CN109873190A - A kind of neutrality Zinc-iron single flow battery - Google Patents
A kind of neutrality Zinc-iron single flow battery Download PDFInfo
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- CN109873190A CN109873190A CN201711248584.4A CN201711248584A CN109873190A CN 109873190 A CN109873190 A CN 109873190A CN 201711248584 A CN201711248584 A CN 201711248584A CN 109873190 A CN109873190 A CN 109873190A
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- zinc
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- flow battery
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- single flow
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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
- 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
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Abstract
The present invention relates to a kind of neutral Zinc-iron single flow batteries.Including monocell or 2 or more single battery group at pile, monocell critical material includes anode, diaphragm, cathode and electrolyte.Positive active material is potassium ion intercalation/deintercalation type solid active material, and electrolyte is the neutral aqueous solution containing zinc salt and sylvite.Anode uses solid active material, avoids positive and negative anodes active material in flow battery and mutually goes here and there problem, improves the coulombic efficiency and active material utilization of battery.Using neutral system, the etching problem of traditional flow battery strong acid and strong base electrolyte is avoided.
Description
Technical field
The present invention relates to flow battery fields, especially single flow battery field.
Background technique
Extensive energy storage technology is the key that realize that renewable energy efficiently utilizes.Water-system alkali metal ion battery has height
It the advantages that safety, low cost, high power density, is widely paid close attention to by researchers.Wherein study earliest be water system lithium from
Sub- battery, however limited by lithium source reserves, the cost advantage of aquo-lithium ion battery does not protrude.And reserves of the potassium in the earth's crust
Much higher than lithium (content of the potassium in the earth's crust be 2.47%, and lithium be only 0.0065%), and lithium ion in the solution migration speed
Degree is fast, therefore water system kalium ion battery has broader practice prospect.However, the biggish ionic radius of potassium ion and high ionization
Potential keeps its optional electrode material limited.It is Prussian blue and the like have perovskite structure, three-dimensional network skeleton, greatly
Gap site be conducive to the quick deintercalation of potassium ion.Therefore, Prussian blue and the like is more appropriate potassium ion electricity
Pond positive electrode.But the negative electrode material of aqueous potassium ion intercalation/deintercalation is limited at present, limits water system potassium ion full battery
Development.
Zinc load is a kind of to study more water system battery cathode, such as nickel-zinc battery, zinc iron cell, zinc-bromine bettery.Tool
There are high capacity, high safety, the advantage of low cost.And the generation of zinc Zhi Jing is the main reason for zinc-base cycle performance of battery is poor.
Summary of the invention
In order to solve the above technical problems, the specific technical solution that the present invention uses is as follows:
A kind of neutrality Zinc-iron single flow battery, including monocell or 2 or more single battery group at pile, monocell packet
Include anode, diaphragm, cathode；Electrolyte is added in positive and negative interpolar；Positive active material is potassium ion intercalation/deintercalation type solid active
Substance；Electrolyte is the neutral aqueous solution containing zinc salt and sylvite.
The molecular formula of potassium ion intercalation/deintercalation type solid active agents is KxMFe(CN6)y·n H2O, wherein x=0~2,
One or more of y=0.5~1, n=0-6, M Fe, Co, Mn, Ni, Cu, the preferred Prussia of positive active material
One of blue, Prussian blue derivative or two kinds or more.
Zinc salt is negative electrode active material in electrolyte, and sylvite is supporting electrolyte, and water is solvent；Zinc salt is zinc chloride, bromine
Change one of zinc, zinc sulfate, zinc nitrate or two kinds or more, the concentration of zinc salt in the electrolytic solution is 0.1~3mol/L.
Sylvite is that supporting electrolyte includes KCl, K2SO4、KNO3One kind or two kinds with supporting electrolyte is in the electrolytic solution
Concentration be 0.5~4mol/L.
Diaphragm is perforated membrane, porous film material be polyolefin, in polyaromatic class, one kind of cellulose acetate or two kinds with
On, film thickness is in 10~100um, the porosity 10-80% of perforated membrane, and 0.5-100 μm of pore diameter range.
Positive active material is attached on plus plate current-collecting body, and used plus plate current-collecting body and cathode are respectively carbon felt, stone
Black plate, carbon cloth, nickel foam, metal mesh or metal plate.
Beneficial effect
Positive active material is potassium ion intercalation/deintercalation type solid active agents, such as Prussian blue and the like；Electrolysis
Liquid is the neutral aqueous solution containing zinc salt and sylvite.Wherein zinc salt is negative electrode active material, and sylvite is supporting electrolyte.Using single liquid
Manifold formula makes zinc salt dissolve and deposit in cathode, improves the efficiency of zinc deposition, avoid the growth of zinc dendrite.Anode uses
Solid active material avoids positive and negative anodes active material in traditional flow battery and mutually goes here and there problem, improves the coulombic efficiency of battery
And active material utilization.Using neutral system, the etching problem of traditional flow battery strong acid and strong base electrolyte is avoided.It is positive and negative
Perforated membrane between pole plays the role of preventing positive and negative anodes contact short circuit and ion is connected.Positive and negative anodes active material and support electrolysis
Matter is cheap, low toxic and environment-friendly substance, and battery is made to have safety and environmental protection, cheap advantage, in electrochemical energy storage
It has broad application prospects in battery technology.
Detailed description of the invention
Fig. 1: the cycle performance of neutral zinc-iron list liquid stream and non-flow battery compares.
Specific implementation method
Experimental example: neutral Zinc-iron single flow battery
Monocell assembling:
(1) with Prussian blue for positive active material.Active material and conductive agent, binder are prepared by mixing into electrode to use
Make neutral zinc-iron flow battery anode.Active material: Super P (conductive agent): PTFE (binder) mass ratio=7:2:1 is rolled over
Electrode slice is rolled into, is pressed in nickel foam.Positive area: 36cm2, active material list amount 50mg cm-2。
(2) with 0.5M ZnSO4+0.5M K2SO4Aqueous solution is electrolyte.
(3) carbon felt is cathode, carries out monocell assembling.
(4) structure of monocell includes: end plate, positive and negative anodes, diaphragm, liquid flow frame, bipolar plates, positive and negative anodes storage tank and pump and
Pipeline composition.
The test of battery performance:
The flow velocity of electrolyte is 10ml/min, charging current 20mA/cm in battery2, charge cutoff voltage 1.8V puts
Electric blanking voltage is 0.1V.
Comparative example: the neutral non-flow battery of zinc-iron
Battery assembly:
(1) with Prussian blue for positive active material.Active material and conductive agent, binder are prepared by mixing into electrode to use
Make neutral zinc-iron flow battery anode.Active material: Super P (conductive agent): PTFE (binder) mass ratio=7:2:1 is rolled over
Electrode slice is rolled into, is pressed in nickel foam.Positive area: 36cm2, active material list amount 50mg cm-2。
(2) with 0.5M ZnSO4+0.5M K2SO4Aqueous solution is electrolyte.
(3) carbon felt is cathode, carries out non-flow battery assembling.
(4) non-flow battery assembling: end plate, positive and negative anodes, diaphragm, liquid flow frame, bipolar plates.
The test of battery performance:
Diaphragm and electrolyte are placed between positive electrode and negative electrode, and the dosage of electrolyte is 50mL, are not flowed, charging current is
20mA/cm2, charge cutoff voltage 1.8V, discharge cut-off voltage 0.1V.
Compared with non-flow battery, single flow battery cycle performance is significantly improved.Using single stream forms, make zinc salt in height
Specific surface dissolution and deposition, improve the efficiency of zinc deposition, the growth of zinc dendrite are avoided, to improve the cyclicity of battery
Energy.
Claims (6)
1. a kind of neutrality Zinc-iron single flow battery, including monocell or 2 or more single battery group at pile, monocell includes
Anode, diaphragm, cathode；Electrolyte is added in positive and negative interpolar；It is characterized in that, positive active material is potassium ion intercalation/deintercalation
Type solid active agents；Electrolyte is the neutral aqueous solution containing zinc salt and sylvite.
2. neutrality Zinc-iron single flow battery according to claim 1, it is characterised in that: potassium ion intercalation/deintercalation type solid
The molecular formula of active material is KxMFe(CN6)y·n H2O, wherein x=0~2, y=0.5~1, n=0-6, M Fe, Co, Mn,
One or more of Ni, Cu, positive active material preferably one of Prussian blue, Prussian blue derivative or two kinds
More than.
3. neutrality single flow battery according to claim 1, it is characterised in that: zinc salt is negative electrode active material in electrolyte
Matter, sylvite are supporting electrolyte, and water is solvent；Zinc salt is one of zinc chloride, zinc bromide, zinc sulfate, zinc nitrate or two kinds
More than, the concentration of zinc salt in the electrolytic solution is 0.1~3mol/L.
4. neutrality single flow battery according to claim 1 or 3, it is characterised in that: sylvite includes for supporting electrolyte
KCl、K2SO4、KNO3One kind or two kinds with, the concentration of supporting electrolyte in the electrolytic solution for 0.5~4mol/L.
5. neutral Zinc-iron single flow battery according to claim 1, it is characterised in that: diaphragm is perforated membrane, porous film material
For in polyolefin, polyaromatic class, the one or two or more kinds of cellulose acetate, film thickness is in 10~100um, the porosity of perforated membrane
10-80%, 0.5-100 μm of pore diameter range.
6. neutral Zinc-iron single flow battery according to claim 1, it is characterised in that: positive active material is attached to positive collection
On fluid, used plus plate current-collecting body and cathode are respectively carbon felt, graphite plate, carbon cloth, nickel foam, metal mesh or metal
Plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711248584.4A CN109873190A (en) | 2017-12-01 | 2017-12-01 | A kind of neutrality Zinc-iron single flow battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711248584.4A CN109873190A (en) | 2017-12-01 | 2017-12-01 | A kind of neutrality Zinc-iron single flow battery |
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| Publication Number | Publication Date |
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| CN109873190A true CN109873190A (en) | 2019-06-11 |
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| CN201711248584.4A Pending CN109873190A (en) | 2017-12-01 | 2017-12-01 | A kind of neutrality Zinc-iron single flow battery |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682407A (en) * | 2012-08-30 | 2014-03-26 | 中国科学院大连化学物理研究所 | Zinc-iron single flow battery |
| WO2014118854A1 (en) * | 2013-01-29 | 2014-08-07 | Sharp Kabushiki Kaisha | Transition metal hexacyanoferrate battery cathode, transition metal hexacyanoferrate cathode battery, method for synthesizing a transition metal hexacyanoferrate battery material, method for fabricating a transition metal hexacyanoferrate battery cathode electrode, and method for using a transition metal hexacyanoferrate battery |
| CN104716374A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Neutral zinc iron double fluid flow battery |
| WO2016026895A1 (en) * | 2014-08-19 | 2016-02-25 | Centre National De La Recherche Scientifique (C.N.R.S) | Electrochemical flow cell |
-
2017
- 2017-12-01 CN CN201711248584.4A patent/CN109873190A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682407A (en) * | 2012-08-30 | 2014-03-26 | 中国科学院大连化学物理研究所 | Zinc-iron single flow battery |
| WO2014118854A1 (en) * | 2013-01-29 | 2014-08-07 | Sharp Kabushiki Kaisha | Transition metal hexacyanoferrate battery cathode, transition metal hexacyanoferrate cathode battery, method for synthesizing a transition metal hexacyanoferrate battery material, method for fabricating a transition metal hexacyanoferrate battery cathode electrode, and method for using a transition metal hexacyanoferrate battery |
| CN104716374A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Neutral zinc iron double fluid flow battery |
| WO2016026895A1 (en) * | 2014-08-19 | 2016-02-25 | Centre National De La Recherche Scientifique (C.N.R.S) | Electrochemical flow cell |
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Application publication date: 20190611 |
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