JPS62223984A - Redox flow battery - Google Patents
Redox flow batteryInfo
- Publication number
- JPS62223984A JPS62223984A JP61068163A JP6816386A JPS62223984A JP S62223984 A JPS62223984 A JP S62223984A JP 61068163 A JP61068163 A JP 61068163A JP 6816386 A JP6816386 A JP 6816386A JP S62223984 A JPS62223984 A JP S62223984A
- Authority
- JP
- Japan
- Prior art keywords
- redox flow
- flow battery
- film
- membrane
- porous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 229920002678 cellulose Polymers 0.000 claims abstract description 6
- 239000001913 cellulose Substances 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 239000004809 Teflon Substances 0.000 claims abstract description 5
- 229920006362 Teflon® Polymers 0.000 claims abstract description 5
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract 2
- 239000012528 membrane Substances 0.000 claims description 41
- 239000007788 liquid Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims 1
- 239000007774 positive electrode material Substances 0.000 claims 1
- 230000010220 ion permeability Effects 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract 1
- 238000003475 lamination Methods 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 239000003014 ion exchange membrane Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M8/02—Details
- H01M8/0289—Means for holding the electrolyte
-
- 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
Landscapes
- 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)
- Fuel Cell (AREA)
Abstract
Description
【発明の詳細な説明】
Ｃ産業上の利用分野］
この発明は、電解液を正極側および負極側に供給し酸化
還元反応により充放電するレドックスフロー電池に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application] The present invention relates to a redox flow battery that supplies an electrolytic solution to a positive electrode side and a negative electrode side and charges and discharges through an oxidation-reduction reaction.
〔従来の技術］
特公昭６０−２５１６３号には、電極貯蔵用２次電池と
してのレドックスフロー電池が開示されている。この種
のレドックスフロー電池では、隔膜により電極セルを正
極側と負極側に分離し、正極側には正極液を負極側には
負極液を供給し酸化還元反応により充放電を行なってい
る。隔膜としては、一般にイオン交換膜が用いられてい
る。[Prior Art] Japanese Patent Publication No. 60-25163 discloses a redox flow battery as a secondary battery for storing electrodes. In this type of redox flow battery, an electrode cell is separated into a positive electrode side and a negative electrode side by a diaphragm, a positive electrode liquid is supplied to the positive electrode side, and a negative electrode liquid is supplied to the negative electrode side, and charging and discharging are performed by an oxidation-reduction reaction. Ion exchange membranes are generally used as diaphragms.
［発明が解決しようとする問題点］
しかしながら、このようなイオン交換膜を隔膜として用
いると、そのイオン透過性が悪いために、セル内部の電
気抵抗は増大し、レドックスフロー電池全体としての充
放電効率が小さくなるという問題点があった。[Problems to be Solved by the Invention] However, when such an ion exchange membrane is used as a diaphragm, the electrical resistance inside the cell increases due to its poor ion permeability, which hinders the charging and discharging of the redox flow battery as a whole. There was a problem that the efficiency was low.
また、イオン交換膜に代えてセルロース系ポリマーなど
の親水性膜を用いると、かかる問題点は解消されるが、
この場合新たに隔膜の機械的強度が低下するという問題
点を生じた。In addition, if a hydrophilic membrane such as a cellulose polymer is used instead of an ion exchange membrane, this problem can be solved, but
In this case, a new problem arises in that the mechanical strength of the diaphragm decreases.
それゆえに、この発明の目的は、充放電エネルギ効率の
改善されたレドックスフロー電池を提供することにあり
、特に隔膜の機械的強度も改善されたレドックスフロー
電池を提供することにある。Therefore, an object of the present invention is to provide a redox flow battery with improved charge/discharge energy efficiency, and particularly to provide a redox flow battery with improved mechanical strength of the diaphragm.
［問題点を解決するための手段］
この発明のレドックスフロー電池においては、正極と負
極との間に、親水性膜と多孔質膜を組合わせた複合膜か
らなる隔膜を設け、該隔膜により電極セルを正極側と負
極側に分離し、正極側には正極液を負極側には負極液を
供給し充放電を行なっている。[Means for Solving the Problems] In the redox flow battery of the present invention, a diaphragm made of a composite membrane in which a hydrophilic membrane and a porous membrane are combined is provided between the positive electrode and the negative electrode, and the diaphragm is used to connect the electrodes. The cell is separated into a positive electrode side and a negative electrode side, and charging and discharging are performed by supplying a positive electrode liquid to the positive electrode side and a negative electrode liquid to the negative electrode side.
［作用］
この発明で用いられる隔膜は、親水性膜と多孔質膜を組
合わせた複合膜から構成されている。多孔質膜はイオン
透過性が非常に優れているため、この複合膜は親水性膜
単独と同様の優れたイオン透過性を有する。したがって
、セル内部の電気抵抗が著しく減少され、充放電エネル
ギ効率が改善される。[Function] The diaphragm used in this invention is composed of a composite membrane that is a combination of a hydrophilic membrane and a porous membrane. Since porous membranes have very good ion permeability, this composite membrane has the same good ion permeability as the hydrophilic membrane alone. Therefore, the electrical resistance inside the cell is significantly reduced and the charging/discharging energy efficiency is improved.
さらに、親水性膜より機械的強度の優れている多孔質膜
が複合化されているため、この発明に用いられる隔膜は
優れた機械的強度ををする。Furthermore, since a porous membrane, which has better mechanical strength than a hydrophilic membrane, is composited, the diaphragm used in the present invention has excellent mechanical strength.
［実施例］
電極面積１５００ｃｍ２を有するセルを１０セル積層さ
れた多段接続型レドックスフロー電池を用い、隔膜とし
てはセルロース系膜（厚み５０μｍ）にテフロン多孔質
＠（孔径１μｍ、厚み１００μｍ）を両側から圧着させ
たものを用い充放電特性試験を行なった。[Example] A multi-stage connected redox flow battery in which 10 cells with an electrode area of 1500 cm2 were stacked was used, and the diaphragm was a cellulose membrane (thickness 50 μm) with Teflon porous @ (pore diameter 1 μm, thickness 100 μm) on both sides. A charge/discharge characteristic test was conducted using the crimped product.
また比較として、テフロン多孔質膜を圧着させていない
セルロース系膜単独を隔膜として用いた場合についても
行なった。For comparison, a case where a cellulose membrane alone without a Teflon porous membrane bonded thereto was used as a diaphragm was also conducted.
実施例により得られたエネルギ効率は、陽イオン交換膜
を用いた従来の場合に比べ優れており、比較例のものと
ほぼ同程度であった。The energy efficiency obtained in the example was superior to that of the conventional case using a cation exchange membrane, and was approximately the same as that of the comparative example.
また、比較例のものでは組み込みの際あるいは電解液流
通の際に隔膜の亀裂や破断が認められたが、本実施例で
は隔膜の亀裂破断は全く認められなかった。Furthermore, in the comparative example, cracks and breaks in the diaphragm were observed during assembly or during electrolyte flow, but no cracks or ruptures in the diaphragm were observed in this example.
以上のことから、この発明のレドックスフロー電池は、
隔膜の機械的強度を低下させることなく、充放電エネル
ギ効率の向上することが確認された。From the above, the redox flow battery of this invention is
It was confirmed that the charge/discharge energy efficiency was improved without reducing the mechanical strength of the diaphragm.
この発明で用いられる親水性膜としては、実施例で用い
たセルロース系膜に限定されることはなく、たとえばエ
チルビニルアルコール共重合体なども用いることができ
る。また、この発明の効果をより充分に発揮するには、
含水率が１０〜２００％のポリマーであることが好まし
い。さらに、表面の親水性を調整するため、表面に親水
性膜より小さな親水性のコーティング層を設けてもよい
。The hydrophilic membrane used in this invention is not limited to the cellulose membrane used in the examples, and for example, ethyl vinyl alcohol copolymer can also be used. In addition, in order to more fully demonstrate the effects of this invention,
Preferably, the polymer has a water content of 10 to 200%. Furthermore, in order to adjust the hydrophilicity of the surface, a hydrophilic coating layer smaller than the hydrophilic film may be provided on the surface.
この発明に用いられる多孔質膜としては、イオン透過性
に優れ、かつ機械的強度および耐酸性に優れた材料であ
ればいかなる材質であってもよい。The porous membrane used in this invention may be made of any material as long as it has excellent ion permeability, mechanical strength, and acid resistance.
たとえば、テフロン多孔質膜、塩化ビニル多孔質膜等が
適当なものとして掲げられる。For example, a Teflon porous membrane, a vinyl chloride porous membrane, etc. are listed as suitable.
親水性膜と多孔質膜を複合化する方法としては、実施例
のように圧着させる方法でもよいし、またラミネート加
工等により貼り会わせた方法でもよい。The method of combining the hydrophilic membrane and the porous membrane may be a method of press-bonding them as in the embodiment, or a method of pasting them together by laminating or the like.
レドックスフロー電池としては、正極液および負極液が
それぞれ別組成の電解液である２液型レドツクスフロー
電池と、正極液および負極液がほぼ同一組成の電解液で
ある１液型レドツクスフロー電池が知られている。この
発明のレドックスフロー電池は、２液型および１液型の
両方に利用され得るものであるが、特に隔膜を通しての
正極液および負極液の混合の影響の少ない１液型にを効
なものである。Redox flow batteries include two-component redox flow batteries, in which the positive and negative electrolytes are electrolytes with different compositions, and one-component redox flow batteries, in which the positive and negative electrolytes are electrolytes with approximately the same composition. It has been known. The redox flow battery of this invention can be used for both two-component type and one-component type, but is particularly effective for one-component type where the mixing of positive and negative electrode liquids through the diaphragm has less influence. be.
［発明の効果］
この発明のレドックスフロー電池では、隔膜として、親
水性膜と多孔質膜を組合わせた複合膜を用いている。多
孔質膜はイオン透過性が非常に優れているため、この複
合膜は親水性膜単独と同程度のイオン透過性を示す。し
たがって、この発明に用いられる隔膜は、電気抵抗が非
常に小さく、セル内部の電気抵抗を減少させるため、充
放電エネルギ効率が著しく改善される。[Effects of the Invention] In the redox flow battery of the present invention, a composite membrane in which a hydrophilic membrane and a porous membrane are combined is used as a diaphragm. Since porous membranes have very good ion permeability, this composite membrane exhibits ion permeability comparable to that of a hydrophilic membrane alone. Therefore, the diaphragm used in the present invention has very low electrical resistance and reduces the electrical resistance inside the cell, thereby significantly improving charge/discharge energy efficiency.
また、多孔質膜は機械的強度に優れているため、この発
明に用いられる隔膜はこの多孔質膜により補強され、セ
ル組み込みまたは運転に際にかかる応力や液圧等によっ
て亀裂破断するおそれがなくなる。In addition, since porous membranes have excellent mechanical strength, the diaphragms used in this invention are reinforced by this porous membrane, eliminating the risk of cracking or breaking due to stress, hydraulic pressure, etc. applied during cell installation or operation. .
Claims (7)
極液を負極に負極液を供給し、充放電を行なうレドック
スフロー電池において、 前記隔膜が、親水性膜と多孔質膜を組合わせた複合膜で
あることを特徴とする、レドックスフロー電池。(1) In a redox flow battery in which a positive electrode and a negative electrode are separated by a diaphragm and charged and discharged by supplying a positive electrode liquid to the positive electrode and a negative electrode liquid to the negative electrode, the diaphragm combines a hydrophilic membrane and a porous membrane. A redox flow battery characterized by a composite membrane.
マーからなることを特徴とする、特許請求の範囲第１項
記載のレドックスフロー電池。(2) The redox flow battery according to claim 1, wherein the hydrophilic membrane is made of a polymer with a water content of 10 to 200%.
ことを特徴とする、特許請求の範囲第１項または第２項
記載のレドックスフロー電池。(3) The redox flow battery according to claim 1 or 2, wherein the hydrophilic membrane is made of a cellulose polymer.
合体からなることを特徴とする、特許請求の範囲第１項
または第２項記載のレドックスフロー電池。(4) The redox flow battery according to claim 1 or 2, wherein the hydrophilic membrane is made of ethylene vinyl alcohol copolymer.
特徴とする、特許請求の範囲第１〜４項のいずれか１項
に記載のレドックスフロー電池。(5) The redox flow battery according to any one of claims 1 to 4, wherein the porous membrane is a Teflon porous membrane.
を特徴とする、特許請求の範囲第１〜４項のいずれか１
項に記載のレドックスフロー電池。(6) Any one of claims 1 to 4, wherein the porous membrane is a vinyl chloride porous membrane.
The redox flow battery described in section.
の正極活物質と負極活物質の双方を含むことを特徴とす
る、特許請求の範囲第１〜６項のいずれか１項に記載の
レドッスクフロー電池。(7) The method according to any one of claims 1 to 6, wherein the positive electrode liquid and the negative electrode liquid each contain substantially equimolar amounts of both the positive electrode active material and the negative electrode active material. Redox flow battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61068163A JPH06105615B2 (en) | 1986-03-25 | 1986-03-25 | Redox flow battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61068163A JPH06105615B2 (en) | 1986-03-25 | 1986-03-25 | Redox flow battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62223984A true JPS62223984A (en) | 1987-10-01 |
| JPH06105615B2 JPH06105615B2 (en) | 1994-12-21 |
Family
ID=13365818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61068163A Expired - Fee Related JPH06105615B2 (en) | 1986-03-25 | 1986-03-25 | Redox flow battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06105615B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109075369A (en) * | 2016-02-26 | 2018-12-21 | 凯斯西储大学 | Composite membrane for flow battery |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105845958B (en) | 2011-12-28 | 2018-04-06 | 旭化成株式会社 | Oxidation, reduction liquid secondary cell and oxidation, reduction liquid secondary cell Electrolyte Membranes |
| JP6002685B2 (en) | 2011-12-28 | 2016-10-05 | 旭化成株式会社 | Redox flow secondary battery and electrolyte membrane for redox flow secondary battery |
| KR101797274B1 (en) | 2011-12-28 | 2017-11-13 | 아사히 가세이 가부시키가이샤 | Redox flow secondary battery and electrolyte membrane for redox flow secondary battery |
| KR20140097255A (en) | 2011-12-28 | 2014-08-06 | 아사히 가세이 이-매터리얼즈 가부시키가이샤 | Redox flow secondary battery and electrolyte membrane for redox flow secondary battery |
| KR102242600B1 (en) | 2016-11-24 | 2021-04-20 | 아사히 가세이 가부시키가이샤 | Carbon foam, membrane electrode composite |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5524389A (en) * | 1978-07-10 | 1980-02-21 | Oronzio De Nora Impianti | Method of storing and discharging energy of |
| JPS6122574A (en) * | 1984-07-09 | 1986-01-31 | Sumitomo Electric Ind Ltd | Cell construction |
-
1986
- 1986-03-25 JP JP61068163A patent/JPH06105615B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5524389A (en) * | 1978-07-10 | 1980-02-21 | Oronzio De Nora Impianti | Method of storing and discharging energy of |
| JPS6122574A (en) * | 1984-07-09 | 1986-01-31 | Sumitomo Electric Ind Ltd | Cell construction |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109075369A (en) * | 2016-02-26 | 2018-12-21 | 凯斯西储大学 | Composite membrane for flow battery |
| JP2019510342A (en) * | 2016-02-26 | 2019-04-11 | ケース ウェスタン リザーブ ユニバーシティＣａｓｅ Ｗｅｓｔｅｒｎ Ｒｅｓｅｒｖｅ Ｕｎｉｖｅｒｓｉｔｙ | Composite membrane for flow battery |
| US11444306B2 (en) | 2016-02-26 | 2022-09-13 | Case Western Reserve University | Composite membranes for flow batteries |
| CN109075369B (en) * | 2016-02-26 | 2023-05-30 | 凯斯西储大学 | Composite membrane for flow battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06105615B2 (en) | 1994-12-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |