded silver/lignin/cobalt oxalate compound in an inert atmosphere, carbonizing at 650 ℃ for 2 hours to obtain a silver-doped lignin carbon/cobalt oxide compound, soaking the product in 1mol/L hydrochloric acid for washing for 3 hours, and then washing, filtering and freeze-drying to obtain the silver-doped lignin porous carbon nanosheet.
Example 6
Weighing 5 parts by mass of sodium lignosulfonate, 0.5 part by mass of silver fluoride and 7.5 parts by mass of calcium oxalate solid powder, adding into 1000 parts by volume of water, and heating and stirring at 50 ℃ for 30min to prepare stable dispersion A. And (3) taking 100 parts by volume of the dispersion liquid A, adding 100 parts by volume of ethanol under the stirring state, standing, and separating out a precipitate to obtain the silver/lignin/calcium oxalate compound. And adding 100 parts by volume of the dispersion liquid A into the prepared silver/lignin/calcium oxalate compound, stirring for 20min, adding 100 parts by volume of ethanol, standing, and separating out the silver/lignin/calcium oxalate compound. Repeating the operation for 6 times, and separating the precipitate to obtain the silver/lignin/calcium oxalate compound compounded by layer self assembly.
Placing the silver/lignin/calcium oxalate compound compounded by layer-by-layer self-assembly in an inert atmosphere, carbonizing at 850 ℃ for 3 hours to obtain a silver-doped lignin carbon/calcium oxide compound, soaking the product in 1mol/L hydrochloric acid for washing for 2 hours, and then washing, filtering and freeze-drying to obtain the silver-doped lignin porous carbon nanosheet.
The prepared silver-doped lignin porous carbon nanosheet is applied to a supercapacitor electrode material and subjected to material characterization and electrochemical testing, and the results are shown in table 1 and figures 1-5.
The microscopic morphology and structure of the samples were characterized by scanning electron microscopy (SEM, Hitachi S-550) and high-resolution field emission transmission electron microscopy (HRTEM, JEOL JEM-2100F,200 kV). The specific surface area and channel structure of the samples were tested using a fully automated specific surface and porosity analyzer (Micromeritics ASAP 2020 instrument).
Electrochemical tests were performed on an electrochemical workstation (CHI660E, shanghai chenghua), all tests using a three-electrode system. The working electrode preparation process comprises the following steps: dispersing the prepared silver-doped lignin porous carbon nanosheet, acetylene black and polytetrafluoroethylene emulsion (solid content is 60 wt%) in absolute ethyl alcohol according to the mass ratio of 8:1:1, fully grinding, coating the ethanol on foamed nickel with the thickness of 1cm multiplied by 1cm after the ethanol is completely volatilized, and tabletting to obtain the working electrode. The counter electrode adopts a platinum sheet electrode, and the reference electrode adopts a saturated calomel electrode. The cyclic voltammetry curve test is completed in a voltage window of-1 to 0V at a scanning speed of 10 to 200 mv/s. The constant direct current charging and discharging curve test is completed in a voltage window of-1 to 0V at a current density of 1.0 to 20.0A/g.
Table 1 shows the lignin carbon-1 and ZnCl prepared by activating the silver-doped lignin porous carbon nanosheets prepared in the above examples with KOH2Comparison of electrochemical properties of the activated lignocellulosic carbon-2.
TABLE 1 electrochemical Properties of silver-doped lignin porous carbon nanosheets
Lignin carbon-1 preparation procedure in table 1: 5 parts by mass of sodium lignosulfonate and 10 parts by mass of KOH are dissolved in 100 parts by volume of water, and the mixture is heated and stirred at 80 ℃ until the water is evaporated to dryness. Fully grinding the obtained solid, then carbonizing the solid for 2 hours at 800 ℃ in an inert atmosphere, soaking the product in 1mol/L hydrochloric acid for washing for 2 hours, and then washing, filtering and freeze-drying the product to obtain lignin carbon-1; the preparation method of the lignin carbon-2 comprises the following steps: weighing 5 parts by mass of sodium lignosulfonate and 10 parts by mass of ZnCl2Dissolved in 100 volume portions of water and heated and stirred at 80 ℃ until the water is evaporated to dryness. Fully grinding the obtained solid, then carbonizing the solid for 2h at 700 ℃ in an inert atmosphere, soaking the product in 1mol/L hydrochloric acid for washing for 2h, and then washing, filtering and freeze-drying the product to obtain the lignin carbon-2.
Specific capacitances of the silver-doped lignin porous carbon nanosheets prepared in the embodiment 1 are 266F/g and 215F/g respectively at current densities of 1.0A/g and 20.0A/g, specific capacitance retention rates are 80.8%, the silver-doped lignin porous carbon nanosheets have good rate performance, and the silver-doped lignin porous carbon nanosheets have obvious performance advantages in lignin porous carbon materials.
In addition, all the silver-doped lignin porous carbon nanosheets prepared in the examples are activated with KOH to prepare lignin carbon-1 and ZnCl2The electrochemical properties of the lignin carbon-2 prepared by activation are compared, and the results show that the specific capacitance and the rate capability of the lignin carbon after oxalate activation and silver doping are obviously improved, and the specific capacitance retention rate is higher than 80%. The gas released in the oxalate thermal decomposition process has stripping and activating effects on lignin, so that the condensation polymerization of lignin in the carbonization process is prevented, the generated metal oxide nanoparticles have certain etching effects on lignin carbon and the effect of supporting a lignin carbon sheet frame, and meanwhile, the carbonization efficiency is effectively improved by silver doping, so that the lignin porous carbon nanosheet with reasonable and rich pore structure and good conductivity is formed, the rapid transmission and diffusion of electrolyte ions in the electrochemical process can be promoted, and the electrochemical performance is improved. And lignin carbon-1, ZnCl prepared by KOH activation2Activation systemThe prepared lignin carbon-2 is seriously agglomerated and has narrow pore size distribution, so that the resistance of electrolyte ion diffusion in the electrochemical process is increased, and the specific capacitance and the rate capability are seriously reduced.
Fig. 1 is a scanning electron microscope image of silver-doped lignin porous carbon nanosheets prepared in example 1 of the present invention. As can be seen from the figure, the prepared lignin carbon is in a relatively regular two-dimensional carbon nano sheet shape, and the structure is loose.
Fig. 2 is a transmission electron microscope image of silver-doped lignin porous carbon nanosheets prepared in example 1 of the present invention. As can be seen from the figure, the silver-doped lignin porous carbon nanosheet has graphene-like folded grains, is very rich in pore structure, and is successfully embedded with a small amount of silver nanoparticles.
Fig. 3 is a nitrogen adsorption and desorption graph and a pore size distribution graph of the silver-doped lignin porous carbon nanosheet prepared in example 1 of the present invention. The absorption and desorption curves of the silver-doped lignin porous carbon nanosheets belong to type IV and have hysteresis loops of type H3. In the region of lower relative pressure, the nitrogen adsorption amount is rapidly increased, indicating that it has a microporous structure, and the hysteresis loop in the region of higher relative pressure indicates that it has a mesoporous structure. The total BET specific surface area of the silver-doped lignin porous carbon nanosheet is 870m2(ii)/g, wherein the specific surface area of the micropores is 265m2(g) the mesoporous specific surface area is 605m2(ii)/g, total pore volume 1.3cm3(ii) in terms of/g. The pore size distribution of the porous membrane is concentrated in micropores of 0.5-2 nm and mesopores of 2-20 nm, and the reasonable pore channel structure and the abundant pore size distribution are favorable for improving the electrochemical performance.
Fig. 4 is a cyclic voltammogram of silver-doped lignin porous carbon nanosheets prepared in example 1 of the present invention. From the figure, the cyclic voltammetry curves of the silver-doped lignin porous carbon nanosheets are similar to rectangular shapes at different scanning speeds, which shows that the silver-doped lignin porous carbon nanosheets have ideal double-layer capacitance characteristics, and the curves do not deform obviously at a high scanning speed of 200mv/s, thereby showing that the silver-doped lignin porous carbon nanosheets have good rate performance.
Fig. 5 is a constant dc charge-discharge curve diagram of the silver-doped lignin porous carbon nanosheet prepared in example 1 of the present invention. The charging and discharging curves of the silver-doped lignin porous carbon nanosheet are similar to isosceles triangle shapes under different current densities, so that the silver-doped lignin porous carbon nanosheet has typical double-layer capacitance characteristics, and the charging and discharging time of the curves is approximately equal, so that the silver-doped lignin porous carbon nanosheet has high coulombic efficiency.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. A preparation method of a silver-doped lignin porous carbon nanosheet is characterized by comprising the following steps:
(1) dispersing sulfonated lignin, silver salt and oxalate in water to obtain a matrix solution;
(2) taking the matrix solution of the volume part A, adding the ethanol of the volume part B while stirring, standing and separating to obtain a silver/lignin/oxalate compound;
(3) taking the same A volume part of matrix solution, adding the silver/lignin/oxalate compound obtained in the step (2) into the matrix solution, uniformly stirring, adding the same B volume part of ethanol, standing and separating to obtain an assembled silver/lignin/oxalate compound;
(4) repeating the step (3) for multiple times to obtain a layer-by-layer self-assembled silver/lignin/oxalate compound;
(5) placing the silver/lignin/oxalate compound subjected to layer-by-layer self-assembly in an inert atmosphere, carbonizing for 2-4 h at 550-850 ℃, and acid washing to obtain a silver-doped lignin porous carbon nanosheet;
the weight ratio of the sulfonated lignin to the silver salt to the oxalate is 100: 5-10: 50 to 150.
2. The preparation method of the silver-doped lignin porous carbon nanosheet according to claim 1, characterized in that: the dispersion is heating stirring dispersion; the total mass concentration of the sulfonated lignin, the silver salt and the oxalate in the matrix solution is 2-10%.
3. The preparation method of the silver-doped lignin porous carbon nanosheet according to claim 1, characterized in that: the volume ratio of the matrix solution to the ethanol is 1:1 each time; the stirring time is 10-30 min.
4. The preparation method of the silver-doped lignin porous carbon nanosheet according to claim 1, characterized in that: the sulfonated lignin is selected from at least one of sodium lignosulfonate, calcium lignosulfonate and magnesium lignosulfonate in red liquor of acid pulping, sulfonated products of alkali lignin in black liquor of alkali pulping and sulfonated products of enzymatic hydrolysis lignin in a biorefinery industrial process; the silver salt comprises at least one of silver nitrate, silver fluoride and silver perchlorate; the oxalate comprises at least one of zinc oxalate, calcium oxalate, magnesium oxalate, ferrous oxalate and cobalt oxalate; and the acid washing refers to washing the carbonized product in 0.5-2 mol/L acid liquor for 1-3 h, and then washing, filtering and drying.
5. Silver-doped lignin porous carbon nanosheet characterized by being obtained according to the preparation method of any one of claims 1 to 4.
6. The application of the silver-doped lignin porous carbon nanosheet in the electrode material of the supercapacitor.
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| CN114524427B (en) * | 2022-02-22 | 2023-04-21 | 华南理工大学 | Accordion-shaped lignin cube carbon material, preparation method thereof and application thereof in super capacitor |
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