CN112707386A - Preparation method and application of waste biomass derived graphene material - Google Patents
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Abstract
The invention discloses a preparation method of a waste biomass derived graphene material, which comprises the following steps: washing biomass waste, drying for the first time, crushing and sieving to obtain biomass waste powder, uniformly mixing the biomass waste powder with a catalyst solution, and drying for the second time to obtain a precursor mixture; carbonizing the obtained precursor mixture at low temperature in an inert atmosphere; transferring the precursor mixture after low-temperature carbonization treatment to a sintering furnace, and sintering in an argon atmosphere or under a low-vacuum condition; and sequentially washing with an acidic solution and water to remove the catalyst, filtering and drying to obtain the waste biomass-derived graphene material. The method takes the waste biomass as the raw material, prepares the graphene massive sample by a simple medium-low temperature catalytic activation method, has the advantages of rich raw materials, low price, low sintering temperature, short sintering time, low energy consumption and the like, and meets the environmental requirements.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage battery materials, and particularly relates to a preparation method and application of a waste biomass-derived graphene material.
Background
Graphene has great application potential in the field of electrochemical energy storage and conversion as a two-dimensional material with a plurality of excellent properties. At present, the method for preparing graphene by taking graphite as a raw material mainly comprises a mechanical stripping method and an oxidation-reduction method. The mechanical stripping method is simple to operate, and can obtain high-quality single-layer or double-layer graphene, but the method is time-consuming and labor-consuming, low in controllability degree and low in yield, and is not suitable for large-scale production. In the process of preparing graphene by the oxidation-reduction method, a large amount of chemical reagents with high toxicity, strong oxidizing property and strong reducing property are consumed, the environmental pollution is serious, and the graphene obtained by oxidation-reduction has low conductivity, so that the application of the graphene is limited. Common graphene preparation methods include a chemical vapor deposition method and an epitaxial growth method using an organic carbon source and silane as raw materials. The vapor deposition method can prepare high-quality and large-area graphene, but has high cost, complex process and harsh reaction conditions. The preparation of graphene by an epitaxial growth method requires high temperature and high vacuum environment, has high requirements on experimental equipment, and is not suitable for large-scale preparation of large-area graphene. Therefore, the search for an alternative green raw material and a green synthetic route is one of the exits of graphene industrial scale.
The biomass resources in China are wide and various, and the treatment mode of the rich agriculture and forestry waste biomass in China is mainly incineration and direct landfill, so that the environmental pollution and the great waste of resources are caused. With the increasing shortage of fossil energy and the deep excavation of the application potential of graphene in the field of energy storage, the preparation and utilization of biomass graphene are widely concerned by researchers. The biomass carbon is considered to be a non-graphitizable carbon, so that the biomass carbon needs to be subjected to high-temperature and high-pressure treatment in the preparation process to be converted into graphene. For example, patent CN105060288A discloses a method for preparing graphene by using biomass waste as a raw material, and the graphitization temperature of the method is as high as 2400-. Patent CN106744830A discloses a method for preparing three-dimensional porous/bi-micro lamellar graphene by using biomass as a carbon source, which has the advantages of low cost and low sintering temperature, but the problem of large amount of waste liquid generated by multiple cleaning treatment steps exists in the preparation process.
Therefore, the research and development of an efficient, low-cost and environment-friendly method for massively preparing a high-quality biomass graphene material is a problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a preparation method and application of a waste biomass-derived graphene material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a waste biomass-derived graphene material comprises the following steps:
(1) pretreatment of biomass waste: washing biomass waste, drying for the first time, crushing and sieving to obtain biomass waste powder, uniformly mixing the biomass waste powder with a catalyst solution, and drying for the second time to obtain a precursor mixture;
(2) low-temperature carbonization treatment: carbonizing the obtained precursor mixture at low temperature in an inert atmosphere;
(3) high-temperature activation graphitization treatment: the precursor mixture is transferred to a sintering furnace after low-temperature carbonization treatment in argon atmosphere or 3.5 multiplied by 10-3-4.6×10-3Sintering under the condition of low vacuum of Mpa;
(4) removing the catalyst by acid washing: and (4) sequentially washing with an acidic solution and water to remove the catalyst in the material obtained in the step (3), filtering and drying to obtain the waste biomass-derived graphene material.
Further, the biomass waste in the step (1) is one or a mixture of a plurality of passion fruit shells, mangosteen shells, coconut shells, walnut shells, shaddock peels, bagasse and straws, and the particle size of the biomass waste powder is 200-500 meshes.
The beneficial effects of the further technical scheme are that: the biomass waste is efficiently utilized, waste is changed into valuable, and the uniform particle size distribution of the biomass waste powder and the derived carbon material is ensured.
Further, in the step (1), the catalyst is one or a mixture of more of ferric nitrate, ferric chloride, nickel nitrate, nickel chloride, cobalt nitrate, cobalt chloride, manganese nitrate, manganese chloride, copper nitrate, copper chloride, zinc nitrate, zinc chloride, potassium hydroxide and potassium carbonate, the mass ratio of the catalyst to the biomass waste powder is 1 (1-5), and the concentration of the catalyst solution is 0.6-2 mol/L.
The beneficial effects of the further technical scheme are that: the cheap catalyst with low content is beneficial to reducing the production cost.
Further, the first drying in the step (1) comprises: drying by blowing at 50-70 deg.C until the water content is 1-5%; the second drying comprises the following steps: vacuum drying at 90-120 deg.C, and oven drying to water content of 0.02% -0.05%.
The beneficial effects of the further technical scheme are that: drying at low temperature to volatilize most of water, and then drying in vacuum to ensure that the material is not oxidized.
Further, the low-temperature carbonization temperature in the step (2) is 350-.
The beneficial effects of the further technical scheme are that: the biomass material is carbonized and pretreated at low temperature for a short time, so that the production cost is reduced, and meanwhile, the phenomenon that the carbonized material is completely converted into graphene in the later sintering is ensured.
Further, the inert atmosphere in the step (2) is argon or nitrogen.
The beneficial effects of the further technical scheme are that: the low-cost inert gas can realize the complete carbonization of the material and inhibit the oxidation of the material, thereby ensuring the high yield of the prepared graphene material.
Further, in the step (3), the temperature of the sintering is rapidly raised to 1200 ℃ at a heating rate of 50-300 ℃/min, the heat preservation time is 5-20min, the sintering pressure is 30-80MPa, and the applied current is 3000A-.
The beneficial effects of the further technical scheme are that: and (3) quickly raising the temperature, instantly activating and catalyzing, tabletting and sintering to generate the layered graphene material.
Further, in the step (4), the acid solution is one or a mixture of more of a hydrochloric acid solution, a sulfuric acid solution and a nitric acid solution, the concentration of the acid solution is 1.5-4.5mol/L, and the pH value of the water washing is 6.5-7.5.
The beneficial effects of the further technical scheme are that: and washing off redundant transition metal ions and acid radical anions so as to avoid reducing the energy storage performance of the material.
Further, the step (4) is carried out until the water content is 0.02-0.05%.
Further, the waste biomass-derived graphene material is composed of multilayer graphene.
The invention also provides application of the waste biomass-derived graphene material in preparation of negative electrode materials of alkaline ion batteries and mixed ion capacitors.
The invention has the beneficial effects that:
(1) according to the method, waste biomass is used as a raw material, and a graphene massive sample is prepared by a simple medium-low temperature catalytic activation method, so that waste is turned into wealth. The invention has the advantages of rich raw materials, low price, low sintering temperature, short sintering time, low energy consumption and the like, and meets the environmental requirements.
(2) The preparation method has the advantages of simple preparation process, short flow, low preparation cost, controllable product quality, high yield and easy realization of large-scale production.
(3) The biomass-derived graphene material prepared by the invention is suitable for the fields of alkaline ion batteries, mixed ion capacitors and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the embodiments will be briefly described below.
Fig. 1 is an XRD pattern of the biomass graphene material obtained in example 1 of the present invention;
fig. 2 is a raman spectrum of the biomass graphene material obtained in example 1 of the present invention;
FIG. 3 is a graph showing the performance of electrochemical cycles obtained in example 5 of the present invention and comparative examples 1 and 2;
FIG. 4 is a graph of electrochemical rate performance obtained in example 6 of the present invention;
fig. 5 is a graph of electrochemical cycle performance of biomass hard carbon used as a negative electrode of a potassium ion battery in comparative example 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Example 1
(1) Washing passion fruit shells with water, carrying out forced air drying treatment at the temperature of 50 ℃, drying until the water content is 5%, crushing, sieving with a 200-mesh sieve to obtain passion fruit shell powder, uniformly mixing the passion fruit shell powder and a nickel chloride solution, wherein the mass ratio of the passion fruit shell powder to the nickel chloride solution is 1:1, the concentration of the nickel chloride solution is 1mol/L, carrying out vacuum drying treatment at the temperature of 90 ℃, and drying until the water content is 0.05% to obtain a precursor mixture;
(2) placing the obtained precursor mixture in a tubular furnace for low-temperature carbonization treatment under the argon atmosphere, heating to 450 ℃ at the speed of 5 ℃/min, and preserving heat for 3 h;
(3) transferring the precursor mixture after low-temperature carbonization treatment to a sintering furnace, sintering in argon atmosphere, rapidly heating to 800 ℃ at a heating rate of 100 ℃/min, keeping the temperature for 10min, sintering at the pressure of 30MPa, and applying an external current of 800A;
(4) and (3) washing the catalyst in the material obtained in the step (3) by using a 1M hydrochloric acid solution and deionized water sequentially and using an ultrasonic cleaning machine, washing the material by using water until the pH value of the solution in the ultrasonic cleaning machine is 6.5, filtering and drying the material until the water content is 0.05%, and thus obtaining the waste biomass-derived graphene material.
(5) The microstructure of the resulting waste biomass-derived graphene material was analyzed. The XRD spectrum in figure 1 shows that the crystal form of the graphene material is good, and figure 2 shows the Raman spectrum of the material at 2700cm-1A graphene 2D peak appears, which indicates that a graphene structure exists in the material.
Example 2
(1) Washing bagasse with water, drying by blowing at 60 ℃, drying until the water content is 1%, crushing, sieving with a 200-mesh sieve to obtain bagasse powder, uniformly mixing the bagasse powder and a copper acetate solution, wherein the mass ratio of the bagasse powder to the copper acetate is 5:1, the concentration of the copper acetate solution is 0.7mol/L, drying under vacuum at 100 ℃ until the water content is 0.05%, and obtaining a precursor mixture;
(2) placing the obtained precursor mixture in a tube furnace for low-temperature carbonization treatment under the argon atmosphere, heating to 600 ℃ at a speed of 10 ℃/min, and preserving heat for 2 h;
(3) transferring the precursor mixture after low-temperature carbonization treatment to a sintering furnace, sintering in argon atmosphere, rapidly heating to 850 ℃ at a heating rate of 100 ℃/min, keeping the temperature for 12min, sintering at a pressure of 50MPa, and applying an external current of 2000A;
(4) and (3) washing the catalyst in the material obtained in the step (3) by using a 3M hydrochloric acid solution and deionized water sequentially and using an ultrasonic cleaning machine, washing the material by using water until the pH value of the solution in the ultrasonic cleaning machine is 7, filtering and drying the material until the water content is 0.05%, and thus obtaining the waste biomass-derived graphene material.
Example 3
(1) Washing coconut shells with water, carrying out forced air drying treatment at the temperature of 70 ℃, drying until the water content is 1%, crushing, sieving with a 100-mesh sieve to obtain coconut shell powder, uniformly mixing the coconut shells with a mixed solution of ferric nitrate and potassium hydroxide, wherein the mass ratio of the coconut shells to the mixed solution of the ferric nitrate and the potassium hydroxide is 2:1, the concentration of the mixed solution of the ferric nitrate and the potassium hydroxide is 1.5mol/L, carrying out vacuum drying treatment at the temperature of 120 ℃, and drying until the water content is 0.05%, thus obtaining a precursor mixture;
(2) placing the obtained precursor mixture in a tube furnace for low-temperature carbonization treatment under the argon atmosphere, heating to 400 ℃ at the speed of 5 ℃/min, and preserving heat for 4 h;
(3) transferring the precursor mixture after low-temperature carbonization treatment to a sintering furnace, sintering in an argon atmosphere, rapidly heating to 900 ℃ at a heating rate of 150 ℃/min, keeping the temperature for 15min, sintering at 80MPa, and applying an external current of 3000A;
(4) and (3) washing with 1M hydrochloric acid solution and deionized water by using an ultrasonic cleaning machine in sequence to remove the catalyst in the material obtained in the step (3), washing with water until the pH value of the solution in the ultrasonic cleaning machine is 7.5, filtering, and drying until the water content is 0.03%, thereby obtaining the waste biomass-derived graphene material.
Example 4
(1) Washing the mangosteen shell with water, carrying out air blast drying treatment at the temperature of 70 ℃, drying until the water content is 1%, crushing, sieving with a 200-mesh sieve to obtain mangosteen shell powder, uniformly mixing the mangosteen shell with a mixed solution of zinc chloride and potassium carbonate, wherein the mass ratio of the mangosteen shell powder to the mixture of the zinc chloride and the potassium carbonate is 3:1, the concentration of the mixed solution of the zinc chloride and the potassium carbonate is 1.2mol/L, carrying out vacuum drying treatment at the temperature of 120 ℃, and drying until the water content is 0.05% to obtain a precursor mixture;
(2) placing the obtained precursor mixture in a tube furnace for low-temperature carbonization treatment under the argon atmosphere, heating to 500 ℃ at the speed of 5 ℃/min, and preserving heat for 3 h;
(3) transferring the precursor mixture after low-temperature carbonization treatment to a sintering furnace, sintering in an argon atmosphere, rapidly heating to 1000 ℃ at a heating rate of 100 ℃/min, keeping the temperature for 10min, sintering at 80MPa, and applying an external current of 3000A;
(4) and (3) washing with 1M hydrochloric acid solution and deionized water by using an ultrasonic cleaning machine in sequence to remove the catalyst in the material obtained in the step (3), washing with water until the pH value of the solution in the ultrasonic cleaning machine is 7, filtering, and drying until the water content is 0.02%, thereby obtaining the waste biomass-derived graphene material.
Example 5
The waste biomass-derived graphene material prepared in example 1 was used as a negative electrode of a potassium ion battery, and a cycle performance test was performed at a voltage range of 0.01 to 2.5V. Under the test condition that the current density is 20mA/g, as shown in figure 3, the initial capacity is 254mAh/g, and after 30 cycles, the capacity is kept to be 247 mAh/g.
Example 6
The waste biomass-derived graphene material prepared in example 1 was used as a negative electrode of a potassium ion battery, and a rate performance test was performed with a voltage range of 0.01 to 2.5V. As shown in FIG. 4, the reversible capacities were 259, 250, 238, 220, and 146mAh/g at current densities of 20, 50, 100, 200, and 500mA/g, respectively.
Example 7
The waste biomass-derived graphene material prepared in example 2 was used as an additive for a silicon/hard carbon negative electrode of a lithium ion battery, with an additive content of 5 wt%, and electrochemical performance was tested. Under the current, the reversible capacity of the first loop is 818mAh/g, and the first coulombic efficiency is 80%.
Example 8
The waste biomass-derived graphene material prepared in example 1 was used as a negative electrode of a lithium ion battery, and an electrochemical performance test was performed with a voltage range of 0.01 to 2.5V. Under the test condition that the current density is 20mA/g, as shown in the figure, the initial reversible capacity is 270mAh/g, the reversible capacity is 127mAh/g after 50 cycles of circulation, and the circulation performance needs to be improved.
Example 9
The waste biomass-derived graphene material prepared in example 1 was used as a negative electrode of a sodium ion battery, and an electrochemical performance test was performed with a voltage range of 0.01 to 2.5V. Under the test condition that the current density is 20mA/g, as shown in the figure, the first reversible capacity is 135mAh/g, and the capacity is still maintained at 115mAh/g after 50 cycles.
Comparative example 1
Washing passion fruit shells with water, carrying out forced air drying treatment at the temperature of 50 ℃, drying until the water content is 1%, crushing, sieving with a 200-mesh sieve to obtain passion fruit shell powder, uniformly mixing the passion fruit shell powder with a nickel chloride solution 1, wherein the mass ratio of the passion fruit shell powder to the nickel chloride is 1:1, the concentration of the nickel chloride solution is 1mol/L, carrying out vacuum drying treatment at the temperature of 90 ℃, and drying until the water content is 0.05% to obtain a precursor mixture;
(2) placing the obtained precursor mixture in a tubular furnace for low-temperature carbonization treatment under the argon atmosphere, heating to 450 ℃ at the speed of 5 ℃/min, and preserving heat for 3 h;
(3) transferring the precursor mixture after low-temperature carbonization treatment to a sintering furnace, sintering in an argon atmosphere, rapidly heating to 900 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 2h, sintering at 30MPa, and applying an external current of 800A;
(4) and (3) washing the catalyst in the material obtained in the step (3) by using a 1M hydrochloric acid solution and deionized water sequentially and using an ultrasonic cleaning machine, washing the material by using water until the pH value of the solution in the ultrasonic cleaning machine is 6.5, filtering and drying the material until the water content is 0.05%, and thus obtaining the waste biomass-derived hard carbon material.
Example 1 a graphene material was obtained, whereas comparative example 1 prepared a hard carbon material.
Comparative example 2
This example used the biomass hard carbon material prepared in comparative example 1 as a negative electrode of a potassium ion battery and was subjected to electrochemical performance test at a voltage ranging from 0.01 to 2.5V. Under the test conditions at a current density of 20mA/g, as shown in FIG. 5. The reversible capacity in the first week is only 149mAh/g, and the capacity after 50 weeks of circulation is kept 147 mAh/g.
The embodiments described above are only a part of the embodiments of the present invention, and not all of them. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. A preparation method of a waste biomass-derived graphene material is characterized by comprising the following steps:
(1) pretreatment of biomass waste: washing biomass waste, drying for the first time, crushing and sieving to obtain biomass waste powder, uniformly mixing the biomass waste powder with a catalyst solution, and drying for the second time to obtain a precursor mixture;
(2) low-temperature carbonization treatment: carbonizing the obtained precursor mixture at low temperature in an inert atmosphere;
(3) high-temperature activation graphitization treatment: the precursor mixture is transferred to a sintering furnace after low-temperature carbonization treatment in argon atmosphere or 3.5 multiplied by 10-3-4.6×10-3Sintering under the condition of low vacuum of Mpa;
(4) removing the catalyst by acid washing: and (4) sequentially washing with an acidic solution and water to remove the catalyst in the material obtained in the step (3), filtering and drying to obtain the waste biomass-derived graphene material.
2. The method for preparing the waste biomass-derived graphene material according to claim 1, wherein the method comprises the following steps: the biomass waste in the step (1) is one or a mixture of a plurality of passion fruit shells, mangosteen shells, coconut shells, walnut shells, shaddock peels, bagasse and straws, and the particle size of the biomass waste powder is 200-mesh and 500-mesh.
3. The method for preparing the waste biomass-derived graphene material according to claim 1, wherein the method comprises the following steps: the catalyst in the step (1) is one or a mixture of more of ferric nitrate, ferric chloride, nickel nitrate, nickel chloride, cobalt nitrate, cobalt chloride, manganese nitrate, manganese chloride, copper nitrate, copper chloride, zinc nitrate, zinc chloride, potassium hydroxide and potassium carbonate, the mass ratio of the catalyst to the biomass waste powder is 1 (1-5), and the concentration of the catalyst solution is 0.6-2 mol/L.
4. The method for preparing the waste biomass-derived graphene material according to claim 1, wherein the method comprises the following steps: the first drying in the step (1) comprises the following steps: drying by blowing at 50-70 deg.C until the water content is 1% -5%; the second drying comprises the following steps: vacuum drying at 90-120 deg.C, and oven drying to water content of 0.02% -0.05%.
5. The method for preparing the waste biomass-derived graphene material according to claim 1, wherein the method comprises the following steps: the low-temperature carbonization temperature in the step (2) is 350-650 ℃, the temperature rising speed is 1-15 ℃/min, and the low-temperature carbonization time is 1-5 h.
6. The method for preparing the waste biomass-derived graphene material according to claim 1, wherein the method comprises the following steps: in the step (3), the temperature of the sintering is rapidly raised to 700-3000 ℃ at the temperature raising rate of 50-300 ℃/min, the heat preservation time is 5-20min, the sintering pressure is 30-80MPa, and the applied current is 800-3000A.
7. The method for preparing the waste biomass-derived graphene material according to claim 1, wherein the method comprises the following steps: the acid solution in the step (4) is one or a mixture of more of a hydrochloric acid solution, a sulfuric acid solution and a nitric acid solution, the concentration of the acid solution is 1.5-4.5mol/L, and the pH value of water washing is 6.5-7.5.
8. The method for preparing the waste biomass-derived graphene material according to claim 1, wherein the method comprises the following steps: and (4) drying until the water content is 0.02-0.05%.
9. The method for preparing the waste biomass-derived graphene material according to claim 1, wherein the method comprises the following steps: the waste biomass-derived graphene material is composed of multi-layer graphene.
10. Use of the waste biomass-derived graphene material of any one of claims 1 to 9 in the manufacture of negative electrode materials for alkaline ion batteries and mixed ion capacitors.
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Cited By (5)
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| CN113307254A (en) * | 2021-06-24 | 2021-08-27 | 武汉科技大学 | Method for preparing three-dimensional porous graphene sheet by using low-temperature double-salt compound and application |
| CN114014315A (en) * | 2021-10-22 | 2022-02-08 | 海南大学 | Molten salt chemical activation method for preparing macroporous graphitized biomass carbon |
| CN114590797A (en) * | 2022-03-01 | 2022-06-07 | 同济大学 | Biomass-based graphene material and preparation method thereof |
| CN114639809A (en) * | 2022-03-18 | 2022-06-17 | 上海电力大学 | Composite hard carbon negative electrode material, preparation method and application |
| CN117457902A (en) * | 2023-12-25 | 2024-01-26 | 宁波容百新能源科技股份有限公司 | Prussian blue positive electrode material, preparation method thereof and battery |
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| CN113307254A (en) * | 2021-06-24 | 2021-08-27 | 武汉科技大学 | Method for preparing three-dimensional porous graphene sheet by using low-temperature double-salt compound and application |
| CN114014315A (en) * | 2021-10-22 | 2022-02-08 | 海南大学 | Molten salt chemical activation method for preparing macroporous graphitized biomass carbon |
| CN114590797A (en) * | 2022-03-01 | 2022-06-07 | 同济大学 | Biomass-based graphene material and preparation method thereof |
| CN114590797B (en) * | 2022-03-01 | 2023-08-04 | 同济大学 | Biomass-based graphene material and preparation method thereof |
| CN114639809A (en) * | 2022-03-18 | 2022-06-17 | 上海电力大学 | Composite hard carbon negative electrode material, preparation method and application |
| CN114639809B (en) * | 2022-03-18 | 2023-10-10 | 上海电力大学 | Composite hard carbon negative electrode material, preparation method and application |
| CN117457902A (en) * | 2023-12-25 | 2024-01-26 | 宁波容百新能源科技股份有限公司 | Prussian blue positive electrode material, preparation method thereof and battery |
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