CN111549449B - Preparation method of lignin-based flexible carbon nanofiber self-supporting electrode material - Google Patents

Preparation method of lignin-based flexible carbon nanofiber self-supporting electrode material Download PDF

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CN111549449B
CN111549449B CN202010364636.XA CN202010364636A CN111549449B CN 111549449 B CN111549449 B CN 111549449B CN 202010364636 A CN202010364636 A CN 202010364636A CN 111549449 B CN111549449 B CN 111549449B
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lignin
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CN111549449A (en
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刘呈坤
吴红
毛雪
孙润军
陈美玉
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Xian Polytechnic University
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Abstract

The invention discloses a preparation method of a lignin-based flexible nano carbon fiber self-supporting electrode material, which comprises the following steps: 1) dissolving a companion spinning polymer and lignin in a solvent in sequence to obtain a precursor solution; wherein the mass ratio of the lignin to the companioning polymer is 7: 3-9: 1, and the mass ratio concentration of the precursor solution is 20-35%; 2) obtaining a precursor composite nanofiber membrane by using the precursor solution through an electrostatic spinning technology; 3) and sequentially carrying out pre-oxidation treatment on the composite nanofiber membrane in an air atmosphere and carbonization treatment in an inert atmosphere to obtain the flexible carbon nanofiber membrane. The carbon nanofibers prepared by the method have large specific surface area and good flexibility, do not need to add a binder, can be directly used as independent electrodes, and reduce the internal resistance of the electrodes; the high specific capacitance can be obtained without adding conductive materials, and the energy storage performance is excellent.

Description

Preparation method of lignin-based flexible carbon nanofiber self-supporting electrode material
Technical Field
The invention belongs to the technical field of biomass carbon nanofiber, and relates to a preparation method of a lignin-based flexible carbon nanofiber self-supporting electrode material.
Background
With the rapid development of global economy, the exhaustion of fossil fuels and the increasing environmental pollution, the demand of people for sustainable and renewable energy is increasing, which prompts people to research efficient and green energy conversion and storage devices to meet the urgent demand of energy in the future world. Among various energy storage devices, super capacitors have received great attention due to their characteristics such as high power density, high cycle stability, and high energy density. The electrode material has an important influence on the energy storage properties. Carbon materials are widely used in the field of electrodes due to their advantages such as good conductivity, stable chemical properties, and multi-level pore size distribution. The raw materials for preparing carbon materials traditionally mainly comprise fossil fuels such as polyacrylonitrile, asphalt and the like, but the raw materials have limited reserves and high price and cause environmental pollution. Based on this, a new carbon fiber raw material is required.
Lignin is the second largest renewable resource with the content second to cellulose in nature, and is the only biomass polymer containing a large amount of aromatic rings, wherein the carbon content is as high as more than 60%, and the lignin is an ideal raw material for preparing carbon fibers. However, due to the complex structure, the utilization rate of lignin is only 10% at present, most lignin is discharged or burned as waste along with wastewater, so that not only is the resource waste caused, but also the environment is seriously polluted. Therefore, the development and utilization of high value of lignin become a hot spot for researchers to research.
Chinese patent CN 110685040a discloses a method for preparing high specific surface area lignin nano carbon fiber and chinese patent CN 109056120a discloses a method for preparing low cost carbon fiber by using lignin, which all prepare carbon fiber, but in the preparation process, catalyst or coupling agent and plasticizer are added or ultraviolet irradiation treatment is carried out, and the preparation process is complex. RSC Advances,2014,4(2014):48336-48343 reports that lignin-based nanoporous carbon is prepared by taking kraft lignin as a carbon source and is used for an electrode material, but the electrode material uses polytetrafluoroethylene as a binder during assembly, so that the internal resistance of an electrode is increased, and the specific capacitance of the electrode material is reduced.
Disclosure of Invention
The invention aims to provide a preparation method of a lignin-based flexible carbon nanofiber self-supporting electrode material, which solves the problems of low lignin utilization rate, brittleness of obtained carbon nanofibers, complex process for assembling an energy storage device and the like in the prior art.
The technical scheme adopted by the invention is that the preparation method of the lignin-based flexible carbon nanofiber self-supporting electrode material is implemented according to the following steps:
step 1: dissolving a companioning polymer in a solvent, stirring for 2-7 hours by using a magnetic stirrer until the solution is clear, then adding lignin, and stirring for 6-12 hours by using a mechanical stirrer to obtain a uniform and stable spinnable precursor solution;
wherein the mass ratio of the lignin to the companioning polymer is 7: 3-9: 1; the mass ratio concentration of the precursor solution is 20-35%; the lignin is any one or a mixture of several of alkaline lignin, hydroxylated alkali lignin, sodium lignosulfonate, calcium lignosulfonate and ammonium alkali lignin; the solvent is dimethyl sulfoxide and N, N-dimethylformamide, and the volume ratio of the two solvents is 5: 5-9: 1;
step 2: performing electrostatic spinning on the precursor solution prepared in the step 1 to obtain a precursor composite nanofiber membrane:
electrostatic spinning process parameters: the temperature is 30-40 ℃, the relative humidity is 25-35 RH%, the applied voltage of the spinning needle is 15-30 kV, the filling speed of the precursor solution is 0.5-1.5 mL/h, and the distance between the receiving device and the needle is 10-20 cm;
and step 3: placing the precursor composite nanofiber membrane prepared in the step 2 in a muffle furnace, and performing pre-oxidation treatment in air atmosphere to obtain a composite nano pre-oxidized fiber membrane;
pre-oxidation process parameters: the temperature rising speed is 1-5 ℃/min, the temperature is gradually raised from room temperature to 200-300 ℃, and the temperature is kept for 1-2 h at the highest temperature;
and 4, step 4: placing the composite nano pre-oxidized fiber membrane obtained in the step 3 in a tubular furnace, and carrying out carbonization treatment in an inert gas atmosphere to obtain a flexible nano carbon fiber membrane;
the carbonization process parameters are as follows: the temperature rising speed is 5-10 ℃/min, the temperature is gradually raised to 800-1400 ℃ from the room temperature, and the temperature is kept for 1-5 h at the highest temperature.
The invention is also characterized in that:
the companion spinning polymer is any one or a mixture of several of polyacrylonitrile, polyvinylpyrrolidone, polyvinylidene fluoride, polyvinyl alcohol, polypropylene glycol, polyvinylidene fluoride, polylactic acid and polycaprolactone.
The inert gas is nitrogen or argon.
The diameter of the flexible carbon nanofiber membrane prepared in the step 4 is 200-400 nm.
The preparation method of the lignin-based flexible carbon nanofiber self-supporting electrode material specifically comprises the following steps:
step 1: dissolving polyacrylonitrile in a mixed solvent of dimethyl sulfoxide and N, N-dimethylformamide, stirring for 2 hours by a magnetic stirrer until the solution is clear, adding alkaline lignin, and continuously stirring for 7 hours, wherein the volume ratio of the dimethyl sulfoxide to the N, N-dimethylformamide is 6:4, and the mass ratio of the alkaline lignin to the polyacrylonitrile is 9: 1; uniformly mixing to prepare a precursor solution with the mass ratio concentration of 30% and the viscosity of 3Pa & s;
step 2: preparing the precursor solution prepared in the step 1 into a precursor composite nanofiber membrane through an electrostatic spinning process; electrostatic spinning process parameters: the spinning temperature is 30 ℃, the relative humidity is 32 RH%, the spinning voltage is 25kV, the perfusion speed is 1.0mL/h, and the distance between the receiving device and the needle head is 15 cm;
and step 3: placing the precursor composite nanofiber membrane prepared in the step 2 in a muffle furnace, and carrying out pre-oxidation treatment in air atmosphere, wherein the temperature is gradually increased from room temperature to 240 ℃, the temperature increase speed is 1 ℃/min, and the temperature is kept at the highest temperature for 2 hours, so as to prepare a composite nano pre-oxidized silk membrane;
and 4, step 4: and (4) placing the composite nano pre-oxidized fiber membrane obtained in the step (3) in a tubular furnace, calcining at a high temperature under a nitrogen atmosphere for carbonization, gradually increasing the temperature from room temperature to 1200 ℃, increasing the temperature at a speed of 5 ℃/min, and preserving the heat at the highest calcining temperature for 1h to obtain the flexible nano carbon fiber membrane.
The preparation method of the lignin-based flexible nano carbon fiber self-supporting electrode material specifically comprises the following steps:
step 1: dissolving polyvinylidene fluoride in a mixed solvent of dimethyl sulfoxide and N, N-dimethylformamide, stirring for 5 hours by a magnetic stirrer until the solution is clarified, adding sodium lignosulfonate, and continuously stirring for 10 hours, wherein the volume ratio of the dimethyl sulfoxide to the N, N-dimethylformamide is 7:3, and the mass ratio of the sodium lignosulfonate to the polyvinylidene fluoride is 8: 2; uniformly mixing to prepare a uniform and stable precursor solution with the mass ratio concentration of 28% and the viscosity of 2.5 Pa.s;
step 2: preparing the precursor solution prepared in the step 1 into a precursor composite nanofiber membrane through an electrostatic spinning process; the electrostatic spinning process parameters are as follows: the spinning temperature is 40 ℃, the relative humidity is 25 RH%, the spinning voltage is 15kV, the perfusion speed is 1.5mL/h, and the distance between the receiving device and the needle head is 18 cm;
and step 3: placing the precursor composite nanofiber membrane prepared in the step 2 in a muffle furnace, and carrying out pre-oxidation treatment in air atmosphere, wherein the temperature is gradually increased from room temperature to 300 ℃, the temperature increase speed is 4 ℃/min, and the temperature is kept at the highest temperature for 1h, so as to prepare a composite nano pre-oxidized silk membrane;
and 4, step 4: and (3) placing the composite nano pre-oxidized fiber membrane obtained in the step (3) in a tubular furnace, calcining at high temperature in argon atmosphere to obtain a flexible nano carbon fiber membrane, gradually increasing the temperature from room temperature to 1100 ℃, keeping the temperature at the speed of 8 ℃/min, and keeping the temperature at the highest calcining temperature for 4 hours to obtain the flexible nano carbon fiber membrane, wherein the average diameter of the nano carbon fiber is 328 nm.
The preparation method of the lignin-based flexible nano carbon fiber self-supporting electrode material specifically comprises the following steps:
step 1: dissolving polylactic acid in a mixed solvent of dimethyl sulfoxide and N, N-dimethylformamide, stirring for 4 hours by a magnetic stirrer until the solution is clear, adding hydroxylated alkali lignin, and continuously stirring for 9 hours, wherein the volume ratio of the dimethyl sulfoxide to the N, N-dimethylformamide is 9:1, and the mass ratio of the hydroxylated alkali lignin to the polylactic acid is 9: 1; uniformly mixing to prepare a uniform and stable precursor solution with the mass ratio concentration of 35% and the viscosity of 4Pa & s;
and 2, step: and (3) preparing the precursor solution prepared in the step (1) into a precursor composite nanofiber membrane through an electrostatic spinning process. Electrostatic spinning process parameters: the spinning temperature is 37 ℃, the relative humidity is 28 RH%, the spinning voltage is 30kV, the perfusion speed is 0.8mL/h, and the distance between the receiving device and the needle head is 20 cm;
and step 3: placing the precursor composite nanofiber membrane prepared in the step 2 in a muffle furnace, and carrying out pre-oxidation treatment under the air atmosphere, wherein the temperature is gradually increased from room temperature to 200 ℃, the temperature increase speed is 3 ℃/min, and the temperature is kept at the highest temperature for 1.5h, so as to prepare a composite nano pre-oxidized silk membrane;
and 4, step 4: and (3) placing the composite nano pre-oxidized fiber membrane obtained in the step (3) in a tubular furnace, calcining at high temperature in nitrogen atmosphere to obtain a flexible nano carbon fiber membrane, gradually increasing the temperature from room temperature to 1400 ℃, keeping the temperature at the highest calcining temperature for 5 hours, and obtaining the flexible nano carbon fiber membrane, wherein the average diameter of the nano carbon fiber is 200 nm.
The preparation method of the lignin-based flexible nano carbon fiber self-supporting electrode material specifically comprises the following steps:
step 1: dissolving polyvinyl alcohol in a mixed solvent of dimethyl sulfoxide and N, N-dimethylformamide, stirring for 7 hours by a magnetic stirrer until the solution is clear, adding ammonium alkali lignin, and continuously stirring for 11 hours, wherein the volume ratio of the dimethyl sulfoxide to the N, N-dimethylformamide is 8:2, and the mass ratio of the ammonium alkali lignin to the polyvinyl alcohol is 7: 3; uniformly mixing to prepare a uniform and stable precursor solution with the mass ratio concentration of 35% and the viscosity of 1Pa & s;
step 2: preparing the precursor solution prepared in the step 1 into a precursor composite nanofiber membrane through an electrostatic spinning process; the electrostatic spinning process parameters are as follows: the spinning temperature is 34 ℃, the relative humidity is 30 RH%, the spinning voltage is 28kV, the perfusion speed is 0.5mL/h, and the distance between the receiving device and the needle head is 12 cm;
and step 3: placing the precursor composite nanofiber membrane prepared in the step 2 in a muffle furnace, and performing pre-oxidation treatment in air atmosphere, wherein the calcination temperature is gradually increased to 260 ℃ from room temperature, the temperature increase speed is 4 ℃/min, and the temperature is kept at the highest temperature for 1.2 hours to prepare a composite nano pre-oxidation wire membrane;
and 4, step 4: and (3) placing the composite nano pre-oxidized fiber membrane obtained in the step (3) in a tubular furnace, calcining at high temperature in nitrogen atmosphere to obtain a flexible nano carbon fiber membrane, gradually increasing the temperature from room temperature to 1300 ℃, keeping the temperature at the speed of 10 ℃/min, and keeping the temperature at the highest calcining temperature for 3 hours to obtain the flexible nano carbon fiber membrane, wherein the average diameter of the nano carbon fiber is 286 nm.
The preparation method of the lignin-based flexible nano carbon fiber self-supporting electrode material specifically comprises the following steps:
step 1: dissolving polyvinylpyrrolidone in a mixed solvent of dimethyl sulfoxide and N, N-dimethylformamide, stirring for 6 hours by a magnetic stirrer until the solution is clear, adding calcium lignosulfonate, and continuously stirring for 12 hours, wherein the volume ratio of the dimethyl sulfoxide to the N, N-dimethylformamide is 5:5, and the mass ratio of the calcium lignosulfonate to the polyvinylpyrrolidone is 9: 1; uniformly mixing to prepare a uniform and stable precursor solution with the mass ratio concentration of 32% and the viscosity of 3.5 Pa.s;
and 2, step: preparing the precursor solution prepared in the step 1 into a precursor composite nanofiber membrane through an electrostatic spinning process, wherein the electrostatic spinning process parameters are as follows: the spinning temperature is 32 ℃, the relative humidity is 35 RH%, the spinning voltage is 22kV, the perfusion speed is 1.2mL/h, and the distance between the receiving device and the needle is 10 cm;
and step 3: placing the precursor composite nanofiber membrane prepared in the step 2 in a muffle furnace, and carrying out pre-oxidation treatment in air atmosphere, wherein the temperature is gradually increased from room temperature to 280 ℃, the temperature increase speed is 5 ℃/min, and the precursor composite nanofiber membrane is kept at the highest calcination temperature for 1h to prepare a composite nano pre-oxidized silk membrane;
and 4, step 4: and (3) placing the composite nano pre-oxidized fiber membrane obtained in the step (3) in a tubular furnace, calcining at high temperature in argon atmosphere to obtain a flexible nano carbon fiber membrane, gradually increasing the temperature from room temperature to 800 ℃, keeping the temperature at the highest calcining temperature for 2 hours, and obtaining the flexible nano carbon fiber membrane, wherein the average diameter of the nano carbon fiber is 400 nm.
The beneficial effects of the invention are: firstly, blending and spinning the lignin and the companioning polymer, wherein 70-90% of the lignin replaces the traditional raw material for preparing the carbon material, and a large amount of high-value utilization of the lignin is realized; secondly, the flexible carbon nanofiber membrane is prepared through electrostatic spinning, pre-oxidation and carbonization processes in sequence, the flexible carbon nanofiber membrane has good flexibility, and the carbon fiber membrane has a large specific surface area (926.4-1503.8 m) without being subjected to activation treatment 2 The/g) provides more storage positions for charges, does not need to add a binder, can be directly used as an independent electrode, and reduces the internal resistance of the electrode; the high specific capacitance can be obtained without adding conductive materials, and the energy storage performance is excellent.
Drawings
FIG. 1 is an optical photograph of a lignin-based flexible filamentous nanocarbon film according to example 1 of the present invention;
FIG. 2 is a field emission scanning electron microscope (FE-SEM) image of a lignin-based flexible carbon nanofiber membrane in example 1 of the present invention;
FIG. 3 is a nitrogen adsorption and desorption curve of the lignin-based flexible carbon nanofiber membrane in example 1 of the present invention;
fig. 4 is a Cyclic Voltammetry (CV) curve of the lignin-based flexible filamentous nanocarbon electrode material in example 1 of the present invention.
Detailed Description
The invention is described in detail below with reference to the drawings and the detailed description.
The invention relates to a preparation method of a lignin-based flexible nano carbon fiber self-supporting electrode material, which is implemented according to the following steps:
step 1: dissolving a companion spinning polymer in a solvent, stirring for 2-7 h by using a magnetic stirrer until the solution is clear, then adding lignin, and stirring for 6-12 h by using a mechanical stirrer to obtain a uniform and stable spinnable precursor solution;
wherein the mass ratio of the lignin to the companion spinning polymer is 7: 3-9: 1; the mass ratio concentration of the precursor solution is 20-35%; the lignin is any one of alkaline lignin, hydroxylated alkali lignin, sodium lignosulfonate, calcium lignosulfonate and ammonium alkali lignin; the solvent is dimethyl sulfoxide and N, N-dimethylformamide, and the volume ratio of the two solvents is 5: 5-9: 1; the viscosity of the precursor solution is 1-4 Pa.s;
step 2: performing electrostatic spinning on the precursor solution prepared in the step 1, when the voltage applied to the tail end of a spinning needle is greater than the surface tension of the spinning needle, jetting a spinning jet flow from the top end of a Taylor cone formed on the surface of a droplet at the tail end of the needle, performing high-speed stretching of electric field force, volatilizing and solidifying a solvent by the jet flow, and finally depositing the jet flow on a receiving device to obtain a precursor composite nanofiber membrane, wherein the prepared composite nanofiber membrane has the characteristics of good appearance, uniform diameter distribution and the like;
the electrostatic spinning process parameters are as follows: the temperature is 30-40 ℃, the relative humidity is 25-35 RH%, the applied voltage of the spinning needle is 15-30 kV, the filling speed of the precursor solution is 0.5-1.5 mL/h, and the distance between the receiving device and the needle is 10-20 cm;
and 3, step 3: placing the precursor composite nanofiber membrane prepared in the step 2 in a muffle furnace, and carrying out pre-oxidation treatment in an air atmosphere to obtain a composite nano pre-oxidized fiber membrane, wherein single fibers of the prepared pre-oxidized fiber membrane are all in a dispersion state and are not adhered;
pre-oxidation process parameters: the heating rate is 1-5 ℃/min, the temperature is gradually increased from room temperature to 200-300 ℃, and the temperature is kept at the highest temperature for 1-2 h;
and 4, step 4: placing the composite nano pre-oxidized fiber membrane obtained in the step 3 in a tubular furnace, calcining at high temperature in an inert gas atmosphere, and carbonizing to finally prepare a flexible nano carbon fiber membrane, wherein the prepared flexible nano carbon fiber membrane has smooth fiber surface, no particles, good continuity and good flexibility;
the carbonization process parameters are as follows: the temperature rising speed is 5-10 ℃/min, the temperature is gradually raised to 800-1400 ℃ from the room temperature, and the temperature is kept for 1-5 h at the highest calcining temperature.
The companion spinning polymer is any one or a mixture of several of polyacrylonitrile, polyvinylpyrrolidone, polyvinylidene fluoride, polyvinyl alcohol, polypropylene glycol, polyvinylidene fluoride, polylactic acid and polycaprolactone.
The inert gas is nitrogen or argon.
The diameter range of the flexible carbon nanofiber membrane prepared in the step 4 is 200-400 nm, and the relative standard deviation is 1-3%. In addition, the specific surface area of the nano carbon fiber is 926.4-1503.8 m 2 And/g, can provide sufficient attachment points for the charge.
Example one
The preparation method of the lignin-based flexible carbon nanofiber self-supporting electrode material specifically comprises the following steps:
step 1: dissolving polyacrylonitrile in a mixed solvent of dimethyl sulfoxide and N, N-dimethylformamide, stirring for 2 hours by a magnetic stirrer until the solution is clear, adding alkaline lignin, and continuously stirring for 7 hours, wherein the volume ratio of the dimethyl sulfoxide to the N, N-dimethylformamide is 6:4, and the mass ratio of the alkaline lignin to the polyacrylonitrile is 9: 1; uniformly mixing to prepare a precursor solution with the mass ratio concentration of 30% and the viscosity of 3Pa & s;
step 2: preparing the precursor solution prepared in the step 1 into a precursor composite nanofiber membrane through an electrostatic spinning process; the electrostatic spinning process parameters are as follows: the spinning temperature is 30 ℃, the relative humidity is 32 RH%, the spinning voltage is 25kV, the perfusion speed is 1.0mL/h, and the distance between the receiving device and the needle head is 15 cm;
and 3, step 3: placing the precursor composite nanofiber membrane prepared in the step 2 in a muffle furnace, and carrying out pre-oxidation treatment in air atmosphere, wherein the temperature is gradually increased from room temperature to 240 ℃, the temperature increase speed is 1 ℃/min, and the temperature is kept at the highest temperature for 2 hours, so as to prepare a composite nano pre-oxidized silk membrane;
and 4, step 4: placing the composite nano pre-oxidized fiber membrane obtained in the step 3 in a tubular furnace, calcining at a high temperature under a nitrogen atmosphere for carbonization treatment, gradually increasing the temperature from room temperature to 1200 ℃, wherein the temperature increasing speed is 5 ℃/min, and preserving the heat at the highest calcining temperature for 1h to obtain the flexible nano carbon fiber membrane shown in the figure 1, wherein the micro morphology of the nano carbon fiber is shown in figure 2, the average diameter of the nano carbon fiber is 230nm, and the relative standard deviation of the nano carbon fiber is 2%; as shown in FIG. 3, the specific surface area was calculated to be 1305.8m based on the nitrogen adsorption-desorption curve and the BET theory 2 The flexible carbon nanofiber can be directly used as an electrode material of a super capacitor and has good electrochemical properties such as high specific capacitance.
The carbon nanofiber membrane is cut into a square with the mass of 1cm multiplied by 1cm, the mass of the carbon nanofiber membrane is 1.3mg, and the carbon nanofiber membrane is loaded on foamed nickel under the condition that no binder or conductive agent is added to prepare the electrode material of the super capacitor. The assembled carbon electrode material was immersed in a 6mol/L potassium hydroxide (KOH) solution for 24h prior to testing. And (3) carrying out three-electrode system test on the carbon nanofiber electrode by using a CHI 660E electrochemical workstation, wherein the prepared carbon nanofiber electrode material is a working electrode, and the saturated calomel and a platinum sheet are respectively used as a reference electrode and an auxiliary electrode. At a scan rate of 100mV s -1 Then, Cyclic Voltammetry (CV) test is carried out in KOH solution with 6mol/h of electrolyte, the obtained CV curve is shown in figure 4, and the specific capacitance is calculated to be up to 195.1F g -1 。
Example two
The preparation method of the lignin-based flexible nano carbon fiber self-supporting electrode material specifically comprises the following steps:
step 1: dissolving polyvinylidene fluoride in a mixed solvent of dimethyl sulfoxide and N, N-dimethylformamide, stirring for 5 hours by a magnetic stirrer until the solution is clarified, adding sodium lignosulfonate, and continuously stirring for 10 hours, wherein the volume ratio of the dimethyl sulfoxide to the N, N-dimethylformamide is 7:3, and the mass ratio of the sodium lignosulfonate to the polyvinylidene fluoride is 8: 2; uniformly mixing to prepare a uniform and stable precursor solution with the mass ratio concentration of 28% and the viscosity of 2.5 Pa.s;
and 2, step: preparing the precursor solution prepared in the step 1 into a precursor composite nanofiber membrane through an electrostatic spinning process; the electrostatic spinning process parameters are as follows: the spinning temperature is 40 ℃, the relative humidity is 25 RH%, the spinning voltage is 15kV, the perfusion speed is 1.5mL/h, and the distance between the receiving device and the needle head is 18 cm;
and 3, step 3: placing the precursor composite nanofiber membrane prepared in the step 2 in a muffle furnace, and carrying out pre-oxidation treatment in air atmosphere, wherein the temperature is gradually increased from room temperature to 300 ℃, the temperature increase speed is 4 ℃/min, and the temperature is kept at the highest temperature for 1h, so as to prepare a composite nano pre-oxidized silk membrane;
and 4, step 4: placing the composite nano pre-oxidized fiber membrane obtained in the step 3 in a tube furnace, calcining at high temperature in argon atmosphere to obtain a flexible nano carbon fiber membrane, gradually increasing the temperature from room temperature to 1100 ℃, increasing the temperature at a speed of 8 ℃/min, and preserving the heat at the highest calcining temperature for 4 hours to obtain the flexible nano carbon fiber membrane, wherein the average diameter of the fiber is 328nm, the relative standard deviation is 1%, and the specific surface area is 1128.3m 2 The polymer can be directly used as an electrode material and has good electrochemical properties such as high specific capacitance.
EXAMPLE III
The preparation method of the lignin-based flexible nano carbon fiber self-supporting electrode material specifically comprises the following steps:
step 1: dissolving polylactic acid in a mixed solvent of dimethyl sulfoxide and N, N-dimethylformamide, stirring for 4 hours by a magnetic stirrer until the solution is clarified, adding hydroxylated alkali lignin, and continuously stirring for 9 hours, wherein the volume ratio of the dimethyl sulfoxide to the N, N-dimethylformamide is 9:1, and the mass ratio of the hydroxylated alkali lignin to the polylactic acid is 9: 1; uniformly mixing to prepare a uniform and stable precursor solution with the mass ratio concentration of 35% and the viscosity of 4Pa & s;
and 2, step: and (2) preparing the precursor solution prepared in the step (1) into a precursor composite nanofiber membrane through an electrostatic spinning process. The electrostatic spinning process parameters are as follows: the spinning temperature is 37 ℃, the relative humidity is 28 RH%, the spinning voltage is 30kV, the perfusion speed is 0.8mL/h, and the distance between the receiving device and the needle head is 20 cm;
and step 3: placing the precursor composite nanofiber membrane prepared in the step 2 in a muffle furnace, and carrying out pre-oxidation treatment under the air atmosphere, wherein the temperature is gradually increased from room temperature to 200 ℃, the temperature increase speed is 3 ℃/min, and the temperature is kept at the highest temperature for 1.5h, so as to prepare a composite nano pre-oxidized silk membrane;
and 4, step 4: placing the composite nano pre-oxidized fiber membrane obtained in the step 3 in a tubular furnace, calcining at high temperature in nitrogen atmosphere to obtain a flexible nano carbon fiber membrane, gradually increasing the temperature from room temperature to 1400 ℃, increasing the temperature at a speed of 6 ℃/min, and preserving the heat at the highest calcining temperature for 5 hours to obtain the flexible nano carbon fiber membrane, wherein the average diameter of the fiber is 200nm, the relative standard deviation is 1%, and the specific surface area is 1503.8m 2 The polymer can be directly used as an electrode material and has good electrochemical properties such as high specific capacitance.
Example four
The preparation method of the lignin-based flexible nano carbon fiber self-supporting electrode material specifically comprises the following steps:
step 1: dissolving polyvinyl alcohol in a mixed solvent of dimethyl sulfoxide and N, N-dimethylformamide, stirring for 7 hours by a magnetic stirrer until the solution is clear, adding ammonium alkali lignin, and continuously stirring for 11 hours, wherein the volume ratio of the dimethyl sulfoxide to the N, N-dimethylformamide is 8:2, and the mass ratio of the ammonium alkali lignin to the polyvinyl alcohol is 7: 3; uniformly mixing to prepare a uniform and stable precursor solution with the mass ratio concentration of 35% and the viscosity of 1Pa & s;
step 2: preparing the precursor solution prepared in the step 1 into a precursor composite nanofiber membrane through an electrostatic spinning process; the electrostatic spinning process parameters are as follows: the spinning temperature is 34 ℃, the relative humidity is 30 RH%, the spinning voltage is 28kV, the perfusion speed is 0.5mL/h, and the distance between the receiving device and the needle head is 12 cm;
and 3, step 3: placing the precursor composite nanofiber membrane prepared in the step 2 in a muffle furnace, and carrying out pre-oxidation treatment in air atmosphere, wherein the temperature is gradually increased from room temperature to 260 ℃, the temperature increase speed is 4 ℃/min, and the temperature is kept at the highest temperature for 1.2h, so as to prepare a composite nano pre-oxidized silk membrane;
and 4, step 4: placing the composite nano pre-oxidized fiber membrane obtained in the step 3 in a tubular furnaceCalcining at high temperature in nitrogen atmosphere to obtain flexible carbon nanofiber membrane, gradually increasing the temperature from room temperature to 1300 ℃, increasing the temperature at a speed of 10 ℃/min, and preserving the heat at the highest calcining temperature for 3h to obtain the flexible carbon nanofiber membrane, wherein the average fiber diameter is 286nm, the relative standard deviation is 2%, and the specific surface area is 1469.5m 2 The polymer can be directly used as an electrode material and has good electrochemical properties such as high specific capacitance.
EXAMPLE five
The preparation method of the lignin-based flexible nano carbon fiber self-supporting electrode material specifically comprises the following steps:
step 1: dissolving polyvinylpyrrolidone in a mixed solvent of dimethyl sulfoxide and N, N-dimethylformamide, stirring for 6 hours by a magnetic stirrer until the solution is clear, adding calcium lignosulfonate, and continuously stirring for 12 hours, wherein the volume ratio of the dimethyl sulfoxide to the N, N-dimethylformamide is 5:5, and the mass ratio of the calcium lignosulfonate to the polyvinylpyrrolidone is 9: 1; uniformly mixing to prepare a uniform and stable precursor solution with the mass ratio concentration of 32% and the viscosity of 3.5 Pa.s;
step 2: preparing the precursor solution prepared in the step 1 into a precursor composite nanofiber membrane through an electrostatic spinning process, wherein the electrostatic spinning process parameters are as follows: the spinning temperature is 32 ℃, the relative humidity is 35 RH%, the spinning voltage is 22kV, the perfusion speed is 1.2mL/h, and the distance between the receiving device and the needle head is 10 cm;
and step 3: placing the precursor composite nanofiber membrane prepared in the step 2 in a muffle furnace, and performing pre-oxidation treatment under air atmosphere, wherein the temperature is gradually increased from room temperature to 280 ℃, the temperature increasing speed is 5 ℃/min, and the temperature is kept at the highest temperature for 1h to prepare a composite nano pre-oxidation silk membrane;
and 4, step 4: placing the composite nano pre-oxidized fiber membrane obtained in the step 3 in a tubular furnace, calcining at high temperature in argon atmosphere to obtain a flexible nano carbon fiber membrane, gradually increasing the temperature from room temperature to 800 ℃, increasing the temperature at a speed of 6 ℃/min, and preserving the heat at the highest calcining temperature for 2 hours to obtain the flexible nano carbon fiber membrane, wherein the average diameter of the fiber is 400nm, the relative standard deviation is 3%, and the specific surface area is 926.4m 2 /g, can be used directlyThe electrode material has good electrochemical properties such as high specific capacitance.
The invention relates to a preparation method of a lignin-based flexible nano carbon fiber self-supporting electrode material, which has the advantages that: the invention realizes a large amount of high-value utilization of lignin, prepares the flexible carbon nanofiber membrane through electrostatic spinning, pre-oxidation and carbonization processes in sequence, has larger specific surface area without activation treatment, can be directly used for electrode materials, has good electrochemical characteristics such as high specific capacitance and the like, and solves the problems of low lignin utilization rate, brittleness of the carbon nanofiber obtained in the preparation process of the prior art, complex process for assembling an energy storage device and the like.

Claims (8)

1. A preparation method of a lignin-based flexible carbon nanofiber self-supporting electrode material is characterized by comprising the following steps:
step 1: dissolving a companioning polymer in a solvent, stirring for 2-7 hours by using a magnetic stirrer until the solution is clear, then adding lignin, and stirring for 6-12 hours by using a mechanical stirrer to obtain a uniform and stable spinnable precursor solution;
wherein the mass ratio of the lignin to the companion spinning polymer is 7: 3-9: 1; the mass ratio concentration of the precursor solution is 20-35%; the lignin is any one or a mixture of several of alkaline lignin, hydroxylated alkali lignin, sodium lignosulfonate, calcium lignosulfonate and ammonium alkali lignin; the solvent is dimethyl sulfoxide and N, N-dimethylformamide, and the volume ratio of the two solvents is 5: 5-9: 1;
step 2: performing electrostatic spinning on the precursor solution prepared in the step 1 to obtain a precursor composite nanofiber membrane:
the electrostatic spinning process parameters are as follows: the temperature is 30-40 ℃, the relative humidity is 25-35 RH%, the applied voltage of the spinning needle is 15-30 kV, the filling speed of the precursor solution is 0.5-1.5 mL/h, and the distance between the receiving device and the needle is 10-20 cm;
and step 3: placing the precursor composite nanofiber membrane prepared in the step 2 in a muffle furnace, and carrying out pre-oxidation treatment in an air atmosphere to obtain a composite nano pre-oxidized silk membrane;
pre-oxidation process parameters: the temperature rising speed is 1-5 ℃/min, the temperature is gradually raised from room temperature to 200-300 ℃, and the temperature is kept for 1-2 h at the highest temperature;
and 4, step 4: placing the composite nano pre-oxidized fiber membrane obtained in the step 3 in a tubular furnace, and carrying out carbonization treatment in an inert gas atmosphere to obtain a flexible nano carbon fiber membrane;
the carbonization process parameters are as follows: the temperature rising speed is 5-10 ℃/min, the temperature is gradually raised to 1100-1400 ℃ from the room temperature, and the temperature is kept for 1-5 h at the highest calcining temperature.
2. The preparation method of the lignin-based flexible carbon nanofiber self-supporting electrode material as claimed in claim 1, wherein the companion spinning polymer is any one or a mixture of polyacrylonitrile, polyvinylpyrrolidone, polyvinylidene fluoride, polyvinyl alcohol, polypropylene glycol, polylactic acid, and polycaprolactone.
3. The preparation method of the lignin-based flexible carbon nanofiber self-supporting electrode material as claimed in claim 1, wherein the inert gas is nitrogen or argon.
4. The preparation method of the lignin-based flexible carbon nanofiber self-supporting electrode material as claimed in claim 1, wherein the fiber diameter of the flexible carbon nanofiber membrane prepared in the step 4 is 200-400 nm.
5. The preparation method of the lignin-based flexible carbon nanofiber self-supporting electrode material as claimed in claim 1, characterized by comprising the following steps:
step 1: dissolving polyacrylonitrile in a mixed solvent of dimethyl sulfoxide and N, N-dimethylformamide, stirring for 2 hours by a magnetic stirrer until the solution is clear, adding alkaline lignin, and continuously stirring for 7 hours, wherein the volume ratio of the dimethyl sulfoxide to the N, N-dimethylformamide is 6:4, and the mass ratio of the alkaline lignin to the polyacrylonitrile is 9: 1; uniformly mixing to prepare a precursor solution with the mass ratio concentration of 30% and the viscosity of 3Pa s;
step 2: preparing the precursor solution prepared in the step 1 into a precursor composite nanofiber membrane through an electrostatic spinning process; electrostatic spinning process parameters: the spinning temperature is 30 ℃, the relative humidity is 32 RH%, the spinning voltage is 25kV, the perfusion speed is 1.0mL/h, and the distance between the receiving device and the needle is 15 cm;
and step 3: placing the precursor composite nanofiber membrane prepared in the step 2 in a muffle furnace, and carrying out pre-oxidation treatment in air atmosphere, wherein the temperature is gradually increased from room temperature to 240 ℃, the temperature increase speed is 1 ℃/min, and the temperature is kept at the highest temperature for 2 hours, so as to prepare a composite nano pre-oxidized silk membrane;
and 4, step 4: and (3) placing the composite nano pre-oxidized fiber membrane obtained in the step (3) in a tubular furnace, calcining at high temperature in a nitrogen atmosphere for carbonization, gradually increasing the temperature from room temperature to 1200 ℃, increasing the temperature at a speed of 5 ℃/min, and preserving the heat at the highest calcining temperature for 1h to obtain the flexible nano carbon fiber membrane.
6. The preparation method of the lignin-based flexible carbon nanofiber self-supporting electrode material as claimed in claim 1, is characterized by comprising the following steps:
step 1: dissolving polyvinylidene fluoride in a mixed solvent of dimethyl sulfoxide and N, N-dimethylformamide, stirring for 5 hours by a magnetic stirrer until the solution is clarified, adding sodium lignosulfonate, and continuously stirring for 10 hours, wherein the volume ratio of the dimethyl sulfoxide to the N, N-dimethylformamide is 7:3, and the mass ratio of the sodium lignosulfonate to the polyvinylidene fluoride is 8: 2; uniformly mixing to prepare a uniform and stable precursor solution with the mass ratio concentration of 28% and the viscosity of 2.5 Pa.s;
and 2, step: preparing the precursor solution prepared in the step 1 into a precursor composite nanofiber membrane through an electrostatic spinning process; electrostatic spinning process parameters: the spinning temperature is 40 ℃, the relative humidity is 25 RH%, the spinning voltage is 15kV, the perfusion speed is 1.5mL/h, and the distance between the receiving device and the needle is 18 cm;
and step 3: placing the precursor composite nanofiber membrane prepared in the step 2 in a muffle furnace, and carrying out pre-oxidation treatment in air atmosphere, wherein the temperature is gradually increased from room temperature to 300 ℃, the temperature increase speed is 4 ℃/min, and the temperature is kept at the highest temperature for 1h, so as to prepare a composite nano pre-oxidized silk membrane;
and 4, step 4: and (4) placing the composite nano pre-oxidized fiber membrane obtained in the step (3) in a tube furnace, calcining at high temperature under argon atmosphere to obtain a flexible nano carbon fiber membrane, gradually increasing the temperature from room temperature to 1100 ℃, keeping the temperature at the temperature rising speed of 8 ℃/min, and keeping the temperature at the highest calcining temperature for 4 hours to obtain the flexible nano carbon fiber membrane, wherein the average diameter of nano carbon fibers is 328 nm.
7. The preparation method of the lignin-based flexible carbon nanofiber self-supporting electrode material as claimed in claim 1, is characterized by comprising the following steps:
step 1: dissolving polylactic acid in a mixed solvent of dimethyl sulfoxide and N, N-dimethylformamide, stirring for 4 hours by a magnetic stirrer until the solution is clear, adding hydroxylated alkali lignin, and continuously stirring for 9 hours, wherein the volume ratio of the dimethyl sulfoxide to the N, N-dimethylformamide is 9:1, and the mass ratio of the hydroxylated alkali lignin to the polylactic acid is 9: 1; uniformly mixing to prepare a uniform and stable precursor solution with the mass ratio concentration of 35% and the viscosity of 4Pa s;
step 2: preparing the precursor solution prepared in the step 1 into a precursor composite nanofiber membrane through an electrostatic spinning process; the electrostatic spinning process parameters are as follows: the spinning temperature is 37 ℃, the relative humidity is 28 RH%, the spinning voltage is 30kV, the perfusion speed is 0.8mL/h, and the distance between the receiving device and the needle is 20 cm;
and step 3: placing the precursor composite nanofiber membrane prepared in the step 2 in a muffle furnace, and carrying out pre-oxidation treatment under the air atmosphere, wherein the temperature is gradually increased from room temperature to 200 ℃, the temperature increase speed is 3 ℃/min, and the temperature is kept at the highest temperature for 1.5h, so as to prepare a composite nano pre-oxidized silk membrane;
and 4, step 4: and (3) placing the composite nano pre-oxidized fiber membrane obtained in the step (3) in a tubular furnace, calcining at high temperature in nitrogen atmosphere to obtain a flexible nano carbon fiber membrane, gradually increasing the temperature from room temperature to 1400 ℃, keeping the temperature at the highest calcining temperature for 5 hours, and obtaining the flexible nano carbon fiber membrane, wherein the average diameter of the nano carbon fiber is 200 nm.
8. The preparation method of the lignin-based flexible carbon nanofiber self-supporting electrode material as claimed in claim 1, is characterized by comprising the following steps:
step 1: dissolving polyvinyl alcohol in a mixed solvent of dimethyl sulfoxide and N, N-dimethylformamide, stirring for 7 hours by a magnetic stirrer until the solution is clear, adding ammonium alkali lignin, and continuously stirring for 11 hours, wherein the volume ratio of the dimethyl sulfoxide to the N, N-dimethylformamide is 8:2, and the mass ratio of the ammonium alkali lignin to the polyvinyl alcohol is 7: 3; uniformly mixing to prepare a uniform and stable precursor solution with the mass ratio concentration of 35% and the viscosity of 1Pa s;
step 2: preparing the precursor solution prepared in the step 1 into a precursor composite nanofiber membrane through an electrostatic spinning process; electrostatic spinning process parameters: the spinning temperature is 34 ℃, the relative humidity is 30 RH%, the spinning voltage is 28kV, the perfusion speed is 0.5mL/h, and the distance between the receiving device and the needle is 12 cm;
and 3, step 3: placing the precursor composite nanofiber membrane prepared in the step 2 in a muffle furnace, and performing pre-oxidation treatment under air atmosphere, wherein the temperature is gradually increased from room temperature to 260 ℃, the temperature increasing speed is 4 ℃/min, and the temperature is kept at the highest temperature for 1.2 hours to prepare a composite nano pre-oxidation wire membrane;
and 4, step 4: and (3) placing the composite nano pre-oxidized fiber membrane obtained in the step (3) in a tubular furnace, calcining at high temperature in nitrogen atmosphere to obtain a flexible nano carbon fiber membrane, gradually increasing the temperature from room temperature to 1300 ℃, keeping the temperature at the speed of 10 ℃/min, and keeping the temperature at the highest calcining temperature for 3 hours to obtain the flexible nano carbon fiber membrane, wherein the average diameter of the nano carbon fiber is 286 nm.
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