CN110265676A - A method of cobalt acid lithium is leached using microbiological fuel cell - Google Patents

A method of cobalt acid lithium is leached using microbiological fuel cell Download PDF

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CN110265676A
CN110265676A CN201910380181.8A CN201910380181A CN110265676A CN 110265676 A CN110265676 A CN 110265676A CN 201910380181 A CN201910380181 A CN 201910380181A CN 110265676 A CN110265676 A CN 110265676A
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acid lithium
cobalt acid
carbon paper
fuel cell
microbiological fuel
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CN110265676B (en
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刘维平
孙扬
徐杰
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Jiangsu University of Technology
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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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/045—Leaching using electrochemical processes
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • 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 present invention relates to a kind of methods for leaching cobalt acid lithium using microbiological fuel cell, on the one hand its surface-active is increased by the modified anode of carbon dust, and greatly speed up electrode surface biochemical reaction process, another aspect cathode chamber does not generate secondary pollution using sodium chloride solution, the two, which combines, improves electron transmission efficiency and MFC system power, constructed MFC open-circuit voltage is greater than 0.724V, and power density is greater than 6822.76mW/m2, the leaching rate of cobalt is greater than 48% in cobalt acid lithium；The method of the present invention operating condition is mild, process flow is simple, do not generate secondary pollution, electricity generation performance is higher simultaneously, leaching process is not necessarily to other Chemical Leaching reagents, is a kind of useless lithium battery that energy conservation and environmental protection realizes waste treatment and waste recycling processing method.

Description

A method of cobalt acid lithium is leached using microbiological fuel cell
Technical field
The present invention relates to waste lithium cell recovery technology fields, and in particular to a kind of to utilize microbiological fuel cell leaching cobalt Trivalent cobalt in sour lithium is simultaneously reduced to cobaltous method.
Background technique
Cobalt acid lithium is widely used in the positive electrode of lithium ion battery, and lithium ion battery has energy density height, service life Long, small in size, light-weight, the features such as having a wide range of application, it is widely used in the fields such as electronic product, automobile, aerospace.By electricity The influence of sub- successive generations of products period and lithium ion battery service life etc. produces largely useless lithium electricity in recent years Pond.Contain a large amount of heavy metal and toxic electrolyte in useless lithium battery, the useless lithium battery of harmless treatment simultaneously recycles valuable metal tool It is significant.
Currently, domestic and international scientific research personnel expands largely aiming at the problem that cobalt acid lithium leaches in useless anode material of lithium battery Research and discussion.Anode material of waste LiCoO battery is put in corrosion resistant closed container by patent (200910059707.9), Sulfuric acid and nitric acid are poured into, refuse battery positive electrode is leached in the case where being passed through industrial pure oxygen, this method, which needs to control, leaches temperature Degree leaches pressure, control sulfuric acid initial concentration and nitric acid initial concentration, extraction time and mixing speed this series of parameters, right Leaching require it is relatively high, it is bigger for the consumption of industrial reagent and industrial pure oxygen.
The positive electrode active materials sulfuric acid-that patent (CN200910304134.1) first splits waste and old lithium ion battery Hydrogen peroxide mixed solution multistage counter current leaches, residual residue salt Ore Leaching.Although the method leaching efficiency is high, can consume A large amount of chemical reagent, while with Cl2It generates, pollutes environment.
Patent (CN101871048A) is separated aluminium flake with lye, first uses sulphur for the powder containing cobalt acid lithium split away off Acid dissolution, then use Na2SO4Or Na2SO3Or Fe powder enriching sulfuric acid carries out reduction of dissolved, is then carried out using 3-6mol/L sulfuric acid High acid dissolution finally removes alkaline earth impurity with precipitating reagent.The method supplementary product onsumption is low, and metal recovery rate is high, but is recycling Need to extract and be stripped the separation for carrying out various metallic solutions in journey, the acid solution amount used is larger, various chemical reagent Processing cost is higher.
Patent (CN 201210432185.4) goes out the aluminium foil in anode material of lithium battery by electrolysis stripping, obtains simultaneously Positive electrode active material lithium cobalt leachate.Although the method technical process is simple, need to provide applied voltage, consumes electric energy.
The existing method for recycling useless anode material of lithium battery mostly uses greatly the methods of acidleach, organic acidleach, alkali leaching, electrolysis Selectivity all leaches positive cobalt acid lithiums, intermediate along with extraction, precipitating, distillation, not only needs to consume a large amount of Chemical reagent also brings along the emission problem of air pollution and waste liquid, complex steps, high operation requirements.
Summary of the invention
In order to solve it is above-mentioned in the prior art it is more using Chemical Leaching reagent and microbiological fuel cell electricity production and Power density is lower, cobalt leaching rate is low technical problem, and provide and a kind of leach cobalt acid lithium using microbiological fuel cell Method.
The invention is realized by the following technical scheme, a method of cobalt acid lithium being leached using microbiological fuel cell, The preparation method is as follows:
It constructs double-chamber microbiological fuel cell (hereinafter referred to as MFC), including cathode chamber and anode chamber, the cathode chamber and sun Separated between pole room by proton exchange membrane；It include cathode made by the carbon paper of load cobalt acid lithium particle, institute in the cathode chamber Stating includes anode made by the modified carbon paper of load carbon dust in anode chamber, and an electricity is connected between the cathode and the anode Resistance；NaCl solution is added in full room in the cathode chamber, tames in the anode chamber by substrate, inoculation of sodium acetate solution Activated sludge；MFC operation electricity production forms power circuit, and leaches the cobalt in cobalt acid lithium.
Further, the carbon paper is to first pass through pretreatment and then loaded again；The preprocessing process are as follows: set The H for being 30% in concentration2O215~30min is impregnated in solution to be rushed repeatedly after immersion with water to remove carbon paper surface impurity Carbon paper surface is washed until its surface p H is invariable, finally by carbon paper drying.
Further, the carbon paper preparation method of the load cobalt acid lithium particle are as follows: mix cobalt acid lithium particle with bonding agent Merge under ultrasonic wave stirring formed the first dispersion, by first dispersion be applied to carbon paper surface and dry to get Load the carbon paper of cobalt acid lithium particle.
Wherein density of the cobalt acid lithium particle in the first dispersion is 0.125~0.25g/mL.
Further, the modified carbon paper preparation method of the load carbon dust are as follows: mix carbon dust with bonding agent and super Stirring forms the second dispersion under sound wave, and second dispersion is applied to the surface of carbon paper and is dried to get load carbon dust Modified carbon paper.
Wherein density of the carbon dust in the second dispersion is 0.125~0.25g/mL.
Wherein the bonding agent be mass fraction be 30%~50% ptfe emulsion, aqueous epoxy resins cream One of liquid, waterglass.Bonding agent need to meet by carbon dust or cobalt acid lithium it is bonding with carbon paper after can meet water it is insoluble, solidification after Thickness is thin, can make the characteristics of carbon paper and carbon dust or cobalt acid lithium close contact.
Further, the spacing of the anode and the cathode is 4~8cm.Electrode spacing is excessive or too small to system production Electrical property has an impact, and will affect the transmitting of proton and electronics.
Further, the concentration of the NaCl solution is 4~5g/L；The concentration of the sodium acetate solution is 2g/L.
Further, the activated sludge of the domestication is tamed and dociled in domestication liquid, in the environment of 25 DEG C of room temperature, darkness, anaerobism Change 6~8 days and obtains；Its inoculum concentration in anode chamber of the activated sludge of the domestication is 0.3~0.35 times of anode chamber's volume, institute The volume ratio of the activated sludge and substrate of stating domestication is 1:2.Domestication is influenced micro- to obtain electricity production strain under certain condition Biology electricity production environmental factor include temperature, pH, dissolved oxygen and concentration, 25 DEG C of electricity production bacterium activity of room temperature are higher, temperature it is too low or Person is too high all to influence its survival rate；Secondly, the process of culture strain should avoid illumination；It is molten in order to make for keeping anaerobic state Solution oxygen and oxidation-reduction potential are maintained at lower level.
Wherein contain in every 1L domestication liquid: 0.2~0.4g of sucrose, 0.2~0.4g of potassium dihydrogen phosphate, dipotassium hydrogen phosphate 0.2 ~0.4g, 0.1~0.2g of triammonium citrate, 0.1~0.3g of sodium chloride, 0.3~0.4g of ammonium chloride, 0.3~0.4g of magnesium chloride, chlorine Change 0.1~0.2g of calcium.
Advantageous effects: one aspect of the present invention increases its surface-active by the modified anode of carbon dust, and greatly speeds up electricity Pole surface biochemical reaction process, another aspect cathode chamber do not generate secondary pollution using sodium chloride solution, and the two, which combines, makes electronics Transmission efficiency and MFC system power improve, and constructed MFC open-circuit voltage is greater than 0.724V, and power density is greater than 6822.76mW/m2, the leaching rate of cobalt is greater than 48% in cobalt acid lithium；On the one hand the present invention is lived using the carbon paper of the modified anode of carbon dust Property sludge in microbial degradation organic matter and discharge electronics make produce electricity flora accumulate in modified anode, modified anode more has Conducive to microorganism growth, the electronics generated is made to be easier to transmit to anode surface, chemical energy is changed into electric energy, leaches useless lithium electricity Cobalt in the positive pole material of lithium cobalt acid of pond；Another aspect the method for the present invention operating condition is mild, process flow is simple, it is secondary not generate Pollution, electricity generation performance is higher simultaneously, leaching process is not necessarily to other Chemical Leaching reagents, is that a kind of energy conservation and environmental protection realizes waste treatment and waste Useless lithium battery recycle processing method.
Detailed description of the invention
Fig. 1 is the MFC schematic device of the method for the present invention building.
Fig. 2 is the voltage versus time curve for the microbiological fuel cell that embodiment 1 and comparative example 1 construct.
Fig. 3 is the power density curve graph for the microbiological fuel cell that embodiment 1 and comparative example 1 construct.
Fig. 4 is the carbon of the anode as made by the modification carbon paper of load carbon dust and the unsupported carbon dust of comparative example 1 in embodiment 1 Anode made by paper, surface both SEM figure.
Fig. 5 is the carbon of the anode as made by the modification carbon paper of load carbon dust and the unsupported carbon dust of comparative example 1 in embodiment 1 Anode made by paper, the graph of pore diameter distribution of the two.
Specific embodiment
The present invention is further described below in conjunction with drawings and the specific embodiments, but does not limit the scope of the invention.
Embodiment 1
(1) carbon paper is modified:
1. carbon paper pre-processes: electrode material of the 6cm × 6cm carbon paper of 0.2cm thickness as anode and cathode is chosen, by carbon Paper is placed in the H that concentration is 30%2O220min is impregnated in solution, to remove its surface impurity, then uses deionized water repeated flushing Then its surface is dried spare until surface p H is invariable.
2. being modified: a, preparing anode: the ptfe emulsion for being 30% by 0.5g200 mesh carbon dust and 4mL mass fraction It pours into beaker, is put into ultrasonic agitation in supersonic wave cleaning machine and disperses 10min to sample in the second dispersion of thick formation, incite somebody to action Second dispersion homogeneous is applied to carbon paper surface, is supported on carbon paper table to what carbon dust uniformly consolidated using the method for drying bonding The modified carbon paper of load carbon dust is made and as anode in face.B, cathode is prepared: in 2. a same method that 0.5g cobalt is sour Lithium powder is dispersed in the ptfe emulsion that 4mL mass fraction is 30% and forms the first dispersion, by the first dispersion It is supported on the carbon paper by 1. handling, the carbon paper of load cobalt acid lithium particle is made and as cathode.
(2) microbiological fuel cell is constructed:
MFC schematic device is as shown in Figure 1, include cathode chamber and anode chamber, two Room dischargeable capacitys are 500mL, described Separated between cathode chamber and anode chamber by proton exchange membrane, the effective area of the proton exchange membrane is 9cm2；The cathode chamber In include cathode made by the carbon paper of load cobalt acid lithium particle, include that the modified carbon paper of load carbon dust is made in the anode chamber At anode, between the cathode and the anode only connection resistance；It is 4g/L's that 500mL concentration is added in the cathode chamber NaCl solution using 320mL concentration is 2g/L sodium acetate solution as substrate, the activated sludge of inoculation domestication in the anode chamber 160mL；The spacing of two electrodes is 6cm；MFC brings into operation, and forms power circuit, and the cobalt in cobalt acid lithium starts to leach.
Wherein the activated sludge of the domestication is to tame 7 days to obtain under 25 DEG C of room temperature dark anaerobic environments in domestication liquid； Wherein contain in every 1L domestication liquid: sucrose 0.38g, potassium dihydrogen phosphate 0.21g, dipotassium hydrogen phosphate 0.21g, triammonium citrate 0.12g, sodium chloride 0.17g, ammonium chloride 0.4g, magnesium chloride 0.4g, calcium chloride 0.12g.
MFC working principle is as shown in Figure 1, act on anode substrate using the Microbial Communities in Activated Sludge of domestication and by its oxygen Change and generates electronics e?, proton H+And metabolite；The e of generation?Being transferred to anode surface from microbial cell restores electrode；e? Cathode is reached via external circuit；The H of generation+It is migrated to cathode chamber and is arrived by the proton exchange membrane of anode chamber and cathode chamber Up to cathode surface；The H that the cobalt acid lithium particle of cathode surface and anode transmitting come in the cathodic compartment+And e?Occur also in cathode surface Original reaction, forms full current circuit.
The postrun open-circuit voltage of measurement MFC simultaneously calculates Co in power density and measurement infusion solution2+Concentration.
Comparative example 1
This comparative example is identical as the preparation method of embodiment 1, and difference is that (1) does not 2. add carbon dust in a, directly will be through It crosses the carbon paper (being collectively referred to as unmodified carbon paper) that (1) is 1. handled and is applied to anode, microbiological fuel cell is made.
The postrun open-circuit voltage of measurement MFC simultaneously calculates Co in power density and measurement infusion solution2+Concentration, data are shown in Table 1.
1 embodiment 1 of table, the data of comparative example 1
Open-circuit voltage (V) Power density (mW/m2) Co2+Concentration (mg/L) Co2+Leaching rate (%)
Embodiment 1 0.724 6822.76 479.6 48
Comparative example 1 0.569 4406.46 326.5 33
After MFC starting, the open-circuit voltage of measurement embodiment 1, comparative example 1, data such as Fig. 2 institute of embodiment 1 and comparative example 1 Show, the voltage of MFC reaches stationary value after 2~3 days, at this point, comparative example 1 it is non-modified carbon paper electrode composition MFC maximum Open-circuit voltage is 0.569V, and the maximum open circuit voltage of the MFC of the modified carbon paper electrode composition of 1 carbon dust of embodiment is 0.724V.Change Open-circuit voltage after property is non-modified 1.27 times.
By steady-state discharge method, embodiment 1, the power density of comparative example 1 and comparative example 2 are calculated after measuring voltage, is implemented The data of example 1 and comparative example 1 are as shown in figure 3, from the figure 3, it may be seen that the MFC for the carbon paper electrode composition that 1 carbon dust of embodiment is modified is maximum Power density is 6822.76mW/m2, the MFC maximum power density of the unmodified carbon paper electrode of comparative example 1 composition is 4406.46mW/ m2.Modified power density is non-modified 1.55 times.
After MFC operation, Co in cobalt acid lithium3+Start to leach, is reduced to stable Co after about 4~5 hours2+, use atom Absorption spectrometry measures Co in solution2+Concentration measures its catholyte of MFC Co of unmodified carbon paper electrode composition in comparative example 12+ Concentration is 326.5mg/L, leaching rate 33%；Its catholyte of MFC Co of the modified carbon paper electrode composition of 1 carbon dust of embodiment2+Concentration For 479.6mg/L, leaching rate 48%, modified leaching rate is non-modified 1.45 times.
Electrode made of electrode made of the modified carbon paper of 1 carbon dust of embodiment and the unmodified carbon paper of comparative example 1, the two table Face SEM schemes as shown in figure 4, electrode surface roughness made of unmodified carbon paper is smaller in Fig. 4 (a), and degree of folding is not high, more It is smooth, but after its surface loads upper carbon dust by drying adhering method, surface is in many tiny particles content heaps in Fig. 4 (b) Folded pattern, the small particle of stacking is compact-sized, a large amount of aperture is produced each other, so that the modified carbon paper of carbon dust exists It is superior to unmodified carbon paper in terms of pore structure, surface roughness and degree of folding, the attachment for being more advantageous to microorganism makes it Show greater activity.
Electrode made of electrode made of the carbon paper modified to 1 carbon dust of embodiment and the unmodified carbon paper of comparative example 1 carries out The observation of pore-size distribution, as shown in figure 5, can be seen that unmodified carbon paper electrode specific surface area is 230.331m by Fig. 5 (a)2/ g, Kong Rongwei 0.209cm3/ g knows that the modified carbon paper electrode specific surface area of load carbon dust is 917.610m by Fig. 5 (b)2/ g, Kong Rongwei 0.668cm3/ g, it is seen that the modification of carbon dust can increase the specific surface area of carbon paper, Kong Rong, and the attachment for being more advantageous to microorganism makes it Greater activity is shown, and cost is relatively low for carbon dust, more conducively MFC industrial application.
Embodiment 2
(1) carbon paper is modified:
1. carbon paper pre-processes: electrode material of the 6cm × 6cm carbon paper of 0.2cm thickness as anode and cathode is chosen, by carbon Paper is placed in the H that concentration is 30%2O215min is impregnated in solution, to remove its surface impurity, then uses deionized water repeated flushing Then its surface is dried spare until surface p H is invariable.
2. being modified: a, preparing anode: the waterglass that 200 mesh carbon dust of 0.5g and 2mL mass fraction are 40% is poured into beaker In, being put into ultrasonic agitation in supersonic wave cleaning machine and being dispersed to sample is in the second dispersion of thick formation, and the second dispersion is equal It is even to be applied to carbon paper surface, carbon paper surface is supported on to what carbon dust uniformly consolidated using the method for drying bonding, load carbon is made The modified carbon paper of powder and as anode.B, it prepares cathode: being dispersed in 0.5g cobalt acid lithium powder in the same method of 2. a In the waterglass that 2mL mass fraction is 40% and the first dispersion is formed, the first dispersion is supported on the carbon by 1. handling On paper, the carbon paper of load cobalt acid lithium particle is made and as cathode.
(2) microbiological fuel cell is constructed:
MFC schematic device is as shown in Figure 1, include cathode chamber and anode chamber, two Room dischargeable capacitys are 500mL, described Separated between cathode chamber and anode chamber by proton exchange membrane, the effective area of the proton exchange membrane is 9cm2；The cathode chamber In include cathode made by the carbon paper of load cobalt acid lithium particle, include that the modified carbon paper of load carbon dust is made in the anode chamber At anode, between the cathode and the anode only connection resistance；It is 4.5g/L that 500mL concentration is added in the cathode chamber NaCl solution, using 320mL concentration be 2g/L sodium acetate solution as substrate, the activated sludge of inoculation domestication in the anode chamber 160mL；The spacing of two electrodes is 4cm；MFC brings into operation, and forms power circuit, and the cobalt in cobalt acid lithium starts to leach.
Wherein the activated sludge of the domestication is to tame 7 days to obtain under 25 DEG C of room temperature dark anaerobic environments in domestication liquid； Wherein contain in every 1L domestication liquid: sucrose 0.2g, potassium dihydrogen phosphate 0.4g, dipotassium hydrogen phosphate 0.4g, triammonium citrate 0.1g, chlorine Change sodium 0.1g, ammonium chloride 0.3g, magnesium chloride 0.3g, calcium chloride 0.1g.
It by steady-state discharge method, measures voltage and calculates power density, the present embodiment maximum open circuit voltage is 0.731V, maximum power density 6870.32mW/m2；Co in infusion solution2+Leaching rate be 49%.
Embodiment 3
(1) carbon paper is modified:
1. carbon paper pre-processes: electrode material of the 6cm × 6cm carbon paper of 0.2cm thickness as anode and cathode is chosen, by carbon Paper is placed in the H that concentration is 30%2O230min is impregnated in solution, to remove its surface impurity, then uses deionized water repeated flushing Then its surface is dried spare until surface p H is invariable.
2. being modified: a, preparing anode: the aqueous epoxy resins cream for being 50% by 0.5g200 mesh carbon dust and 3mL mass fraction Liquid pours into beaker, is put into supersonic wave cleaning machine ultrasonic agitation and is dispersed to sample in the second dispersion of thick formation, by the Two dispersion homogeneous are applied to carbon paper surface, are supported on carbon paper surface to what carbon dust uniformly consolidated using the method for drying bonding, The modified carbon paper of load carbon dust is made and as anode.B, cathode is prepared: in the same method of 2. a by 0.5g cobalt acid lithium powder End is dispersed in the aqueous epoxy resin emulsion that 3mL mass fraction is 50% and is formed the first dispersion, and the first dispersion is born It is loaded on the carbon paper by 1. handling, the carbon paper of load cobalt acid lithium particle is made and as cathode.
(2) microbiological fuel cell is constructed:
MFC schematic device is as shown in Figure 1, include cathode chamber and anode chamber, two Room dischargeable capacitys are 500mL, described Separated between cathode chamber and anode chamber by proton exchange membrane, the effective area of the proton exchange membrane is 9cm2；The cathode chamber In include cathode made by the carbon paper of load cobalt acid lithium particle, include that the modified carbon paper of load carbon dust is made in the anode chamber At anode, between the cathode and the anode only connection resistance；It is 5g/L's that 500mL concentration is added in the cathode chamber NaCl solution using 320mL concentration is 2g/L sodium acetate solution as substrate, the activated sludge of inoculation domestication in the anode chamber 160mL；The spacing of two electrodes is 8cm；MFC brings into operation, and forms power circuit, and the cobalt in cobalt acid lithium starts to leach.
Wherein the activated sludge of the domestication is to tame 7 days to obtain under 25 DEG C of room temperature dark anaerobic environments in domestication liquid； Wherein contain in every 1L domestication liquid: sucrose 0.4g, potassium dihydrogen phosphate 0.3g, dipotassium hydrogen phosphate 0.3g, triammonium citrate 0.2g, chlorine Change sodium 0.3g, ammonium chloride 0.3g, magnesium chloride 0.3g, calcium chloride 0.2g.
By steady-state discharge method, measures voltage and calculate power density, the present embodiment maximum open circuit voltage is 0.736V, maximum power density 6893.11mW/m2；Co in infusion solution2+Leaching rate be 49%.
Comparative example 2
2 groups of dual chamber MFC devices are built, building method is same as Example 3, the difference is that: NaCl is molten in cathode chamber The concentration of liquid is respectively 3g/L, 6g/L.
By steady-state discharge method, measures voltage and calculate Co2+Leaching rate.
The data of Examples 1 to 3 and comparative example 2 are shown in Table 2.
The data of table 2 Examples 1 to 3 and comparative example 2
From the data of table 2 it is found that NaCl solution concentration can influence electricity production and the Co of microorganism2+Leaching rate, NaCl solution Concentration is in the range of 4~5g/L, the open-circuit voltage and Co of MFC2+Leaching rate is higher, and the too low meeting of NaCl concentration in comparative example 2 It causes cathode chamber ion concentration relatively low, electron transmission is had an impact, so that leaching rate is influenced, and high salt concentration will affect biology Film (membrane structure formed on the electrode when bioelectrochemistry reaction occurs for electricity-producing microorganism) microbiological resistance, to influence Bioactivity, so that electricity production and leaching rate are relatively low.The research having at present uses phosphate buffer as MFC catholyte, to mention High conductivity, but add phosphate buffer and will increase the content of phosphorus in water, cause the secondary pollution of water body；And the present invention uses Microorganism electricity generation can be improved in suitable concentration range as catholyte in NaCl solution, improves electron transport rate, into And make the open-circuit voltage and Co of MFC2+Leaching rate is in higher level.
Comparative example 3
3 groups of dual chamber MFC devices are built, device dischargeable capacity 500mL, building method is same as Example 3, and difference exists In: the volume ratio of activated sludge and anode substrate is respectively 1:1,1:3,1:4 in anode chamber, inquires into sludge concentration and produces electricity to MFC The influence of performance.
By steady-state discharge method, voltage is measured.
The open-circuit voltage data of embodiment 3 and comparative example 3 are shown in Table 3.
The open-circuit voltage for the MFC that 3 embodiment 3 of table and comparative example 3 are built
Embodiment 3 and comparative example 3 the result shows that: when sludge and substrate volume ratio are 1:4, maximum open circuit voltage is 0.403V, when sludge is 1:3 with substrate volume ratio, maximum open circuit voltage 0.511V, when sludge and substrate volume ratio are 1:2 When, maximum open circuit voltage 0.736V, it is hereby achieved that maximum open circuit voltage is in suitable range with the increasing of sludge concentration Add and increase, this is because utilizable electricity production bacterium is more with the increase of sludge concentration.But when sludge and substrate volume Maximum open circuit voltage is 0.704V when than for 1:1, does not continue to rise, this may be the bottom because as sludge concentration rises The content of object declines therewith, and voltage is caused to decline.

Claims (10)

1. a kind of method for leaching cobalt acid lithium using microbiological fuel cell, which is characterized in that the preparation method is as follows:
Double-chamber microbiological fuel cell, including cathode chamber and anode chamber are constructed, is handed between the cathode chamber and anode chamber by proton Change film separation；
Include cathode made by the carbon paper of load cobalt acid lithium particle in the cathode chamber, includes load carbon dust in the anode chamber Anode made by modified carbon paper connects a resistance between the cathode and the anode；
NaCl solution is added in full room in the cathode chamber, tames in the anode chamber by substrate, inoculation of sodium acetate solution Activated sludge, so that double-chamber microbiological fuel cell operation electricity production is formed power circuit, and leach the cobalt in cobalt acid lithium.
2. a kind of method for leaching cobalt acid lithium using microbiological fuel cell according to claim 1, which is characterized in that institute Stating carbon paper is to first pass through pretreatment and then loaded again；The preprocessing process are as follows: carbon paper is placed in the H that concentration is 30%2O2 15~30min is impregnated in solution, to remove carbon paper surface impurity, with water repeated flushing carbon paper surface until its table after immersion Face pH is invariable, finally by carbon paper drying for standby.
3. a kind of method for leaching cobalt acid lithium using microbiological fuel cell according to claim 1 or 2, feature exist In the carbon paper preparation method of the load cobalt acid lithium particle are as follows: mix cobalt acid lithium particle with bonding agent and under ultrasonic wave Stirring forms the first dispersion, and first dispersion is applied to the surface of carbon paper and is dried to get load cobalt acid lithium particle Carbon paper.
4. a kind of method for leaching cobalt acid lithium using microbiological fuel cell according to claim 3, which is characterized in that institute Stating density of the cobalt acid lithium particle in the first dispersion is 0.125~0.25g/mL；The bonding agent is that mass fraction is 30% One of~50% ptfe emulsion, aqueous epoxy resins, waterglass.
5. a kind of method for leaching cobalt acid lithium using microbiological fuel cell according to claim 1 or 2, feature exist In the modified carbon paper preparation method of the load carbon dust are as follows: mix carbon dust with bonding agent and stir formation under ultrasonic wave Second dispersion is applied to the surface of carbon paper and dries the carbon paper modified to get load carbon dust by the second dispersion.
6. a kind of method for leaching cobalt acid lithium using microbiological fuel cell according to claim 5, which is characterized in that institute Stating density of the carbon dust in the second dispersion is 0.125~0.25g/mL；The bonding agent is that mass fraction is 30%~50% Ptfe emulsion, aqueous epoxy resins, one of waterglass.
7. a kind of method for leaching cobalt acid lithium using microbiological fuel cell according to claim 1, which is characterized in that institute Stating the spacing between anode and the cathode is 4~8cm.
8. a kind of method for leaching cobalt acid lithium using microbiological fuel cell according to claim 1, which is characterized in that institute The concentration for stating NaCl solution is 4~5g/L；The concentration of the sodium acetate solution is 2g/L.
9. a kind of method for leaching cobalt acid lithium using microbiological fuel cell according to claim 1, which is characterized in that institute State domestication activated sludge be in domestication liquid, 25 DEG C of room temperature, darkness, anaerobic environment obtain for lower domestication 6~8 days；It is described to tame and docile Its inoculum concentration in anode chamber of the activated sludge of change is 0.3~0.35 times of anode chamber's dischargeable capacity, and the activity of the domestication is dirty The volume ratio of mud and substrate is 1:2.
10. a kind of method for leaching cobalt acid lithium using microbiological fuel cell according to claim 9, which is characterized in that Contain in domestication liquid described in every 1L: 0.2~0.4g of sucrose, 0.2~0.4g of potassium dihydrogen phosphate, 0.2~0.4g of dipotassium hydrogen phosphate, lemon 0.1~0.2g of lemon acid triamine, 0.1~0.3g of sodium chloride, 0.3~0.4g of ammonium chloride, 0.3~0.4g of magnesium chloride, calcium chloride 0.1~ 0.2g。
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