CN104518221B - 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 PDFInfo
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- CN104518221B CN104518221B CN201310454457.5A CN201310454457A CN104518221B CN 104518221 B CN104518221 B CN 104518221B CN 201310454457 A CN201310454457 A CN 201310454457A CN 104518221 B CN104518221 B CN 104518221B
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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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
- 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
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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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8684—Negative electrodes
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- 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
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- 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
Technical field
The present invention relates to the liquid flow energy storage battery field in chemical energy storage technology, the more particularly to electricity of all-vanadium flow battery
Pole.
Background technology
Power output and capacity are separate because it has for all-vanadium flow battery, and system design is flexible；Energy efficiency is high, the longevity
Life length, operation stability and reliability height, self discharge is low；The addressing free degree is big, and pollution-free, maintenance is simple, and operation cost is low, peace
The advantages of full property is high, has vast potential for future development, it is considered to be solve solar energy, wind energy etc. renewable in terms of scale energy storage
The effective ways of energy electricity generation system randomness and intermittent unstable state feature, in renewable energy power generation and intelligent grid construction
In have great demand.
Different from the function of general chemistry power electrode, the electrode of all-vanadium flow battery is chemical energy storage system charge and discharge
The place of reaction, the electrode of this kind of battery is not involved in itself electrochemical reaction, and the active material in electrolyte solution is in electrode table
Face receives or provides electronics to complete battery chemistries reaction, carries out the transformation between electric energy and chemical energy and realizes the storage of energy
Or release.
At present, it is exactly Cost Problems to restrict the business-like major limitation of all-vanadium flow battery.Its cost is reduced, main solution
Certainly method has two：One is the cost for reducing each critical material, the such as cost of amberplex, electrolyte, pole dual-pole board；One
To improve the working current density of battery operation.Because the raising of working current density can improve the power density of battery, i.e.,
Bigger power output can be realized with same pile, but also can reduce floor space and the space of energy-storage system, carry
The mobility of high its adaptive capacity to environment and system, extends the application of liquid flow energy storage battery.However, working current density
Raising can cause the reduction of voltage efficiency and energy efficiency.For the work for improving battery on the premise of energy efficiency is not reduced
Make current density, it is necessary to reduce battery polarization, i.e. ohmic polarization, activation polarization and concentration polarization as much as possible, reduce electricity
Crushing consumes.
All-vanadium flow battery to be dissolved in finite concentration sulfuric acid solution in different valence state vanadium ion as battery charging and discharging when
The active material of both positive and negative polarity electrode reaction.Battery diaphragm allows H ions to pass freely through, and limits passing through for V ions.Electrode reaction
Equation is as follows：
Positive pole：
Negative pole：
Electrode is used as one of the critical component of liquid flow energy storage battery, and impact of its performance to liquid flow energy storage battery is very big.Electricity
The electro catalytic activity of pole directly determines the intrinsic reaction rate of electrochemical reaction, largely affects the work electricity of battery
Current density and energy efficiency.
Both positive and negative polarity uses identical carbon materials in traditional flow battery, and goes to process electrode using identical method of modifying
Material.And in fact, due to the redox reaction on both positive and negative polarity be it is different, material with carbon element align cathode oxidation reduction electricity to
Electro catalytic activity is also different, therefore positive and negative pole material should be treated with a certain discrimination.Research shows that the positive pole of all-vanadium flow battery polarizes simultaneously
Less, its activation polarization is mainly made up of negative pole polarization, therefore is had little significance for the modified of positive pole, should be put research emphasis
On negative pole is modified.
Additionally, all-vanadium flow battery is operationally, when especially working at higher current densities, negative pole is easy to analysis occur
Hydrogen reacts, and absorption can penetrate into electrode and the diffusion in electrode in the hydrogen atom of electrode surface, cause hydrogen blister, hydrogen embrittlement etc. to damage
Evil, has a strong impact on the working life of battery.Therefore, the generation of evolving hydrogen reaction is avoided as far as possible.
At present for reducing liquid flow energy storage battery activation polarization and suppressing evolving hydrogen reaction in published patent document
Method mainly has：
（1）Oxidation modification process is carried out to electrode material such as graphite felt, carbon paper etc., in carbon fiber surface oxygen-containing sense is modified
Group, improves the electro catalytic activity of electrode, reduces the activation polarization of battery, such as patent CN101465417A and CN101182678A
Disclosed in the method that electrochemical oxidation is carried out to graphite felt.
（2）Metalized is carried out to electrode material such as graphite felt, carbon paper etc., i.e., on carbon fiber surface modified metal from
Son, such as Sun（Sun,B.T.;Skyllas-Kazacos,M.Chemical Modification and
Electrochemical Behavior of Graphite Fiber in Acidic Vanadium
Solution.Electrochim.Acta1991,36,513-517.）Mn has been modified on carbon fiber surface2+、Te4+、In3+With
Ir3+Deng discovery Ir3+Raising to the electro catalytic activity of electrode material most has effect, but because the use of noble metal causes electrode
High expensive, so be not appropriate for large-scale application.
（3）Add some redox reaction current potentials in the electrolytic solution less than V2+/V3+The other elements of reaction potential, such as
Cr3+、Zn2+Deng（Patent WO2011136256A1）, the method limits negative pole by the simple chargeable capacity for improving negative pole
Local overcharge is suppressing the generation of side reaction.Even if yet with without overcharge generation, evolving hydrogen reaction can also be accompanied by V2+/
V3+Reaction is carried out simultaneously, therefore the method can't reduce liberation of hydrogen.
The content of the invention
The present invention is intended to provide a kind of difunctional negative pole and its application as all-vanadium flow battery negative pole.
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, including the electro-catalysis containing Bi of carbon basal body material and its surface modification
Agent, wherein,
The carbon basal body material is carbon felt, graphite felt, carbon paper and carbon cloth or their combination；
The elctro-catalyst containing Bi is Bi simple substance, Bi2O3, Bi halide, Bi slaines；
The Bi halide is fluorination bismuth, bismuth chloride, bismuth bromide or bismuth iodide, it is therefore preferable to bismuth chloride and bismuth bromide；
The Bi slaines are bismuth sulfate, bismuth nitrate, bismuth phosphate, formic acid bismuth or bismuth acetate, it is therefore preferable to bismuth sulfate, nitric acid
Bismuth；
The loading mass ratio containing Bi elctro-catalysts is 0.05~10%, it is preferable that for 0.1~5%, it is highly preferred that
For 0.2~3%, loading is too low, not notable to the raising effect of electro catalytic activity, and loading is too high, and Bi catalyst is in carbon fiber
Surface is easily reunited, and can also reduce its catalytic effect；
The particle size containing Bi elctro-catalysts is 1nm~5 μm, it is preferable that for 2~500nm；
The high electrocatalytic active electrode can be prepared by infusion process：
Carbon basal body material is immersed in dissolved with the inorganic of finite concentration bismuth oxide, Bi slaines or Bi halide or
In organic solution, take out after stirring or ultrasonic disperse, be put in drying box and be dried.Dried carbon basal body material can be used directly
Make the negative pole of all-vanadium flow battery, also can under an inert atmosphere be warming up to 400~800 DEG C, preferably 500~600 DEG C, lead to H2Constant temperature
Reaction 0.1-3h, by Bi3+Bi is reduced into, then is cooled to room temperature under an inert atmosphere and make all-vanadium flow battery negative pole electrode material
Material.
The Bi slaines are bismuth sulfate, bismuth nitrate, bismuth phosphate, formic acid bismuth or bismuth acetate, it is therefore preferable to bismuth sulfate, nitric acid
Bismuth；
The Bi halide is fluorination bismuth, bismuth chloride, bismuth bromide or bismuth iodide, it is therefore preferable to bismuth chloride and bismuth bromide；
The inorganic solution is nitric acid, sulfuric acid, hydrochloric acid or phosphoric acid solution；
The organic solution is ethylene glycol, formic acid, acetic acid solution；
The inert gas is one kind or their mixed gas in nitrogen, argon gas or helium.
Alternatively, the high electrocatalytic active electrode can be prepared by electrochemical deposition method：
Bi in electric depositing solution3+Concentration is 0.001-0.2M, and carbon basal body material, as working electrode, is Bi to electrode
Plate, graphite cake or platinum electrode, using direct current electrochemical deposition, current density is 2~200mA/cm2, it is preferable that for 10~
80mA/cm2；Sedimentation time is 2s~30min, it is preferable that for 5s~1min.
Alternatively, the high electrocatalytic active electrode also can be prepared by electroless plating method：
Carbon basal body material is put in prepreg solution, 1~30min of soaking at room temperature, preferably 2~10min；It is put into colloid palladium work
Change 2~30min of activation process, preferably 5~10min in liquid, be washed with deionized；It is put into solution glue（10~500ml of hydrochloric acid
L-1）1~10min of middle process, it is 7.0 or so that deionized water is washed to pH；It is then placed in carrying out chemical plating in plating solution, by ammoniacal liquor
It is 9~10 to adjust plating solution pH, and bath temperature maintains 70~90 DEG C, and electroless plating time is 1~10min.
The prepreg solution consists of stannous chloride：4~100g L-1, hydrochloric acid：10~500ml L-1；
The 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；
The plating solution consists of bismuth chloride：3~100g L-1, sodium hypophosphite：2~100g L-1, sodium citrate：3~100g
L-1, ammonium chloride：5~200g L-1。
The difunctional negative pole is used in all-vanadium flow battery as all-vanadium flow battery negative pole.
The invention has the advantages that：
（1）Using the present invention difunctional negative pole, because carbon material surface has supported nanometer Bi elctro-catalyst, with compared with
The higher electro catalytic activity of other metals such as Pb, Cd, In, Zn and Ca, can reduce the activation polarization of flow battery, improve electricity
The working current density in pond；Simultaneously it has higher overpotential of hydrogen evolution, can suppress liberation of hydrogen, improves battery in high workload electric current
Life-span under density.
（2）Using the difunctional negative pole of the present invention, because carbon material surface has supported nanometer Bi elctro-catalyst, greatly carry
High electrode material V2+/V3+The electro catalytic activity and electrochemical reversibility of redox reaction, reduces charge-transfer resistance,
Improve the voltage efficiency and energy efficiency of all-vanadium flow battery.
（3）Using the all-vanadium flow battery of difunctional negative pole of the invention, in energy efficiency more than 80% premise is maintained at
Under, working current density can bring up to 120mA/cm2So that the battery weight of identical power output, volume and cost are equal
Substantially reduce.
（4）The electrode preparation method of the present invention is simple, the material for being used be carbon materials cheap and easy to get and price simultaneously
Not sufficiently expensive Bi slaines, with commercialization application value.
Description of the drawings
Fig. 1 is the cyclic voltammetry curve figure that Bi modifies carbon felt in carbon felt and comparative example 1 in the embodiment of the present invention 1, and scanning is fast
Rate：10mV/s；
Fig. 2 is in 80mA/cm using the all-vanadium flow monocell of electrode in negative pole in the embodiment of the present invention 1 and comparative example 12
When charging and discharging curve；
Fig. 3 is in different electric currents using the all-vanadium flow monocell of electrode in negative pole in the embodiment of the present invention 1 and comparative example 1
Voltage efficiency during density；
Fig. 4 is in different electric currents using the all-vanadium flow monocell of electrode in negative pole in the embodiment of the present invention 1 and comparative example 1
Energy efficiency during density；
Fig. 5 be in the embodiment of the present invention 1 all-vanadium flow monocell in 140mA/cm2When and comparative example 1 in all-vanadium flow list
Battery is in 80mA/cm2When voltage efficiency cyclic curve figure；
Fig. 6 be in the embodiment of the present invention 1 all-vanadium flow monocell in 140mA/cm2When and comparative example 1 in all-vanadium flow list
Battery is in 80mA/cm2When energy efficiency cyclic curve figure.
Specific 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 into 0.01M Bi (NO3)3HNO3In solution, take out after ultrasonic disperse 30min,
It is put in drying box 105 DEG C and is dried 10h, then will be supported with Bi (NO3)3Carbon felt 600 DEG C are warming up in nitrogen atmosphere, lead to
Enter H2Isothermal reaction 1h, by Bi3+Bi is reduced into, then is cooled to room temperature in a nitrogen atmosphere, using scales/electronic balance weighing Bi is determined
Loading mass ratio be 1%.
To test the electro-chemical activity that vanadium ion oxidation-reduction pair modifies Carbon felt surface in Bi, prepared by embodiment 1
Bi modifications carbon felt has carried out cyclic voltammetry.Carbon felt is modified as working electrode using Bi, non-porous graphite cake is satisfied as to electrode
With calomel electrode as reference electrode, the electro-chemical test instrument for adopting for Shanghai Chen Hua companies CHI612 type electrochemical operations
Stand.Compound concentration is the electrolyte of 0.1M V (II)+0.1M V (III)+3M H2SO4, to V (II)/V (III) electricity to modifying in Bi
The electro-chemical activity of Carbon felt surface is studied, and sweep limits is respectively -0.7V~-0.2V, and sweep speed is 10mV/s.This reality
The cyclic voltammetry curve of the modification carbon felt of Bi in example is applied as shown in figure 1, comparing in Bi modification carbon felts and comparative example V in unmodified carbon felt
(II) electrochemical oxidation of/V (III), reduction peak position and peak current size understand that Bi modifications carbon felt is unmodified compared with comparative example
Carbon felt has the electro catalytic activity and electrochemical reversibility for significantly improving.
The Bi prepared from embodiment 1 is modified and carbon felt of the size for 8cm × 6cm × 0.6cm is cut in carbon felt as negative pole,
Monocell is assembled into as positive pole using the carbon felt of unmodified Bi, charge-discharge performance test is carried out.Anode electrolyte is 1.5M
VO2+3M H2SO4Solution 60ml, electrolyte liquid is 1.5M V3+3M H2SO4Solution 60ml.It is in 80mA/cm2When fill
Discharge curve is as shown in Fig. 2 there it can be seen that Bi modifies carbon felt has compared with unmodified carbon felt in comparative example and relatively low initially fill
Piezoelectric voltage and higher initial discharge voltage.Bi modify battery efficiency such as Fig. 3 under different current densities of carbon felt monocell with
Shown in Fig. 4, current efficiency（CE）, voltage efficiency（VE）And energy efficiency（EE）In being summarised in table 1.It is unmodified with comparative example 1
Carbon felt is compared, and the voltage efficiency of Bi modifications carbon felt monocell is in 80mA/cm in the present embodiment2Current density under carry from 86.8%
To 89.6%, energy efficiency can reach 84.4% to height；In 120mA/cm2High current density under voltage efficiency from 80.3% improve
To 86%, energy efficiency brings up to 81.8%, and current density is higher, improves effect more notable.The voltage efficiency and energy of the battery
The cyclic curve figure of amount efficiency as shown in Figure 5 and Figure 6, compared with comparative example 1, in 300 circulations, its voltage efficiency and energy
Amount efficiency is without substantially decay.Used in the monocell and comparative example 4 and 5 that positive pole in comparative example 2 modifies carbon felt using Bi
The carbon felt of other metal-modifieds is compared, and voltage efficiency and energy efficiency are also greatly improved.
Used in each embodiment of table 1 Bi modification material with carbon elements as monocell and the monocell in comparative example of negative pole Bu Tong electric
Battery efficiency during current density
Comparative example 1
Using the carbon felt of Yongdeng magnificence carbon new material Co., Ltd production as comparative example, the carbon felt is without any place
Reason, cuts the carbon felt that size is 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 VO2+3M H2SO4Solution 60ml, electrolyte liquid is 1.5M V3+3M H2SO4Solution 60ml.
Its battery efficiency under different current densities is as shown in table 1.
Comparative example 2
The Bi prepared from embodiment 1 is modified and carbon felt of the size for 8cm × 6cm × 0.6cm is cut in carbon felt as positive pole,
Monocell is assembled into as negative pole using the carbon felt of unmodified Bi, monocell is assembled into, charge-discharge performance test is carried out.Positive pole electricity
Solution liquid is 1.5M VO2+3M H2SO4Solution 60ml, electrolyte liquid is 1.5M V3+3M H2SO4Solution 60ml.It is not
With the battery efficiency under current density as shown in table 1, voltage efficiency（VE）And energy efficiency（EE）With basic phase in comparative example 1
Together.
Comparative example 3
The Bi prepared from embodiment 1 is modified and carbon felt of the size for 8cm × 6cm × 0.6cm is cut in carbon felt as positive and negative
Pole is assembled into monocell, carries out charge-discharge performance test.Anode electrolyte is 1.5M VO2+3M H2SO4Solution 60ml, negative pole
Electrolyte is 1.5M V3+3M H2SO4Solution 60ml.Its battery efficiency under different current densities is as shown in table 1, voltage
Efficiency（VE）And energy efficiency（EE）Efficiency than being the monocell that negative pole uses Bi modification carbon felts is low.
Comparative example 4
The carbon felt of certain size is immersed in into 0.01M Pb (NO3)2HNO3In solution, take out after ultrasonic disperse 30min,
It is put in drying box 105 DEG C and is dried 10h, then will be supported with Pb (NO3)2Carbon felt 600 DEG C are warming up in nitrogen atmosphere, lead to
Enter H2Isothermal reaction 1h, by Pb2+Pb is reduced into, then is cooled to room temperature in a nitrogen atmosphere, using scales/electronic balance weighing Pb is determined
Loading mass ratio be 1%.
Modify from the Pb of above-mentioned preparation and carbon felt of the size for 8cm × 6cm × 0.6cm is cut in carbon felt as negative pole, use
Unmodified carbon felt is assembled into monocell as positive pole, carries out charge-discharge performance test.Anode electrolyte is 1.5M VO2+3M
H2SO4Solution 60ml, electrolyte liquid is 1.5M V3+3M H2SO4Solution 60ml.Its battery effect under different current densities
Rate is as shown in table 1, voltage efficiency（VE）And energy efficiency（EE）It is lower than the efficiency of the monocell that negative pole modifies carbon felt using Bi.
Comparative example 5
The carbon felt of certain size is immersed in into 0.01M Zn (NO3)2HNO3In solution, take out after ultrasonic disperse 30min,
It is put in drying box 105 DEG C and is dried 10h, then will be supported with Zn (NO3)2Carbon felt 600 DEG C are warming up in nitrogen atmosphere, lead to
Enter H2Isothermal reaction 1h, by Zn2+Zn is reduced into, then is cooled to room temperature in a nitrogen atmosphere, using scales/electronic balance weighing Zn is determined
Loading mass ratio be 1%.
Modify from the Zn of above-mentioned preparation and carbon felt of the size for 8cm × 6cm × 0.6cm is cut in carbon felt as negative pole, use
Unmodified carbon felt is assembled into monocell as positive pole, carries out charge-discharge performance test.Anode electrolyte is 1.5M VO2+3M
H2SO4Solution 60ml, electrolyte liquid is 1.5M V3+3M H2SO4Solution 60ml.Its battery effect under different current densities
Rate is as shown in table 1, voltage efficiency（VE）And energy efficiency（EE）It is lower than the efficiency of the monocell that negative pole modifies carbon felt using Bi.
Comparative example 6
The carbon felt of certain size is immersed in into 0.1M Bi (NO3)3HNO3In solution, take out after ultrasonic disperse 30min, put
Enter in drying box 105 DEG C and be dried 10h, then will be supported with Bi (NO3)3Carbon felt 600 DEG C are warming up in nitrogen atmosphere, be passed through
H2Isothermal reaction 1h, by Bi3+Bi is reduced into, then is cooled to room temperature in a nitrogen atmosphere, determine Bi's using scales/electronic balance weighing
Loading mass ratio is 10%.
Modify from the Bi of above-mentioned preparation and carbon felt of the size for 8cm × 6cm × 0.6cm is cut in carbon felt as negative pole, use
Unmodified carbon felt is assembled into monocell as positive pole, carries out charge-discharge performance test.Anode electrolyte is 1.5M VO2+3M
H2SO4Solution 60ml, electrolyte liquid is 1.5M V3+3M H2SO4Solution 60ml.Its battery effect under different current densities
Rate is as shown in table 1, voltage efficiency（VE）And energy efficiency（EE）The carbon felt that Bi loadings are 1% is used than negative pole in embodiment 1
The efficiency of monocell is low.
Comparative example 7
The carbon felt of certain size is immersed in into 0.0005M Bi (NO3)3HNO3In solution, take after ultrasonic disperse 30min
Go out, be put in drying box 105 DEG C and be dried 10h, then will be supported with Bi (NO3)3Carbon felt 600 DEG C are warming up in nitrogen atmosphere,
It is passed through H2Isothermal reaction 1h, by Bi3+Bi is reduced into, then is cooled to room temperature in a nitrogen atmosphere, determined using scales/electronic balance weighing
The loading mass ratio of Bi is 0.05%.
Modify from the Bi of above-mentioned preparation and carbon felt of the size for 8cm × 6cm × 0.6cm is cut in carbon felt as negative pole, use
Unmodified carbon felt is assembled into monocell as positive pole, carries out charge-discharge performance test.Anode electrolyte is 1.5M VO2+3M
H2SO4Solution 60ml, electrolyte liquid is 1.5M V3+3M H2SO4Solution 60ml.Its battery effect under different current densities
Rate is as shown in table 1, voltage efficiency（VE）And energy efficiency（EE）The carbon felt that Bi loadings are 1% is used than negative pole in embodiment 1
The efficiency of monocell is low.
Comparative example 8
The carbon felt of certain size is immersed in the sulfuric acid solution of 0.01M BiF, is taken out after ultrasonic disperse 30min, be put into
120 DEG C are dried 10h in drying box, determine that the loading mass ratio of BiF is 0.1% using scales/electronic balance weighing.
Modify from the Bi of above-mentioned preparation and carbon felt of the size for 8cm × 6cm × 0.6cm is cut in carbon felt as negative pole, use
Unmodified carbon felt is assembled into monocell as positive pole, carries out charge-discharge performance test.Anode electrolyte is 1.5M VO2+3M
H2SO4Solution 60ml, electrolyte liquid is 1.5M V3+3M H2SO4Solution 60ml.Its battery effect under different current densities
Rate is as shown in table 1, voltage efficiency（VE）And energy efficiency（EE）Than the monocell that negative pole in embodiment 7 modifies carbon felt using BiCl
Efficiency it is low.
Comparative example 9
The carbon felt of certain size is immersed in the formic acid solution of 0.01M formic acid bismuths, is taken out after ultrasonic disperse 30min, put
Enter in drying box 120 DEG C and be dried 10h, determine that the loading mass ratio of formic acid bismuth is 3% using scales/electronic balance weighing.
Modify from the Bi of above-mentioned preparation and carbon felt of the size for 8cm × 6cm × 0.6cm is cut in carbon felt as negative pole, use
Unmodified carbon felt is assembled into monocell as positive pole, carries out charge-discharge performance test.Anode electrolyte is 1.5M VO2+3M
H2SO4Solution 60ml, electrolyte liquid is 1.5M V3+3M H2SO4Solution 60ml.Its battery effect under different current densities
Rate is as shown in table 1, voltage efficiency（VE）And energy efficiency（EE）Bi is used than negative pole in embodiment 82(SO4)3The list of modification carbon felt
The efficiency of battery is low.
Embodiment 2
Electric depositing solution is by 12g/L BiCl3, 55g/L tartaric acid, 100g/L glycerine and 45g/L sodium chloride solutions composition,
The pH value watery hydrochloric acid of solution is adjusted to 1.0 or so.It is graphite cake to electrode using the carbon felt of certain size as working electrode, adopts
Direct current electrochemical deposition is used, current density is 10mA/cm2, sedimentation time is 10s.Determine the load of Bi using scales/electronic balance weighing
Carrying capacity mass ratio is 1%.The negative material not only has high electrocatalytic active, can reduce the electrification of liquid flow energy storage battery
Polarization is learned, the working current density of battery is improved；And with high overpotential of hydrogen evolution, liberation of hydrogen can be suppressed, battery is improved in height
Life-span under working current density.
With embodiment 1, difference from Example 1 is monocell assembling evaluation and test condition：Modified using the present embodiment Bi
Used as the all-vanadium flow battery of negative pole, current density is 80mA/cm to carbon felt2When, voltage efficiency and energy efficiency are respectively 89.3%
With 84.2%；Current density brings up to 120mA/cm2When, voltage efficiency and energy efficiency still remain in 85.6% and 81.7%.
In 300 circulations, its voltage efficiency and energy efficiency are without substantially decay.
Embodiment 3
The graphite felt of certain size is immersed in into 0.02M Bi (NO3)3Ethylene glycol solution in, take after ultrasonic disperse 30min
Go out, be put in drying box 200 DEG C and be dried 10h, then will be supported with Bi (NO3)3Graphite felt 500 are warming up in nitrogen atmosphere
DEG C, it is passed through H2Isothermal reaction 2h, by Bi3+Bi is reduced into, then is cooled to room temperature in a nitrogen atmosphere, it is true using scales/electronic balance weighing
The loading mass ratio for determining Bi is 2%.The negative material not only has high electrocatalytic active, can reduce liquid energy-storage electricity
The activation polarization in pond, improves the working current density of battery；And with high overpotential of hydrogen evolution, liberation of hydrogen can be suppressed, improve
Life-span of the battery under high workload current density.
With embodiment 1, difference from Example 1 is monocell assembling evaluation and test condition：Modified using the present embodiment Bi
Used as the all-vanadium flow battery of negative pole, current density is 80mA/cm to graphite felt2When, voltage efficiency and energy efficiency are respectively
88.9% and 84.2%；Current density brings up to 120mA/cm2When, voltage efficiency and energy efficiency still remain in 84.8% He
81.1%.In 300 circulations, its voltage efficiency and energy efficiency are without substantially decay.
Embodiment 4
The carbon paper of certain size is immersed in into 0.005M BiCl3HCl solution in, after ultrasonic disperse 60min take out, put
Enter in drying box 105 DEG C and be dried 10h, then will be supported with BiCl3Carbon paper 550 DEG C are warming up in argon gas atmosphere, be passed through H2It is permanent
Temperature reaction 0.5h, by Bi3+Bi is reduced into, then is cooled to room temperature under an argon atmosphere, using scales/electronic balance weighing the load of Bi is determined
Carrying capacity mass ratio is 0.8%.The negative material not only has high electrocatalytic active, can reduce the electricity of liquid flow energy storage battery
Chemical polarization, improves the working current density of battery；And with high overpotential of hydrogen evolution, liberation of hydrogen can be suppressed, improve battery and exist
Life-span under high workload current density.
With embodiment 1, difference from Example 1 is monocell assembling evaluation and test condition：Using Bi modified carbons of the present invention
Used as the all-vanadium flow battery of negative pole, current density is 80mA/cm to paper2When, voltage efficiency and energy efficiency are respectively 91.0% He
85.8%；Current density brings up to 120mA/cm2When, voltage efficiency and energy efficiency still remain in 87.4% and 82.9%.
In 300 circulations, its voltage efficiency and energy efficiency are without substantially decay.
Embodiment 5
The carbon felt of certain size is put into by 20g L-1Stannous chloride and 200ml L-1In the prepreg solution of hydrochloric acid composition, room
Temperature immersion 10min；Then it is put into by 1g L-1Palladium bichloride, 20g L-1Stannous chloride, 40g L-1Sodium stannate and 100ml L-1Hydrochloric acid
Activation process 10min in the colloidal pd activation solution of composition, is washed with deionized；Place into 100ml L-1Hydrochloric acid solution glue in
5min is processed, it is 7.0 or so that deionized water is washed to pH；It is then placed in by 10g L-1Bismuth chloride, 20g L-1Sodium hypophosphite, 20g
L-1Sodium citrate and 40g L-1Chemical plating is carried out in the plating solution of ammonium chloride composition, it is 9~10 to adjust plating solution pH by ammoniacal liquor, plating
Liquid temp maintains 80 DEG C, and electroless plating time is 2min.The carbon felt of Bi modifications is finally obtained, using scales/electronic balance weighing Bi is determined
Loading mass ratio be 2%.The negative material not only has high electrocatalytic active, can reduce liquid flow energy storage battery
Activation polarization, improves the working current density of battery；And with high overpotential of hydrogen evolution, liberation of hydrogen can be suppressed, improve battery
Life-span under high workload current density.
With embodiment 1, difference from Example 1 is monocell assembling evaluation and test condition：Modified using the present embodiment Bi
Used as the all-vanadium flow battery of negative pole, current density is 80mA/cm to carbon felt2When, voltage efficiency and energy efficiency are respectively 91.5%
With 86.2%；Current density brings up to 120mA/cm2When, voltage efficiency and energy efficiency still remain in 87.8% and 83.3%.
In 300 circulations, its voltage efficiency and energy efficiency are without substantially decay.
Embodiment 6
The carbon felt of certain size is immersed in into 0.02M Bi (NO3)3HNO3In solution, take out after ultrasonic disperse 30min,
It is put in drying box 105 DEG C and is dried 10h, then will be supported with Bi (NO3)3Carbon felt 600 DEG C of constant temperature are warming up in air atmosphere
Reaction 1h, makes Bi (NO3)3Resolve into Bi2O3, room temperature is subsequently cooled to, determine Bi using scales/electronic balance weighing2O3Loading matter
Amount is than being 3%.The negative material not only has high electrocatalytic active, can reduce the activation polarization of liquid flow energy storage battery,
Improve the working current density of battery；And with high overpotential of hydrogen evolution, liberation of hydrogen can be suppressed, battery is improved in high workload electric current
Life-span under density.
With embodiment 1, difference from Example 1 is monocell assembling evaluation and test condition：Modified using the present embodiment Bi
Used as the all-vanadium flow battery of negative pole, current density is 80mA/cm to carbon felt2When, voltage efficiency and energy efficiency are respectively 89.5%
With 84.3%；Current density brings up to 120mA/cm2When, voltage efficiency and energy efficiency still remain in 85% and 81.2%.
In 300 circulations, its voltage efficiency and energy efficiency are without substantially decay.
Embodiment 7
The carbon felt of certain size is immersed in into 0.02M BiCl3HCl solution in, after ultrasonic disperse 30min take out, be put into
105 DEG C are dried 10h in drying box, and using scales/electronic balance weighing BiCl is determined3Loading mass ratio be 3%.The negative material is not
Only there is high electrocatalytic active, the activation polarization of liquid flow energy storage battery can be reduced, the operating current for improving battery is close
Degree；And with high overpotential of hydrogen evolution, liberation of hydrogen can be suppressed, improve life-span of the battery under high workload current density.
With embodiment 1, difference from Example 1 is monocell assembling evaluation and test condition：Modified using the present embodiment Bi
Used as the all-vanadium flow battery of negative pole, current density is 80mA/cm to carbon felt2When, voltage efficiency and energy efficiency are respectively 89.6%
With 84.8%；Current density brings up to 120mA/cm2When, voltage efficiency and energy efficiency still remain in 85% and 81.5%.
In 300 circulations, its voltage efficiency and energy efficiency are without substantially decay.
Embodiment 8
The graphite felt of certain size is immersed in into 0.05M Bi2(SO4)3H2SO4In solution, take after ultrasonic disperse 60min
Go out, be put in drying box 120 DEG C and be dried 10h, using scales/electronic balance weighing Bi is determined2(SO4)3Loading mass ratio be 4%.Should
Negative material not only has high electrocatalytic active, can reduce the activation polarization of liquid flow energy storage battery, improves battery
Working current density；And with high overpotential of hydrogen evolution, liberation of hydrogen can be suppressed, improve longevity of the battery under high workload current density
Life.
With embodiment 1, difference from Example 1 is monocell assembling evaluation and test condition：Modified using the present embodiment Bi
Used as the all-vanadium flow battery of negative pole, current density is 80mA/cm to graphite felt2When, voltage efficiency and energy efficiency are respectively
89.3% and 84.5%；Current density brings up to 120mA/cm2When, voltage efficiency and energy efficiency still remain in 84.7% He
81%.In 300 circulations, its voltage efficiency and energy efficiency are without substantially decay.
Embodiment 9
Electric depositing solution is 0.05M Bi2(SO4)3H2SO4Solution.It is right using the carbon cloth of certain size as working electrode
Electrode is graphite cake, and using direct current electrochemical deposition, current density is 40mA/cm2, sedimentation time is 300s.Using electronics day
The flat loading mass ratio for weighing determination Bi is 4%.The negative material not only has high electrocatalytic active, can reduce liquid
The activation polarization of stream energy-storage battery, improves the working current density of battery；And with high overpotential of hydrogen evolution, analysis can be suppressed
Hydrogen, improves life-span of the battery under high workload current density.
With embodiment 1, difference from Example 1 is monocell assembling evaluation and test condition：Modified using the present embodiment Bi
Used as the all-vanadium flow battery of negative pole, current density is 80mA/cm to carbon cloth2When, voltage efficiency and energy efficiency are respectively 88.2%
With 83.7%；Current density brings up to 120mA/cm2When, voltage efficiency and energy efficiency still remain in 83.8% and 80.6%.
In 300 circulations, its voltage efficiency and energy efficiency are without substantially decay.
Embodiment 10
The carbon paper of certain size is put into by 40g L-1Stannous chloride and 100ml L-1In the prepreg solution of hydrochloric acid composition, room
Temperature immersion 2min；Then it is put into by 1g L-1Palladium bichloride, 40g L-1Stannous chloride, 77.5g L-1Sodium stannate and 300ml L-1Hydrochloric acid
Activation process 8min in the colloidal pd activation solution of composition, is washed with deionized；Place into 100ml L-1Hydrochloric acid solution glue in
4min is processed, it is 7.0 or so that deionized water is washed to pH；It is then placed in by 20g L-1Bismuth chloride, 20g L-1Sodium hypophosphite, 10g
L-1Sodium citrate and 35g L-1Chemical plating is carried out in the plating solution of ammonium chloride composition, it is 9 to adjust plating solution pH by ammoniacal liquor, plating bath temperature
Degree maintains 80 DEG C, and electroless plating time is 2min.The carbon paper of Bi modifications is finally obtained, using scales/electronic balance weighing the load of Bi is determined
Carrying capacity mass ratio is 3%.The negative material not only has high electrocatalytic active, can reduce the electrification of liquid flow energy storage battery
Polarization is learned, the working current density of battery is improved；And with high overpotential of hydrogen evolution, liberation of hydrogen can be suppressed, battery is improved in height
Life-span under working current density.
With embodiment 1, difference from Example 1 is monocell assembling evaluation and test condition：Modified using the present embodiment Bi
Used as the all-vanadium flow battery of negative pole, current density is 80mA/cm to carbon paper2When, voltage efficiency and energy efficiency are respectively 91.8%
With 86.3%；Current density brings up to 120mA/cm2When, voltage efficiency and energy efficiency still remain in 87.4% and 83.1%.
In 300 circulations, its voltage efficiency and energy efficiency are without substantially decay.
Claims (4)
1. application of a kind of difunctional negative pole as all-vanadium flow battery negative pole, it is characterised in that：The difunctional negative pole conduct
All-vanadium flow battery negative pole is used in all-vanadium flow battery, and difunctional negative pole is, using carbon materials as matrix, to repair on its surface
Elctro-catalyst containing Bi is decorated with, elctro-catalyst containing Bi is Bi simple substance, Bi2O3, in Bi halide or Bi slaines one
Plant or more than two kinds；Wherein Bi halide is one or more in fluorination bismuth, bismuth chloride, bismuth bromide or bismuth iodide；
Bi slaines are one or more in bismuth sulfate, bismuth nitrate, bismuth phosphate, formic acid bismuth or bismuth acetate；It is described electric containing Bi
Deposition of the catalyst on matrix is 0.05 ~ 10wt% of difunctional negative pole；
Anode electrolyte is 1.5M VO in the all-vanadium flow battery2+3M H 2 SO 4Solution, electrolyte liquid is
1.5M V3+3M H2 SO4Solution, positive electrode surface is unmodified Bi elctro-catalysts.
2. the difunctional negative pole according to claim 1, it is characterised in that：The particle size containing Bi elctro-catalysts
For 1nm ~ 5 m.
3. the difunctional negative pole according to claim 1, it is characterised in that：The carbon materials is carbon felt, graphite felt, carbon
One kind in paper or carbon cloth or more than two kinds of complex in them.
4. the difunctional negative pole according to claim 1, it is characterised in that：The difunctional negative pole passes through infusion process, electricity
One kind in chemical deposition, electroless plating method or chemical vapour deposition technique, will contain Bi elctro-catalysts and be prepared in matrix surface, shape
Into electrocatalyst layers containing Bi.
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| CN106654298A (en) * | 2016-11-11 | 2017-05-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Negative electrode material with Sn-containing electrocatalyst of vanadium redox flow battery and preparation method for negative electrode material |
| CN106450356A (en) * | 2016-11-11 | 2017-02-22 | 攀钢集团攀枝花钢铁研究院有限公司 | Anode material of Sn-containing electrocatalyst and preparation method thereof |
| CN106410218A (en) * | 2016-11-11 | 2017-02-15 | 攀钢集团攀枝花钢铁研究院有限公司 | Sn electric catalyst vanadium cell negative electrode material and preparation method thereof |
| CN106981650B (en) * | 2017-02-10 | 2020-03-13 | 中山大学 | Preparation method of nanoscale elemental bismuth |
| CN107039670B (en) * | 2017-03-14 | 2021-01-12 | 香港科技大学 | Novel method and system for storing energy by using electric fuel |
| CN107146915B (en) * | 2017-04-10 | 2019-08-27 | 中山大学 | A kind of preparation method of porous bismuth-carbon composite |
| CN108212141B (en) * | 2018-01-02 | 2020-09-29 | 温州大学 | Preparation method and application of bismuth oxide/bismuth nanosheet composite material |
| CN110518260A (en) * | 2019-08-29 | 2019-11-29 | 辽宁金谷炭材料股份有限公司 | A kind of production method of modified vanadium cell porous electrode graphite felt |
| CN110783533B (en) * | 2019-11-05 | 2022-11-15 | 南开大学 | Metal electrode protection method using metal halide as protection layer |
| CN111359603A (en) * | 2020-03-12 | 2020-07-03 | 辽宁大学 | Bismuth-based self-supporting electrocatalyst, preparation method thereof and application of bismuth-based self-supporting electrocatalyst in ammonia production by nitrogen reduction |
| CN112054215A (en) * | 2020-08-05 | 2020-12-08 | 深圳大学 | Composite electrode for redox flow battery based on all vanadium and preparation method thereof |
| CN114256466A (en) * | 2020-09-25 | 2022-03-29 | 中国科学院金属研究所 | Negative electrode material for hydrogen evolution inhibition type vanadium battery and preparation method thereof |
| CN113659150A (en) * | 2021-07-09 | 2021-11-16 | 江苏大学 | Composite dual-functional electrode for eutectic solvent electrolyte flow battery |
| CN113753876B (en) * | 2021-07-20 | 2023-06-27 | 中南大学 | Potassium ion battery anode material and preparation method thereof |
| TWI801032B (en) * | 2021-12-13 | 2023-05-01 | 國立臺灣科技大學 | Negative electrode of redox flow battery and manufacturing method of the same |
| CN115064713A (en) * | 2022-05-31 | 2022-09-16 | 成都理工大学 | Spinel-loaded negative electrode material and preparation method and application thereof |
| CN115566132A (en) * | 2022-10-24 | 2023-01-03 | 湖南大学 | Silver-bismuth dual-functional electrode and preparation method and application thereof |
| CN116779883B (en) * | 2023-08-25 | 2023-10-17 | 寰泰储能科技股份有限公司 | Bismuth-doped all-vanadium redox flow battery electrode and preparation method thereof |
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