CN109873187A - The preparation method and electrode of a kind of zinc-iron flow battery electrode and application - Google Patents
The preparation method and electrode of a kind of zinc-iron flow battery electrode and application Download PDFInfo
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- CN109873187A CN109873187A CN201711246780.8A CN201711246780A CN109873187A CN 109873187 A CN109873187 A CN 109873187A CN 201711246780 A CN201711246780 A CN 201711246780A CN 109873187 A CN109873187 A CN 109873187A
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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
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Abstract
The invention discloses a kind of zinc-iron flow battery method for processing positive pole and applications, electrode material is soaked in the acidic aqueous solution of ferrocyanide and ferric ion and is handled, compared with former untreated electrode material, the electrode material has higher electrode activity, the conductivity of battery can effectively be improved, and then the cycle performance and battery efficiency of battery are improved, while the charge/discharge capacity and energy density of battery greatly improved.
Description
Technical field
The present invention relates to a kind of alkaline system zinc-iron flow battery electrode material and preparation method thereof and its in alkalinity
Application in system zinc-iron flow battery.
Background technique
Liquid flow energy storage battery is a kind of electrochemical energy storage new technology, compared with other energy storage technologies, has energy conversion effect
Rate height, system flexible design, capacitance of storage is big, addressing is free, can the advantages such as deep discharge, safety and environmental protection, maintenance cost be low, can
It is cut with being widely used in the energy storage of the renewable energy power generations such as wind energy, solar energy, emergency power system, stand-by station and electric system
Peak load etc..Alkaline system zinc-iron flow battery is due to highly-safe, stability is good, the service life is long (service life > 15 year), cost
A kind of low advantage, it is considered to be liquid flow energy storage battery with very high development potentiality.
Currently, restricting the commercialized major limitation of alkaline system zinc-iron flow battery is exactly cost problem.Reduce its at
This, there are two main solutions: one is the cost for reducing each critical material, such as amberplex, electrolyte, pole dual-pole board
Cost；One is the power density for improving battery.Because improving the power density of battery, so that it may be realized more with same pile
Big power output, but also occupied area and the space of energy-storage system can be reduced, improve its adaptive capacity to environment and system
Mobility, extend the application field of liquid flow energy storage battery.And the power density of battery is improved it is necessary to improve its work electricity
Current density.However, the raising of working current density will lead to the reduction of voltage efficiency and energy efficiency.In order to not reduce energy
The working current density of battery is improved under the premise of efficiency, it is necessary to reduction battery polarization as much as possible, i.e. ohmic polarization, electrification
Polarization and concentration polarization are learned, voltage loss is reduced.
Critical component one of of the electrode as alkaline system zinc-iron flow battery, influence of the performance to liquid flow energy storage battery
Greatly.Alkaline system zinc-iron electrode of liquid flow cell material in the prior art there are processes more, high production cost, electro-catalysis are living
The problems such as property is poor.And the electro catalytic activity of electrode directly determines the intrinsic reaction rate of electrochemical reaction, largely shadow
Ring the working current density and energy efficiency of battery.Therefore, in order to obtain high working current density and energy efficiency, again
Improve the electro catalytic activity of electrode material as far as possible using suitable activation method.
Summary of the invention
Present invention aims to overcome that existing zinc-iron flow battery electrode material there are the problem of, a kind of zinc-iron liquid is provided
Galvanic battery positive electrode.The reactivity and conductivity of anode can be greatly improved, to obtain that cost is extremely cheap, performance
Electrode material that is excellent, being suitble to alkaline system zinc-iron flow battery.
To achieve the above object, The technical solution adopted by the invention is as follows:
It is first soaked in electrode material in the aqueous solution of ferrocyanide, the water of ferric ion is then added thereto
Solution, immersion 0.5~taking-up electrode water cleans for use repeatedly afterwards for 24 hours；Wherein the aqueous solution of ferrocyanide and ferric iron from
At least a kind of in the aqueous solution of son is acidic aqueous solution, or is added after the aqueous solution that ferric ion is added into system
Acid makes immersion system in acidity；
Or, electrode material is first soaked in the aqueous solution of ferrocyanide, trivalent iron salt is then added thereto, soaks
Bubble 0.5~taking-up electrode water cleans for use repeatedly afterwards for 24 hours；Wherein the aqueous solution of ferrocyanide is acidic aqueous solution, or in
It is added after trivalent iron salt and acid is added into system, make immersion system in acidity；
Or, electrode material is first soaked in the aqueous solution of ferric ion, ferrocyanide is then added thereto
Aqueous solution, immersion 0.5~for 24 hours afterwards clean electrode taking-up for use repeatedly with water；The wherein aqueous solution and trivalent of ferrocyanide
At least a kind of in the aqueous solution of iron ion is acidic aqueous solution, or is added after the aqueous solution that ferric ion is added into system
Enter acid, makes immersion system in acidity；
Or, electrode material is first soaked in the aqueous solution of ferric ion, ferrocyanide is then added thereto,
Immersion 0.5~for 24 hours afterwards clean electrode taking-up for use repeatedly with water；Wherein the aqueous solution of ferric ion is acidic aqueous solution,
Or acid is added into system after ferrocyanide is added, make immersion system in acidity；
Or, electrode material is soaked in the aqueous solution of ferrocyanide and ferric ion, acid is added into system, makes
Immersion system is in acidity, immersion 0.5~for 24 hours afterwards clean electrode taking-up for use repeatedly with water；
In immersion system, the whole molar concentration of ferrous cyanogen root is 0.01~1mol/L；The whole molar concentration of ferric ion
0.01~1.5mol/L；Proton end molar concentration is 0.001~0.1mol/L.
Acid is one of hydrochloric acid, sulfuric acid, nitric acid, acetic acid or two kinds or more, ferrocyanide in solution: ferric iron from
Son: H+Molar ratio 1:1~1.5:0.05~0.2 of three.
Wherein, soaking temperature is 0~80 DEG C.
The electrode is carbon felt, carbon cloth or carbon paper material.
The cation of the ferrocyanide is one of potassium ion, sodium ion or two kinds or more；The yin of trivalent iron salt
Ion is one of chloride ion, nitrate ion, sulfate ion or two kinds or more.
Application of electrode is in zinc-iron flow battery after the processing.
Zinc-iron flow battery is Alkaline Zinc iron liquid galvanic battery or neutral zinc-iron flow battery, preferably Alkaline Zinc iron liquid galvanic electricity
Pond；Cathode is zinc electrode.
Processing method of the invention can occur to react as follows when ferrocyanide coexists with ferric ion and hydrogen ion:
3Fe(CN)6 4-+4Fe3+→Fe4[Fe(CN)6]3
Since electrode is soaked in reaction solution, Prussian blue on electrode surface and internal meeting in-situ deposition
Grain.
Beneficial outcomes of the invention
(1) electrode material prepared by the present invention, conductivity greatly improve, and then reduce alkaline system zinc-iron liquid energy-storage
Battery operation efficiency greatly improved in the internal resistance of battery.
(2) electrode material prepared by the present invention, the activity that reacts greatly improve compared with primary electrode material, make positive and negative in battery
Active material reaction in pole is accelerated, and zinc simple substance depositing homogeneous, electrolyte utilization rate increases, so as to extend battery.
(3) present invention has expanded the type and use scope of alkaline system zinc-iron electrode for flow energy storage battery material.
Such electrode material preparation method is simple, environmental friendly, and active material concentration is high.Compared with primary electrode material, with
Treated that alkaline system zinc-iron flow battery that electrode material is assembled into has higher comprehensive performance for this.
Detailed description of the invention
Fig. 1 is electrode material prepared by embodiment 1 and comparative example 1 in alkaline system zinc-iron flow battery, in 80mA
cm-2Current density under charge-discharge performance comparison.
Specific embodiment
The following examples are not intended to limit the scope of the invention to further explanation of the invention.
Embodiment 1
The carbon felt for cutting appropriately sized 6mm thickness, is first soaked in the aqueous solution of the ferrocyanide of 0.5mol/L at 20 DEG C
In, the rear acid solution that 0.7mol/L ferric ion is added, taking-up electrode water cleans repeatedly after impregnating 12h, dries spare.It is molten
Ferrocyanide in liquid: ferric ion: H+The Final molar ratio 1:1.4:0.1 of three
Using the electrode material of preparation as positive, cathode be zinc electrode, bipolar plates are graphite plate, amberplex is Du
The Nafion membrane that company, nation produces, effective area 48cm2, Alkaline Zinc iron liquid galvanic battery is assembled, current density is 80mA cm-2, just
Zincic acid ion concentration is 0.5mol L in electrolyte liquid-1, the concentration of ferrous cyanogen root cyanide ion is 1mol L-1.Assembling
Alkaline system zinc-iron flow battery coulombic efficiency (CE) is 98.8%, and voltage efficiency (VE) is 89.1%, and energy efficiency (EE) is
88.0%.Battery life > 100 circulations.Comparative example 1 (anode is unprocessed)
Compared with Example 1, electrode material is changed to untreated 6mm carbon felt, other conditions are constant.Battery coulombic efficiency
It is 88.6%, voltage efficiency 83.3%, energy efficiency 73.8%.Battery life < 20 circulations.
Compared with untreated electrode material, the coulomb of the alkaline system zinc-iron flow battery of electrode material of the present invention is utilized
The cyclical stability of efficiency, energy efficiency and battery all increases significantly.Illustrate by being impregnated using Prussian blue solution
Prepare electrode material, effectively improve the conductivity and reactivity of electrode material, thus improve battery efficiency and
Cyclical stability.
Embodiment 2
The carbon felt for cutting appropriately sized 6mm thickness, is first soaked in the aqueous solution of the ferric ion of 0.6mol/L at 40 DEG C
In, the acid solution of the rear ferrocyanide that 0.5mol/L is added, taking-up electrode water cleans repeatedly after impregnating 20h, dries spare.
Ferrocyanide in solution: ferric ion: H+The Final molar ratio 1:1.2:0.1 of three.Other conditions are the same as embodiment 1.
Embodiment 3
The carbon felt for cutting appropriately sized 6mm thickness, is first soaked in the aqueous solution of the ferrocyanide of 0.5mol/L at 20 DEG C
In, the rear aqueous solution that 0.7mol/L ferric ion is added, then mixed solution is adjusted to acidity with dilute hydrochloric acid, it is taken after impregnating 12h
Electrode water cleans repeatedly out, dries spare.Ferrocyanide in solution: ferric ion: H+The Final molar ratio 1 of three:
1.4:0.1.Other conditions are the same as embodiment 1.
Embodiment 4
With embodiment 1,6mm thickness carbon felt is changed to 4 1mm thickness carbon paper materials, other conditions are constant.
Claims (8)
1. a kind of preparation method of zinc-iron flow battery electrode, it is characterised in that:
It is first soaked in electrode material in the aqueous solution of ferrocyanide, the aqueous solution of ferric ion is then added thereto,
Immersion 0.5~taking-up electrode water cleans for use repeatedly afterwards for 24 hours；The wherein water of the aqueous solution of ferrocyanide and ferric ion
At least a kind of in solution is acidic aqueous solution, or acid is added into system after the aqueous solution that ferric ion is added, and makes to soak
Foam system is in acidity；
Or, electrode material is first soaked in the aqueous solution of ferrocyanide, trivalent iron salt is then added thereto, impregnates 0.5
~taking-up electrode water cleans for use repeatedly afterwards for 24 hours；Wherein the aqueous solution of ferrocyanide is acidic aqueous solution, or in addition three
Acid is added after valence molysite into system, makes immersion system in acidity；
Or, electrode material is first soaked in the aqueous solution of ferric ion, the water-soluble of ferrocyanide is then added thereto
Liquid, immersion 0.5~for 24 hours afterwards clean electrode taking-up for use repeatedly with water；Wherein the aqueous solution of ferrocyanide and ferric iron from
At least a kind of in the aqueous solution of son is acidic aqueous solution, or is added after the aqueous solution that ferric ion is added into system
Acid makes immersion system in acidity；
Or, electrode material is first soaked in the aqueous solution of ferric ion, ferrocyanide is then added thereto, impregnates
0.5~for 24 hours afterwards clean electrode taking-up for use repeatedly with water；Wherein the aqueous solution of ferric ion is acidic aqueous solution, or in
It is added after ferrocyanide and acid is added into system, make immersion system in acidity；
Or, electrode material is soaked in the aqueous solution of ferrocyanide and ferric ion, acid is added into system, makes to impregnate
System is in acidity, immersion 0.5~for 24 hours afterwards clean electrode taking-up for use repeatedly with water；
In immersion system, the whole molar concentration of ferrous cyanogen root is 0.01~1mol/L；The whole molar concentration 0.01 of ferric ion
~1.5mol/L；Proton end molar concentration is 0.001~0.1mol/L.
2. preparation method according to claim 1, it is characterised in that: the electrode is carbon felt, carbon cloth or carbon paper material.
3. preparation method according to claim 1, it is characterised in that: soaking temperature is 0~80 DEG C.
4. preparation method according to claim 1, it is characterised in that:
Acid is one of hydrochloric acid, sulfuric acid, nitric acid, acetic acid or two kinds or more.
5. preparation method according to claim 1, it is characterised in that: ferrous cyanogen root in solution: ferric ion: H+Three
Molar ratio 1:1~1.5:0.1.
6. preparation method according to claim 1, it is characterised in that: the cation of ferrocyanide be potassium ion, sodium from
One of son or two kinds or more；The anion of trivalent iron salt be one of chloride ion, nitrate ion, sulfate ion or
Two kinds or more.
7. a kind of anode that any preparation method of claim 1-6 prepares.
8. a kind of application of electrode described in claim 7, it is characterised in that: the electrode is applied to zinc-iron liquid stream electricity as anode
Chi Zhong.Application according to claim 3, it is characterised in that: zinc-iron flow battery is Alkaline Zinc iron liquid galvanic battery or neutrality
Zinc-iron flow battery, preferably Alkaline Zinc iron liquid galvanic battery, battery cathode are zinc electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711246780.8A CN109873187A (en) | 2017-12-01 | 2017-12-01 | The preparation method and electrode of a kind of zinc-iron flow battery electrode and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711246780.8A CN109873187A (en) | 2017-12-01 | 2017-12-01 | The preparation method and electrode of a kind of zinc-iron flow battery electrode and application |
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| CN109873187A true CN109873187A (en) | 2019-06-11 |
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| CN104201396A (en) * | 2014-08-29 | 2014-12-10 | 清华大学深圳研究生院 | Carbon electrode modified by cerium-zirconium oxide, preparation method and flow battery |
| CN104269527A (en) * | 2014-09-23 | 2015-01-07 | 浙江大学 | Preparation method and application of in-situ carbon-compounded prussian blue type compound thin film |
| CN105233794A (en) * | 2015-10-26 | 2016-01-13 | 合肥工业大学 | Preparation method for prussian blue/graphene/carbon fiber composite material |
| WO2016026895A1 (en) * | 2014-08-19 | 2016-02-25 | Centre National De La Recherche Scientifique (C.N.R.S) | Electrochemical flow cell |
| CN106532090A (en) * | 2016-10-28 | 2017-03-22 | 深圳职业技术学院 | Xuan-paper-enhanced non-fluorinated ionic membrane for flow battery, and preparation method for Xuan-paper-enhanced non-fluorinated ionic membrane |
| CN107863536A (en) * | 2017-10-16 | 2018-03-30 | 香港科技大学 | Multiple dimensioned porous electrode applied to flow battery and its preparation method and application |
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2017
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Patent Citations (6)
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| WO2016026895A1 (en) * | 2014-08-19 | 2016-02-25 | Centre National De La Recherche Scientifique (C.N.R.S) | Electrochemical flow cell |
| CN104201396A (en) * | 2014-08-29 | 2014-12-10 | 清华大学深圳研究生院 | Carbon electrode modified by cerium-zirconium oxide, preparation method and flow battery |
| CN104269527A (en) * | 2014-09-23 | 2015-01-07 | 浙江大学 | Preparation method and application of in-situ carbon-compounded prussian blue type compound thin film |
| CN105233794A (en) * | 2015-10-26 | 2016-01-13 | 合肥工业大学 | Preparation method for prussian blue/graphene/carbon fiber composite material |
| CN106532090A (en) * | 2016-10-28 | 2017-03-22 | 深圳职业技术学院 | Xuan-paper-enhanced non-fluorinated ionic membrane for flow battery, and preparation method for Xuan-paper-enhanced non-fluorinated ionic membrane |
| CN107863536A (en) * | 2017-10-16 | 2018-03-30 | 香港科技大学 | Multiple dimensioned porous electrode applied to flow battery and its preparation method and application |
Non-Patent Citations (2)
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| CONGXIN XIE等: ""A Low-Cost Neutral Zinc–Iron Flow Battery with High Energy Density for Stationary Energy Storage"", 《ANGEWANDTE CHEMIE-INTERNATIONAL EDITION》 * |
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Application publication date: 20190611 |
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