CN111809052A - Method for leaching lithium cobaltate by photocatalytic microbial fuel cell - Google Patents

Method for leaching lithium cobaltate by photocatalytic microbial fuel cell Download PDF

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CN111809052A
CN111809052A CN202010582746.3A CN202010582746A CN111809052A CN 111809052 A CN111809052 A CN 111809052A CN 202010582746 A CN202010582746 A CN 202010582746A CN 111809052 A CN111809052 A CN 111809052A
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photocatalytic
ppy
cathode
composite material
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CN111809052B (en
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刘维平
徐杰
韩思贤
胡俊
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Jiangsu University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Abstract

The invention discloses a method for leaching lithium cobaltate by a photocatalytic microbial fuel cell, which comprises the steps of constructing a double-chamber microbial fuel cell, wherein the double-chamber microbial fuel cell comprises a cathode chamber and an anode chamber, and the cathode chamber and the anode chamber are separated by a proton exchange membrane; the anode chamber comprises an anode made of pretreated carbon paper, and the cathode chamber comprises a load of PPy/TiO2A resistor is externally connected between the anode and the cathode, and a light source is externally connected to the cathode;and sodium acetate solution is taken as a substrate in the anode chamber and inoculated with the acclimated anaerobic sludge, sodium chloride solution is fully filled in the cathode chamber, then the pH is adjusted, the cathode and the anode are connected to form a closed loop, and cobalt in lithium cobaltate is leached at the cathode. The method is simple, and is a lithium cobaltate treatment and recovery mode which is green, environment-friendly and low in cost.

Description

Method for leaching lithium cobaltate by photocatalytic microbial fuel cell
Technical Field
The invention relates to the technical field of waste lithium battery recovery, in particular to a method for leaching lithium cobaltate by a photocatalytic microbial fuel cell.
Background
Lithium cobaltate is widely applied to mobile phones, notebook computers and other electronic equipment due to the characteristics of small volume, light weight, high energy density and the like. With the increasing demand and the updating of electronic products, a large number of waste lithium batteries are generated. The lithium batteries have abundant valuable metal content and high recovery value. Wherein, the cobalt content accounts for 5 to 20 percent of the lithium battery and is an important component of the anode material. Therefore, cobalt recovery is one of the main objectives in the disposal of spent lithium batteries. The traditional waste lithium battery treatment method mainly comprises pyrometallurgy, wet leaching, bioleaching and the like. The methods provide a theoretical basis for the treatment of the waste lithium ion batteries, but the huge energy consumption, the expensive cost and the serious secondary pollution promote people to seek a treatment technology which is lower in cost, efficient, green and environment-friendly.
The patent (CN107221724A) firstly disassembles the waste lithium battery, obtains the positive powder of the waste lithium battery through pretreatment, adds a certain amount of vulcanizing agent to calcine to obtain metal sulfide and lithium compound, and then adds water to stir and separate to obtain lithium-containing filtrate. Although the total recovery rate of lithium is high, reaching 97.43%, and the method has little environmental pollution, a large amount of chemical reagents and fossil fuels are consumed in the recovery process, and the cost is high.
The patent (CN107083484A) firstly crushes the waste lithium battery, respectively uses sodium hydroxide and hydrochloric acid to adjust the pH value, recovers the aluminum hydroxide precipitate, then adds sulfuric acid and hydrogen peroxide for leaching, finally adds oxalic acid solution and sodium carbonate in turn, and recovers the lithium filtrate. Although the method can realize the recovery of various metals such as aluminum, cobalt, lithium, nickel and the like, a large amount of acid reagents are consumed in the recovery process, and acid gases such as oxalic acid and the like are generated, so that the environment is polluted.
Dissolving waste lithium battery powder of patent (CN107058742A) with acid, extracting the solution to obtain lithium-containing material liquid, adjusting pH, extracting, washing and back-extracting to obtain a lithium salt back-extraction liquid, and removing oil, evaporating, cooling, crystallizing, filtering and drying the back-extraction liquid to obtain the anhydrous lithium salt. The method has high metal recovery rate and low auxiliary material consumption, but in the recovery process, a plurality of operations such as extraction, back extraction and the like are required, the steps are complicated, and the operation requirement is high.
In the patent (CN109722538A), under the atmosphere of constant temperature argon, a graphite rod is taken as an anode, lithium cobaltate sheets in waste lithium batteries are taken as a cathode, the two electrode sheets are placed in molten salt, and constant voltage is applied for electrolysis to obtain Co or CoO powder. The method is simple to operate and pollution-free, but needs to control the temperature and the voltage, and increases the energy consumption.
Disclosure of Invention
The invention aims to provide a method for leaching lithium cobaltate from a photocatalytic microbial fuel cell, which is simple, low in cost, green and environment-friendly and has high cobalt leaching rate in the lithium cobaltate.
The invention is realized by the following technical scheme:
a method for leaching lithium cobaltate by a photocatalytic microbial fuel cell is characterized in that,
constructing a double-chamber microbial fuel cell, which comprises a cathode chamber and an anode chamber, wherein the cathode chamber and the anode chamber are separated by a proton exchange membrane;
the anode chamber comprises an anode made of pretreated carbon paper, and the cathode chamber comprises a load of PPy/TiO2The cathode and the lithium cobaltate are made of modified carbon paper of the photocatalytic composite material, a resistor is externally connected between the anode and the cathode, and a light source is externally added to the cathode;
and sodium acetate solution is used as a substrate in the anode chamber and inoculated with acclimated anaerobic sludge, sodium chloride solution is fully filled in the cathode chamber, then the pH is adjusted, the cathode and the anode are connected to form a closed loop, and cobalt in lithium cobaltate is leached out from the cathode. In one aspect of the invention, the supported polypyrrole/titanium dioxide (PPy/TiO) is prepared by a chemical oxidation method2) The modified carbon paper of the photocatalytic composite material widens TiO2Spectral response range, improved light energy utilization rate and photoelectron separation degree, and enhanced recombinationThe photocatalytic efficiency of the composite material, and the other side is to load polypyrrole/titanium dioxide (PPy/TiO)2) The modified carbon paper of the photocatalytic composite material is used as a cathode of a double-chamber Microbial Fuel Cell (MFC), optical energy and chemical energy are converted into electric energy, the electron transfer efficiency and the leaching rate of cathode Co (II) are improved, and the method is a green, environment-friendly and low-cost method for treating and recovering lithium cobaltate.
Further, the pretreatment process of the carbon paper comprises the following steps: soaking the carbon paper in dilute sulfuric acid for 10-30 min, washing with deionized water for 3-5 times, and drying at 60-80 deg.c for 20-24 hr.
Further, the PPy/TiO2The preparation method of the photocatalytic composite material comprises the following steps:
(1) adding TiO into the mixture2Drying, then ultrasonically dispersing into a mixed solution of hydrochloric acid and pyrrole monomers, and stirring to obtain a first dispersion solution;
(2) anhydrous FeCl is added3Dispersing in methanol solution to obtain second dispersion solution, slowly dropwise adding the first mixture solution into the second mixture solution for reaction, washing with hydrochloric acid, anhydrous ethanol and distilled water in sequence after reaction until the product is neutral, collecting the product, drying, and grinding to obtain PPy/TiO2A photocatalytic composite material.
Further, the PPy/TiO2The preparation method of the photocatalytic composite material comprises the following steps: in the step (1), the drying temperature is 60-70 ℃, the drying time is 20-24 hours, and the TiO is2And the mass volume ratio of the mixed solution is 1g/mL, the volume of the pyrrole monomer accounts for 1-2% of the volume of the mixed solution, and the concentration of the hydrochloric acid is 1.2 mol/L.
Further, the PPy/TiO2The preparation method of the photocatalytic composite material comprises the following steps: the anhydrous FeCl in the step (2)3And the mass-to-volume ratio of the methanol solution is 0.1-0.15g/mL, and the volume ratio of the first dispersion to the second dispersion is 5: 1, the reaction time is 8-12 hours, the drying temperature is 50-60 ℃, and the drying time is 18-24 hours.
Further, the PPy/TiO supported2The preparation method of the modified carbon paper of the photocatalytic composite material comprises the following steps:
(1) weighing the PPy/TiO2PPy/TiO prepared by preparation method of photocatalytic composite material2Mixing the photocatalytic composite material with a binder, adding N-methyl pyrrolidone, uniformly stirring, and grinding to obtain a dispersion material;
(2) coating the dispersion material on the pretreated carbon paper, and then drying to obtain the PPy/TiO load2Modified carbon paper of photocatalytic composite material.
Further, the PPy/TiO supported2The preparation method of the modified carbon paper of the photocatalytic composite material comprises the following steps: in the step (1), the binder is polytetrafluoroethylene, and the PPy/TiO2The mass ratio of the photocatalytic composite material to the binder is 4: 1, said PPy/TiO2The mass ratio of the photocatalytic composite material to the N-methylpyrrolidone is 1: 2.
Further, the PPy/TiO supported2The preparation method of the modified carbon paper of the photocatalytic composite material comprises the following steps: the drying in the step (2) is vacuum drying, the drying temperature is 50-70 ℃, and the drying time is 20-24 hours.
Further, the volume ratio of the anaerobic sludge to the sodium acetate solution is 8: 17, the sum of the volumes of said anaerobic sludge and said sodium acetate solution being equal to the effective volume of said anode chamber.
Further, the concentration of the sodium chloride solution is 100-200mmol/L, the concentration of the sodium acetate solution is 0.5-2.0g/L, the adjustment range of the pH is 2-6, the mass-to-volume ratio of the lithium cobaltate to the sodium chloride solution is 0.1-0.2mg/mL, and the light source and the cathode of the microbial fuel cell are kept at a distance of 30-70 cm.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention takes carbon paper as a substrate and loads polypyrrole/titanium dioxide (PPy/TiO)2) A photocatalytic composite material is added, and then the supported polypyrrole/titanium dioxide (PPy/TiO)2) The carbon paper of the photocatalytic composite material is used as the cathode of the microbial fuel cell, so that the cathode electrode shows excellent photocatalytic performance, the electricity generation performance of the cell and the leaching rate of lithium cobaltate are improved, and the carbon paper is used under the illumination conditionThen, polypyrrole/titanium dioxide (PPy/TiO) is supported2) The maximum power density and the maximum Co (II) leaching rate of the microbial fuel cell constructed by using the photocatalytic composite material modified carbon paper as the cathode are 10425.7 mW.m respectively-247.8 percent of the total weight of the carbon paper, which is far higher than 5292.5 mW.m of the blank carbon paper-2And 25.5%;
(2) the invention utilizes the supported polypyrrole/titanium dioxide (PPy/TiO)2) The modified carbon paper of the photocatalytic composite material is used as the cathode of the microbial fuel cell, so that the modified carbon paper is combined with the Microbial Fuel Cell (MFC), the light energy and the chemical energy are fully utilized, the number of electrons is increased, and the transfer efficiency of the electrons is improved;
(3) the method adopts the loaded polypyrrole/titanium dioxide (PPy/TiO)2) The modified carbon paper of the photocatalytic composite material is used as a cathode electrode, electrons are directly generated at the cathode, the loss of the electrons in the transfer process is reduced, a Co (III) electron acceptor can receive more electrons, the utilization rate of the electrons is greatly improved, the whole system has no extra consumption in the electricity generation and leaching processes, and the method is a green, environment-friendly and low-cost lithium cobaltate treatment and recovery mode.
Drawings
FIG. 1 is a schematic diagram of a photocatalytic Microbial Fuel Cell (MFC) device constructed in accordance with the present invention;
FIG. 2 shows the polypyrrole/titanium dioxide (PPy/TiO) support in example 12) Modified carbon paper of photocatalytic composite material, carbon paper of comparative example 1 and TiO-loaded comparative example 22The carbon paper of the photocatalytic material is used as a cathode to construct the output voltage of the photocatalytic Microbial Fuel Cell (MFC);
FIG. 3 shows the polypyrrole/titanium dioxide (PPy/TiO) support in example 12) Modified carbon paper of photocatalytic composite material, carbon paper of comparative example 1 and TiO-loaded comparative example 22The carbon paper of the photocatalytic material is used as a cathode to construct the power density of a photocatalytic Microbial Fuel Cell (MFC);
FIG. 4 shows the polypyrrole/titanium dioxide (PPy/TiO) support in example 12) Modified carbon paper of photocatalytic composite material and TiO-loaded paper in comparative example 22A Scanning Electron Microscope (SEM) spectrum of the carbon paper of the photocatalytic material;
FIG. 5 shows polypyrrole/titanium dioxide (PPy/TiO) in example 12) Photocatalytic composite material and TiO-Supported composite Material in comparative example 22IR spectra of both carbon papers of photocatalytic material.
Detailed Description
Example 1
Mono, polypyrrole/titanium dioxide (PPy/TiO)2) Preparing the photocatalytic composite material modified carbon paper:
(1) pretreatment of the carbon paper: selecting 50 x 1mm carbon paper as a material of an anode and a cathode of a Microbial Fuel Cell (MFC), soaking the carbon paper in dilute sulfuric acid for 30 minutes, washing the carbon paper with deionized water for 3 times after soaking to remove impurities on the surface of the carbon paper, drying the carbon paper for 24 hours at 60 ℃, connecting the dried carbon paper with a copper wire, coating epoxy resin on a joint, and placing the carbon paper in a drying dish for later use;
(2) polypyrrole/titanium dioxide (PPy/TiO)2) Preparing a photocatalytic composite material: weighing 10.0g of titanium dioxide (TiO)2) Drying in an oven at 60 ℃ for 24 hours, ultrasonically dispersing the dried titanium dioxide into 100.0mL of mixed solution of hydrochloric acid and pyrrole monomer, and stirring to obtain a first dispersion liquid (wherein the pyrrole monomer is 1.25mL, the hydrochloric acid is 98.75mL, and the concentration of the hydrochloric acid is 1.2 mol/L); ② 2.3g of anhydrous FeCl3Dispersing in 20.0mL of methanol solution to obtain a second dispersion, slowly dripping all the first dispersion into the second dispersion, stirring for reaction for 12 hours to fully polymerize pyrrole monomer on the surface of titanium dioxide, repeatedly washing the reaction product with 1.2mol/L hydrochloric acid, absolute ethyl alcohol and distilled water until the product is neutral, collecting the product, drying at 60 ℃ for 18 hours, and manually grinding the product for 10 minutes to obtain polypyrrole/titanium dioxide (PPy/TiO)2) A photocatalytic composite material;
(3) supported polypyrrole/titanium dioxide (PPy/TiO)2) Preparing modified carbon paper of the photocatalytic composite material: 300.0mg of polypyrrole/titanium dioxide (PPy/TiO) is weighed respectively2) The photocatalytic composite material and 75.0mg of polytetrafluoroethylene were added, followed by 600.0mg of N-methylpyrrolidone, followed by manual grinding for 10 minutes to obtain a powderBulk materials; uniformly coating the carbon paper pretreated in the step (1) with a dispersion material, and then carrying out vacuum drying at 50 ℃ for 24 hours to obtain the loaded polypyrrole/titanium dioxide (PPy/TiO)2) Modified carbon paper of photocatalytic composite material;
secondly, constructing a Microbial Fuel Cell (MFC): a two-chamber microbial fuel cell (as shown in figure 1) is constructed, and comprises a cathode chamber and an anode chamber, wherein the effective volumes of the cathode chamber and the anode chamber are both 500mL, the cathode chamber and the anode chamber are separated by a proton exchange membrane, and the effective area of the proton exchange membrane is 8cm2(ii) a The anode chamber comprises an anode made of pretreated carbon paper, and the cathode chamber comprises a polypyrrole/titanium dioxide (PPy/TiO) load2) The cathode is made of modified carbon paper of a photocatalytic composite material, a resistor is connected between the anode and the cathode, 160mL of acclimated anaerobic sludge is added into an anode chamber as inoculation sludge, 340mL of 2g/L sodium acetate solution is used as a substrate, 500mL of 100mmol/L sodium chloride solution and 0.05g of lithium cobaltate solid powder are filled into a cathode chamber, the pH value is adjusted to be 2, a 100W incandescent lamp is additionally arranged at the position 70cm outside the cathode, the cathode and the anode are connected through a copper wire to form a closed loop, and Co (II) is leached out from the cathode.
The work principle of Co (II) leaching of a photocatalytic Microbial Fuel Cell (MFC) is shown in figure 1, an anode substrate is oxidized under the catalysis of microbes to generate protons and electrons, the protons are transferred to a cathode through a proton exchange membrane, the electrons reach the cathode through an external circuit, meanwhile, a photocathode generates free electrons under the illumination condition, and part of the electrons are LiCoO2(Co (III)) is utilized, reduction reaction is carried out, the reduction reaction is carried out at a cathode to obtain Co (II), and the other part of electrons are reacted with protons and O in air2Combining to generate water. Co (II) leaching mechanism:
anode:
Figure BDA0002552998240000081
cathode: 4H++O2+4e-→2H2O Co3++e-→Co2+
The open circuit voltage, power density and Co (ii) concentration in the catholyte after the photocatalytic Microbial Fuel Cell (MFC) was operated were measured, and the specific results are shown in table 1.
Comparative example 1
Comparative example 1 is prepared by the same procedure as in example 1, except that the cathode of the Microbial Fuel Cell (MFC) was a blank carbon paper after pretreatment.
The open circuit voltage, power density and Co (ii) concentration in the catholyte after the photocatalytic Microbial Fuel Cell (MFC) was operated were measured, and the specific results are shown in table 1.
Comparative example 2
Comparative example 2 is prepared by the same procedure as in example 1, except that TiO was added to the cathode of the Microbial Fuel Cell (MFC) as described in step (3) of example 1 above2Loaded on carbon paper.
The open circuit voltage, power density and Co (ii) concentration in the catholyte after the photocatalytic Microbial Fuel Cell (MFC) was operated were measured, and the specific results are shown in table 1.
Table 1 shows the data for example 1, comparative example 1 and comparative example 2:
Figure BDA0002552998240000091
TABLE 1
After the MFC was started, the output voltages of example 1, comparative example 1, and comparative example 2 were recorded, and the data is shown in fig. 2, in which the output voltage of the MFC rapidly increased at the initial stage of the start of the device, and a 400 Ω resistor was connected after the output voltage was stabilized. As can be seen from fig. 2, after the resistor is connected, the output voltage of the MFC is reduced, which is caused by the series voltage division of the external resistor. After the MFC system was operated for 15 days, the output voltage of the MFCs constructed in comparative example 1 and comparative example 2 was reduced to 0.1V or less, the apparatus was stopped, and example 1 was loaded with polypyrrole/titanium dioxide (PPy/TiO)2) The output voltage of the MFC constructed by using the modified carbon paper of the photocatalytic composite material as the cathode is not reduced to be below 0.1V, because the photocathode can continuously generate weak current.
The output current was measured by the steady state discharge method to calculate the output current of example 1, comparative example 1 and comparative example2 Power Density, data shown in FIG. 3, polypyrrole/titanium dioxide (PPy/TiO) loading in example 12) The maximum power density of MFC constructed by using modified carbon paper of the photocatalytic composite material as a cathode is 10425.7 mW.m-25292.5 mW.m carbon paper of comparative example 1-2And comparative example 2TiO2Modified carbon paper 5618.2 mW.m-21.97 and 1.86 times.
After the photocatalytic MFC operation is finished, the concentration of Co (II) in the catholyte is measured by an atomic absorption spectrometer and is shown in Table 1. As can be seen from Table 1, the supported polypyrrole/titanium dioxide (PPy/TiO)2) The leaching rate of Co (II) of the cathode of the modified carbon paper of the photocatalytic composite material is 47.8 percent, namely the carbon paper and TiO respectively2The leaching rate of the modified carbon paper is 1.87 times and 1.76 times. Therefore, the visible light catalytic MFC has a great promotion effect on the leaching rate of Co (II).
Scanning Electron Microscopy (SEM) on the PPy/TiO sample of example 12Photocatalytic composite material and pure TiO of comparative example 22Characterization of the photocatalytic Material, as shown in FIG. 4, pure TiO in FIG. 4(a)2The photocatalytic material has non-uniform particle size and agglomeration phenomenon; but sensitizing TiO with PPy2FIG. 4(b) PPy/TiO2The surface appearance of the photocatalytic composite material is spherical, the particle size is small, the particles are uniformly dispersed and have more pores, and PPy is adsorbed on TiO2The surface of the particles being hindered by TiO2The agglomeration among the particles is more beneficial to the absorption of the photocatalytic composite material to visible light.
Testing of PPy/TiO in example 12Photocatalytic composite material and pure TiO of comparative example 22IR spectra of both photocatalytic materials, as shown in FIG. 5, on pure TiO2Photocatalytic Material Infrared Spectroscopy, 3422 and 1617cm-1Corresponding O-H stretching and bending vibration; 622 and 524cm-1Is TiO2Stretching vibration of medium Ti-O in sensitizing TiO with PPy2Then, PPy/TiO2The appearance of a characteristic peak of polypyrrole in the infrared spectrum of the photocatalytic composite material shows that the PPy/TiO successfully prepared by a chemical oxidation method2A composite material.
Example 2
Mono, polypyrrole/titanium dioxide (PPy/TiO)2) Preparing the photocatalytic composite material modified carbon paper:
(1) pretreatment of the carbon paper: selecting 50 x 1mm carbon paper as a material of an anode and a cathode of a Microbial Fuel Cell (MFC), soaking the carbon paper in dilute sulfuric acid for 10 minutes, washing the carbon paper with deionized water for 5 times after soaking to remove impurities on the surface of the carbon paper, drying the carbon paper at 80 ℃ for 22 hours, connecting the dried carbon paper with a copper wire, coating epoxy resin on a joint, and placing the carbon paper in a drying dish for later use;
(2) polypyrrole/titanium dioxide (PPy/TiO)2) Preparing a photocatalytic composite material: weighing 10.0g of titanium dioxide (TiO)2) Drying in an oven at 70 ℃ for 20 hours, ultrasonically dispersing the dried titanium dioxide into 100.0mL of mixed solution of hydrochloric acid and pyrrole monomer, and stirring to obtain a first dispersion solution (wherein the pyrrole monomer is 1.00mL, the hydrochloric acid is 99.00mL, and the concentration of the hydrochloric acid is 1.2 mol/L); ② adding 3.0g of anhydrous FeCl3Dispersing in 20.0mL of methanol solution to obtain a second dispersion, slowly dripping all the first dispersion into the second dispersion, stirring and reacting for 8 hours to fully polymerize pyrrole monomer on the surface of titanium dioxide, repeatedly washing the reaction product with 1.2mol/L hydrochloric acid, absolute ethyl alcohol and distilled water in sequence until the product is neutral, collecting the product, drying at 50 ℃ for 24 hours, and manually grinding the product for 10 minutes to obtain polypyrrole/titanium dioxide (PPy/TiO)2) A photocatalytic composite material;
(3) supported polypyrrole/titanium dioxide (PPy/TiO)2) Preparing modified carbon paper of the photocatalytic composite material: 300.0mg of polypyrrole/titanium dioxide (PPy/TiO) is weighed respectively2) Adding 600.0mg of N-methyl pyrrolidone into the photocatalytic composite material and 75.0mg of polytetrafluoroethylene, and manually grinding for 10 minutes to obtain a dispersion material; uniformly coating the carbon paper pretreated in the step (1) with a dispersion material, and then drying the carbon paper at 70 ℃ for 20 hours in vacuum to obtain the loaded polypyrrole/titanium dioxide (PPy/TiO)2) Modified carbon paper of photocatalytic composite material;
secondly, constructing a Microbial Fuel Cell (MFC): constructing a two-compartment microbial fuel cell (as shown in FIG. 1) comprising a cathodeThe effective volume of the two polar chambers is 500mL, the cathode chamber and the anode chamber are separated by a proton exchange membrane, and the effective area of the proton exchange membrane is 8cm2(ii) a The anode chamber comprises an anode made of pretreated carbon paper, and the cathode chamber comprises a polypyrrole/titanium dioxide (PPy/TiO) load2) The cathode is made of modified carbon paper of a photocatalytic composite material, a resistor is connected between the anode and the cathode, 160mL of acclimated anaerobic sludge is added into an anode chamber as inoculation sludge, 340mL of sodium acetate solution with the concentration of 0.5g/L is used as a substrate, then 500mL of sodium chloride solution with the concentration of 200mmol/L and 0.1g of lithium cobaltate solid powder are filled into a cathode chamber, the pH value is adjusted to be 6, a 100W incandescent lamp is additionally arranged at a position 30cm outside the cathode, the cathode and the anode are connected through a copper wire to form a closed loop, and Co (II) is leached out from the cathode.
The open circuit voltage, power density and Co (ii) concentration in the catholyte after the photocatalytic MFC was operated were measured, and the specific results are shown in table 2.
Comparative example 3
A set of photocatalytic MFC devices was constructed, and comparative example 3 was constructed in a manner identical to that of example 2, except that the cathode of comparative example 3 was not provided with an additional light source and was placed in the dark.
The current and voltage and the cathode Co (II) leaching rate are measured, and the corresponding power density is calculated by a steady-state discharge method, and the specific data are shown in a table 2.
Table 2 shows the data for example 2 and comparative example 3:
Figure BDA0002552998240000121
Figure BDA0002552998240000131
TABLE 2
As can be seen from the data in Table 2, example 2 supports polypyrrole/titanium dioxide (PPy/TiO) in an illuminated environment2) Maximum power density of MFC (microbial fuel cell) constructed by taking modified carbon paper of photocatalytic composite material as cathode is 10138.9 mW.m-2Comparative example 3 Supported polypyrrole in dark EnvironmentTitanium dioxide (PPy/TiO)2) Maximum power density of MFC (microbial fuel cell) constructed by taking modified carbon paper of photocatalytic composite material as cathode is 5618.2 mW.m-21.8 times of the total weight of the product, and has larger promotion.
After the operation of the photocatalytic MFC device, under the influence of light, the photocatalytic composite material starts to generate free electrons at the cathode, which are converted by LiCoO2By using the catalyst, the catalyst is reduced to Co (II). The Co (II) leaching rate in example 2 was 1.6 times that in comparative example 3. Therefore, the photocatalytic composite material electrode has great promotion effect on Co (II) leaching.
Example 3
Mono, polypyrrole/titanium dioxide (PPy/TiO)2) Preparing the photocatalytic composite material modified carbon paper:
(1) pretreatment of the carbon paper: selecting 50 x 1mm carbon paper as a material of an anode and a cathode of a Microbial Fuel Cell (MFC), soaking the carbon paper with dilute sulfuric acid for 20 minutes, washing with deionized water for 4 times after soaking to remove impurities on the surface of the carbon paper, drying for 20 hours at 70 ℃, connecting the dried carbon paper with a copper wire, coating epoxy resin at a joint, and placing the carbon paper in a drying dish for later use;
(2) polypyrrole/titanium dioxide (PPy/TiO)2) Preparing a photocatalytic composite material: weighing 10.0g of titanium dioxide (TiO)2) Drying in a 65 ℃ oven for 22 hours, ultrasonically dispersing the dried titanium dioxide into 100.0mL of mixed solution of hydrochloric acid and pyrrole monomer, and stirring to obtain a first dispersion solution (wherein the pyrrole monomer is 2.00mL, the hydrochloric acid is 98.00mL, and the concentration of the hydrochloric acid is 1.2 mol/L); ② 2.0g of anhydrous FeCl3Dispersing in 20.0mL of methanol solution to obtain a second dispersion, slowly dripping all the first dispersion into the second dispersion, stirring for reaction for 10 hours to fully polymerize pyrrole monomer on the surface of titanium dioxide, repeatedly washing the reaction product with 1.2mol/L hydrochloric acid, absolute ethyl alcohol and distilled water until the product is neutral, collecting the product, drying at 55 ℃ for 20 hours, and manually grinding the product for 10 minutes to obtain polypyrrole/titanium dioxide (PPy/TiO)2) A photocatalytic composite material;
(3) supported polypyrrole/titanium dioxide(PPy/TiO2) Preparing modified carbon paper of the photocatalytic composite material: 300.0mg of polypyrrole/titanium dioxide (PPy/TiO) is weighed respectively2) Adding 600.0mg of N-methyl pyrrolidone into the photocatalytic composite material and 75.0mg of polytetrafluoroethylene, and manually grinding for 10 minutes to obtain a dispersion material; uniformly coating the carbon paper pretreated in the step (1) with a dispersion material, and then drying the carbon paper at the temperature of 60 ℃ for 22 hours in vacuum to obtain the loaded polypyrrole/titanium dioxide (PPy/TiO)2) Modified carbon paper of photocatalytic composite material;
secondly, constructing a Microbial Fuel Cell (MFC): a two-chamber microbial fuel cell (as shown in figure 1) is constructed, and comprises a cathode chamber and an anode chamber, wherein the effective volumes of the cathode chamber and the anode chamber are both 500mL, the cathode chamber and the anode chamber are separated by a proton exchange membrane, and the effective area of the proton exchange membrane is 8cm2(ii) a The anode chamber comprises an anode made of pretreated carbon paper, and the cathode chamber comprises a polypyrrole/titanium dioxide (PPy/TiO) load2) The cathode is made of modified carbon paper of a photocatalytic composite material, a resistor is connected between the anode and the cathode, 160mL of acclimated anaerobic sludge is added into an anode chamber as inoculation sludge, 340mL of 1.2g/L sodium acetate solution is used as a substrate, 500mL of 150mmol/L sodium chloride solution and 0.07g of lithium cobaltate solid powder are filled into a cathode chamber, the pH value is adjusted to be 4, a 100W incandescent lamp is additionally arranged at a position 50cm outside the cathode, the cathode and the anode are connected through a copper wire to form a closed loop, and Co (II) is leached out of the cathode.
The open-circuit voltage, power density and Co (II) concentration in catholyte after the operation of the photocatalytic MFC were measured, in this example 3, the open-circuit voltage was 0.660V, and the maximum power density was 8464mW/m2The leaching rate of the cathode Co (II) is 44.8 percent.
The above-mentioned preferred embodiments of the present invention are provided for illustration only and not for the purpose of limiting the invention. Obvious variations or modifications of the present invention are within the scope of the present invention.

Claims (10)

1. A method for leaching lithium cobaltate by a photocatalytic microbial fuel cell is characterized in that,
constructing a double-chamber microbial fuel cell, which comprises a cathode chamber and an anode chamber, wherein the cathode chamber and the anode chamber are separated by a proton exchange membrane;
the anode chamber comprises an anode made of pretreated carbon paper, and the cathode chamber comprises a load of PPy/TiO2The cathode and the lithium cobaltate are made of modified carbon paper of the photocatalytic composite material, a resistor is externally connected between the anode and the cathode, and a light source is externally added to the cathode;
and sodium acetate solution is used as a substrate in the anode chamber and inoculated with acclimated anaerobic sludge, sodium chloride solution is fully filled in the cathode chamber, then the pH is adjusted, the cathode and the anode are connected to form a closed loop, and cobalt in lithium cobaltate is leached out from the cathode.
2. The method for leaching lithium cobaltate by using the photocatalytic microbial fuel cell as claimed in claim 1, wherein the pretreatment process of the carbon paper is as follows: soaking the carbon paper in dilute sulfuric acid for 10-30 min, washing with deionized water for 3-5 times, and drying at 60-80 deg.c for 20-24 hr.
3. The method for leaching lithium cobaltate by using the photocatalytic microbial fuel cell as claimed in claim 1, wherein the PPy/TiO is2The preparation method of the photocatalytic composite material comprises the following steps:
(1) adding TiO into the mixture2Drying, then ultrasonically dispersing into a mixed solution of hydrochloric acid and pyrrole monomers, and stirring to obtain a first dispersion solution;
(2) anhydrous FeCl is added3Dispersing in methanol solution to obtain second dispersion, slowly dropwise adding the first dispersion into the second dispersion for reaction, washing with hydrochloric acid, anhydrous ethanol and distilled water in sequence after reaction until the product is neutral, collecting the product, drying, and grinding to obtain PPy/TiO2A photocatalytic composite material.
4. The method for leaching lithium cobaltate by using the photocatalytic microbial fuel cell as claimed in claim 3, wherein the method is characterized in thatThen, the PPy/TiO2The preparation method of the photocatalytic composite material comprises the following steps: in the step (1), the drying temperature is 60-70 ℃, the drying time is 20-24 hours, and the TiO is2And the mass volume ratio of the mixed solution is 1g/mL, the volume of the pyrrole monomer accounts for 1-2% of the volume of the mixed solution, and the concentration of the hydrochloric acid is 1.2 mol/L.
5. The method for leaching lithium cobaltate by using the photocatalytic microbial fuel cell as claimed in claim 3, wherein the PPy/TiO is2The preparation method of the photocatalytic composite material comprises the following steps: the anhydrous FeCl in the step (2)3And the mass-to-volume ratio of the methanol solution is 0.1-0.15g/mL, and the volume ratio of the first dispersion to the second dispersion is 5: 1, the reaction time is 8-12 hours, the drying temperature is 50-60 ℃, and the drying time is 18-24 hours.
6. The method for leaching lithium cobaltate by using the photocatalytic microbial fuel cell as claimed in claim 1, wherein the PPy/TiO load is PPy/TiO2The preparation method of the modified carbon paper of the photocatalytic composite material comprises the following steps:
(1) weighing the PPy/TiO of any one of claims 3-52PPy/TiO prepared by preparation method of photocatalytic composite material2Mixing the photocatalytic composite material with a binder, adding N-methyl pyrrolidone, uniformly stirring, and grinding to obtain a dispersion material;
(2) coating the dispersion material on the pretreated carbon paper, and then drying to obtain the PPy/TiO load2Modified carbon paper of photocatalytic composite material.
7. The method for leaching lithium cobaltate by using the photocatalytic microbial fuel cell as claimed in claim 6, wherein the PPy/TiO load is PPy/TiO2The preparation method of the modified carbon paper of the photocatalytic composite material comprises the following steps: in the step (1), the binder is polytetrafluoroethylene, and the PPy/TiO2The mass ratio of the photocatalytic composite material to the binder is 4: 1, said PPy/TiO2Photocatalytic composite material and said N-methylThe mass ratio of the pyrrolidone is 1: 2.
8. The method for leaching lithium cobaltate by using the photocatalytic microbial fuel cell as claimed in claim 6, wherein the PPy/TiO load is PPy/TiO2The preparation method of the modified carbon paper of the photocatalytic composite material comprises the following steps: the drying in the step (2) is vacuum drying, the drying temperature is 50-70 ℃, and the drying time is 20-24 hours.
9. The method for leaching lithium cobaltate by using the photocatalytic microbial fuel cell as claimed in claim 1, wherein the volume ratio of the anaerobic sludge to the sodium acetate solution is 8: 17, the sum of the volumes of said anaerobic sludge and said sodium acetate solution being equal to the effective volume of said anode chamber.
10. The method for leaching lithium cobaltate by using the photocatalytic microbial fuel cell as claimed in claim 1, wherein the concentration of the sodium chloride solution is 100-200mmol/L, the concentration of the sodium acetate solution is 0.5-2.0g/L, the pH is adjusted within the range of 2-6, the mass-to-volume ratio of the lithium cobaltate to the sodium chloride solution is 0.1-0.2mg/mL, and the light source is kept at a distance of 30-70cm from the cathode of the microbial fuel cell.
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