CN104518221A - Double-function negative electrode and applications of double-function negative electrode as all-vanadium flow battery negative electrode - Google Patents

Double-function negative electrode and applications of double-function negative electrode as all-vanadium flow battery negative electrode Download PDF

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CN104518221A
CN104518221A CN201310454457.5A CN201310454457A CN104518221A CN 104518221 A CN104518221 A CN 104518221A CN 201310454457 A CN201310454457 A CN 201310454457A CN 104518221 A CN104518221 A CN 104518221A
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bismuth
negative pole
difunctional
battery
carbon felt
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CN104518221B (en
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刘涛
张华民
李先锋
杨晓飞
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • 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
    • H01M2004/8684—Negative 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

Abstract

The invention relates to an all-vanadium flow battery double-function negative electrode, wherein a carbon material is adopted as a substrate, a Bi-containing electro-catalyst is modified on the surface of the substrate, the Bi-containing electro-catalyst is one or more than two selected from a Bi elementary substance, Bi2O3, a Bi halide and a Bi metal salt, the Bi halide is bismuth fluoride, bismuth trichloride, bismuth bromide, or bismuth iodide, and the Bi metal salt is bismuth sulfate, bismuth nitrate, bismuth phosphate, bismuth formate or bismuth acetate. According to the present invention, the electrode is suitable for the negative electrode of the all-vanadium flow battery, the electrocatalysis activity and the electrochemical reversibility of the electrode material on the V<2+>/V<3+> oxidation reduction reaction can be substantially improved, and the charge transfer resistance can be reduced; and the high hydrogen evolution overpotential is provided so as to inhibit the occurrence of the hydrogen evolution reaction and prolong the service life of the battery.

Description

A kind of difunctional negative pole and the application as all-vanadium flow battery negative pole thereof
Technical field
The present invention relates to the liquid flow energy storage battery field in chemical energy storage technology, particularly the electrode of all-vanadium flow battery.
Background technology
All-vanadium flow battery has power output because of it and capacity is separate, and system is flexible; Energy efficiency is high, and the life-span is long, operation stability and reliability high, self discharge is low; The addressing degree of freedom is large, pollution-free, safeguard simple, operation cost is low, fail safe advantages of higher, in scale energy storage, there is vast potential for future development, be considered to the effective ways solving the renewable energy system randomness such as solar energy, wind energy and intermittent unstable state feature, in renewable energy power generation and intelligent grid construction, have great demand.
Different from the function of general chemistry power electrode, the electrode of all-vanadium flow battery is the place of chemical energy storage system charge and discharge reaction, the electrode of this kind of battery itself does not participate in electrochemical reaction, active material in electrolyte solution accepts at electrode surface or provides electronics to complete battery chemistries reaction, carries out the transformation between electric energy and chemical energy and realizes storage or the release of energy.
At present, restricting the business-like main restriction of all-vanadium flow battery is exactly Cost Problems.Reduce its cost, main solution has two: one to be the cost reducing each critical material, as the cost of amberplex, electrolyte, pole dual-pole board; One for improving the working current density of battery operation.Because the raising of working current density can improve the power density of battery, namely larger power stage can be realized with same pile, but also floor space and the space of energy-storage system can be reduced, improve the mobility of its adaptive capacity to environment and system, the application of expansion liquid flow energy storage battery.But the raising of working current density can cause the reduction of voltage efficiency and energy efficiency.In order to improve the working current density of battery under the prerequisite not reducing energy efficiency, just needing to reduce battery polarization as much as possible, i.e. ohmic polarization, electrochemical polarization and concentration polarization, reducing voltage loss.
All-vanadium flow battery is to be dissolved in the active material that the different valence state vanadium ion in finite concentration sulfuric acid solution is both positive and negative polarity electrode reaction during battery charging and discharging.Battery diaphragm allows H ion freely to pass through, and limits passing through of V ion.Electrode reaction equation is as follows:
Positive pole:
Negative pole:
Electrode is as one of the critical component of liquid flow energy storage battery, and the impact of its performance on liquid flow energy storage battery is very big.The electro catalytic activity of electrode directly determines the intrinsic reaction rate of electrochemical reaction, affects working current density and the energy efficiency of battery largely.
In tradition flow battery, both positive and negative polarity uses identical carbon materials, and uses identical method of modifying to go to process electrode material.And in fact, because the redox reaction on both positive and negative polarity is different, the electro catalytic activity that material with carbon element aligns cathode oxidation reduction electricity right is also different, therefore positive and negative pole material should be treated with a certain discrimination.Research shows the positive pole polarization of all-vanadium flow battery and not quite, its electrochemical polarization is primarily of negative pole polarization composition, and the modification therefore for positive pole has little significance, and research emphasis should be placed in negative pole modification.
In addition, all-vanadium flow battery operationally, when working especially at higher current densities, negative pole is easy to occur evolving hydrogen reaction, the hydrogen atom being adsorbed on electrode surface can infiltrate electrode and spread in electrode, causes the infringement such as hydrogen blister, hydrogen embrittlement, has a strong impact on the working life of battery.Therefore, the generation of evolving hydrogen reaction will be avoided as far as possible.
For reducing liquid flow energy storage battery electrochemical polarization and suppressing the method for evolving hydrogen reaction to mainly contain in current published patent documentation:
(1) to electrode material as graphite felt, carbon paper etc. carry out oxidation modification process, oxygen-containing functional group is modified at carbon fiber surface, improve the electro catalytic activity of electrode, reduce the electrochemical polarization of battery, graphite felt is carried out to the method for electrochemical oxidation disclosed in patent CN101465417A and CN101182678A.
(2) to electrode material as graphite felt, carbon paper etc. carry out metalized, i.e. modified metal ion on carbon fiber surface, as (Sun, B.T. such as Sun; Skyllas-Kazacos, M.Chemical Modification and Electrochemical Behavior ofGraphite Fiber in Acidic Vanadium Solution.Electrochim.Acta1991,36,513-517.) on carbon fiber surface, modified Mn 2+, Te 4+, In 3+and Ir 3+deng, find Ir 3+there is most effect to the raising of the electro catalytic activity of electrode material, but cause the high expensive of electrode, so and be not suitable for large-scale application due to the use of noble metal.
(3) some redox reaction current potentials are added in the electrolytic solution lower than V 2+/ V 3+other elements of reaction potential, as Cr 3+, Zn 2+deng (patent WO2011136256A1), the method limits the local overcharge of negative pole to suppress the generation of side reaction by the simple chargeable capacity improving negative pole.But owing to occurring even without overcharge, evolving hydrogen reaction also can along with V 2+/ V 3+reaction is carried out simultaneously, and therefore the method can't reduce liberation of hydrogen.
Summary of the invention
The present invention aims to provide a kind of difunctional negative pole and the application as all-vanadium flow battery negative pole thereof.
For achieving the above object, the technical solution used in the present invention is:
A kind of difunctional negative pole used for all-vanadium redox flow battery, comprise carbon basal body material and its finishing containing Bi eelctro-catalyst, wherein,
Described carbon basal body material is carbon felt, graphite felt, carbon paper and carbon cloth or their combination;
Described is Bi simple substance, Bi containing Bi eelctro-catalyst 2o 3, Bi halide, Bi slaine;
Described Bi halide, for fluoridizing bismuth, bismuth chloride, bismuth bromide or bismuth iodide, is preferably bismuth chloride and bismuth bromide;
Described Bi slaine is bismuth sulfate, bismuth nitrate, bismuth phosphate, formic acid bismuth or bismuth acetate, is preferably bismuth sulfate, bismuth nitrate;
The described loading mass ratio containing Bi eelctro-catalyst is 0.05 ~ 10%, preferably, be 0.1 ~ 5%, more preferably, be 0.2 ~ 3%, loading is too low, not remarkable to the raising effect of electro catalytic activity, loading is too high, and Bi catalyst is easily reunited at carbon fiber surface, also can reduce its catalytic effect;
The described particle size containing Bi eelctro-catalyst is 1nm ~ 5 μm, preferably, is 2 ~ 500nm;
Described high electrocatalytic active electrode is prepared by infusion process:
Carbon basal body material soaking is being dissolved with in the halid inorganic or organic solution of finite concentration bismuth oxide, Bi slaine or Bi, is stirring or take out after ultrasonic disperse, put into drying box dry.Dried carbon basal body material directly can be used as the negative pole of all-vanadium flow battery, also can be warming up to 400 ~ 800 DEG C under an inert atmosphere, preferably 500 ~ 600 DEG C, logical H 2isothermal reaction 0.1-3h, by Bi 3+be reduced into Bi, then be cooled to room temperature under an inert atmosphere and make all-vanadium flow battery negative pole electrode material.
Described Bi slaine is bismuth sulfate, bismuth nitrate, bismuth phosphate, formic acid bismuth or bismuth acetate, is preferably bismuth sulfate, bismuth nitrate;
Described Bi halide, for fluoridizing bismuth, bismuth chloride, bismuth bromide or bismuth iodide, is preferably bismuth chloride and bismuth bromide;
Described inorganic solution is nitric acid, sulfuric acid, hydrochloric acid or phosphoric acid solution;
Described organic solution is ethylene glycol, formic acid, acetic acid solution;
Described inert gas is a kind of in nitrogen, argon gas or helium or their mist.
Alternatively, described high electrocatalytic active electrode is prepared by electrochemical deposition method:
Bi in electric depositing solution 3+concentration is 0.001-0.2M, and carbon basal body material, as work electrode, is Bi plate, graphite cake or platinum electrode to electrode, and adopt direct current chemical deposition, current density is 2 ~ 200mA/cm 2, preferably, be 10 ~ 80mA/cm 2; Sedimentation time is 2s ~ 30min, preferably, is 5s ~ 1min.
Alternatively, described high electrocatalytic active electrode is also prepared by electroless plating method:
Carbon basal body material is put into presoak, soaking at room temperature 1 ~ 30min, preferably 2 ~ 10min; Put into colloidal pd activation solution activation processing 2 ~ 30min, preferably 5 ~ 10min, spends deionized water; Put into and separate glue (hydrochloric acid 10 ~ 500ml L -1) middle process 1 ~ 10min, deionized water washing is about 7.0 to pH; Then put into plating solution and carry out chemical plating, regulate plating solution pH to be 9 ~ 10 by ammoniacal liquor, bath temperature maintains 70 ~ 90 DEG C, and electroless plating time is 1 ~ 10min.
Described presoak consists of stannous chloride: 4 ~ 100g L -1, hydrochloric acid: 10 ~ 500ml L -1;
Described activating solution consists of palladium bichloride: 0.1 ~ 2g L -1, stannous chloride: 4 ~ 100g L -1, sodium stannate: 10 ~ 200g L -1, hydrochloric acid: 10 ~ 500ml L -1;
Described plating solution consists of bismuth chloride: 3 ~ 100g L -1, sodium hypophosphite: 2 ~ 100g L -1, natrium citricum: 3 ~ 100g L -1, ammonium chloride: 5 ~ 200g L -1.
Described difunctional negative pole is used in all-vanadium flow battery as all-vanadium flow battery negative pole.
Tool of the present invention has the following advantages:
(1) difunctional negative pole of the present invention is adopted, because carbon material surface has supported nanometer Bi eelctro-catalyst, there is the electro catalytic activity higher compared with other metals such as Pb, Cd, In, Zn and Ca, the electrochemical polarization of flow battery can be reduced, improve the working current density of battery; It has higher overpotential of hydrogen evolution simultaneously, can suppress liberation of hydrogen, improves the life-span of battery under high workload current density.
(2) adopt difunctional negative pole of the present invention, because carbon material surface has supported nanometer Bi eelctro-catalyst, drastically increase electrode material V 2+/ V 3+the electro catalytic activity of redox reaction and electrochemical reversibility, reduce charge-transfer resistance, improves voltage efficiency and the energy efficiency of all-vanadium flow battery.
(3) adopt the all-vanadium flow battery of the difunctional negative pole of the present invention, remain on the prerequisite of more than 80% in energy efficiency under, working current density can bring up to 120mA/cm 2, the battery weight of identical power output, volume and cost are reduced all greatly.
(4) electrode preparation method of the present invention is simple, and the material used is the Bi slaine that carbon materials cheap and easy to get and price are very not expensive, has commercialization application value.
Accompanying drawing explanation
Fig. 1 is the cyclic voltammetry curve figure of carbon felt in Bi modified carbon felt and comparative example 1 in the embodiment of the present invention 1, sweep speed: 10mV/s;
Fig. 2 adopts the all-vanadium flow monocell of electrode in negative pole and comparative example 1 in the embodiment of the present invention 1 at 80mA/cm 2time charging and discharging curve;
Fig. 3 is the voltage efficiency of all-vanadium flow monocell when different current density adopting electrode in negative pole and comparative example 1 in the embodiment of the present invention 1;
Fig. 4 is the energy efficiency of all-vanadium flow monocell when different current density adopting electrode in negative pole and comparative example 1 in the embodiment of the present invention 1;
Fig. 5 be in the embodiment of the present invention 1 all-vanadium flow monocell at 140mA/cm 2time and comparative example 1 in all-vanadium flow monocell at 80mA/cm 2time voltage efficiency cyclic curve figure;
Fig. 6 be in the embodiment of the present invention 1 all-vanadium flow monocell at 140mA/cm 2time and comparative example 1 in all-vanadium flow monocell at 80mA/cm 2time energy efficiency cyclic curve figure.
Embodiment
Below by specific embodiment in detail the present invention is described in detail.
Embodiment 1
The carbon felt of certain size is immersed in 0.01M Bi (NO 3) 3hNO 3in solution, take out after ultrasonic disperse 30min, put into drying box 105 DEG C of dry 10h, then will be supported with Bi (NO 3) 3carbon felt in nitrogen atmosphere, be warming up to 600 DEG C, pass into H 2isothermal reaction 1h, by Bi 3+be reduced into Bi, then be cooled to room temperature in a nitrogen atmosphere, use scales/electronic balance weighing to determine that the loading mass ratio of Bi is 1%.
For test vanadium ion oxidation-reduction pair is at the electro-chemical activity of Bi modification Carbon felt surface, cyclic voltammetry is carried out to Bi modified carbon felt prepared by embodiment 1.Using Bi modified carbon felt as work electrode, atresia graphite cake is as to electrode, and saturated calomel electrode is as reference electrode, and the electro-chemical test instrument of employing is the CHI612 type electrochemical workstation of Shanghai Chen Hua company.Compound concentration is the electrolyte of 0.1M V (II)+0.1M V (III)+3M H2SO4, V (II)/V (III) electricity is studied the electro-chemical activity modifying Carbon felt surface at Bi, sweep limits is respectively-0.7V ~-0.2V, and sweep speed is 10mV/s.In the present embodiment, the cyclic voltammetry curve of Bi modified carbon felt as shown in Figure 1, compare the electrochemical oxidation of V (II)/V (III) on unmodified carbon felt in Bi modified carbon felt and comparative example, reduction peak position and peak current size known, Bi modified carbon felt has compared with carbon felt unmodified in comparative example the electro catalytic activity and electrochemical reversibility that significantly improve.
From embodiment 1 the Bi modified carbon felt of preparation cut be of a size of 8cm × 6cm × 0.6cm carbon felt as negative pole, use the carbon felt of unmodified Bi to be assembled into monocell as positive pole, carry out charge-discharge performance test.Anode electrolyte is 1.5M VO 2+3M H 2sO 4solution 60ml, electrolyte liquid is 1.5M V 3+3M H 2sO 4solution 60ml.It is at 80mA/cm 2time charging and discharging curve as shown in Figure 2, therefrom can find out, Bi modified carbon felt has lower initial charge voltage and higher initial discharge voltage compared with carbon felt unmodified in comparative example.The battery efficiency of Bi modified carbon felt monocell under different current density as shown in Figure 3 and Figure 4, sum up in Table 1 by current efficiency (CE), voltage efficiency (VE) and energy efficiency (EE).Compared with carbon felt unmodified in comparative example 1, in the present embodiment, the voltage efficiency of Bi modified carbon felt monocell is at 80mA/cm 2current density under brought up to 89.6% from 86.8%, energy efficiency can reach 84.4%; At 120mA/cm 2high current density under voltage efficiency brought up to 86% from 80.3%, energy efficiency brings up to 81.8%, and current density is higher, improve effect more remarkable.As shown in Figure 5 and Figure 6, compared with comparative example 1, in 300 circulations, its voltage efficiency and energy efficiency are all without obviously decay for the voltage efficiency of this battery and the cyclic curve figure of energy efficiency.Using in the monocell of Bi modified carbon felt and comparative example 4 and 5 with positive pole in comparative example 2 uses the carbon felt of other metal-modifieds to compare, and voltage efficiency and energy efficiency have also been obtained and significantly improve.
Use Bi modified carbon material as the battery efficiency of monocell in the monocell of negative pole and comparative example when different current density in each embodiment of table 1
Comparative example 1
Adopt the carbon felt of Yongdeng grand carbon element new material Co., Ltd production as comparative example, this carbon felt, without any process, cuts the carbon felt being of a size of 8cm × 6cm × 0.6cm and is assembled into monocell as both positive and negative polarity, carry out charge-discharge performance test.Anode electrolyte is 1.5M VO 2+3M H 2sO 4solution 60ml, electrolyte liquid is 1.5M V 3+3M H 2sO 4solution 60ml.Its battery efficiency under different current density is as shown in table 1.
Comparative example 2
From embodiment 1 the Bi modified carbon felt of preparation cut be of a size of 8cm × 6cm × 0.6cm carbon felt as positive pole, use the carbon felt of unmodified Bi to be assembled into monocell as negative pole, be assembled into monocell, carry out charge-discharge performance test.Anode electrolyte is 1.5M VO 2+3M H 2sO 4solution 60ml, electrolyte liquid is 1.5M V 3+3M H 2sO 4solution 60ml.Its battery efficiency under different current density is as shown in table 1, and voltage efficiency (VE) is substantially identical with comparative example 1 with energy efficiency (EE).
Comparative example 3
From embodiment 1, the Bi modified carbon felt of preparation cuts the carbon felt being of a size of 8cm × 6cm × 0.6cm and is assembled into monocell as both positive and negative polarity, carries out charge-discharge performance test.Anode electrolyte is 1.5M VO 2+3M H 2sO 4solution 60ml, electrolyte liquid is 1.5M V 3+3M H 2sO 4solution 60ml.Its battery efficiency under different current density is as shown in table 1, and voltage efficiency (VE) and energy efficiency (EE) use the efficiency of the monocell of Bi modified carbon felt low than just negative pole.
Comparative example 4
The carbon felt of certain size is immersed in 0.01M Pb (NO 3) 2hNO 3in solution, take out after ultrasonic disperse 30min, put into drying box 105 DEG C of dry 10h, then will be supported with Pb (NO 3) 2carbon felt in nitrogen atmosphere, be warming up to 600 DEG C, pass into H 2isothermal reaction 1h, by Pb 2+be reduced into Pb, then be cooled to room temperature in a nitrogen atmosphere, use scales/electronic balance weighing to determine that the loading mass ratio of Pb is 1%.
From the Pb modified carbon felt of above-mentioned preparation cut be of a size of 8cm × 6cm × 0.6cm carbon felt as negative pole, use the carbon felt of unmodified to be assembled into monocell as positive pole, carry out charge-discharge performance test.Anode electrolyte is 1.5M VO 2+3M H 2sO 4solution 60ml, electrolyte liquid is 1.5M V 3+3M H 2sO 4solution 60ml.Its battery efficiency under different current density is as shown in table 1, and voltage efficiency (VE) and energy efficiency (EE) use the efficiency of the monocell of Bi modified carbon felt low than negative pole.
Comparative example 5
The carbon felt of certain size is immersed in 0.01M Zn (NO 3) 2hNO 3in solution, take out after ultrasonic disperse 30min, put into drying box 105 DEG C of dry 10h, then will be supported with Zn (NO 3) 2carbon felt in nitrogen atmosphere, be warming up to 600 DEG C, pass into H 2isothermal reaction 1h, by Zn 2+be reduced into Zn, then be cooled to room temperature in a nitrogen atmosphere, use scales/electronic balance weighing to determine that the loading mass ratio of Zn is 1%.
From the Zn modified carbon felt of above-mentioned preparation cut be of a size of 8cm × 6cm × 0.6cm carbon felt as negative pole, use the carbon felt of unmodified to be assembled into monocell as positive pole, carry out charge-discharge performance test.Anode electrolyte is 1.5M VO 2+3M H 2sO 4solution 60ml, electrolyte liquid is 1.5M V 3+3M H 2sO 4solution 60ml.Its battery efficiency under different current density is as shown in table 1, and voltage efficiency (VE) and energy efficiency (EE) use the efficiency of the monocell of Bi modified carbon felt low than negative pole.
Comparative example 6
The carbon felt of certain size is immersed in 0.1M Bi (NO 3) 3hNO 3in solution, take out after ultrasonic disperse 30min, put into drying box 105 DEG C of dry 10h, then will be supported with Bi (NO 3) 3carbon felt in nitrogen atmosphere, be warming up to 600 DEG C, pass into H 2isothermal reaction 1h, by Bi 3+be reduced into Bi, then be cooled to room temperature in a nitrogen atmosphere, use scales/electronic balance weighing to determine that the loading mass ratio of Bi is 10%.
From the Bi modified carbon felt of above-mentioned preparation cut be of a size of 8cm × 6cm × 0.6cm carbon felt as negative pole, use the carbon felt of unmodified to be assembled into monocell as positive pole, carry out charge-discharge performance test.Anode electrolyte is 1.5M VO 2+3M H 2sO 4solution 60ml, electrolyte liquid is 1.5M V 3+3M H 2sO 4solution 60ml.Its battery efficiency under different current density is as shown in table 1, and voltage efficiency (VE) and energy efficiency (EE) use Bi loading to be that the efficiency of the monocell of the carbon felt of 1% is low than negative pole in embodiment 1.
Comparative example 7
The carbon felt of certain size is immersed in 0.0005M Bi (NO 3) 3hNO 3in solution, take out after ultrasonic disperse 30min, put into drying box 105 DEG C of dry 10h, then will be supported with Bi (NO 3) 3carbon felt in nitrogen atmosphere, be warming up to 600 DEG C, pass into H 2isothermal reaction 1h, by Bi 3+be reduced into Bi, then be cooled to room temperature in a nitrogen atmosphere, use scales/electronic balance weighing to determine that the loading mass ratio of Bi is 0.05%.
From the Bi modified carbon felt of above-mentioned preparation cut be of a size of 8cm × 6cm × 0.6cm carbon felt as negative pole, use the carbon felt of unmodified to be assembled into monocell as positive pole, carry out charge-discharge performance test.Anode electrolyte is 1.5M VO 2+3M H 2sO 4solution 60ml, electrolyte liquid is 1.5M V 3+3M H 2sO 4solution 60ml.Its battery efficiency under different current density is as shown in table 1, and voltage efficiency (VE) and energy efficiency (EE) use Bi loading to be that the efficiency of the monocell of the carbon felt of 1% is low than negative pole in embodiment 1.
Comparative example 8
The carbon felt of certain size is immersed in the sulfuric acid solution of 0.01M BiF, takes out after ultrasonic disperse 30min, put into drying box 120 DEG C of dry 10h, use scales/electronic balance weighing to determine that the loading mass ratio of BiF is 0.1%.
From the Bi modified carbon felt of above-mentioned preparation cut be of a size of 8cm × 6cm × 0.6cm carbon felt as negative pole, use the carbon felt of unmodified to be assembled into monocell as positive pole, carry out charge-discharge performance test.Anode electrolyte is 1.5M VO 2+3M H 2sO 4solution 60ml, electrolyte liquid is 1.5M V 3+3M H 2sO 4solution 60ml.Its battery efficiency under different current density is as shown in table 1, and voltage efficiency (VE) and energy efficiency (EE) use the efficiency of the monocell of BiCl modified carbon felt low than negative pole in embodiment 7.
Comparative example 9
Be immersed in the formic acid solution of 0.01M formic acid bismuth by the carbon felt of certain size, take out after ultrasonic disperse 30min, put into drying box 120 DEG C of dry 10h, the loading mass ratio using scales/electronic balance weighing determination formic acid bismuth is 3%.
From the Bi modified carbon felt of above-mentioned preparation cut be of a size of 8cm × 6cm × 0.6cm carbon felt as negative pole, use the carbon felt of unmodified to be assembled into monocell as positive pole, carry out charge-discharge performance test.Anode electrolyte is 1.5M VO 2+3M H 2sO 4solution 60ml, electrolyte liquid is 1.5M V 3+3M H 2sO 4solution 60ml.Its battery efficiency under different current density is as shown in table 1, and voltage efficiency (VE) and energy efficiency (EE) use Bi than negative pole in embodiment 8 2(SO 4) 3the efficiency of the monocell of modified carbon felt is low.
Embodiment 2
Electric depositing solution is by 12g/L BiCl 3, 55g/L tartaric acid, 100g/L glycerine and 45g/L sodium chloride solution composition, the pH value watery hydrochloric acid of solution is adjusted to about 1.0.Using the carbon felt of certain size as work electrode, be graphite cake to electrode, adopt direct current chemical deposition, current density is 10mA/cm 2, sedimentation time is 10s.Scales/electronic balance weighing is used to determine that the loading mass ratio of Bi is 1%.This negative material not only has high electrocatalytic active, can reduce the electrochemical polarization of liquid flow energy storage battery, improves the working current density of battery; And there is high overpotential of hydrogen evolution, can liberation of hydrogen be suppressed, improve the life-span of battery under high workload current density.
Monocell assembling evaluation and test condition is with embodiment 1, and difference from Example 1 is: adopt the present embodiment Bi modified carbon felt as the all-vanadium flow battery of negative pole, current density is 80mA/cm 2time, voltage efficiency and energy efficiency are respectively 89.3% and 84.2%; Current density brings up to 120mA/cm 2time, voltage efficiency and energy efficiency still remain on 85.6% and 81.7%.In 300 circulations, its voltage efficiency and energy efficiency are without obvious decay.
Embodiment 3
The graphite felt of certain size is immersed in 0.02M Bi (NO 3) 3ethylene glycol solution in, take out after ultrasonic disperse 30min, put into drying box 200 DEG C of dry 10h, then will be supported with Bi (NO 3) 3graphite felt in nitrogen atmosphere, be warming up to 500 DEG C, pass into H 2isothermal reaction 2h, by Bi 3+be reduced into Bi, then be cooled to room temperature in a nitrogen atmosphere, use scales/electronic balance weighing to determine that the loading mass ratio of Bi is 2%.This negative material not only has high electrocatalytic active, can reduce the electrochemical polarization of liquid flow energy storage battery, improves the working current density of battery; And there is high overpotential of hydrogen evolution, can liberation of hydrogen be suppressed, improve the life-span of battery under high workload current density.
Monocell assembling evaluation and test condition is with embodiment 1, and difference from Example 1 is: adopt the present embodiment Bi to modify the all-vanadium flow battery of graphite felt as negative pole, current density is 80mA/cm 2time, voltage efficiency and energy efficiency are respectively 88.9% and 84.2%; Current density brings up to 120mA/cm 2time, voltage efficiency and energy efficiency still remain on 84.8% and 81.1%.In 300 circulations, its voltage efficiency and energy efficiency are all without obviously decay.
Embodiment 4
The carbon paper of certain size is immersed in 0.005M BiCl 3hCl solution in, take out after ultrasonic disperse 60min, put into drying box 105 DEG C of dry 10h, then will be supported with BiCl 3carbon paper in argon gas atmosphere, be warming up to 550 DEG C, pass into H 2isothermal reaction 0.5h, by Bi 3+be reduced into Bi, then be cooled to room temperature under an argon atmosphere, use scales/electronic balance weighing to determine that the loading mass ratio of Bi is 0.8%.This negative material not only has high electrocatalytic active, can reduce the electrochemical polarization of liquid flow energy storage battery, improves the working current density of battery; And there is high overpotential of hydrogen evolution, can liberation of hydrogen be suppressed, improve the life-span of battery under high workload current density.
Monocell assembling evaluation and test condition is with embodiment 1, and difference from Example 1 is: adopt Bi of the present invention to modify the all-vanadium flow battery of carbon paper as negative pole, current density is 80mA/cm 2time, voltage efficiency and energy efficiency are respectively 91.0% and 85.8%; Current density brings up to 120mA/cm 2time, voltage efficiency and energy efficiency still remain on 87.4% and 82.9%.In 300 circulations, its voltage efficiency and energy efficiency are all without obviously decay.
Embodiment 5
The carbon felt of certain size is put into by 20g L -1stannous chloride and 200ml L -1in the presoak of hydrochloric acid composition, soaking at room temperature 10min; Then put into by 1g L -1palladium bichloride, 20g L -1stannous chloride, 40g L -1sodium stannate and 100ml L -1activation processing 10min in the colloidal pd activation solution of hydrochloric acid composition, spends deionized water; Put into 100ml L again -1hydrochloric acid solution glue in process 5min, deionized water washing to pH be about 7.0; Then put into by 10g L -1bismuth chloride, 20g L -1sodium hypophosphite, 20g L -1natrium citricum and 40g L -1carry out chemical plating in the plating solution of ammonium chloride composition, regulate plating solution pH to be 9 ~ 10 by ammoniacal liquor, bath temperature maintains 80 DEG C, and electroless plating time is 2min.Finally obtain the carbon felt that Bi modifies, use scales/electronic balance weighing to determine that the loading mass ratio of Bi is 2%.This negative material not only has high electrocatalytic active, can reduce the electrochemical polarization of liquid flow energy storage battery, improves the working current density of battery; And there is high overpotential of hydrogen evolution, can liberation of hydrogen be suppressed, improve the life-span of battery under high workload current density.
Monocell assembling evaluation and test condition is with embodiment 1, and difference from Example 1 is: adopt the present embodiment Bi modified carbon felt as the all-vanadium flow battery of negative pole, current density is 80mA/cm 2time, voltage efficiency and energy efficiency are respectively 91.5% and 86.2%; Current density brings up to 120mA/cm 2time, voltage efficiency and energy efficiency still remain on 87.8% and 83.3%.In 300 circulations, its voltage efficiency and energy efficiency are all without obviously decay.
Embodiment 6
The carbon felt of certain size is immersed in 0.02M Bi (NO 3) 3hNO 3in solution, take out after ultrasonic disperse 30min, put into drying box 105 DEG C of dry 10h, then will be supported with Bi (NO 3) 3carbon felt in air atmosphere, be warming up to 600 DEG C of isothermal reaction 1h, make Bi (NO 3) 3resolve into Bi 2o 3, be then cooled to room temperature, use scales/electronic balance weighing to determine Bi 2o 3loading mass ratio be 3%.This negative material not only has high electrocatalytic active, can reduce the electrochemical polarization of liquid flow energy storage battery, improves the working current density of battery; And there is high overpotential of hydrogen evolution, can liberation of hydrogen be suppressed, improve the life-span of battery under high workload current density.
Monocell assembling evaluation and test condition is with embodiment 1, and difference from Example 1 is: adopt the present embodiment Bi modified carbon felt as the all-vanadium flow battery of negative pole, current density is 80mA/cm 2time, voltage efficiency and energy efficiency are respectively 89.5% and 84.3%; Current density brings up to 120mA/cm 2time, voltage efficiency and energy efficiency still remain on 85% and 81.2%.In 300 circulations, its voltage efficiency and energy efficiency are all without obviously decay.
Embodiment 7
The carbon felt of certain size is immersed in 0.02M BiCl 3hCl solution in, take out after ultrasonic disperse 30min, put into drying box 105 DEG C of dry 10h, use scales/electronic balance weighing determine BiCl 3loading mass ratio be 3%.This negative material not only has high electrocatalytic active, can reduce the electrochemical polarization of liquid flow energy storage battery, improves the working current density of battery; And there is high overpotential of hydrogen evolution, can liberation of hydrogen be suppressed, improve the life-span of battery under high workload current density.
Monocell assembling evaluation and test condition is with embodiment 1, and difference from Example 1 is: adopt the present embodiment Bi modified carbon felt as the all-vanadium flow battery of negative pole, current density is 80mA/cm 2time, voltage efficiency and energy efficiency are respectively 89.6% and 84.8%; Current density brings up to 120mA/cm 2time, voltage efficiency and energy efficiency still remain on 85% and 81.5%.In 300 circulations, its voltage efficiency and energy efficiency are all without obviously decay.
Embodiment 8
The graphite felt of certain size is immersed in 0.05M Bi 2(SO 4) 3h 2sO 4in solution, take out after ultrasonic disperse 60min, put into drying box 120 DEG C of dry 10h, use scales/electronic balance weighing to determine Bi 2(SO 4) 3loading mass ratio be 4%.This negative material not only has high electrocatalytic active, can reduce the electrochemical polarization of liquid flow energy storage battery, improves the working current density of battery; And there is high overpotential of hydrogen evolution, can liberation of hydrogen be suppressed, improve the life-span of battery under high workload current density.
Monocell assembling evaluation and test condition is with embodiment 1, and difference from Example 1 is: adopt the present embodiment Bi to modify the all-vanadium flow battery of graphite felt as negative pole, current density is 80mA/cm 2time, voltage efficiency and energy efficiency are respectively 89.3% and 84.5%; Current density brings up to 120mA/cm 2time, voltage efficiency and energy efficiency still remain on 84.7% and 81%.In 300 circulations, its voltage efficiency and energy efficiency are all without obviously decay.
Embodiment 9
Electric depositing solution is 0.05M Bi 2(SO 4) 3h 2sO 4solution.Using the carbon cloth of certain size as work electrode, be graphite cake to electrode, adopt direct current chemical deposition, current density is 40mA/cm 2, sedimentation time is 300s.Scales/electronic balance weighing is used to determine that the loading mass ratio of Bi is 4%.This negative material not only has high electrocatalytic active, can reduce the electrochemical polarization of liquid flow energy storage battery, improves the working current density of battery; And there is high overpotential of hydrogen evolution, can liberation of hydrogen be suppressed, improve the life-span of battery under high workload current density.
Monocell assembling evaluation and test condition is with embodiment 1, and difference from Example 1 is: adopt the present embodiment Bi to modify the all-vanadium flow battery of carbon cloth as negative pole, current density is 80mA/cm 2time, voltage efficiency and energy efficiency are respectively 88.2% and 83.7%; Current density brings up to 120mA/cm 2time, voltage efficiency and energy efficiency still remain on 83.8% and 80.6%.In 300 circulations, its voltage efficiency and energy efficiency are all without obviously decay.
Embodiment 10
The carbon paper of certain size is put into by 40g L -1stannous chloride and 100ml L -1in the presoak of hydrochloric acid composition, soaking at room temperature 2min; Then put into by 1g L -1palladium bichloride, 40g L -1stannous chloride, 77.5g L -1sodium stannate and 300ml L -1activation processing 8min in the colloidal pd activation solution of hydrochloric acid composition, spends deionized water; Put into 100ml L again -1hydrochloric acid solution glue in process 4min, deionized water washing to pH be about 7.0; Then put into by 20g L -1bismuth chloride, 20g L -1sodium hypophosphite, 10gL -1natrium citricum and 35g L -1carry out chemical plating in the plating solution of ammonium chloride composition, regulate plating solution pH to be 9 by ammoniacal liquor, bath temperature maintains 80 DEG C, and electroless plating time is 2min.Finally obtain the carbon paper that Bi modifies, use scales/electronic balance weighing to determine that the loading mass ratio of Bi is 3%.This negative material not only has high electrocatalytic active, can reduce the electrochemical polarization of liquid flow energy storage battery, improves the working current density of battery; And there is high overpotential of hydrogen evolution, can liberation of hydrogen be suppressed, improve the life-span of battery under high workload current density.
Monocell assembling evaluation and test condition is with embodiment 1, and difference from Example 1 is: adopt the present embodiment Bi to modify the all-vanadium flow battery of carbon paper as negative pole, current density is 80mA/cm 2time, voltage efficiency and energy efficiency are respectively 91.8% and 86.3%; Current density brings up to 120mA/cm 2time, voltage efficiency and energy efficiency still remain on 87.4% and 83.1%.In 300 circulations, its voltage efficiency and energy efficiency are all without obviously decay.

Claims (6)

1. a difunctional negative pole, is characterized in that: described difunctional negative pole is using carbon materials as matrix, has containing Bi eelctro-catalyst in its finishing, is Bi simple substance, Bi containing Bi eelctro-catalyst 2o 3, one or two or more kinds in Bi halide or Bi slaine; Wherein Bi halide is for fluoridizing bismuth, bismuth chloride, bismuth bromide or bismuth iodide; Bi slaine is bismuth sulfate, bismuth nitrate, bismuth phosphate, formic acid bismuth or bismuth acetate.
2. difunctional negative pole according to claim 1, is characterized in that: described is 0.05 ~ 10wt% of difunctional negative pole containing the deposition of Bi eelctro-catalyst on matrix.
3. difunctional negative pole according to claim 1, is characterized in that: the described particle size containing Bi eelctro-catalyst is 1nm ~ 5 μm.
4. difunctional negative pole according to claim 1, is characterized in that: described carbon materials is a kind of in carbon felt, graphite felt, carbon paper or carbon cloth or the complex of more than two kinds in them.
5. difunctional negative pole according to claim 1, is characterized in that: described difunctional negative pole will be prepared in matrix surface containing Bi eelctro-catalyst by infusion process, electrochemical deposition method, electroless plating method or chemical vapour deposition technique, is formed containing Bi electrocatalyst layers.
6. an application for the arbitrary described difunctional negative pole of claim 1-5, is characterized in that: described difunctional negative pole is used in all-vanadium flow battery as all-vanadium flow battery negative pole.
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