CN103266331B - The self-driven microorganism electrolysis cell coupled system of a kind of microbiological fuel cell reclaims the method for simple substance cobalt from cobalt acid lithium - Google Patents

Abstract

Utilize microbiological fuel cell MFCs self-driven and the microorganism electrolysis cell MECs that is coupled reclaims the method for simple substance cobalt from cobalt acid lithium, anode is directly connected with negative electrode, and the negative electrode of MFCs is connected by resistance with the anode of MECs.MFCs cathode compartment is equipped with catholyte and cobalt acid lithium particle; The settling pond mud of inoculation sewage work of anolyte compartment is as electrochemical activity microorganism.MECs cathode compartment is equipped with the aqueous solution containing Co (II); The settling pond mud of inoculation sewage work of anolyte compartment is as electrochemical activity microorganism.Anode and cathode material are graphite material.The present invention is that original position utilizes the output electric energy of MFCs to provide effective way, is also without additional electrical energy input, provides broad space without the application of the MECs of catholyte acidity restriction.

Description

The self-driven microorganism electrolysis cell coupled system of a kind of microbiological fuel cell reclaims the method for simple substance cobalt from cobalt acid lithium

Technical field

The invention belongs to field of microbial electromechanical technology, specifically utilize microbiological fuel cell MFCs and microorganism electrolysis cell MECs features, Co (III) in conjunction with cobalt acid lithium particle leaches into liquid phase Co (II), is reduced to the change of the partial potential of simple substance cobalt by liquid phase Co (II), realizes being driven by Co (III) MFCs leached as Co (II) and the Co that is coupled (II) is reduced to the MECs process of simple substance cobalt.

Background technology

Microbiological fuel cell (MicrobialFuelCells, MFCs) and microorganism electrolysis cell (MicrobialElectrolysisCells, MECs) include anolyte compartment, anode electrode, cathode compartment, cathode electrode, proton exchange membrane.Unlike, the Gibbs free energy that the negative electrode of MFCs and anode react is less than zero, and reaction can spontaneously be carried out, and system exports electric energy; On the contrary, the Gibbs free energy that the negative electrode of MECs and anode react is greater than zero, and reaction can not spontaneously be carried out, and the external world needs the reaction of input energy drives to carry out.Utilize the MFCs exporting electric energy to drive and be coupled and need to input the MECs of electric energy, while can directly utilizing MFCs electric energy in position, at the valuable chemical of MFCs and MECs cathodic synthesis, MFCs and MECs anode also can be utilized to remove organic pollutant simultaneously, process cleans is the inevitable requirement of sustainability social development.

Cobalt is the important rare metal producing lithium ion battery, and content reaches 15 – 20% in the battery.Along with lithium ion battery a large amount of production and widely use, its environmental problem brought is also day by day serious.Meanwhile, China is again the largest production of lithium ion battery, consumption and export State, accounts for global share more than 1/3, also urgent to the demand of cobalt.Clean, reclaim rare metal cobalt in waste and old lithium ion battery efficiently, not only effectively solve battery pollution, and recycling waste, there is obvious environmental benefit, economic benefit and social benefit.

Cobalt in lithium ion battery with cobalt acid lithium (LiCoO ₂) exist, traditional recovery method mainly comprises Physical, chemical method, biological process, mainly by LiCoO ₂middle Co (III) is reduced to liquid phase Co (II) through Ore Leaching, and subsequently by liquid phase Co (II) through advanced treatment (electroless plating, solvent extraction, galvanic deposit) Call Provision, there is energy consumption and the shortcoming such as cost is high, secondary pollution, by product is many, the cycle is long, usefulness is low, technique is loaded down with trivial details.As emerging technology, although MFCs can by LiCoO ₂in particle, Co (III) is reduced to solubilised state Co (II), but also needs advanced treatment could from liquid phase Call Provision; And the output electric energy of MFCs does not obtain effective Collection and use.Although MECs can leach LiCoO ₂and obtain simple substance cobalt, but system needs to input large energy; And catholyte need be defined as stronger sour environment.Seek materialized preparation that more clean, short distance and cobalt acid lithium resource utilize combined technology, be still people pay close attention to focus.

For pH2.0, LiCoO ₂the theoretical oxidation reduction potential that middle Co (III) is reduced to Co (II) is 1.845V, is CO with organism (for sodium acetate) exhaustive oxidation ₂redox-potential (– 0.30V) can MFCs be configured to; And Co (II) reduction and pH have nothing to do, the theoretical oxidation reduction potential Jin that Co (II) under any pH (calculating with 50mg/L) is reduced to simple substance cobalt is – 0.373V, redox-potential (– 0.30V due to lower than organism (for sodium acetate)), need MECs be built, be occurred by the reaction of input energy drives.Therefore, if with Co (III) leaching for the self-driven and Co that is coupled (II) of the MFCs of Co (II) is reduced to the MECs of simple substance cobalt, can while the clean recovery realizing simple substance cobalt in waste and old lithium ion battery, for original position utilizes the output electric energy of MFCs to provide effective way; Simultaneously also for providing broad space without additional electrical energy input, the application of MECs that limits without catholyte acidity.

Summary of the invention

The invention provides a kind of clean, without outside energy consumption, the self-driven microorganism electrolysis cell technology of microbiological fuel cell that reclaims simple substance cobalt from cobalt acid lithium.

The present invention utilizes the self-driven MECs of MFCs from cobalt acid lithium, reclaim the method for simple substance cobalt, add the inorganic acid solutions such as hydrochloric acid at the cathode compartment of MFCs, cathode electrode is the electro-conductive material such as carbon-point and carbon felt, cobalt acid lithium add-on≤100g/L (w/v), cobalt acid lithium granularity 8 ~ 9 μm, cobalt acid lithium particle is attached to cathode electrode surface.

CoCl is added at the cathode compartment of MECs ₂solution, cathode electrode is the electro-conductive materials such as carbon-point.

In the anolyte compartment of MFCs and MECs, electrochemical activity microorganism and anolyte are all housed, anode electrode is the electro-conductive material such as carbon-point and carbon felt.

The negative electrode of MFCs and MECs anode are coupled by series resistance and are connected, by electric current in this resistor collecting and counting circuit.

Inoculation sewage work of described anolyte compartment settling pond mud is as electrochemical activity microorganism.

The pH:6.8 – 7.0 of described settling pond mud; Specific conductivity: 0.80 – 0.93mS/cm; Suspension solid substance: 30 – 35g/L; Chemical oxygen demand (COD) (COD): 150 – 300mg/L.

Anolyte composition is: 12.0mM sodium acetate; 5.8mMNH ₄cl; 1.7mMKCl; 17.8mMNaH ₂pO ₄h ₂o; 32.3mMNa ₂hPO ₄; Mineral element: 12.5mL/L (consists of MgSO ₄: 3.0g/L; MnSO ₄h ₂o:0.5g/L; NaCl:1.0g/L; FeSO ₄7H ₂o:0.1g/L; CaCl ₂2H ₂o:0.1g/L; CoCl ₂6H ₂o:0.1g/L; ZnCl ₂: 0.13g/L; CuSO ₄5H ₂o:0.01g/L; KAl (SO ₄) ₂12H ₂o:0.01g/L; H ₃bO ₃: 0.01g/L; Na ₂moO ₄: 0.025g/L; NiCl ₂6H ₂o:0.024g/L; Na ₂wO ₄2H ₂o:0.024g/L); VITAMIN: 12.5mL/L (consists of vitamins B ₁: 5.0g/L; Vitamins B ₂: 5.0g/L; Vitamins B ₃: 5.0g/L; Vitamins B ₅: 5.0g/L; Vitamins B ₆: 10.0g/L; Vitamins B ₁₁: 2.0g/L; Vitamin H: 2.0g/L; Para-amino benzoic acid: 5.0g/L; Thioctic Acid: 5.0g/L; Nitrilotriacetic acid: 1.5g/L).

MFCs and MECs anolyte compartment of the present invention needs to keep oxygen-free environment, by passing into nitrogen to realize anaerobic condition in operational process.

MFCs operation phase flow process of the present invention is: the organism in anolyte is by microbiological oxidation in anolyte compartment, and the proton that process produces enters cathode compartment through proton through film, and electronics imports negative electrode by external circuit.At cathode electrode surface, the proton H-H reaction in the electronics that Co (III) and the negative electrode of attachment cobalt acid lithium particle provide and solution, is reduced to solubilised state Co (II).MECs operation phase flow process of the present invention is: the organism in anolyte is by microbiological oxidation in anolyte compartment, and the electronics that MFCs produces imports MECs negative electrode.At cathode electrode surface, solubilised state Co (II) obtains the electronics that negative electrode provides, and is reduced to simple substance cobalt, thus realizes the self-driven MECs coupling process of MFCs reclaiming simple substance cobalt from cobalt acid lithium.MFCs and MECs anolyte compartment can be containing organic municipal wastewater, and MFCs and MECs cathode compartment to occur with cobalt acid lithium be respectively the reaction that Co (III) is reduced to Co (II), Co (II) is reduced to simple substance cobalt of substrate of setting out, system original position utilizes MFCs electric energy, without the need to additionally inputting energy to MECs, without the need to keeping the sour environment that MECs catholyte is stronger.While recovery Metal Values From Spent Lithium-ion Batteries cobalt, also can process the organic sewages such as municipal administration, reach good environmental pollution improvement and resource utilization effect.Process cleans, has environment and ecological benefits, Social benefit and economic benefit concurrently.

Accompanying drawing and subordinate list explanation

Fig. 1 is the structural representation that the self-driven MECs coupled system of MFCs of the present invention reclaims simple substance cobalt from cobalt acid lithium particle.

Fig. 2 is the time variation diagram that the Co (II) of cobalt acid lithium in the MFCs of embodiment 1 leaches.

Fig. 3 is the time variation diagram that in the MECs of embodiment 1, Co (II) reduces.

Fig. 4 is the polarization curve of the MFCs of embodiment 1.

Fig. 5 is the cyclic voltammetry curve of the MECs of embodiment 1.

In figure: 1 carbon-point; 2MFCs anolyte compartment; 3 carbon felts; 4 ion-exchange membranees; 5MFCs cathode compartment; 6 carbon felts; 7 cobalt acid lithium particles; 8 carbon-points; 9 reference electrodes; 10 data acquisition board; 11 external resistances; 12 reference electrodes; 13 carbon-points; 14MECs anolyte compartment; 15 carbon felts; 16 ion-exchange membranees; 17MECs cathode compartment; 18 simple substance cobalts; 19 carbon-points.

Embodiment

Embodiment 1

Step one: build MFCs and MECs, as shown in Figure 1: MFCs anolyte compartment 2 and cathode compartment 5, MECs anolyte compartment 14 and cathode compartment 17 are synthetic glass material, anolyte compartment's liquor capacity of MFCs and MECs is 15mL, the cathode chamber solution volume of MFCs and MECs is 25mL, separate with ion-exchange membrane (CMI-7000) 4 or 16, to connect between MFCs and MECs 10 Ω small resistors 11, to collect and electric current in counting circuit.

Step 2: respectively MFCs anode electrode (carbon-point and carbon felt) and cathode electrode (carbon-point and carbon felt) are placed in MFCs anolyte compartment 2 and cathode compartment 5, MECs anode electrode (carbon-point and carbon felt) and cathode electrode (carbon-point) are placed in MECs anolyte compartment 14 and cathode compartment 17.Carbon-point (Beijing three industry carbon material company) apparent size is 0.8cm × 3.5cm, carbon felt (Beijing three industry carbon material company) apparent size is 3.0cm × 2.0cm × 1.0cm).Respectively at MFCs anolyte compartment and MECs cathode compartment access reference electrode 9 and 12, collect small resistor 11 both end voltage and calculating current by computer and data collecting system 10; MFCs anode and MECs cathode potential is collected according to reference electrode.

Step 3: 0.25g cobalt acid lithium powder (granularity 8 ~ 9 μm), MFCs cathode electrode 8 are placed in 100mL deionized water, 100rpm magnetic agitation 20min, cobalt acid lithium particle is adsorbed on carbon felt completely, thus obtained MFCs leach and reduces the cathode electrode of Co (III) in the sour lithium of cobalt.

Step 4: the 0.01MHCl solution adding 25mL at MFCs cathode compartment, expose to the sun nitrogen 20min.

Step 5: add CoCl in the 25mL borate buffer (0.1M, pH6.0) of MECs cathode compartment ₂, make its concentration be 50mg/L.

Step 6: add 15mL nutrient solution respectively in MFCs and MECs anolyte compartment, it consists of 12.0mM sodium acetate; 5.8mMNH ₄cl; 1.7mMKCl; 17.8mMNaH ₂pO ₄h ₂o; 32.3mMNa ₂hPO ₄; Mineral element: 12.5mL/L (MgSO ₄: 3.0g/L; MnSO ₄h ₂o:0.5g/L; NaCl:1.0g/L; FeSO ₄7H ₂o:0.1g/L; CaCl ₂2H ₂o:0.1g/L; CoCl ₂6H ₂o:0.1g/L; ZnCl ₂: 0.13g/L; CuSO ₄5H ₂o:0.01g/L; KAl (SO ₄) ₂12H ₂o:0.01g/L; H ₃bO ₃: 0.01g/L; Na ₂moO ₄: 0.025g/L; NiCl ₂6H ₂o:0.024g/L; Na ₂wO ₄2H ₂o:0.024g/L); VITAMIN: 12.5mL/L (vitamins B ₁: 5.0g/L; Vitamins B ₂: 5.0g/L; Vitamins B ₃: 5.0g/L; Vitamins B ₅: 5.0g/L; Vitamins B ₆: 10.0g/L; Vitamins B ₁₁: 2.0g/L; Vitamin H: 2.0g/L; Para-amino benzoic acid: 5.0g/L; Thioctic Acid: 5.0g/L; Nitrilotriacetic acid: 1.5g/L).Anolyte compartment's inoculation sewage work settling pond mud 10g (Dalian Ling Shuihe sewage work).Anolyte exposes to the sun after nitrogen 20min and seals.

Step 7: the MFCs negative electrode of step 3 and the MFCs cathode compartment of step 4 and catholyte are assembled.Tame under device being placed in room temperature (20 – 25 ° C) and run.When electric current drops to below 0.02mA, namely complete one-period, and add above-mentioned medium component.When continuous three cycle output voltage stabilizations are in similar value, show the domestication of anode electrochemical active bacteria and start successfully.

Step 8: the MECs carbon-point negative electrode of step 2 is combined with the MECs cathode compartment of step 5 and catholyte.Tame under device being placed in room temperature (20 – 25 ° C) and run.When the electric current under certain voltage drops to below 0.02mA, namely complete one-period, and add above-mentioned medium component.

Step 9: by the MECs of MFCs actuation step eight in step 7.

Step 10: regularly sample, analyzes Co (II) content in liquid phase; Characterize MFCs polarization curve and MECs cyclic voltammetry curve; Calculate the ratio leaching yield of cobalt acid lithium, the ratio yield of simple substance cobalt, the negative electrode coulombic efficiency of MFCs, system energy efficiency and sour effective rate of utilization, MECs negative electrode coulombic efficiency and system energy efficiency and MFCs – MECs system total efficiency.

Following table 1 is the total efficiency of the sour effective rate of utilization of cobalt acid lithium than leaching yield, the ratio yield of simple substance cobalt, MFCs negative electrode coulombic efficiency, MFCs system energy efficiency, MFCs of embodiment 1, MECs negative electrode coulombic efficiency, MECs system energy efficiency and MFCs – MECs coupled system.

The self-driven MECs coupled system of MFCs of this enforcement example reclaims simple substance cobalt from cobalt acid lithium.The reaction occurred at MFCs negative electrode is formula (1), and the reaction carried out at MECs negative electrode is formula (2), and the net reaction of cobalt experience is as shown in (3).The ratio leaching yield (Y of cobalt acid lithium _liCoO2), the ratio yield (Y of simple substance cobalt _co), MFCs negative electrode coulombic efficiency (CE _mFC), MECs negative electrode coulombic efficiency (CE _mEC), MFCs system energy efficiency (η _mFC), MECs system energy efficiency (η _mEC), MFCs – MECs coupled system total efficiency (η _sys) and the calculating of sour effective rate of utilization (AUE) of MFCs such as formula (shown in 4) – (11).

LiCoO ₂(s)+4H ⁺+e ^-→Co ²⁺+Li ⁺+2H ₂O(1)

Co ²⁺+2e ^-→Co(2)

LiCoO ₂(s)+4H ⁺+3e ^-→Co+Li ⁺+2H ₂O(3)

$Y_{{\mathrm{LiCoO}}_2}=\frac{{\mathrm{\Δn}}_{{\mathrm{Co}}^{2+}}\×V_{\mathrm{ca}}\×a_1\×M_{{\mathrm{LiCoO}}_2}}{1000\×M_{\mathrm{Co}}\×V_{\mathrm{an}}\×{\mathrm{\ΔCOD}}_{\mathrm{MFC}}}---\left(4\right)$

$Y_{\mathrm{Co}}=\frac{{\mathrm{\Δn}}_{{\mathrm{Co}}^{2+}}\×V_{\mathrm{ca}}\×a_2}{1000\×V_{\mathrm{an}}{\mathrm{\ΔCOD}}_{\mathrm{MEC}}}---\left(5\right)$

${\mathrm{CE}}_{\mathrm{MFC}}=\frac{\∫\mathrm{Idt}}{96485\×\frac{4\×{\mathrm{\ΔCOD}}_{\mathrm{MFC}}\×V_{\mathrm{an}}}{M_{O_2}}}\×100\%---\left(6\right)$

${\mathrm{CE}}_{\mathrm{MEC}}=\frac{\∫\mathrm{Idt}}{96485\×\frac{4\×{\mathrm{\ΔCOD}}_{\mathrm{MEC}}\×V_{\mathrm{an}}}{M_{O_2}}}\×100\%---\left(7\right)$

${\mathrm{\η}}_{\mathrm{MFC}}=\frac{b_1\×V_{\mathrm{ca}}\×\mathrm{\Δ}\left[{\mathrm{Co}}^{2+}\right]\×96485}{1000\×M_{\mathrm{Co}}\×\∫\mathrm{Idt}}\×100\%---\left(8\right)$

${\mathrm{\η}}_{\mathrm{MEC}}=\frac{b_2\×V_{\mathrm{ca}}\×\mathrm{\Δ}\left[{\mathrm{Co}}^{2+}\right]\×96485}{1000\×M_{\mathrm{Co}}\×\∫\mathrm{Idt}}\×100\%---\left(9\right)$

${\mathrm{\η}}_{\mathrm{sys}}=\frac{{\mathrm{\Δn}}_{{\mathrm{Co}}^{2+}}\×V_{\mathrm{ca}}\×\frac{b_1}{1000\×M_{\mathrm{Co}}}+{\mathrm{\Δn}}_{{\mathrm{Co}}^{2+}}\×V_{\mathrm{ca}}\×\frac{b_2}{1000\×M_{\mathrm{Co}}}}{(V_{\mathrm{an}}{\mathrm{\ΔCOD}}_{\mathrm{MFC}}+V_{\mathrm{an}}{\mathrm{\ΔCOD}}_{\mathrm{MEC}})\×\frac{4}{M_{O_2}}}\×100\%---\left(10\right)$

$\mathrm{AUE}=\frac{4\×{\mathrm{\Δn}}_{{\mathrm{Co}}^{2+}}\×V_{\mathrm{ca}}}{1000\×M_{\mathrm{Co}}\×V_{\mathrm{ca}}\×\mathrm{\Δ}\left[H^{+}\right]}\×100\%---\left(11\right)$

Δ n _co2+be the changing value (mg/L) of the concentration of cobalt ions of the initial and final state of reaction in MFC or MEC, 1 is the stoichiometric number ratio of the sour lithium of cobalt and Co (II); a ₁and a ₂the stoichiometric number ratio of cobalt acid lithium and Co (II), Co (II) and simple substance cobalt respectively; b ₁and b ₂unit cobalt acid lithium leaching and the electronic number (mol/mol) required for unit Co (II) reduction respectively; M _liCoO2and M _cothe relative molecular mass (g/mol) of cobalt acid lithium and cobalt, V _anthe anolyte volume (L) of MFC or MEC, V _cathe catholyte volume (L) of MFC or MEC, Δ COD _mFCwith Δ COD _mECthe changing value (g/L) of chemical oxygen demand (COD) in MFC and MEC respectively, I is electric current in loop (A), t is reactor working time (s), and Δ [H+] is the hydrogen ion concentration changing value (mol/L) of the initial and final state of MFC cathode compartment, M _liCoO2, M _coand M _o2be average molecular or the nucleidic mass (g/mol) of cobalt acid lithium, simple substance cobalt and oxygen respectively, 96485 is Faraday's number, (C/mole ^-); 4 be unit amount of substance oxygen obtain electronic number (mol/mol), 1000 is dimension conversion unit (mg/g).

Result: in reaction times 0-6h, in MFCs, Co (II) concentration is increased to 12.7 ± 0.2mg/L (Fig. 2) gradually.And MFCs drive, starting point concentration is in the MECs of 50mg/L, Co (II) concentration is reduced to 35.1 ± 0.2mg/L (Fig. 3) gradually, while showing that this MFCs leaches cobalt acid lithium, output electrical energy drive MECs is utilized to be reduced by Co (II).The open circuit voltage of MFCs system is 0.80V, and maximum output electric energy is 1.0W/m ³(4.4A/m ³) (Fig. 4).Cyclic voltammetric analysis shows, the redox peak Chu Xian – 0.30V of MECs negative electrode and+0.20V, and maximum current window Wei – 1.35mA (– 0.3V) (Fig. 5), coincide with the reduction potential of Co (II), show that Co (II) is reduced at MECs electrode surface.

During system cloud gray model 6h, the cobalt acid lithium of MFCs is 0.65 ± 0.01gCo/gCOD than leaching yield, and negative electrode coulombic efficiency is 26 ± 2%, and system energy efficiency is 22 ± 1%, and the effective rate of utilization of acid is 9 ± 0% (tables 1); The simple substance cobalt of MECs is 0.83 ± 0.14gCo/gCOD than yield, and negative electrode coulombic efficiency is 44 ± 7%, and system energy efficiency is 52 ± 1% (tables 1); MFCs – MECs coupled system total efficiency is 11 ± 2%.These results show, the self-driven MECs coupled system of MFCs can from cobalt acid lithium efficient recovery simple substance cobalt, system is without the need to inputting energy.Municipal wastewater can be processed while utilizing MFCs electric energy, recovery Metal Values From Spent Lithium-ion Batteries cobalt in position; Also be without additional electrical energy input, provide broad space without the MECs application of catholyte acidity restriction.Process cleans is pollution-free, has environment and ecological benefits, Social benefit and economic benefit concurrently.

Claims (5)

1. utilize microbiological fuel cell MFCs self-driven microorganism electrolysis cell MECs coupled system from cobalt acid lithium, reclaim a method for simple substance cobalt, it is characterized in that,

The anode of MFCs is connected with the cathode coupling of MECs;

Add inorganic acid solution at the cathode compartment of MFCs, cathode electrode is electro-conductive material, cobalt acid lithium add-on≤100g/L (w/v), and cobalt acid lithium particle is attached to cathode electrode surface;

CoCl is added at the cathode compartment of MECs ₂solution, cathode electrode is electro-conductive material;

In the anolyte compartment of MFCs and MECs, electrochemical activity microorganism and anolyte are all housed, anode electrode is electro-conductive material;

The negative electrode of MFCs and MECs anode are coupled by series resistance and are connected, and by electric current in this resistor collecting and counting circuit, described series resistance is 1 ~ 1000;

The settling pond mud of inoculation sewage work of anolyte compartment is as electrochemical activity microorganism.

2. method according to claim 1, is characterized in that, described electro-conductive material is carbon-point or carbon felt.

3. method according to claim 1 and 2, is characterized in that, described settling pond sludge pH: 6.8 – 7.0; Specific conductivity: 0.80 – 0.93mS/cm; Suspension solid substance: 30 – 35g/L; Chemical oxygen demand (COD): 150 – 300mg/L.

4. method according to claim 1 and 2, is characterized in that, described MFCs and MECs anolyte composition is: 12.0mM sodium acetate; 5.8mMNH ₄cl; 1.7mMKCl; 17.8mMNaH ₂pO ₄h ₂o; 32.3mMNa ₂hPO ₄; Mineral element: 12.5mL/L, consists of MgSO ₄: 3.0g/L; MnSO ₄h ₂o:0.5g/L; NaCl:1.0g/L; FeSO ₄7H ₂o:0.1g/L; CaCl ₂2H ₂o:0.1g/L; CoCl ₂6H ₂o:0.1g/L; ZnCl ₂: 0.13g/L; CuSO ₄5H ₂o:0.01g/L; KAl (SO ₄) ₂12H ₂o:0.01g/L; H ₃bO ₃: 0.01g/L; Na ₂moO ₄: 0.025g/L; NiCl ₂6H ₂o:0.024g/L; Na ₂wO ₄2H ₂o:0.024g/L; VITAMIN: 12.5mL/L, consists of vitamins B ₁: 5.0g/L; Vitamins B ₂: 5.0g/L; Vitamins B ₃: 5.0g/L; Vitamins B ₅: 5.0g/L; Vitamins B ₆: 10.0g/L; Vitamins B ₁₁: 2.0g/L; Vitamin H: 2.0g/L; Para-amino benzoic acid: 5.0g/L; Thioctic Acid: 5.0g/L; Nitrilotriacetic acid: 1.5g/L.

5. method according to claim 3, is characterized in that, described MFCs and MECs anolyte composition is: 12.0mM sodium acetate; 5.8mMNH ₄cl; 1.7mMKCl; 17.8mMNaH ₂pO ₄h ₂o; 32.3mMNa ₂hPO ₄; Mineral element: 12.5mL/L, consists of MgSO ₄: 3.0g/L; MnSO ₄h ₂o:0.5g/L; NaCl:1.0g/L; FeSO ₄7H ₂o:0.1g/L; CaCl ₂2H ₂o:0.1g/L; CoCl ₂6H ₂o:0.1g/L; ZnCl ₂: 0.13g/L; CuSO ₄5H ₂o:0.01g/L; KAl (SO ₄) ₂12H ₂o:0.01g/L; H ₃bO ₃: 0.01g/L; Na ₂moO ₄: 0.025g/L; NiCl ₂6H ₂o:0.024g/L; Na ₂wO ₄2H ₂o:0.024g/L; VITAMIN: 12.5mL/L, consists of vitamins B ₁: 5.0g/L; Vitamins B ₂: 5.0g/L; Vitamins B ₃: 5.0g/L; Vitamins B ₅: 5.0g/L; Vitamins B ₆: 10.0g/L; Vitamins B ₁₁: 2.0g/L; Vitamin H: 2.0g/L; Para-amino benzoic acid: 5.0g/L; Thioctic Acid: 5.0g/L; Nitrilotriacetic acid: 1.5g/L.