CN114212783A - Biomass energy storage material and preparation method thereof - Google Patents
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- 239000011232 storage material Substances 0.000 title claims abstract description 48
- 239000002028 Biomass Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 61
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- 239000000463 material Substances 0.000 claims abstract description 25
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- 238000000926 separation method Methods 0.000 claims description 7
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- 238000004519 manufacturing process Methods 0.000 claims description 2
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- 239000011159 matrix material Substances 0.000 abstract description 8
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- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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Abstract
The invention provides a biomass energy storage material and a preparation method thereof, and the biomass energy storage material comprises a graphene-like nitrogen-doped carbon material and a lignosulfonate material, wherein the graphene-like nitrogen-doped carbon material is of a lamellar structure, and the lignosulfonate material is loaded between graphene-like nitrogen-doped carbon material lamellae. The biomass energy storage material disclosed by the invention takes lignosulfonate as an energy storage matrix, takes a graphene-like nitrogen-doped carbon material as a conductive matrix, the lignosulfonate contains quinone/hydroquinone groups and has electrochemical oxidation and reduction characteristics, the graphene-like nitrogen-doped carbon material has high specific surface area and good conductivity, the graphene-like lamellar structure provides good contact for the lignosulfonate, nitrogen atoms are doped to provide the conductivity of the graphene-like material and promote electron transmission, and the biomass energy storage material obtains high energy storage density and energy storage efficiency due to the synergistic effect of the conductivity of the graphene-like nitrogen-doped carbon and the electrochemical oxidation and reduction of the lignosulfonate.
Description
Technical Field
The invention belongs to the field of energy storage materials, and particularly relates to a biomass energy storage material and a preparation method thereof.
Background
In recent years, the energy crisis has become increasingly severe due to the rapid increase in energy demand in modern life, and in order to cope with these problems, the development of high-performance energy storage devices has been rapidly progressing. In recent years, new interest has been generated in the development of biomass-based material energy storage devices.
Lignin, which originates from forests and is also a by-product of pulp industry processing and fuel production, is considered to be one of the most promising biopolymers. Lignin consists of amorphous, heterogeneous, highly cross-linked phenolic polymers. The main lignin separation processes used at present are the sulfite process, the sulfate process, and the like, in which lignosulfonate produced by the sulfite process has sulfonic acid groups, hydroxyl groups, carboxyl groups, and the like. In terms of energy storage, lignosulfonates contain a large number of quinone/hydroquinone groups that can be electrochemically oxidized and reduced in a two electron process. Since lignosulfonates are non-conductive, it is desirable that the conductive matrix be complexed with the lignosulfonate, carry charge to the quinone/hydroquinone redox sites of the lignosulfonate, and allow charge storage within the lignosulfonate. In this direction, conductive polymers, carbon nanotubes, etc. have been compounded with lignosulfonate as a conductive matrix, but these composite materials still have to be improved in conductivity, energy storage density and energy storage efficiency.
Disclosure of Invention
In view of the above, the present invention is directed to a biomass energy storage material and a preparation method thereof, in which lignosulfonate is used as an energy storage matrix, and a graphene-like nitrogen-doped carbon material is used as a conductive matrix, so as to improve energy storage density and energy storage efficiency of the energy storage material.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the utility model provides a biomass energy storage material, includes graphite alkene nitrogen-doped carbon material and lignosulfonate material, graphite alkene nitrogen-doped carbon material has the structure of similar graphite alkene, is lamellar structure, is a carbon material that has the nitrogen atom doping, and nitrogen exists with pyridine nitrogen, pyrrole nitrogen, lignosulfonate material load in graphite alkene nitrogen-doped carbon material lamella is between.
Further, the amount percentage of the nitrogen substance in the graphene-like nitrogen-doped carbon material is 3% -8%, and may be 3%, 4%, 5%, 6%, 7%, 8%, for example.
Further, the specific surface area of the graphene-like nitrogen-doped carbon material is 400-900m2G, may be, for example, 400m2/g、500m2/g、600m2/g、700m2/g、800m2/g、900m2The thickness is 0.1 to 3 μm, for example, 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, and the thickness is not too small or too large, which is not good for the stability of the material, and too large is not good for charge transfer and electron transport.
The preparation method of the biomass energy storage material comprises the following steps:
mixing lignosulfonate with water to form lignosulfonate solution, mixing the lignosulfonate solution with the graphene-like nitrogen-doped carbon material to obtain turbid liquid, and performing solid-liquid separation and drying on the turbid liquid to obtain the biomass energy storage material.
Further, the preparation method of the graphene-like nitrogen-doped carbon material comprises the following steps:
mixing melamine, polyvinylpyrrolidone and ammonium chloride, adding a solvent, ball-milling uniformly to obtain slurry, drying the slurry A to obtain a solid, and roasting the solid in an air atmosphere to obtain the graphene-like nitrogen-doped carbon material.
Further, the mass ratio of melamine to polyvinylpyrrolidone to ammonium chloride is 1-3: 1-2: 1-3, which can be, for example, 1:1:1, 1:2:1, 1:1:2, 2:1:1, 3:1:2 or 3:2: 1; preferably, the mass ratio of melamine, polyvinylpyrrolidone, ammonium chloride and solvent is 1:0.5-1, and may be, for example, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1: 1.
Further, the rotation speed of the ball milling is 200-.
Further, the lignosulfonate is sodium lignosulfonate.
Further, the mixing method of the lignosulfonate solution and the graphene-like nitrogen-doped carbon material is heating oscillation or ultrasonic dispersion, the solid-liquid separation method is suction filtration or centrifugal separation, and the drying method comprises rotary evaporation.
An energy storage device comprises an electrode, wherein the electrode comprises the biomass energy storage material or the biomass energy storage material prepared according to the preparation method, the electrode is a positive electrode or a negative electrode, and the energy storage device refers to an electrochemical device capable of storing and releasing electric energy, and comprises but is not limited to a super capacitor and the like.
Compared with the prior art, the biomass energy storage material and the preparation method have the following advantages:
the biomass energy storage material disclosed by the invention takes lignosulfonate as an energy storage matrix, takes a graphene-like nitrogen-doped carbon material as a conductive matrix, the lignosulfonate contains quinone/hydroquinone groups and has electrochemical oxidation and reduction characteristics, the graphene-like nitrogen-doped carbon material has high specific surface area and good conductivity, the graphene-like lamellar structure provides good contact for the lignosulfonate, nitrogen atoms are doped to provide the conductivity of the graphene-like material and promote electron transmission, and the biomass energy storage material obtains high energy storage density and energy storage efficiency due to the synergistic effect of the conductivity of the graphene-like nitrogen-doped carbon and the electrochemical oxidation and reduction of the lignosulfonate.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is an SEM image of a biomass energy storage material prepared in example 4 of the invention;
fig. 2 is an SEM image of a graphene-like nitrogen-doped carbon material in example 4 of the present invention;
fig. 3 is a nitrogen isothermal adsorption and desorption curve of a graphene-like nitrogen-doped material in embodiment 4 of the present invention;
fig. 4 is a spectrum of N1s of a graphene-like nitrogen-doped material in example 4 of the present invention;
FIG. 5 is a CV diagram of the graphene-like nitrogen-doped material and the biomass energy storage material at 100mV/s in example 4 of the present invention;
fig. 6 is a constant current charge and discharge curve of the graphene-like nitrogen-doped material and the biomass energy storage material in embodiment 4 of the present invention under a condition of 1A/g.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to the following examples and accompanying drawings.
Example 1
The preparation method of the biomass energy storage material in the embodiment comprises the following steps:
1) 1g of melamine, 0.1g of polyvinylpyrrolidone, 2g of ammonium chloride and 2g of water were mixed, and the mixture was put into a mortar and manually ground for 0.5 hour to obtain slurry A. And (3) putting the A into a rotary evaporator for rotary evaporation, setting the rotating speed to be 40r/min and the temperature to be 40 ℃, and evaporating for 36 hours to obtain a solid B. Putting the solid B into a porcelain boat, putting the porcelain boat into a muffle furnace, heating to 900 ℃ at a heating rate of 5 ℃/min, and keeping for 2 hours to obtain a graphene-like nitrogen-doped carbon material, wherein the nitrogen content of the graphene-like nitrogen-doped carbon material is 1%; the specific surface area of the graphene-like nitrogen-doped carbon material is 326m2(ii)/g; the thickness of the graphene-like nitrogen-doped carbon material sheet layer is 2.3 mu m.
2) Dissolving lignosulfonate in deionized water to prepare 100mL of 5mg/mL lignosulfonate solution, and adding 80mg of graphene nitrogen-doped carbon material into the solution to obtain a suspension. Heating the suspension to 50 ℃, stirring for 50 minutes, carrying out ultrasound in an ultrasonic instrument for 5 minutes, carrying out suction filtration on the suspension to obtain a solid, and drying in a forced air drying oven for 8 hours to obtain the graphene-like nitrogen-doped carbon and lignosulfonate composite material, wherein the material is the biomass energy storage material.
Example 2
The preparation method of the biomass energy storage material in the embodiment comprises the following steps:
1) mixing 1g of melamine, 2g of polyvinylpyrrolidone, 1g of ammonium chloride and 1.5g of water, placing the mixture in a ball mill, sealing, and carrying out ball milling at the ball milling speed of 200r/min for 1 hour to obtain slurry A. And (3) putting the A into a rotary evaporator for rotary evaporation, setting the rotating speed at 70r/min and the temperature at 60 ℃, and evaporating for 18 hours to obtain a solid B. Putting the solid B into a porcelain boat, putting the porcelain boat into a muffle furnace, heating to 550 ℃ at the heating rate of 5 ℃/min, and keeping for 5 hours to obtain the graphene-like nitrogen dopingA carbon material, wherein the nitrogen proportion in the graphene-like nitrogen-doped carbon material is 3.6%; the specific surface area of the graphene-like nitrogen-doped carbon material is 308m2(ii)/g; the thickness of the graphene-like nitrogen-doped carbon material sheet layer is 1.1 mu m.
2) Dissolving lignosulfonate in deionized water to prepare 100mL of 4mg/mL lignosulfonate solution, and adding 40mg of graphene nitrogen-doped carbon material into the solution to obtain a suspension. Heating the suspension to 50 ℃, stirring for 50 minutes, performing ultrasound in an ultrasonic instrument for 15 minutes, performing suction filtration on the suspension to obtain a solid, and drying in a drying oven for 12 hours to obtain the graphene-like nitrogen-doped carbon and lignosulfonate composite material, wherein the material is the biomass energy storage material.
Example 3
The preparation method of the biomass energy storage material in the embodiment comprises the following steps:
1) mixing 1g of melamine, 2g of polyvinylpyrrolidone, 2g of ammonium chloride and 1g of water, placing the mixture in a ball mill, sealing, and carrying out ball milling for 2 hours at a ball milling speed of 200r/min to obtain slurry A. And (3) putting the A into a rotary evaporator for rotary evaporation, setting the rotating speed at 70r/min and the temperature at 60 ℃, and evaporating for 18 hours to obtain a solid B. Putting the solid B into a porcelain boat, putting the porcelain boat into a muffle furnace, heating to 650 ℃ at a heating rate of 5 ℃/min, and keeping for 5 hours to obtain a graphene-like nitrogen-doped carbon material, wherein the nitrogen content of the graphene-like nitrogen-doped carbon material is 4%; the specific surface area of the graphene-like nitrogen-doped carbon material is 455m2(ii)/g; the thickness of the graphene-like nitrogen-doped carbon material sheet layer is 2.9 mu m.
2) Dissolving lignosulfonate in deionized water to prepare 100mL of 4mg/mL lignosulfonate solution, and adding 30mg of graphene-like nitrogen-doped carbon material into the solution to obtain a suspension. Heating the suspension to 50 ℃, stirring for 50 minutes, performing ultrasound in an ultrasonic instrument for 15 minutes, performing suction filtration on the suspension to obtain a solid, and drying in a drying oven for 12 hours to obtain the graphene-like nitrogen-doped carbon and lignosulfonate composite material, wherein the material is the biomass energy storage material.
Example 4
The preparation method of the biomass energy storage material in the embodiment comprises the following steps:
1) 1g of melamine, 1g of polyvinylpyrrolidone, 1g of ammonium chloride and 1.5g of water are mixed, placed in a ball mill, sealed, and subjected to ball milling at the speed of 200r/min for 1 hour to obtain slurry A. And (3) putting the A into a rotary evaporator for rotary evaporation, setting the rotating speed at 70r/min and the temperature at 60 ℃, and evaporating for 18 hours to obtain a solid B. Putting the solid B into a porcelain boat, putting the porcelain boat into a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, and keeping for 5 hours to obtain a graphene-like nitrogen-doped carbon material, wherein the nitrogen content of the graphene-like nitrogen-doped carbon material is 3%; the specific surface area of the graphene-like nitrogen-doped carbon material is 411m2(ii)/g; the thickness of the graphene-like nitrogen-doped carbon material sheet layer is 0.1 mu m.
2) Dissolving lignosulfonate in deionized water to prepare 100mL of 4mg/mL lignosulfonate solution, and adding 40mg of graphene nitrogen-doped carbon material into the solution to obtain a suspension. Heating the suspension to 50 ℃, stirring for 50 minutes, performing ultrasound in an ultrasonic instrument for 15 minutes, performing suction filtration on the suspension to obtain a solid, and drying in a drying oven for 12 hours to obtain the graphene-like nitrogen-doped carbon and lignosulfonate composite material, wherein the material is the biomass energy storage material.
From fig. 2, it can be seen that the graphene-like nitrogen-doped carbon material has a lamellar structure. As can be seen from fig. 1, the graphene-like nitrogen-doped carbon and lignosulfonate compounded biomass energy storage material retains a lamellar structure, and the thickness of the lamellar structure is increased.
As can be seen from FIG. 3, the specific surface area of the nitrogen-doped carbon material similar to graphene is 411m2/g。
As can be seen from fig. 4, 3 peaks of the high-resolution N1s spectral decomposition of the graphene-like nitrogen-doped carbon material and the biomass energy storage material correspond to pyridine nitrogen, pyrrole nitrogen and quaternary nitrogen, respectively.
Electrochemical test Using CHI 760D electrochemical workstation, a conventional three-electrode configuration was used, i.e., working electrode, counter electrode, reference electrode, platinum as counter electrode, and Saturated Calomel Electrode (SCE)) As a reference electrode. At 1mol/L H2SO4The method is carried out in an electrolyte, and Cyclic Voltammetry (CV) tests are carried out under a voltage window of 0-0.8V (vs. SCE), and the scanning rates are 1, 10, 20, 50 and 100mV/s respectively. Charging and Discharging (GCD) are also carried out in a voltage window of 0-0.8V (vs. SCE), and the charging and discharging multiplying power is 1, 2, 5, 10 and 20A/g respectively.
As can be seen from fig. 5, the CV curve of the graphene-like nitrogen-doped carbon material exhibits a rectangle with a distinct hump, which is formed by the double electric layer of nitrogen-doped carbon and the pseudocapacitance; two pairs of obvious reversible redox peaks appear on a CV curve of the biomass energy storage material, which indicates that a sample is triggered by a quinone/hydroquinone group of lignosulfonate and a pseudo-capacitor of a graphene-like nitrogen-doped carbon material together in the energy storage process.
The specific capacitance of the graphene-like nitrogen-doped carbon material and the biomass energy storage material at 1A/g is 212F/g and 545F/g respectively, which can be calculated from the charge-discharge curve of FIG. 6, and shows that the electrochemical performance of the biomass energy storage material is remarkably improved.
Comparative example 1
The preparation method of the biomass energy storage material in the comparative example comprises the following steps:
1) putting 1g of melamine into a porcelain boat, putting the porcelain boat into a tube furnace, wherein the reaction atmosphere is nitrogen (the purity is 99.9%), heating to 650 ℃ at the heating rate of 5 ℃/min, and keeping for 4 hours to obtain a nitrogen-doped carbon material, wherein the nitrogen content in the nitrogen-doped carbon material is 0.9%; the specific surface area of the nitrogen-doped carbon material is 118m2/g。
2) Dissolving lignosulfonate in a mixed solution of acetone and water (acetone accounts for 70% of the volume of the mixed solution), preparing 100mL of 4mg/mL KL solution, and adding 40mg of nitrogen-doped carbon material into the solution to obtain a suspension. Heating the suspension to 50 ℃, stirring for 50 minutes, performing ultrasound in an ultrasonic instrument for 15 minutes, performing suction filtration on the suspension to obtain a solid, and drying in a drying oven for 12 hours to obtain a nitrogen-doped carbon and lignosulfonate composite material, wherein the material is the biomass energy storage material.
Comparative example 2
The preparation method of the biomass energy storage material in the comparative example comprises the following steps:
1) uniformly mixing 5g of lignin and 2g of potassium hydroxide powder, placing the mixture into a porcelain boat, placing the porcelain boat into a tubular furnace, wherein the reaction atmosphere is nitrogen (the purity is 99.9%), heating to 850 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 4 hours, grinding the obtained solid into powder, washing the powder to be neutral by using dilute hydrochloric acid and deionized water, and drying in a 60 ℃ blast oven to obtain a porous carbon material, wherein the specific surface area of the porous carbon material is 228m2(ii)/g; the total pore volume of the porous carbon material is 1.13cm3(ii)/g; the porous material has a pore structure of macropores and mesopores, and the sum of the volumes of the macropores and the mesopores accounts for 72.67% of the total pore volume of the hierarchical porous material.
2) Dissolving lignosulfonate in deionized water to obtain 100mL of 4mg/mL lignosulfonate solution, and adding 40mg of porous carbon material into the solution to obtain a suspension. Heating the suspension to 50 ℃, stirring for 50 minutes, performing ultrasound in an ultrasonic instrument for 15 minutes, performing suction filtration on the suspension to obtain a solid, and drying in a drying oven for 12 hours to obtain a porous carbon and lignosulfonate composite material, wherein the material is the biomass energy storage material.
Comparative example 3
The preparation method of the biomass energy storage material in the comparative example comprises the following steps:
1) mixing 5g of commercial activated carbon material with 100mL of dilute nitric acid with the volume fraction of 40%, refluxing for 4 hours at 80 ℃, centrifugally washing, then washing to neutrality by using deionized water, and then drying in a blast oven at 60 ℃ to obtain the activated carbon material, wherein the specific surface area of the activated carbon material is 79.61m2/g。
2) Dissolving lignosulfonate in deionized water to obtain 100mL lignosulfonate solution of 4mg/mL, and adding 40mg activated carbon material to the solution to obtain suspension. Heating the suspension to 50 ℃, stirring for 50 minutes, performing ultrasound in an ultrasonic instrument for 15 minutes, performing suction filtration on the suspension to obtain a solid, and drying in a drying oven for 12 hours to obtain the material compounded by the activated carbon and the lignosulfonate, wherein the material is the biomass energy storage material.
Electrochemical performance tests were performed on the biomass energy storage materials of examples 1 to 3 and comparative examples 1 to 3 in the same manner as in example 4, and the results at a charge/discharge rate of 1A/g are shown in Table 1.
TABLE 1 electrochemical Performance test results
| Group of | Specific capacitance |
| Example 1 | 282F/g |
| Example 2 | 301F/g |
| Example 3 | 393F/g |
| Example 4 | 545F/g |
| Comparative example 1 | 333F/g |
| Comparative example 2 | 295F/g |
| Comparative example 3 | 207F/g |
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A biomass energy storage material is characterized in that: the graphene-like nitrogen-doped carbon material is of a lamellar structure, and the lignosulfonate material is loaded between graphene-like nitrogen-doped carbon material lamellae.
2. The biomass energy storage material of claim 1, wherein: the amount percentage of nitrogen substances in the graphene-like nitrogen-doped carbon material is 3% -8%.
3. The biomass energy storage material of claim 1, wherein: the specific surface area of the graphene-like nitrogen-doped carbon material is 400-900m2A thickness of 0.1 to 3 μm per gram.
4. The preparation method of the biomass energy storage material according to any one of claims 1 to 3, characterized by comprising the following steps:
mixing lignosulfonate with water to form lignosulfonate solution, mixing the lignosulfonate solution with the graphene-like nitrogen-doped carbon material to obtain turbid liquid, and performing solid-liquid separation and drying on the turbid liquid to obtain the biomass energy storage material.
5. The preparation method of claim 4, wherein the preparation method of the graphene-like nitrogen-doped carbon material comprises the following steps:
mixing melamine, polyvinylpyrrolidone and ammonium chloride, adding a solvent, ball-milling uniformly to obtain slurry, drying the slurry A to obtain a solid, and roasting the solid in an air atmosphere to obtain the graphene-like nitrogen-doped carbon material.
6. The method of claim 5, wherein: the mass ratio of melamine to polyvinylpyrrolidone to ammonium chloride is 1-3: 1-2: 1-3; preferably, the mass sum of melamine, polyvinylpyrrolidone and ammonium chloride to the solvent is 1: 0.5-1.
7. The method of claim 5, wherein: the rotation speed of ball milling is 200-.
8. The method of claim 5, wherein: the lignosulfonate is sodium lignosulfonate.
9. The method of claim 4, wherein: the mixing method of the lignosulfonate solution and the graphene-like nitrogen-doped carbon material is heating oscillation or ultrasonic dispersion, the solid-liquid separation method is suction filtration or centrifugal separation, and the drying method comprises rotary evaporation.
10. An energy storage device comprising an electrode comprising the biomass energy storage material according to any one of claims 1 to 3 or the biomass energy storage material produced by the production method according to any one of claims 4 to 9.
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