CN109346754A - A kind of flow battery of high power density - Google Patents
A kind of flow battery of high power density Download PDFInfo
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- CN109346754A CN109346754A CN201811213075.2A CN201811213075A CN109346754A CN 109346754 A CN109346754 A CN 109346754A CN 201811213075 A CN201811213075 A CN 201811213075A CN 109346754 A CN109346754 A CN 109346754A
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- electrolyte
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- flow battery
- power density
- seperation film
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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
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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 invention discloses a kind of flow batteries of high power density, upper cover, the lower head being connected including cylinder and respectively with cylinder, first electrolyte entrance is set on upper cover, first electrolyte outlet is set on lower head, second electrolyte entrance and the second electrolyte outlet are set on cylinder, end seal and lower end seal is respectively set in the end of cylinder, upper end seal and lower end seal are connected separately with hollow seperation film, first electrode is set on the inside of hollow seperation film, second electrode is set on the inside of hollow seperation film outside, cylinder.The electrode packed density of flow battery of the invention is larger, and the contact area of electrolyte and electrode is bigger, and electrochemical reaction is carried out more quickly in electrode surface, reduces the activation polarization of battery.The big density filling of the carry out such as hollow-fibre membrane of caliber very little can be used in the tubular separation membrane of flow battery, increases the membrane area of inside battery unit volume, increases the power density of battery in unit volume.
Description
Technical field
The present invention relates to flow battery, specially a kind of flow battery of high power density.
Background technique
Zinc-bromine flow battery is a kind of novel extensive electrochemical energy storage technology, is become by the valence state of reactive substance
Change the mutual conversion realized between electric energy and chemical energy.In flow battery, active material is stored in electrolyte, has flowing
Property.Flow battery is generally made of the pipe-line systems such as pile, electrolyte and its holding vessel, pump, and wherein pile is mainly by seperation film
(including ion-conductive membranes, micropore nanofiltration membrane etc.), positive or negative pole electrode, collector plate etc. are constituted.In cell operations, point
Phenomena such as playing the role of separating battery plus-negative plate from film, preventing internal short-circuit or self discharge.Since seperation film is in pile
In central role, structure and material will directly affect the chemical property and working efficiency of flow battery.
In current research and practice, the seperation film inside flow battery is usually slab construction.Flow battery is with this
The seperation film of slab construction is axis, successively symmetrically stacks flat electrode, liquid flow frame, pole plate etc. at both ends, stacks
Several grades of single batteries are clamped among two end plates, and pile is formed after being fixed.The assembly process of this battery is numerous
It is trivial, and electrolyte is easy leakage in the process of running.Inside existing plate type hydraulic galvanic battery, electrolyte is in film and bipolar plates structure
At the flowing of narrow plane chamber interior, be also filled with porous electrode in the chamber, the flowing for further limiting electrolyte is empty
Between.When battery is larger, electrolyte is very big in flow resistance wherein.In the process of running, since electrolyte is in plate
The phenomenon that flowing between electrode is easy to appear dead zone, is easy to appear dead zone or is unevenly distributed, prevent electrolyte is from abundant
It utilizes.Furthermore this battery limited is in contact of the seperation film with the packed density of electrode, electrolyte with electrode, positive and negative anodes electrolyte
Between factors, the power density such as charge-exchange be difficult to be promoted, there are bottlenecks.In existing plate type hydraulic galvanic battery, it is limited to point
From film, electrode, bipolar plates thickness, the thickness of the monocell as the basic repetitive unit of battery pile is about 5~10mm, unit bodies
The effective area (positive or negative pole is wherein) of product battery pack single electrode is about 50~200m2/m3.Existing plate type hydraulic galvanic battery
In, it is all 50-200m that the effective area of seperation film and the effective area of single electrode are close in unit volume battery pile2/m3
Summary of the invention
Goal of the invention: it is an object of the present invention to provide a kind of flow batteries of high power density.
Technical solution: a kind of flow battery of high power density of the present invention, including cylinder and respectively with cylinder phase
Upper cover even, lower head are arranged the first electrolyte entrance on upper cover, the first electrolyte outlet, cylinder are arranged on lower head
End seal and lower end seal, upper end seal is respectively set in the second electrolyte entrance of upper setting and the second electrolyte outlet, the end of cylinder
Hollow seperation film is connected separately with lower end seal, first electrode is set on the inside of hollow seperation film, on the outside of hollow seperation film, in cylinder
Second electrode is arranged in side.First electrolyte is flowed into along the first electrolyte entrance, is flowed into inside hollow seperation film through upper end seal, with the
The contact of one electrode, is honored as a queen through lower end and flows out along the first electrolyte outlet；Second electrolyte is flowed into along the second electrolyte entrance, is entered
It contacts in cylinder with second electrode, is then flowed out along the second electrolyte outlet.
First electrolyte entrance, the first electrolyte outlet quantity be one or more.The quantity of hollow seperation film with
The quantity of first electrode is identical, and the quantity of the hollow seperation film is one or more.The quantity of second electrode is one or more
It is a.First electrode, second electrode are by titanium silk, carbon felt, graphite felt or high molecular polymer matrix and conductive carbon materials composite wood
Material is made, large specific surface area and electrochemical corrosion resistant.
Hollow seperation film is box seperation film or tubular separation membrane.The length and width of box seperation film are 2~100 centimetres, axis
It is 2~300 centimetres to length.The outer diameter of tubular separation membrane is 0.5~50 millimeter, and pipe thickness is 0.1~20mm, axial length
It is 50~2000 millimeters.Tubular separation membrane is micropore nanofiltration membrane.The pore-size distribution of micropore nanofiltration membrane is 5~950nm, and hole density is
Square centimeter 100,000 or more.
The utility model has the advantages that compared to the prior art the present invention, has the characteristics that following conspicuousness:
1, the contact area of fluid cell electrolyte of the invention and electrode is bigger, allows electrochemical reaction in electrode
Surface carries out more quickly, and bigger electrode effective area can provide more active reactions for the electrochemical reaction in battery
Site, and then the activation polarization of battery is reduced, improve battery operation efficiency；
2, the big density filling of the carry out such as hollow-fibre membrane of caliber very little can be used in the tubular separation membrane of flow battery, increases
The big membrane area of inside battery unit volume, increases the power density of battery in unit volume, the present invention is provided using pipe
The flow battery of formula seperation film or box seperation film and its auxiliary electrode, when using the seperation film that caliber is 2~3mm, unit
The effective area of seperation film is up to 300~900m in volume battery pack2/m3, the index is much higher than existing plate type hydraulic galvanic electricity
Pond, bigger membrane area can exchange for the charge of inside battery and provide more effective channels, reduce the ohmic internal resistance of battery,
Improve cell voltage efficiency；
3, the hollow tubular structure of tubular separation membrane, so that the stress along each section is symmetrical, the pipe of same thickness
The mechanical strength of formula seperation film is higher than flat seperation film, can bear bigger inside and outside hydraulic pressure difference, be resistant to identical hydraulic pressure difference
Under conditions of, the film thickness of tubular separation membrane will be lower than flat seperation film, can reduce by film thickness bring ohmage；
4, in hollow seperation film especially tubular separation membrane internal operation, flowing is limited electrolyte by round tube wall,
It is easily achieved evenly dispersed flowing；
5, hollow seperation film can be quickly and easily formed using techniques such as phase inversion, extrusion molding, gel casting methods,
And the accuracy controlling of membrane structure may be implemented, it is produced convenient for subsequent amplification.
Detailed description of the invention
Fig. 1 is single hose film zinc-bromine flow battery basic structure schematic diagram；
Fig. 2 is multitube film zinc-bromine flow battery basic structure schematic diagram；
Fig. 3 is single box film zinc-bromine flow battery basic structure schematic diagram；
Fig. 4 is multi-tank film zinc-bromine flow battery basic structure schematic diagram.
Specific embodiment
Such as Fig. 1, for single hose film zinc-bromine flow battery, a hollow seperation film 10 is placed in inside cylinder 1, hollow separation
The both ends of film 10 are connected with upper end seal 8, lower end seal 9 respectively, wherein upper end seal 8,9 connector drum of lower end seal, 1 inside and middle space division
From 10 outside of film, 1 both ends of cylinder are connected with upper cover 2, lower head 3 respectively, wherein have first electrolyte to enter on upper cover 2
Mouthfuls 4, there is first electrolyte outlet 5 on lower head 3, a positive or negative pole first electrode 11 is located in hollow seperation film 10
Portion, corresponding two positive or negative pole second electrodes 12 are located on the outside of hollow seperation film 10, inside cylinder 1, hollow seperation film
10 be tubular separation membrane.There are second electrolyte entrance 6 and second electrolyte outlet 7 on cylinder 1.First electrolyte from
First electrolyte entrance 4 flows into, and flows into inside tubular separation membrane, contacts with first electrode 11, after lower end seal 3 through upper end seal 2
It is flowed out by the first electrolyte outlet 5；Second electrolyte flows into inside cylinder 1 from the second electrolyte entrance 6, with two second electrodes
12 contacts, flow out along the second electrolyte outlet 7.Inside the second electrolyte entrance 6 and cylinder 1 on cylinder 1, outside tubular separation membrane
Portion, the second electrolyte outlet 7 are connected, and constitute electrolyte main pipeline all the way；Inside upper cover 2, tubular separation membrane, lower head 3
It is connected, constitutes another way electrolyte main pipeline.Between two-way electrolyte main pipeline, by upper end seal 2, tubular separation membrane, lower end
Envelope 3 separates.Second electrolyte entrance 6, the second electrolyte outlet 7 are managed by pipeline and external positive or cathode fluid reservoir and pump etc.
Road system is connected, and forms electrolyte loop all the way；First electrolyte entrance 4, the first electrolyte outlet 5 are passing through pipeline and outside just
Pole or the pipe-line systems such as cathode fluid reservoir and pump are connected, and form another way electrolyte loop.
Such as Fig. 2, for multitube film liquid galvanic battery, four hollow seperation films 10 are placed in inside cylinder 1, hollow seperation film 10
For tubular separation membrane, the both ends of tubular separation membrane are connected with upper end seal 8, lower end seal 9 respectively, wherein upper end seal 8, lower end seal 9 connect
1 inside of connect cylinder body is on the outside of tubular separation membrane, and 1 both ends of cylinder are connected with upper cover 2, lower head 3 respectively, wherein on upper cover 2
There is first electrolyte entrance 4, there is first electrolyte outlet 5, four positive or negative pole first electrodes 11 on lower head 3
Inside hollow seperation film 10, corresponding four positive or negative pole second electrodes 12 be located at 10 outside of hollow seperation film,
Inside simplified 1.There are second electrolyte entrance 6 and second electrolyte outlet 7 on cylinder 1.First electrolyte is from first
Electrolyte entrance 4 flows into, and flows into inside tubular separation membrane through upper end seal 2, contacts with first electrode 11, by the after lower end seal 3
The outflow of one electrolyte outlet 5；Second electrolyte flows into inside cylinder 1 from the second electrolyte entrance 6, connects with two second electrodes 12
Touching is flowed out along the second electrolyte outlet 7.The second electrolyte entrance 6 on cylinder 1 with inside cylinder 1, outside tubular separation membrane,
Second electrolyte outlet 7 is connected, and constitutes electrolyte main pipeline all the way；Inside upper cover 2, tubular separation membrane, lower head 3 is connected
It is logical, constitute another way electrolyte main pipeline.Between two-way electrolyte main pipeline, by upper end seal 2, tubular separation membrane, lower end seal 3 every
It opens.Second electrolyte entrance 6, the second electrolyte outlet 7 pass through pipeline and external positive or the pipelines such as cathode fluid reservoir and pump system
System is connected, and forms electrolyte loop all the way；First electrolyte entrance 4, the first electrolyte outlet 5 by pipeline and external positive or
The pipe-line systems such as cathode fluid reservoir and pump are connected, and form another way electrolyte loop.
Such as Fig. 3, four root canal formula seperation films and corresponding four positive or negative poles are provided in multitube film liquid galvanic battery
11, four positive or negative pole second electrodes 12 of first electrode.The tubular type seperation film quantity that is arranged in flow battery and it is corresponding just
The quantity of pole or cathode first electrode 11, positive or negative pole second electrode 12 is not limited thereto, herein not to of the invention
Protection scope generates restriction effect.
Such as Fig. 4, there is first electrolyte to enter on the upper cover 2 of single hose film liquid galvanic battery or multitube film liquid galvanic battery
Mouthfuls 4, there is first electrolyte outlet 5 on lower head 3, second electrolyte entrance 6 and one second are provided on cylinder 1
Electrolyte outlet 7.But the function of electrolyte entrance is only the channel that electrolyte flows in or out flow cell pile,
There is no be arranged on the quantity of the first electrolyte entrance 4 for clearly limiting, therefore being arranged on upper cover 2, lower head 3 its quantity
The quantity of the second electrolyte entrance 6 and the second electrolyte outlet 7 that are arranged in the quantity of first electrolyte outlet 5, cylinder 1 is not
It is confined to this.
A kind of single hose film liquid galvanic battery and a kind of embodiment of multitube film liquid galvanic battery are only provided in the present embodiment,
But in the flow battery of high power density provided by the invention, the form of seperation film is not limited to hollow tubular membrane, can also
It is substituted using remaining films such as hollow box films.
Above-mentioned cylinder 1, upper cover 2 and lower head 3 are all made of anti-corrosion material and are made, preferably by plastics, glass reinforced plastic or stainless
Steel material is made.The outer diameter of tubular separation membrane be 0.5~50mm, pipe thickness be 0.1~20mm, axial length be 50~
2000mm.Tubular separation membrane can be micropore nanofiltration membrane, be manufactured using high molecular material, and the pore-size distribution of micropore nanofiltration membrane is 5
~950nm, hole density are square centimeter 100,000 or more.Tubular separation membrane is also possible to amberplex, uses macromolecule material
Material manufacture.This exchange membrane can be anion-exchange membrane, and anion selectivity is allowed to pass through；It is also possible to cationic exchange
Film allows cation selective to pass through.First electrode 11, second electrode 12 use large specific surface area, and electrochemical corrosion resistant material
Material is made, specially the mixture of carbon felt, graphite felt or high molecular polymer matrix and a certain proportion of conductive carbon materials.
First electrolyte and the second electrolyte are the bromide solutions containing complexing agent, and 1- butyl -1- methylpyrrole may be selected in complexing agent
Alkane bromide or 1- methyl-1-ethyl phosphonium bromide pyrrolidines can be added in electrolyte and centainly be helped to increase the conductivity of electrolyte
Electrolyte, such as ammonium chloride, potassium chloride.
In UF membrane field, when the flat seperation film of macromolecule of thickness about 1mm is assembled into membrane module, can only it be resistant to
The transmembrane pressure of 0.1Mpa, and when polymeric hollow fiber separating film of thickness only about 0.1mm is assembled into membrane module, can be resistant to
The transmembrane pressure of 0.3Mpa.In zinc-bromine flow battery field, flat seperation film is in order to guarantee film strength, usually using thick
The microporous separation membrane of about 1~2mm is spent, the membrane module of this form has certain deficiency center membrane position in cell operation
The shear stress being subject to is higher than surrounding position, and seperation film is easy to appear breakage herein.And tubular type seperation film compare under answer
Power is more uniformly spread, it is not easy to answer inside and outside differential pressure and mechanical damage occurs, in turn result in self-discharge of battery.Ohm of seperation film
Resistance is directly proportional to its thickness, the about big film of general thickness, and Ohmic resistance is also bigger.For example, with a thickness of the flow battery of 2mm
Microporous separator film, surface resistivity are about 1~2 Ω cm-2, and tubular type or box seperation film, wall thickness can for 0.1~
0.2mm, corresponding surface resistivity are about 0.1~0.5 Ω cm-2.The Europe of battery can be reduced using tubular type or box seperation film
Nurse internal resistance improves the voltage efficiency of battery.
Claims (10)
1. a kind of flow battery of high power density, it is characterised in that: be connected including cylinder (1) and respectively with cylinder (1) upper
End socket (2), lower head (3) are arranged the first electrolyte entrance (4) on the upper cover (2), are arranged on the lower head (3)
The second electrolyte entrance (6) and the second electrolyte outlet (7), the cylinder is arranged on the cylinder (1) in one electrolyte outlet (5)
End seal (8) and lower end seal (9) is respectively set in the end of body (1), during the upper end seal (8) and lower end seal (9) are connected separately with
First electrode (11) are arranged in empty seperation film (10), hollow seperation film (10) inside, hollow seperation film (10) outside, cylinder
Second electrode (12) are set on the inside of body (1).
2. a kind of flow battery of high power density according to claim 1, it is characterised in that: first electrolyte enters
The quantity of mouthful (4), the first electrolyte outlet (5) is one or more.
3. a kind of flow battery of high power density according to claim 1, it is characterised in that: the hollow seperation film
(10) quantity is identical as the quantity of first electrode (11), and the quantity of the hollow seperation film (10) is one or more.
4. a kind of flow battery of high power density according to claim 1, it is characterised in that: the second electrode (12)
Quantity be one or more.
5. a kind of flow battery of high power density according to claim 1, it is characterised in that: the hollow seperation film
It (10) is box seperation film or tubular separation membrane.
6. a kind of flow battery of high power density according to claim 5, it is characterised in that: the box seperation film
Long and width is 2~100 centimetres, and axial length is 2~300 centimetres.
7. a kind of flow battery of high power density according to claim 5, it is characterised in that: the tubular separation membrane
Outer diameter is 0.5~50 millimeter, and pipe thickness is 0.1~20mm, and axial length is 50~2000 millimeters.
8. a kind of flow battery of high power density according to claim 5 or 7, it is characterised in that: the tubulose separation
Film is micropore nanofiltration membrane.
9. a kind of flow battery of high power density according to claim 8, it is characterised in that: the micropore nanofiltration membrane
Pore-size distribution is 5~950nm, and hole density is square centimeter 100,000 or more.
10. a kind of flow battery of high power density according to claim 1, it is characterised in that: the first electrode
(11), second electrode (12) is by titanium silk, carbon felt, graphite felt or high molecular polymer matrix and conductive carbon materials composite material system
At.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811213075.2A CN109346754B (en) | 2018-10-17 | 2018-10-17 | High-power-density flow battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811213075.2A CN109346754B (en) | 2018-10-17 | 2018-10-17 | High-power-density flow battery |
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| CN109346754A true CN109346754A (en) | 2019-02-15 |
| CN109346754B CN109346754B (en) | 2022-02-15 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201549546U (en) * | 2009-11-26 | 2010-08-11 | 承德万利通实业集团有限公司 | Columnar flow battery device |
| CN102315473A (en) * | 2011-06-28 | 2012-01-11 | 北京好风光储能技术有限公司 | Lithium ion flow redox battery |
| CN106975358A (en) * | 2017-05-18 | 2017-07-25 | 深圳市微润灌溉技术有限公司 | With the tubular type membrane separator and cleaning method of tubular film material manufacture |
| WO2018091042A1 (en) * | 2016-11-19 | 2018-05-24 | Friedrich-Schiller-Universität Jena | Redox flow battery for storing electrical energy, having radially arranged hollow fiber membranes |
| DE102016122284A1 (en) * | 2016-11-19 | 2018-05-24 | Friedrich-Schiller-Universität Jena | Redox flow battery for storing electrical energy with hollow-fiber membranes |
| CN108352541A (en) * | 2015-11-18 | 2018-07-31 | 阿瓦隆电池（加拿大）公司 | Electrode assembly and electrolyte distribution obtain improved flow battery |
-
2018
- 2018-10-17 CN CN201811213075.2A patent/CN109346754B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201549546U (en) * | 2009-11-26 | 2010-08-11 | 承德万利通实业集团有限公司 | Columnar flow battery device |
| CN102315473A (en) * | 2011-06-28 | 2012-01-11 | 北京好风光储能技术有限公司 | Lithium ion flow redox battery |
| CN108352541A (en) * | 2015-11-18 | 2018-07-31 | 阿瓦隆电池（加拿大）公司 | Electrode assembly and electrolyte distribution obtain improved flow battery |
| WO2018091042A1 (en) * | 2016-11-19 | 2018-05-24 | Friedrich-Schiller-Universität Jena | Redox flow battery for storing electrical energy, having radially arranged hollow fiber membranes |
| DE102016122284A1 (en) * | 2016-11-19 | 2018-05-24 | Friedrich-Schiller-Universität Jena | Redox flow battery for storing electrical energy with hollow-fiber membranes |
| CN106975358A (en) * | 2017-05-18 | 2017-07-25 | 深圳市微润灌溉技术有限公司 | With the tubular type membrane separator and cleaning method of tubular film material manufacture |
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