CN110981280B - Preparation method and application of reed biochar-based composite cathode material - Google Patents

Preparation method and application of reed biochar-based composite cathode material Download PDF

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CN110981280B
CN110981280B CN201911299166.7A CN201911299166A CN110981280B CN 110981280 B CN110981280 B CN 110981280B CN 201911299166 A CN201911299166 A CN 201911299166A CN 110981280 B CN110981280 B CN 110981280B
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reed
biochar
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polyaniline
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CN110981280A (en
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杨俏
关庆誉
高超
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Dalian University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
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Abstract

The invention discloses a preparation method and application of a reed biochar-based composite cathode material, and belongs to the technical field of electrode material preparation. The method of the invention selects reed as biochar raw material, and the reed after being defoliated, cleaned and dried is ground to obtain reed powder; putting the ground reed powder into a tubular furnace, and pyrolyzing at a certain heating rate for a certain heating time to obtain charcoal powder; and mixing the charcoal powder, polyaniline and polyethylene binder according to a mass ratio of 5:1:4, and putting the mixture into a tubular furnace for pyrolysis at a certain heating rate for a certain heating time to finally obtain the charcoal-based composite cathode material. The reed biochar-based composite cathode material prepared by the invention has good conductivity, water resistance and biocompatibility, and can be used as a cathode of a sediment microbial fuel cell.

Description

Preparation method and application of reed biochar-based composite cathode material
Technical Field
The invention relates to the technical field of electrode material preparation, in particular to a preparation method of a biochar-based composite cathode material taking reed as a raw material and application of the biochar-based composite cathode material in a sediment microbial fuel cell.
Background
The microbial fuel cell is a technology for converting chemical energy into electric energy, and the specific principle is that extracellular electrogenesis bacteria attached to and growing on the surface of an anode metabolize substrates and generate electrons, the electrons are transferred to the anode through the electrogenesis bacteria and migrate to a cathode through an external circuit, and the directional movement of the electrons is formed to form current. The microbial fuel cell can use organic matters in sewage as a substrate so as to realize the treatment of pollutants and the generation of electric energy at the same time. Different from the traditional sewage treatment mode, the microbial fuel cell can recycle the energy in the sewage.
The electrode characteristics of microbial fuel cells have a great influence on the electricity generating capacity, and therefore, new electrodes are often developed to improve the electricity generating performance. Biochar is a carbon-rich black solid substance formed by pyrolyzing biomass such as animals and plants under the condition of oxygen deficiency. The raw materials for preparing the biochar are very easy to obtain, so the cost is low. Biochar is commonly used for soil improvement to increase soil fertility. The carbon-rich porous characteristic of the biochar also makes the biochar possible to be a potential electrode material.
Disclosure of Invention
In order to achieve the purpose, the invention provides a preparation method and application of a reed biochar-based composite cathode material, so that an electrode material with good conductivity, water resistance and biocompatibility is obtained, and the electrode material can be used as a cathode of a sediment microbial fuel cell.
The invention adopts the following technical scheme:
a preparation method of a reed biochar-based composite cathode material comprises the following steps:
(1) and removing leaves of the collected reeds, cleaning, putting the reeds into a drying oven for drying, and grinding the dried reeds to obtain reed powder.
(2) Weighing reed powder, compacting in a mould, and placing the mould in a tubular furnace; then introducing nitrogen for 20min to exhaust oxygen in the tube furnace; then the temperature is raised to 100 ℃ and the temperature is kept constant for 20 min; and after the preheating is finished, the temperature is increased to 700 ℃, the constant temperature is kept for 2 hours at the temperature so that the reed powder is pyrolyzed, and finally, the reed powder sample is naturally cooled to the room temperature to obtain a black product.
(3) And (3) uniformly mixing and grinding the black product obtained after cooling in the step (2), and then sieving the mixture through a 100-mesh sieve to obtain the charcoal powder with the particle size of below 150 microns.
(4) Uniformly mixing the charcoal powder obtained in the step (3) with polyaniline and polyethylene binder according to the mass ratio of 5:1:4, putting the mixture into a mold, compacting, putting the mold into a tubular furnace, and introducing nitrogen to exhaust oxygen; and then, heating to 180-220 ℃, pyrolyzing for 1.5h, and finally naturally cooling to room temperature to obtain the biochar/polyaniline/polyethylene binder composite material.
The drying temperature in the step (1) is 75 ℃, and the drying time is more than 12 h.
The heating rate in the step (2) and the step (4) is 10 ℃/min.
The biochar/polyaniline/polyethylene binder composite material prepared by the method is applied to the cathode of the sediment microbial fuel cell: and (3) taking a platinum sheet electrode as an auxiliary electrode, taking an Ag/AgCl electrode as a reference electrode, taking the biochar/polyaniline/polyethylene binder composite material prepared by the method as a cathode, matching electrolyte, and assembling the sediment microbial fuel cell.
The invention has the beneficial effects that: the reed biochar-based composite cathode material prepared by the invention has good formability, electron transfer capacity and porous structure, and when the material is used as the cathode of a sediment microbial fuel cell, the power generation capacity of the SMFC can be effectively improved, the internal resistance of a system can be reduced, and good water resistance and biocompatibility are embodied, so the material is an electrode material with application potential.
Drawings
Fig. 1 is an SEM image of the biochar/polyaniline/polyethylene binder composite prepared in example 1.
Fig. 2 is an SEM image of the biochar/polyaniline/polyethylene binder composite prepared in the comparative example.
Fig. 3 is an EIS graph of the biochar/polyaniline/polyethylene binder composites prepared in example 1 and comparative example.
Fig. 4 shows the SMFC polarization curve change for the cathode run of the biochar/polyaniline/polyethylene binder composites prepared in example 1 and comparative example.
Fig. 5 shows the SMFC power density curve change for the cathode run of the biochar/polyaniline/polyethylene binder composites made in example 1 and comparative example.
Detailed Description
For better understanding of the technical solutions and advantages of the present invention, the following description will be further described with reference to the accompanying drawings and embodiments.
Example 1
A preparation method of a reed biochar-based composite cathode material comprises the following steps:
(1) the collected reeds are subjected to leaf removal and cleaning, then are put into a 75 ℃ oven to be dried for more than 12 hours, and the dried reeds are ground to obtain reed powder.
(2) Weighing reed powder, compacting in a mould, and placing the mould in a tube furnace. Then, 20min of nitrogen was introduced to exhaust the oxygen from the tube furnace. Heating to 100 deg.C at a speed of 10 deg.C/min, and preheating at 100 deg.C for 20 min; after the preheating is finished, the temperature is increased to 700 ℃ at the speed of 10 ℃/min, the temperature is kept constant at the temperature for 2h to ensure that the reed powder is pyrolyzed, and finally, the reed powder sample is naturally cooled to the room temperature to obtain a black product.
(3) And (3) uniformly mixing and grinding the black product obtained after cooling in the step (2), and then sieving the mixture through a 100-mesh sieve to obtain the charcoal powder with the particle size of below 150 microns.
(4) Uniformly mixing the charcoal powder obtained in the step (3) with polyaniline and polyethylene binder according to the mass ratio of 5:1:4, putting the mixture into a mold, compacting the mixture, putting the mold into a tubular furnace, and introducing nitrogen to exhaust oxygen; and then heating to 200 ℃ at the speed of 10 ℃/min for pyrolysis for 1.5h, and finally naturally cooling to room temperature to obtain the biochar/polyaniline/polyethylene binder composite material.
Comparative example
(1) The collected reeds are subjected to leaf removal and cleaning, then are put into a 75 ℃ oven to be dried for more than 12 hours, and the dried reeds are ground to obtain reed powder.
(2) Weighing reed powder, compacting in a mould, and placing the mould in a tube furnace. Then, 20min of nitrogen was introduced to exhaust the oxygen from the tube furnace. Then the temperature is increased to 100 ℃ at the speed of 10 ℃/min, and the temperature is kept constant at 100 ℃ for 20min for preheating; after the preheating is finished, the temperature is increased to 700 ℃ at the speed of 10 ℃/min, the constant temperature is kept for 2h at the temperature, so that the material is pyrolyzed, and finally, the sample is naturally cooled to the room temperature, so that a black product is obtained.
(3) And (3) uniformly mixing and grinding the black product obtained after cooling in the step (2), and then sieving the mixture through a 100-mesh sieve to obtain the charcoal powder.
(4) Uniformly mixing the charcoal powder obtained in the step (3) with polyaniline and polyethylene binder according to the mass ratio of 4:1:5, putting the mixture into a mold, compacting the mixture, putting the mold into a tubular furnace, and introducing nitrogen to exhaust oxygen; and then heating to 200 ℃ at the speed of 10 ℃/min for pyrolysis for 1.5h, and finally naturally cooling to room temperature to obtain the biochar/polyaniline/polyethylene binder composite material.
As can be seen from the SEM images of fig. 1 and fig. 2 with different mass ratios, the intrinsic structure of the biochar is not changed with the addition of the polyaniline and the polyethylene binder, and the modification of the polyethylene binder makes the particle spacing of the material smaller, enhancing the moldability of the material; and the polyaniline is dispersed on the surface of the biochar, so that the conductivity of the composite material is enhanced.
FIG. 3 is a view showing an area of 1cm2The biochar/polyaniline/polyethylene binder composite materials prepared in example 1 and comparative example were respectively attached to electrode holders as working electrodes using a platinum sheet electrode as an auxiliary electrode and an Ag/AgCl electrode as a reference electrode, and electrochemical tests were performed in a 1mM potassium ferricyanide mixed solution (containing 0.1M KCl).
Using an electrochemical workstation, and adjusting the frequency parameter of the sinusoidal signal to be 0.01-10 when the open-circuit voltage is stable5HZAnd the AC amplitude parameter is 0.007, and the electrochemical impedance spectroscopy is carried out. As can be seen from the low frequency slopes of the two materials in fig. 3, the composite material prepared in example 1 has a smaller impedance than the composite material prepared in comparative example, and thus it is considered that the composite material prepared in example 1 has a better conductive ability than the composite material prepared in comparative example.
As can be seen in fig. 4, the slope of the polarization curve of the composite material prepared in accordance with example 1 was reduced after replacement of the cathode, indicating a lower internal resistance relative to commercial carbon felt; the slope of the polarization curve of the composite material prepared by carrying the comparative example is increased, which shows that the composite material has higher internal resistance and is not suitable for practical application.
As can be seen from FIG. 5, the maximum power density of the SMFC loaded with the composite material prepared in example 1 was from 2.25. + -. 0.1mW m when the cathode of the SMFC was replaced with two kinds of biochar composites from a commercial carbon felt, respectively-2The increase is 5.25 +/-0.1 mW m-2. While the maximum power density of the SMFC carrying the composite material prepared in the comparative example is reduced to 1mW m-2About, only 45% of the original maximum power density.
Therefore, the test on the biochar-based composite material prepared in the example 1 shows that the biochar-based composite material has application potential.

Claims (6)

1. A preparation method of a reed biochar-based composite cathode material is characterized by comprising the following steps:
(1) removing leaves of the reed, cleaning, drying in an oven, and grinding the dried reed to obtain reed powder;
(2) placing reed powder in a mould, compacting, then placing in a tubular furnace, and introducing nitrogen to exhaust oxygen in the tubular furnace; then the temperature is raised to 100 ℃ and the temperature is kept constant for 20 min; after the constant-temperature preheating is finished, the temperature is increased to 700 ℃, the constant temperature is kept at 700 ℃ for 2 hours to ensure that the reed powder is pyrolyzed, and finally, the reed powder sample is naturally cooled to the room temperature to obtain a black product;
(3) uniformly mixing and grinding the black product obtained in the step (2), and screening to obtain charcoal powder;
(4) uniformly mixing the charcoal powder obtained in the step (3) with polyaniline and polyethylene binder according to the mass ratio of 5:1:4, placing the mixture into a mold, compacting the mold, placing the mold into a tubular furnace, and introducing nitrogen to exhaust oxygen; and then heating to 180-220 ℃, pyrolyzing at constant temperature for 1.5h, and cooling to room temperature to obtain the biochar/polyaniline/polyethylene binder composite material.
2. The production method according to claim 1, wherein the drying temperature in the step (1) is 75 ℃ and the drying time is 12 hours or more.
3. The method according to claim 1 or 2, wherein the charcoal powder of step (3) has a particle size of 150 μm or less.
4. The production method according to claim 1 or 2, wherein the temperature increase rate in the step (2) and the step (4) is 10 ℃/min.
5. The production method according to claim 3, wherein the temperature increase rate in the steps (2) and (4) is 10 ℃/min.
6. The application of the biochar/polyaniline/polyethylene binder composite material prepared by the preparation method according to any one of claims 1 to 5 is characterized in that a substrate sludge microbial fuel cell is assembled by taking a platinum sheet electrode as an auxiliary electrode, an Ag/AgCl electrode as a reference electrode and the biochar/polyaniline/polyethylene binder composite material as a cathode and matching electrolyte.
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CN107732256A (en) * 2017-10-10 2018-02-23 常州大学 One kind prepares MFC electrode materials and its chemical property using agricultural wastes
CN109721044A (en) * 2018-12-24 2019-05-07 哈尔滨工业大学 A kind of preparation method and applications of the three-dimensional porous charcoal from cone

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Publication number Priority date Publication date Assignee Title
CN107732256A (en) * 2017-10-10 2018-02-23 常州大学 One kind prepares MFC electrode materials and its chemical property using agricultural wastes
CN109721044A (en) * 2018-12-24 2019-05-07 哈尔滨工业大学 A kind of preparation method and applications of the three-dimensional porous charcoal from cone

Non-Patent Citations (1)

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Title
Nanostructured polyaniline-coated anode for improving microbial fuel cell power output;Ali Mehdinia等;《Chemical Papers》;20131231;第67卷(第8期);第1096-1102页 *

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