JPH0521312B2 - - Google Patents
Info
- Publication number
- JPH0521312B2 JPH0521312B2 JP60123703A JP12370385A JPH0521312B2 JP H0521312 B2 JPH0521312 B2 JP H0521312B2 JP 60123703 A JP60123703 A JP 60123703A JP 12370385 A JP12370385 A JP 12370385A JP H0521312 B2 JPH0521312 B2 JP H0521312B2
- Authority
- JP
- Japan
- Prior art keywords
- ruthenium
- zinc
- electrode
- carbon plate
- supported
- 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 - Lifetime
Links
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 23
- 229910052707 ruthenium Inorganic materials 0.000 claims description 23
- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 9
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 9
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 description 9
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229940102001 zinc bromide Drugs 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Inorganic materials Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- DDFGPANTDSVNPE-UHFFFAOYSA-L zinc;dibromide;hydrate Chemical compound O.[Zn+2].[Br-].[Br-] DDFGPANTDSVNPE-UHFFFAOYSA-L 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/365—Zinc-halogen accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- 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
- Y02E60/10—Energy storage using batteries
-
- 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
Description
（産業上の利用分野）
本発明は、電気自動車用、電力貯蔵用等の二次
電池、特に亜鉛−臭素二次電池に使用される電極
およびその製造方法に関する。
（従来技術）
亜鉛−臭素二次電池は、上部に集合電池群を収
容した電解槽、負極液循環ポンプ、正極液循環ポ
ンプ、熱交換器、負極液タンク、正極液タンク、
セパレーター等から構成され、電解液には臭化亜
鉛水溶液が用いられ、集合電池群は亜鉛を負極活
物質とし、臭素を正極活物質として用いられてい
る。
この亜鉛−臭素二次電池は、充電時正極から発
生する臭素は多臭化テトラアルキルアンモニウム
のような多臭化物として貯蔵され、充電完了状態
では充電により電解液の臭化亜鉛濃度が減少す
る。放電時は多臭化物を集合電池へ供給する。放
電完了時は、電解液の臭化亜鉛濃度は増加する。
ところで斯かる亜鉛−臭素二次電池に用いる電
極には、従来、炭素板を塩化ルテニウム溶液に浸
して、塩化ルテニウムを含浸させ、乾燥後水素雰
囲気中で還元して、ルテニウムを担持させた電極
が一般に採用されてきた。
（発明が解決しようとする問題点）
然し乍ら、このようにして製造したルテニウム
担持電極は、ルテニウムが金属状態であること、
電解液として臭化亜鉛水和物を使用しているた
め、金属ルテニウムが電解液と反応して使用中に
電解液中に溶出し、電流効率の劣化を引きおこす
という欠点を有していた。
そこで本発明は、上記従来の亜鉛−臭素二次電
池用電極の問題点を解消すべくなされたもので、
所要量の酸化ルテニウムが均一に担持され、使用
中電解液中にルテニウムが溶出しない亜鉛−臭素
二次電池用電極およびその製造方法を提供するこ
とを目的とするものである。
（問題点を解決しようとする手段）
本発明の亜鉛−臭素二次電池用電極は、炭素板
に酸化ルテニウムを担持したことを特徴とするも
のである。
また本発明の亜鉛−臭素二次電池用電極の製造
方法は、炭素板にルテニウムを担持した後、これ
を酸化性雰囲気中で加熱してルテニウムを酸化ル
テニウムにすることを特徴とするものである。
本発明の方法において、炭素板にルテニウムを
担持する方法として、スパツタリングによりルテ
ニウムを直接担持するかあるいは塩化ルテニウム
溶液を含浸乾燥後還元性雰囲気中で280〜750℃に
加熱して塩化ルテニウムをルテニウムに還元する
ようにすれば、ルテニウムを強固に担持すること
ができるので好ましい。また担持されたルテニウ
ムを加熱して酸化するとき、120℃未満では十分
に酸化せず、500℃を超えると炭素板の消耗が激
しくなるので120℃〜500℃の範囲が好ましい。
実施例 １
厚さ２mm、幅150mm、高さ150mmの炭素板にスパ
ツタリングによりルテニウムを２mg／cm2担持し、
それを酸素雰囲気中150℃で30分間加熱し、酸化
ルテニウムを2.6mg／cm2担持した電極を製造した。
実施例 ２
空孔率50％、厚さ２mm、幅150mm、高さ150mmの
多孔性炭素板を１ｇ／の塩化ルテニウム水溶液
に浸漬し、次いで含浸した水溶液の水分を蒸発し
て乾燥させた後、水素雰囲気中450℃、40分間還
元処理し、さらに大気中450℃で30分間加熱して、
酸化ルテニウムを2.6mg／cm2担持した電極を製造
した。
（従来例）
大気中450℃の加熱以外は全て実施例２と同じ
方法でルテニウムを２mg／cm2担持した電極を製造
した。
このようにして製造した実施例１、２および従
来例の亜鉛−臭素二次電池用電極について、まず
飽和臭素水により、電極からのルテニウムの溶出
テストを行つたところ表１のような結果を得た。
(Industrial Application Field) The present invention relates to an electrode used in secondary batteries for electric vehicles, power storage, etc., particularly zinc-bromine secondary batteries, and a method for manufacturing the same. (Prior art) A zinc-bromine secondary battery consists of an electrolytic cell containing a group of assembled batteries in the upper part, a negative electrode liquid circulation pump, a positive electrode liquid circulation pump, a heat exchanger, a negative electrode liquid tank, a positive electrode liquid tank,
It is composed of separators, etc., and an aqueous zinc bromide solution is used as the electrolyte, and the assembled battery group uses zinc as the negative electrode active material and bromine as the positive electrode active material. In this zinc-bromine secondary battery, bromine generated from the positive electrode during charging is stored as a polybromide such as tetraalkylammonium polybromide, and when charging is complete, the concentration of zinc bromide in the electrolyte decreases due to charging. During discharge, polybromide is supplied to the assembled battery. At the end of discharge, the concentration of zinc bromide in the electrolyte increases. By the way, electrodes used in such zinc-bromine secondary batteries have conventionally been prepared by soaking a carbon plate in a ruthenium chloride solution to impregnate it with ruthenium chloride, drying it, and then reducing it in a hydrogen atmosphere to support ruthenium. It has been generally adopted. (Problems to be Solved by the Invention) However, in the ruthenium-supported electrode produced in this manner, ruthenium is in a metallic state;
Since zinc bromide hydrate is used as the electrolyte, metal ruthenium reacts with the electrolyte and is eluted into the electrolyte during use, causing deterioration in current efficiency. Therefore, the present invention was made to solve the above problems of the conventional zinc-bromine secondary battery electrode.
It is an object of the present invention to provide an electrode for a zinc-bromine secondary battery and a method for manufacturing the same, in which a required amount of ruthenium oxide is uniformly supported and ruthenium does not dissolve into an electrolytic solution during use. (Means for Solving the Problems) The electrode for a zinc-bromine secondary battery of the present invention is characterized in that ruthenium oxide is supported on a carbon plate. Further, the method for producing an electrode for a zinc-bromine secondary battery of the present invention is characterized by supporting ruthenium on a carbon plate and then heating it in an oxidizing atmosphere to convert the ruthenium into ruthenium oxide. . In the method of the present invention, ruthenium is supported on a carbon plate by directly supporting ruthenium by sputtering, or by impregnating and drying a ruthenium chloride solution and heating it to 280 to 750°C in a reducing atmosphere to convert ruthenium chloride into ruthenium. Reduction is preferable because ruthenium can be strongly supported. Further, when the supported ruthenium is heated and oxidized, the temperature is preferably in the range of 120°C to 500°C, since sufficient oxidation will not occur if the temperature is less than 120°C, and if it exceeds 500°C, the carbon plate will be severely consumed. Example 1 Ruthenium was supported at 2 mg/cm 2 by sputtering on a carbon plate with a thickness of 2 mm, a width of 150 mm, and a height of 150 mm.
This was heated at 150° C. for 30 minutes in an oxygen atmosphere to produce an electrode carrying 2.6 mg/cm 2 of ruthenium oxide. Example 2 A porous carbon plate with a porosity of 50%, a thickness of 2 mm, a width of 150 mm, and a height of 150 mm was immersed in a 1 g/a ruthenium chloride aqueous solution, and then the water in the impregnated aqueous solution was evaporated and dried. Reduction treatment was performed at 450°C for 40 minutes in a hydrogen atmosphere, and further heating was performed at 450°C for 30 minutes in the air.
An electrode supporting 2.6 mg/cm 2 of ruthenium oxide was manufactured. (Conventional Example) An electrode carrying 2 mg/cm 2 of ruthenium was manufactured in the same manner as in Example 2 except for heating at 450° C. in the air. For the zinc-bromine secondary battery electrodes of Examples 1 and 2 and the conventional example manufactured in this way, we first conducted a ruthenium elution test from the electrodes using saturated bromine water, and the results shown in Table 1 were obtained. Ta.
【表】
また、実施例１、実施例２および従来例の電極
を用いて亜鉛−臭素二次電池を組み立て、電流効
率を測定したところ、表２のような結果を得た。
さらにその電池の電解液をルテニウムについて原
子吸光分析したところ、表２右欄に示す結果を得
た。[Table] Furthermore, when zinc-bromine secondary batteries were assembled using the electrodes of Example 1, Example 2, and the conventional example, and the current efficiency was measured, the results shown in Table 2 were obtained.
Furthermore, when the electrolyte of the battery was subjected to atomic absorption spectroscopy for ruthenium, the results shown in the right column of Table 2 were obtained.
【表】
以上の説明でわかるように本発明の亜鉛−臭素
二次電池用電極は、飽和臭素水によるルテニウム
の溶出、電解液中へのルテニウムの溶出がなく、
電流効率の劣化もほとんどないすぐれた亜鉛−臭
素二次電池用電極である。
（発明の効果）
以上の説明で判るように本発明の亜鉛−臭素二
次電池用電極は、酸化ルテニウムが担持されてい
るので、電解液中へのルテニウムの溶出がなく、
電流効率の劣化も殆どないものである。また本発
明の製造方法によれば、炭素板に所要量の酸化ル
テニウムを強固に均一に担持でき、電極性能の優
れた亜鉛−臭素二次電池用電極を得ることができ
るという優れた効果がある。[Table] As can be seen from the above explanation, the zinc-bromine secondary battery electrode of the present invention does not elute ruthenium with saturated bromine water or into the electrolyte.
This is an excellent electrode for zinc-bromine secondary batteries with almost no deterioration in current efficiency. (Effects of the Invention) As can be seen from the above explanation, since the electrode for zinc-bromine secondary batteries of the present invention supports ruthenium oxide, there is no elution of ruthenium into the electrolyte.
There is almost no deterioration in current efficiency. Further, according to the manufacturing method of the present invention, the required amount of ruthenium oxide can be firmly and uniformly supported on the carbon plate, and an electrode for a zinc-bromine secondary battery with excellent electrode performance can be obtained, which is an excellent effect. .
Claims (1)
徴とする亜鉛−臭素二次電池用電極。 ２ 炭素板にルテニウムを担持した後、これを酸
化性雰囲気中で加熱してルテニウムを酸化ルテニ
ウムにすることを特徴とする亜鉛−臭素二次電池
用電極の製造方法。 ３ ルテニウムを、炭素板にスパツタリングによ
り担持することを特徴とする特許請求の範囲第２
項記載の方法。 ４ ルテニウムを、炭素板に塩化ルテニウム水溶
液を含浸し、乾燥し、これを還元性雰囲気中で
280〜750℃に加熱して塩化ルテニウムをルテニウ
ムに還元することにより担持することを特徴とす
る特許請求の範囲第２項記載の方法。[Claims] 1. An electrode for a zinc-bromine secondary battery, characterized in that ruthenium oxide is supported on a carbon plate. 2. A method for producing an electrode for a zinc-bromine secondary battery, which comprises supporting ruthenium on a carbon plate and then heating the ruthenium in an oxidizing atmosphere to convert the ruthenium into ruthenium oxide. 3. Claim 2, characterized in that ruthenium is supported on a carbon plate by sputtering.
The method described in section. 4 Ruthenium is prepared by impregnating a carbon plate with a ruthenium chloride aqueous solution, drying it, and drying it in a reducing atmosphere.
3. The method according to claim 2, wherein the ruthenium chloride is supported by heating to 280 to 750°C to reduce ruthenium chloride to ruthenium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60123703A JPS61284058A (en) | 1985-06-07 | 1985-06-07 | Electrode for zinc-bromine secondary battery and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60123703A JPS61284058A (en) | 1985-06-07 | 1985-06-07 | Electrode for zinc-bromine secondary battery and its manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61284058A JPS61284058A (en) | 1986-12-15 |
| JPH0521312B2 true JPH0521312B2 (en) | 1993-03-24 |
Family
ID=14867253
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60123703A Granted JPS61284058A (en) | 1985-06-07 | 1985-06-07 | Electrode for zinc-bromine secondary battery and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61284058A (en) |
-
1985
- 1985-06-07 JP JP60123703A patent/JPS61284058A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61284058A (en) | 1986-12-15 |
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