JPH06105615B2 - Redox flow battery - Google Patents
Redox flow batteryInfo
- Publication number
- JPH06105615B2 JPH06105615B2 JP61068163A JP6816386A JPH06105615B2 JP H06105615 B2 JPH06105615 B2 JP H06105615B2 JP 61068163 A JP61068163 A JP 61068163A JP 6816386 A JP6816386 A JP 6816386A JP H06105615 B2 JPH06105615 B2 JP H06105615B2
- Authority
- JP
- Japan
- Prior art keywords
- redox flow
- negative electrode
- positive electrode
- porous membrane
- flow battery
- 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.)
- Expired - Fee Related
Links
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)
Description
【発明の詳細な説明】 ［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。TECHNICAL FIELD The present invention relates to a redox flow battery in which an electrolytic solution is supplied to a positive electrode side and a negative electrode side and is charged and discharged by a redox 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 solution is supplied to the positive electrode side and a negative electrode solution is supplied to the negative electrode side, and charging and discharging are performed by an oxidation-reduction reaction. An ion exchange membrane is generally used as the diaphragm.
［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 electric resistance inside the cell increases due to its poor ion permeability, and the charge and discharge of the entire redox flow battery is increased. 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。Further, when a hydrophilic membrane such as a cellulosic polymer is used instead of the ion exchange membrane, such a problem is solved,
In this case, a new problem arises that the mechanical strength of the diaphragm is lowered.
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 membrane mechanical strength.
［問題点を解決するための手段］ 特許請求の範囲第１項記載の発明によるレドックスフロ
ー電池は、正極と負極との間を隔膜により分離し、正極
に正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、正極液および負極液が、そ
れぞれほぼ等モルの正極活物質と負極活物質の双方を含
み、隔膜が、10〜200％の含水率のポリマーであるセル
ロース系ポリマーと、多孔質膜とを組合せた複合膜であ
ることを特徴としている。[Means for Solving the Problems] The redox flow battery according to the invention of claim 1 separates the positive electrode and the negative electrode with a diaphragm, and supplies the positive electrode liquid to the positive electrode and the negative electrode liquid to the negative electrode. In a redox flow battery that performs charging and discharging, the positive electrode liquid and the negative electrode liquid each contain both an approximately equimolar amount of the positive electrode active material and the negative electrode active material, and the diaphragm is a cellulose-based polymer having a water content of 10 to 200%. It is characterized by being a composite membrane in which a polymer and a porous membrane are combined.
好ましくは、多孔質膜は、ポリテトラフルオロエチレン
多孔質膜であるとよい。Preferably, the porous membrane is a polytetrafluoroethylene porous membrane.
また、好ましくは、多孔質膜は、塩化ビニル多孔質膜で
あるとよい。Also, preferably, the porous membrane is a vinyl chloride porous membrane.
特許請求の範囲第４項記載の発明によるレドックスフロ
ー電池は、正極と負極との間を隔膜により分離し、正極
に正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、正極液および負極液が、そ
れぞれほぼ等モルの正極活物質と負極活物質の双方を含
み、隔膜が、10〜200％の含水率のポリマーであるエチ
レンビニルアルコール共重合体と、多孔質膜とを組合せ
た複合膜であることを特徴としている。The redox flow battery according to the invention of claim 4, wherein the positive electrode and the negative electrode are separated by a diaphragm, the positive electrode liquid is supplied to the positive electrode, the negative electrode liquid is supplied to the negative electrode, and the redox flow battery is charged and discharged. The positive electrode liquid and the negative electrode liquid each contain both a positive electrode active material and a negative electrode active material of approximately equimolar, the diaphragm, an ethylene vinyl alcohol copolymer is a polymer having a water content of 10 ~ 200%, and a porous film. It is characterized by being a composite membrane in which
好ましくは、多孔質膜は、ポリテトラフルオロエチレン
多孔質膜であるとよい。Preferably, the porous membrane is a polytetrafluoroethylene porous membrane.
また、好ましくは、多孔質膜は、塩化ビニル多孔質膜で
あるとよい。Also, preferably, the porous membrane is a vinyl chloride porous membrane.
［作用］ この発明で用いられる隔膜は、10〜200％の含水率のポ
リマーであるセルロース系ポリマーまたはエチレンビニ
ルアルコール共重合体からなる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 membrane used in the present invention is composed of a composite membrane in which a hydrophilic membrane made of a cellulose-based polymer or an ethylene vinyl alcohol copolymer having a water content of 10 to 200% or a porous membrane is combined. ing. Since the porous membrane has very good ion permeability, this composite membrane has the same excellent ion permeability as the hydrophilic membrane alone. Therefore, the electrical resistance inside the cell is significantly reduced, and the charge / discharge 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有する。Furthermore, since the porous membrane, which is superior in mechanical strength to the hydrophilic membrane, is combined, 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）にポリテトラフルオロエチレ
ン多孔質膜（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] Using a multi-stage connection type redox flow battery in which 10 cells having an electrode area of 1500 cm 2 were stacked, a cellulosic membrane (thickness 50 μm) and a polytetrafluoroethylene porous membrane (pore diameter 1 μm, thickness 100 μm) were used as diaphragms. ) Was pressure-bonded from both sides, and a charge / discharge characteristic test was performed.
また比較として、ポリテトラフルオロエチレン多孔質膜
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。Further, as a comparison, a case where a cellulosic membrane alone without a polytetrafluoroethylene porous membrane being pressure-bonded was used as a diaphragm was also performed.
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 the conventional case using the cation exchange membrane, and was almost 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。In addition, in the comparative example, cracks and fractures of the diaphragm were observed at the time of assembling or flowing the electrolytic solution, but cracks and fractures of the diaphragm were not observed at all 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 the present invention is
It was confirmed that the charge / discharge energy efficiency was improved without lowering 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 film used in the present invention is not limited to the cellulose-based film used in the examples, and for example, ethyl vinyl alcohol copolymer can be used. Further, in order to exert the effects of the present invention more sufficiently,
It is preferable that the polymer has a water content of 10 to 200%.
Further, 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。たとえば、ポリテト
ラフルオロエチレン多孔質膜、塩化ビニル多孔質膜等が
適当なものとして掲げられる。The porous membrane used in the present invention may be made of any material as long as it has excellent ion permeability, mechanical strength and acid resistance. For example, polytetrafluoroethylene porous membrane, vinyl chloride porous membrane and the like are listed as appropriate ones.
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。As a method for forming a composite of the hydrophilic film and the porous film, a pressure bonding method as in the examples may be used, or a lamination method or the like may be used.
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液型レドックスフロー
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液型レドッ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液型に有効
なものである。As a redox flow battery, a two-pack type redox flow battery in which the positive electrode solution and the negative electrode solution are electrolytic solutions having different compositions and a one-pack type redox flow battery in which the positive electrode solution and the negative electrode solution are substantially the same composition are known. Has been. The redox flow battery of the present invention can be used for both a two-pack type and a one-pack type, and is particularly effective for the one-pack type in which the influence of the mixing of the positive electrode liquid and the negative electrode liquid through the diaphragm is small. .
［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、10
〜200％の含水率のポリマーであるセルロース系ポリマ
ーまたはエチレンビニルアルコール共重合体からなる親
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壁は、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。[Effect of the Invention] In the redox flow battery of the present invention, as the diaphragm, 10
A composite membrane is used which is a combination of a hydrophilic membrane made of a cellulosic polymer having a water content of ˜200% or an ethylene vinyl alcohol copolymer, and a porous membrane. Since the porous membrane has very good ion permeability, this composite membrane exhibits the same ion permeability as the hydrophilic membrane alone. Therefore, the partition wall used in the present invention has a very small electric resistance and reduces the electric resistance inside the cell, so that the charge / discharge energy efficiency is remarkably improved.
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の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。Further, since the porous membrane is excellent in mechanical strength, the diaphragm used in the present invention is reinforced by this porous membrane, and there is no risk of crack breakage due to stress or hydraulic pressure applied during cell incorporation or operation. .
Claims (6)
極に正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、 前記正極液および負極液が、それぞれほぼ等モルの正極
活物質と負極活物質の双方を含み、 前記隔膜が、10〜200％の含水率のポリマーであるセル
ロース系ポリマーと、多孔質膜とを組合せた複合膜であ
ることを特徴とする、レドックスフロー電池。1. A redox flow battery in which a positive electrode and a negative electrode are separated by a diaphragm, a positive electrode liquid is supplied to the positive electrode, and a negative electrode liquid is supplied to the negative electrode to perform charging and discharging, and the positive electrode liquid and the negative electrode liquid are approximately equal to each other. It is characterized by comprising both a mole of the positive electrode active material and the negative electrode active material, wherein the diaphragm is a composite membrane in which a cellulosic polymer which is a polymer having a water content of 10 to 200% and a porous membrane are combined. , Redox flow batteries.
レン多孔質膜であ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 porous membrane is a polytetrafluoroethylene porous membrane.
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。3. The redox flow battery according to claim 1, wherein the porous membrane is a vinyl chloride porous membrane.
極に正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、 前記正極液および負極液が、それぞれほぼ等モルの正極
活物質と負極活物質の双方を含み、 前記隔膜が、10〜200％の含水率のポリマーであるエチ
レンビニルアルコール共重合体と、多孔質膜とを組合せ
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。4. A redox flow battery in which a positive electrode and a negative electrode are separated by a diaphragm, a positive electrode liquid is supplied to the positive electrode, and a negative electrode liquid is supplied to the negative electrode to perform charging and discharging, and the positive electrode liquid and the negative electrode liquid are approximately equal to each other. It contains both a positive electrode active material and a negative electrode active material in moles, the diaphragm is a composite film that combines an ethylene vinyl alcohol copolymer, which is a polymer having a water content of 10 to 200%, and a porous film. Characteristic redox flow battery.
レン多孔質膜であることを特徴とする、特許請求の範囲
第４項記載のレドックスフロー電池。5. The redox flow battery according to claim 4, wherein the porous membrane is a polytetrafluoroethylene porous membrane.
ることを特徴とする、特許請求の範囲第４項記載のレド
ックスフロー電池。6. The redox flow battery according to claim 4, wherein the porous membrane is a vinyl chloride porous membrane.
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 JPS62223984A (en) | 1987-10-01 |
| JPH06105615B2 true 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 (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013100079A1 (en) | 2011-12-28 | 2013-07-04 | 旭化成イーマテリアルズ株式会社 | Redox flow secondary battery and electrolyte membrane for redox flow secondary batteries |
| WO2013100082A1 (en) | 2011-12-28 | 2013-07-04 | 旭化成イーマテリアルズ株式会社 | Redox flow secondary battery and electrolyte membrane for redox flow secondary battery |
| EP3091598A1 (en) | 2011-12-28 | 2016-11-09 | Asahi Kasei Kabushiki Kaisha | Redox flow secondary battery and electrolyte membrane for redox flow secondary batteries |
| US9905875B2 (en) | 2011-12-28 | 2018-02-27 | Asahi Kasei Kabushiki Kaisha | Redox flow secondary battery and electrolyte membrane for redox flow secondary battery |
| WO2018096895A1 (en) | 2016-11-24 | 2018-05-31 | 旭化成株式会社 | Carbon foam and membrane electrode composite |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017147568A1 (en) | 2016-02-26 | 2017-08-31 | Case Western Reserve University | Composite membranes for flow batteries |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1212303B (en) * | 1978-07-10 | 1989-11-22 | Elche Ltd | REDOX ACCUMULATOR. |
| 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
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013100079A1 (en) | 2011-12-28 | 2013-07-04 | 旭化成イーマテリアルズ株式会社 | Redox flow secondary battery and electrolyte membrane for redox flow secondary batteries |
| WO2013100082A1 (en) | 2011-12-28 | 2013-07-04 | 旭化成イーマテリアルズ株式会社 | Redox flow secondary battery and electrolyte membrane for redox flow secondary battery |
| EP3091598A1 (en) | 2011-12-28 | 2016-11-09 | Asahi Kasei Kabushiki Kaisha | Redox flow secondary battery and electrolyte membrane for redox flow secondary batteries |
| EP3091599A1 (en) | 2011-12-28 | 2016-11-09 | Asahi Kasei Kabushiki Kaisha | Redox flow secondary battery and electrolyte membrane for redox flow secondary batteries |
| US9799906B2 (en) | 2011-12-28 | 2017-10-24 | Asahi Kasei Kabushiki Kaisha | Redox flow secondary battery and electrolyte membrane for redox flow secondary battery |
| US9905875B2 (en) | 2011-12-28 | 2018-02-27 | Asahi Kasei Kabushiki Kaisha | Redox flow secondary battery and electrolyte membrane for redox flow secondary battery |
| US10256493B2 (en) | 2011-12-28 | 2019-04-09 | Asahi Kasei Kabushiki Kaisha | Redox flow secondary battery and electrolyte membrane for redox flow secondary battery |
| WO2018096895A1 (en) | 2016-11-24 | 2018-05-31 | 旭化成株式会社 | Carbon foam and membrane electrode composite |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62223984A (en) | 1987-10-01 |
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