CN109346754B - High-power-density flow battery - Google Patents

High-power-density flow battery Download PDF

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Publication number
CN109346754B
CN109346754B CN201811213075.2A CN201811213075A CN109346754B CN 109346754 B CN109346754 B CN 109346754B CN 201811213075 A CN201811213075 A CN 201811213075A CN 109346754 B CN109346754 B CN 109346754B
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separation membrane
electrolyte
end enclosure
membrane
electrode
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CN109346754A (en
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何振宇
李欣
杨冬梅
曾雨竹
陈永华
吕宏水
杨志宏
朱金大
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State Grid Corp of China SGCC
NARI Group Corp
Nari Technology Co Ltd
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State Grid Corp of China SGCC
NARI Group Corp
Nari Technology Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/18Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184Regeneration by electrochemical means
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The invention discloses a high-power-density flow battery, which comprises a cylinder body, an upper end enclosure and a lower end enclosure, wherein the upper end enclosure and the lower end enclosure are respectively connected with the cylinder body, a first electrolyte inlet is arranged on the upper end enclosure, a first electrolyte outlet is arranged on the lower end enclosure, a second electrolyte inlet and a second electrolyte outlet are arranged on the cylinder body, an upper end enclosure and a lower end enclosure are respectively arranged at the end part of the cylinder body, the upper end enclosure and the lower end enclosure are respectively connected with a hollow separation membrane, a first electrode is arranged on the inner side of the hollow separation membrane, and a second electrode is arranged on the outer side of the hollow separation membrane and the inner side of the cylinder body. The flow battery has the advantages that the filling density of the electrode is high, the contact area of the electrolyte and the electrode is large, the electrochemical reaction can be rapidly carried out on the surface of the electrode, and the electrochemical polarization of the battery is reduced. The tubular separation membrane of the flow battery can be filled with hollow fiber membranes with small pipe diameters in a large density, so that the membrane area of the unit volume in the battery is increased, and the power density of the battery in the unit volume is increased.

Description

High-power-density flow battery
Technical Field
The invention relates to a flow battery, in particular to a flow battery with high power density.
Background
The zinc-bromine flow battery is a novel large-scale electrochemical energy storage technology, and the mutual conversion between electric energy and chemical energy is realized through the valence state change of reactive active substances. In the flow battery, the active material is stored in the electrolyte and has fluidity. The flow cell generally comprises a pile, an electrolyte and a storage tank thereof, a pump and other pipeline systems, wherein the pile mainly comprises a separation membrane (comprising an ion conduction membrane, a microporous nanofiltration membrane and the like), an anode or cathode electrode, a collector plate and the like. In the working process of the battery, the separation membrane plays a role in separating the anode and the cathode of the battery, and the phenomena of internal short circuit or self-discharge and the like are prevented. Due to the core role of the separation membrane in the stack, the structure and material of the separation membrane directly affect the electrochemical performance and the working efficiency of the flow battery.
In current research and practice, the separation membrane inside a flow battery is generally a flat plate structure. The flow battery takes the separation membrane with the flat plate structure as a central axis, flat electrodes, flow frames, polar plates and the like are symmetrically stacked at two ends of the flow battery in sequence, and a plurality of stacked single batteries are clamped between two end plates and are compressed and fixed to form a galvanic pile. The assembly process of the battery is complicated, and the electrolyte is easy to leak in the operation process. In the existing flat-plate flow battery, electrolyte flows in a narrow plane chamber formed by a membrane and a bipolar plate, and the chamber is also filled with a porous electrode, so that the flowing space of the electrolyte is further limited. When the battery is large in scale, the flow resistance of the electrolyte therein is large. In the operation process, dead zones are easy to occur due to the flowing of the electrolyte between the flat electrodes, and the phenomenon of the dead zones or uneven distribution is easy to occur, so that the electrolyte cannot be fully utilized. In addition, the battery is limited by factors such as the filling density of the separation membrane and the electrode, the contact between the electrolyte and the electrode, charge exchange between the positive electrolyte and the negative electrolyte and the like, the power density is difficult to improve, and a bottleneck exists. In the existing flat-plate flow battery, the thickness of a separation membrane, an electrode and a bipolar plate is limited, the thickness of a single cell serving as a basic repeating unit of a battery stack is about 5-10 mm, and the effective area (among a positive electrode and a negative electrode) of the single electrode of a unit-volume battery pack is about 50-200 m2/m3. In the existing flat-plate flow battery, the effective area of a separation membrane in a unit volume battery stack is close to that of a single electrode and is 50-200 m2/m3
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a flow battery with high power density.
The technical scheme is as follows: the invention relates to a high-power-density flow battery, which comprises a cylinder body, an upper end enclosure and a lower end enclosure, wherein the upper end enclosure and the lower end enclosure are respectively connected with the cylinder body, a first electrolyte inlet is arranged on the upper end enclosure, a first electrolyte outlet is arranged on the lower end enclosure, a second electrolyte inlet and a second electrolyte outlet are arranged on the cylinder body, an upper end enclosure and a lower end enclosure are respectively arranged at the end part of the cylinder body, the upper end enclosure and the lower end enclosure are respectively connected with a hollow separation membrane, a first electrode is arranged on the inner side of the hollow separation membrane, and a second electrode is arranged on the outer side of the hollow separation membrane and the inner side of the cylinder body. The first electrolyte flows in along a first electrolyte inlet, flows into the hollow separation membrane through the upper end seal, contacts with the first electrode, and flows out along a first electrolyte outlet after the lower end seal; the second electrolyte flows in along the second electrolyte inlet, enters the cylinder body and contacts the second electrode, and then flows out along the second electrolyte outlet.
The number of the first electrolyte inlets and the number of the first electrolyte outlets are one or more. The number of the hollow separation membranes is the same as the number of the first electrodes, and the number of the hollow separation membranes is one or more. The number of the second electrodes is one or more. The first electrode and the second electrode are made of titanium wires, carbon felts, graphite felts or composite materials of high polymer matrixes and conductive carbon materials, have large specific surface areas and are resistant to electrochemical corrosion.
The hollow separation membrane is a box-type separation membrane or a tubular separation membrane. The length and width of the box-type separation membrane are 2-100 cm, and the axial length is 2-300 cm. The tubular separation membrane has an outer diameter of 0.5 to 50mm, a tube wall thickness of 0.1 to 20mm, and an axial length of 50 to 2000 mm. The tubular separation membrane is a microporous nanofiltration membrane. The pore diameter distribution of the microporous nanofiltration membrane is 5-950 nm, and the pore density is more than 10 ten thousand square centimeters.
Has the advantages that: compared with the prior art, the invention has the following remarkable characteristics:
1. the contact area between the electrolyte of the flow battery and the electrode is larger, so that the electrochemical reaction can be carried out on the surface of the electrode more quickly, and the larger effective area of the electrode can provide more active reaction sites for the electrochemical reaction in the battery, thereby reducing the electrochemical polarization of the battery and improving the operation efficiency of the battery;
2. the tubular separation membrane of the flow battery can be filled with hollow fiber membranes and the like with small pipe diameters in a large density mode, the membrane area of the unit volume in the battery is increased, and the power density of the battery in the unit volume is increased2/m3The index is far higher than that of the existing flat-plate flow battery, and the larger membrane area can provide more effective channels for charge exchange inside the battery, reduce the ohmic internal resistance of the battery and improve the voltage efficiency of the battery;
3. the hollow tubular structure of the tubular separation membrane ensures that the stress along each section is symmetrically distributed, the mechanical strength of the tubular separation membrane with the same thickness is higher than that of a flat-plate type separation membrane, the tubular separation membrane can bear larger internal and external hydraulic pressure difference, the membrane thickness of the tubular separation membrane is lower than that of the flat-plate type separation membrane under the condition of enduring the same hydraulic pressure difference, and the ohmic impedance brought by the membrane thickness can be reduced;
4. when the electrolyte runs inside the hollow separation membrane, particularly the tubular separation membrane, the flow of the electrolyte is limited by the circular tube wall, so that the uniformly dispersed flow is easily realized;
5. the hollow separation membrane can be quickly and conveniently formed by using processes such as a phase inversion method, an extrusion method, a gel casting method and the like, and the precise regulation and control of the membrane structure can be realized, thereby facilitating the subsequent amplification production.
Drawings
FIG. 1 is a schematic diagram of the basic structure of a single-tube membrane zinc bromine flow battery;
FIG. 2 is a schematic diagram of the basic structure of a multi-tube membrane zinc bromine flow battery;
FIG. 3 is a schematic diagram of the basic structure of a single-box membrane zinc bromine flow battery;
fig. 4 is a schematic diagram of the basic structure of a multi-box membrane zinc bromine flow battery.
Detailed Description
As shown in fig. 1, for a single-tube membrane zinc-bromine flow battery, a hollow separation membrane 10 is disposed inside a cylinder 1, two ends of the hollow separation membrane 10 are respectively connected with an upper end seal 8 and a lower end seal 9, wherein the upper end seal 8 and the lower end seal 9 connect the inside of the cylinder 1 with the outside of the hollow separation membrane 10, two ends of the cylinder 1 are respectively connected with an upper end cap 2 and a lower end cap 3, wherein the upper end cap 2 is provided with a first electrolyte inlet 4, the lower end cap 3 is provided with a first electrolyte outlet 5, a first positive electrode or negative electrode 11 is disposed inside the hollow separation membrane 10, two corresponding second positive electrodes or negative electrodes 12 are disposed outside the hollow separation membrane 10 and inside the cylinder 1, and the hollow separation membrane 10 is a tubular separation membrane. The barrel 1 has a second electrolyte inlet 6 and a second electrolyte outlet 7. The first electrolyte flows in from a first electrolyte inlet 4, flows into the tubular separation membrane through an upper end seal 2, contacts with a first electrode 11, and flows out from a first electrolyte outlet 5 after passing through a lower end seal 9; the second electrolyte flows into the interior of the cylinder 1 from the second electrolyte inlet 6, contacts the two second electrodes 12, and flows out along the second electrolyte outlet 7. A second electrolyte inlet 6 on the cylinder body 1 is communicated with the interior of the cylinder body 1, the exterior of the tubular separation membrane and a second electrolyte outlet 7 to form a main electrolyte pipeline; the upper seal head 2, the inside of the tubular separation membrane and the lower seal head 3 are communicated to form another main electrolyte pipeline. The two electrolyte main pipelines are separated by an upper end seal 2, a tubular separation membrane and a lower end seal 9. A second electrolyte inlet 6 and a second electrolyte outlet 7 are connected with external anode or cathode liquid storage tanks, pumps and other pipeline systems through pipelines to form an electrolyte loop; the first electrolyte inlet 4 and the first electrolyte outlet 5 are connected with external anode or cathode liquid storage tanks, pumps and other pipeline systems through pipelines to form another electrolyte loop.
As shown in fig. 2, for a multi-tube membrane-liquid flow battery, four hollow separation membranes 10 are disposed inside a cylinder 1, each hollow separation membrane 10 is a tubular separation membrane, two ends of each tubular separation membrane are respectively connected to an upper end seal 8 and a lower end seal 9, wherein the upper end seal 8 and the lower end seal 9 connect the inside of the cylinder 1 with the outside of the tubular separation membrane, two ends of the cylinder 1 are respectively connected to an upper end seal 2 and a lower end seal 3, wherein the upper end seal 2 is provided with a first electrolyte inlet 4, the lower end seal 3 is provided with a first electrolyte outlet 5, four positive or negative first electrodes 11 are disposed inside the hollow separation membranes 10, and corresponding four positive or negative second electrodes 12 are disposed outside the hollow separation membranes 10 and inside the cylinder 1. The barrel 1 has a second electrolyte inlet 6 and a second electrolyte outlet 7. The first electrolyte flows in from a first electrolyte inlet 4, flows into the tubular separation membrane through an upper end seal 2, contacts with a first electrode 11, and flows out from a first electrolyte outlet 5 after passing through a lower end seal 9; the second electrolyte flows into the interior of the cylinder 1 from the second electrolyte inlet 6, contacts the two second electrodes 12, and flows out along the second electrolyte outlet 7. A second electrolyte inlet 6 on the cylinder body 1 is communicated with the interior of the cylinder body 1, the exterior of the tubular separation membrane and a second electrolyte outlet 7 to form a main electrolyte pipeline; the upper seal head 2, the inside of the tubular separation membrane and the lower seal head 3 are communicated to form another main electrolyte pipeline. The two electrolyte main pipelines are separated by an upper end seal 2, a tubular separation membrane and a lower end seal 9. A second electrolyte inlet 6 and a second electrolyte outlet 7 are connected with external anode or cathode liquid storage tanks, pumps and other pipeline systems through pipelines to form an electrolyte loop; the first electrolyte inlet 4 and the first electrolyte outlet 5 are connected with external anode or cathode liquid storage tanks, pumps and other pipeline systems through pipelines to form another electrolyte loop.
As shown in fig. 3, the multi-tube membrane liquid flow battery is provided with four tube-type separation membranes and four corresponding positive or negative first electrodes 11 and four corresponding positive or negative second electrodes 12. The number of the tubular separation membranes and the corresponding number of the positive or negative first electrodes 11 and the positive or negative second electrodes 12 in the flow battery are not limited thereto, and do not limit the scope of the present invention.
As shown in fig. 4, the upper end enclosure 2 of the single-tube membrane liquid flow battery or the multi-tube membrane liquid flow battery has a first electrolyte inlet 4, the lower end enclosure 3 has a first electrolyte outlet 5, and the cylinder 1 has a second electrolyte inlet 6 and a second electrolyte outlet 7. However, the electrolyte inlet and outlet function is only a passage for the electrolyte to flow into or flow out of the flow cell stack, and the number thereof is not specifically limited, and thus the number of the first electrolyte inlets 4 provided on the upper head 2, the number of the first electrolyte outlets 5 provided on the lower head 3, and the number of the second electrolyte inlets 6 and the second electrolyte outlets 7 provided on the cylinder 1 are not limited thereto.
In the present embodiment, only one single-tube membrane-liquid flow cell and one multi-tube membrane-liquid flow cell are provided, but the form of the separation membrane in the high-power-density flow cell provided by the present invention is not limited to the hollow tube type membrane, and other membranes such as a hollow box type membrane may be used instead.
The cylinder body 1, the upper sealing head 2 and the lower sealing head 3 are all made of anticorrosive materials, preferably plastic, glass fiber reinforced plastic or stainless steel materials. The outer diameter of the tubular separation membrane is 0.5-50 mm, the thickness of the tube wall is 0.1-20 mm, and the axial length is 50-2000 mm. The tubular separation membrane can be a microporous nanofiltration membrane and is made of high polymer materials, the pore size distribution of the microporous nanofiltration membrane is 5-950 nm, and the pore density is more than 10 ten thousand square centimeters. The tubular separation membrane may be an ion exchange membrane and is made of a polymer material. Such an exchange membrane may be an anion exchange membrane, allowing anions to selectively pass through; it may also be a cation exchange membrane, allowing cations to selectively pass through. The first electrode 11 and the second electrode 12 are made of electrochemical corrosion-resistant materials with large specific surface area, specifically carbon felt, graphite felt or a mixture of a high molecular polymer matrix and a certain proportion of conductive carbon materials. The first electrolyte and the second electrolyte are zinc bromide solutions containing complexing agents, the complexing agents can be 1-butyl-1-methylpyrrolidine bromide or 1-methyl-1-ethylpyrrolidine bromide, and in order to increase the conductivity of the electrolytes, certain auxiliary electrolytes such as ammonium chloride, potassium chloride and the like can be added into the electrolytes.
In the field of membrane separation, when a high molecular flat plate type separation membrane with the thickness of about 1mm is assembled into a membrane component, the high molecular flat plate type separation membrane can only tolerate the transmembrane pressure difference of 0.1 MPa, and when the high molecular hollow fiber separation membrane with the thickness of only about 0.1 mm is assembled into the membrane componentA transmembrane pressure difference of 0.3 MPa. In the field of zinc-bromine flow batteries, a microporous separation membrane with the thickness of about 1-2 mm is generally used for a flat-plate separation membrane in order to ensure the strength of the membrane, and the membrane assembly in such a form has the defect that the shear stress applied to the central part of the membrane is higher than that applied to the peripheral parts in the operation process of the battery, so that the separation membrane is easy to break. Compared with the tubular separation membrane, the tubular separation membrane has more uniform stress distribution and is not easy to cause mechanical damage due to internal and external pressure difference, thereby causing self-discharge of the battery. The ohmic resistance of a separation membrane is proportional to its thickness, and generally, a membrane having a large thickness has a larger ohmic resistance. For example, the flow battery micropore separation membrane with the thickness of 2mm has the surface resistivity of about 1-2 omega cm-2The wall thickness of the tubular or box-type separation membrane can be 0.1-0.2 mm, and the corresponding surface resistivity is about 0.1-0.5 omega cm-2. The use of the tubular or box-type separation membrane can reduce the ohmic internal resistance of the battery and improve the voltage efficiency of the battery.

Claims (5)

1. A high power density flow battery, characterized by: the device comprises a cylinder body (1), and an upper end enclosure (2) and a lower end enclosure (3) which are respectively connected with the cylinder body (1), wherein a first electrolyte inlet (4) is arranged on the upper end enclosure (2), a first electrolyte outlet (5) is arranged on the lower end enclosure (3), a second electrolyte inlet (6) and a second electrolyte outlet (7) are arranged on the cylinder body (1), an upper end enclosure (8) and a lower end enclosure (9) are respectively arranged at the end part of the cylinder body (1), the upper end enclosure (8) and the lower end enclosure (9) are respectively connected with a hollow separation membrane (10), a first electrode (11) is arranged at the inner side of the hollow separation membrane (10), and a second electrode (12) is arranged at the outer side of the hollow separation membrane (10) and the inner side of the cylinder body (1); the hollow separation membrane (10) is a box-type separation membrane or a tubular separation membrane; the tubular separation membrane is a microporous nanofiltration membrane, the pore size distribution of the microporous nanofiltration membrane is 5-950 nm, and the pore density is more than 10 ten thousand per square centimeter; the length and width of the box-type separation membrane are 2-100 cm, and the axial length is 2-300 cm; the thickness of the tube wall of the tubular separation membrane is 0.1-20 mm, the axial length is 50-2000 mm, and when the tubular separation membrane with the tube diameter of 2-3 mm is used, the effective area of the separation membrane in a unit volume battery pack reaches 300-900 m2/m3
2. The high power density flow battery of claim 1, wherein: the number of the first electrolyte inlets (4) and the number of the first electrolyte outlets (5) are one or more.
3. The high power density flow battery of claim 1, wherein: the number of the hollow separation membranes (10) is the same as that of the first electrodes (11), and the number of the hollow separation membranes (10) is one or more.
4. The high power density flow battery of claim 1, wherein: the number of the second electrodes (12) is one or more.
5. The high power density flow battery of claim 1, wherein: the first electrode (11) and the second electrode (12) are made of titanium wires, carbon felts, graphite felts or composite materials of high polymer matrixes and conductive carbon materials.
CN201811213075.2A 2018-10-17 2018-10-17 High-power-density flow battery Active CN109346754B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
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
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

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102016122284A1 (en) * 2016-11-19 2018-05-24 Friedrich-Schiller-Universität Jena Redox flow battery for storing electrical energy with hollow-fiber membranes
DE102016122285A1 (en) * 2016-11-19 2018-05-24 Friedrich-Schiller-Universität Jena Redox flow battery for storing electrical energy with radially arranged hollow fiber membranes

Patent Citations (4)

* Cited by examiner, † Cited by third party
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
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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