JPH02257577A - Metal-air secondary cell - Google Patents
Metal-air secondary cellInfo
- Publication number
- JPH02257577A JPH02257577A JP1079846A JP7984689A JPH02257577A JP H02257577 A JPH02257577 A JP H02257577A JP 1079846 A JP1079846 A JP 1079846A JP 7984689 A JP7984689 A JP 7984689A JP H02257577 A JPH02257577 A JP H02257577A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- gas diffusion
- metal
- oxide catalyst
- air
- 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
- 238000009792 diffusion process Methods 0.000 claims abstract description 71
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 229910019981 La1-xCaxCoO3 Inorganic materials 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 67
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 46
- 239000001301 oxygen Substances 0.000 description 46
- 229910052760 oxygen Inorganic materials 0.000 description 46
- 238000000034 method Methods 0.000 description 25
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 24
- 238000004519 manufacturing process Methods 0.000 description 24
- 239000000843 powder Substances 0.000 description 20
- 229910052725 zinc Inorganic materials 0.000 description 16
- 239000011701 zinc Substances 0.000 description 16
- 238000007600 charging Methods 0.000 description 15
- 238000006722 reduction reaction Methods 0.000 description 15
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 14
- 230000009467 reduction Effects 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000004809 Teflon Substances 0.000 description 6
- 229920006362 Teflon® Polymers 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 241001408449 Asca Species 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- 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
- H01M4/8605—Porous electrodes
- H01M4/8615—Bifunctional electrodes for rechargeable cells
-
- 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
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は金属−空気２次電池に係り、特に高出力放電及
び高速充電が可能な金属−空気２次電池に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a metal-air secondary battery, and particularly to a metal-air secondary battery capable of high-output discharge and high-speed charging.
［従来の技術及び先行技術］
アルカリ水溶液中での酸素の電気化学的還元反応は、燃
料電池や金属−空気電池において極めて重要である。[Prior Art and Prior Art] The electrochemical reduction reaction of oxygen in aqueous alkaline solutions is extremely important in fuel cells and metal-air cells.
本発明者らは、特に金属−空気電池用のガス拡散型酸素
電極、とりわけ酸素還元陰極としてカーボンを主体とし
たテフロン（ポリテトラフルオロエチレン）結着型ガス
拡散型酸素電極、即ちガス拡散型カーボン電極について
、種々検討を重ねてきた。The present inventors have developed a gas diffusion type oxygen electrode for metal-air batteries, particularly a Teflon (polytetrafluoroethylene) bonded gas diffusion type oxygen electrode mainly composed of carbon as an oxygen reduction cathode, that is, a gas diffusion type oxygen electrode for use in metal-air batteries. Various studies have been conducted regarding electrodes.
第２図は一般的なガス拡散型カーボン電極を示す断面図
である。FIG. 2 is a sectional view showing a general gas diffusion type carbon electrode.
図示の如く、ガス拡散電極（ガス拡散型カーボン電極）
１０は、ガス拡散層１２と反応層１３との２層とされて
おり、ガス拡散層１２は炭素及びテフロンよりなり、反
応層は炭素、テフロン及び酸化物触媒よりなる。このよ
うなガス拡散電極１０にはＮｉメツシュ１４等の導電線
がホットプレス等により埋設される。使用に際して、ガ
ス拡散層１２は空気、酸素等のガス側に、反応層１３は
ＫＯＨ等のアルカリ水溶液側に設置される。As shown, gas diffusion electrode (gas diffusion type carbon electrode)
10 has two layers: a gas diffusion layer 12 and a reaction layer 13. The gas diffusion layer 12 is made of carbon and Teflon, and the reaction layer is made of carbon, Teflon, and an oxide catalyst. A conductive wire such as a Ni mesh 14 is buried in such a gas diffusion electrode 10 by hot pressing or the like. In use, the gas diffusion layer 12 is placed on the side of a gas such as air or oxygen, and the reaction layer 13 is placed on the side of an alkaline aqueous solution such as KOH.
木発明者らは、先にこのようなガス拡散型カーボン電極
に用いられる酸化物触媒として、下記組成に代表される
ランタン系ペロブスカイト型酸化物触媒が有効であるこ
とを見出した（「日本化学会誌Ｊ１９８６年Ｎｏ、６第
７５１〜７５５頁）。The inventors have previously discovered that lanthanum-based perovskite-type oxide catalysts represented by the composition below are effective as oxide catalysts used in such gas diffusion type carbon electrodes ("Journal of the Chemical Society of Japan"). J1986 No. 6, pp. 751-755).
Ｌ ａ ｏｊ Ｓ ｒ ｏ４ Ｆ ｅ
ａｓ Ｍ １１．４ ０ ３（Ｍ＝Ｍｎ、
Ｃｏ）
そして、電流密度の向上、電極活性の向上、電位の安定
化などの電極性能、作動性能等のより一層の改善を目的
として、炭素及びポリテトラフルオロエチレンを含むガ
ス拡散層と、炭素、ポリテトラフルオロエチレン及び酸
化物触媒を含む反応層とを備えるガス拡散型酸素電極に
おいて、酸化物触媒として下記（Ｉ）又は（■りの組成
を有するペロブストカイト型酸化物触媒を用いたガス拡
散型酸素電極を提案し、本出願人より特許出願した（特
願昭６３−１５５６６２号。以下「先願」という。）。L a oj S r o4 F e
as M 11.4 0 3 (M=Mn,
Co) For the purpose of further improving electrode performance such as improving current density, improving electrode activity, and stabilizing potential, and operating performance, a gas diffusion layer containing carbon and polytetrafluoroethylene, carbon, In a gas diffusion type oxygen electrode comprising a reaction layer containing polytetrafluoroethylene and an oxide catalyst, gas diffusion using a perovstite type oxide catalyst having the following composition (I) or (■) as the oxide catalyst. proposed a type oxygen electrode, and filed a patent application with the present applicant (Japanese Patent Application No. 155662/1983 (hereinafter referred to as the "prior application")).
Ｌａｄ−ｘＣａｘＣｏＯ３
（ただし、０．０５≦ｘ≦０．９）
Ｌａｄ−、Ｃａ、 ＭｎＯ３
（ただし、０．０５≦ｙ≦０．９）
上記先願によれば、金属−空気１次電池の酸素還元極（
陰極）として極めて優れた性能を有するガス拡散型酸素
電極が提供される。Lad-xCaxCoO3 (however, 0.05≦x≦0.9) Lad-, Ca, MnO3 (however, 0.05≦y≦0.9) According to the above prior application, oxygen in a metal-air primary battery Reducing electrode (
A gas diffusion type oxygen electrode having extremely excellent performance as a cathode) is provided.
［発明が解決しようとする課題］
ところで、金属−空気１次電池に対して、金属−空気２
次電池は、安価でエネルギー密度の高いことから、工業
的に極めて有用である。[Problem to be solved by the invention] By the way, in contrast to the metal-air primary battery, the metal-air secondary battery
Secondary batteries are extremely useful industrially because they are inexpensive and have high energy density.
金属−空気電池を２次電池に応用する場合に、空気極を
そのまま充電用対極として共用する方法と空気極とは別
に、充電用対極として第３の電極を設ける方法がある。When applying a metal-air battery to a secondary battery, there are two methods: using the air electrode as it is as a counter electrode for charging, and providing a third electrode as a counter electrode for charging in addition to the air electrode.
充電時には、電極上で酸素が発生し、電極が陽極酸化を
受は易いために、従来において、多くは後者の方法が取
り入れられていた。しかし、この方法は、電池構造の複
雑化に伴う、エネルギー密度の減少、操作の複雑化等の
問題がある。Since oxygen is generated on the electrodes during charging and the electrodes are susceptible to anodic oxidation, the latter method has conventionally been adopted in most cases. However, this method has problems such as a decrease in energy density and a complicated operation due to the complexity of the battery structure.
このため、充電用対極として第３の電極を設けることな
く、空気極を充電用電極（酸素発生電極）として共用す
ることが可能な金属−空気２次電池の開発が望まれてい
る。しかして、このような高性能金属−空気２次電池の
実現には、酸素（空気）の電気化学的還元反応における
性能が高いだけでなく、陽極における充電時の酸素発生
に対しても高性能であるといった両機能を備えたガス拡
散電極の開発が必要とされる。Therefore, it is desired to develop a metal-air secondary battery in which the air electrode can also be used as a charging electrode (oxygen generating electrode) without providing a third electrode as a charging counter electrode. In order to realize such a high-performance metal-air secondary battery, it is necessary not only to have high performance in the electrochemical reduction reaction of oxygen (air), but also to have high performance against oxygen generation during charging at the anode. There is a need to develop a gas diffusion electrode that has both functions.
本発明は上記従来の実情に鑑みてなされたものであり、
高出力放電及び高速充電が可能な金属−空気２次電池を
提供することを目的とする。The present invention has been made in view of the above-mentioned conventional situation,
An object of the present invention is to provide a metal-air secondary battery capable of high-output discharge and high-speed charging.
［課題を解決するための手段］
本発明の金属−空気２次電池は、空気電極として、炭素
及びポリテトラフルオロエチレンを含むガス拡散層と、
炭素、ポリテトラフルオロエチレン及び酸化物触媒を含
む反応層とを備えるガス拡散電極であって、酸化物触媒
として下記組成を有するペロブスカイト型・酸化物触媒
を用いたガス拡散電極を備えてなることを特徴とする。[Means for Solving the Problems] The metal-air secondary battery of the present invention includes, as an air electrode, a gas diffusion layer containing carbon and polytetrafluoroethylene;
A gas diffusion electrode comprising a reaction layer containing carbon, polytetrafluoroethylene, and an oxide catalyst, the gas diffusion electrode comprising a perovskite-type oxide catalyst having the following composition as the oxide catalyst. Features.
Ｌａｄ−Ｘ Ｃａ、Ｃｏｏｓ
（ただし、０．０５≦ｘ≦０．９）
即ち、本発明者らは、前記先願により提案されたガス拡
散型酸素電極のうち、Ｌａｄ−ＣａｘＣｏ０ｚ （た
だし、０．０５≦ｘ≦０．９）を酸化物触媒として用い
たガス拡散電極は、酸素還元特性に優れ、従来の電極に
比べて高電流密度が得られる上に、酸素発生電極として
も著しく優れた特性を備え、高速充電が可能であること
を見出し、本発明を完成させた。Lad-X Ca, Coos (however, 0.05≦x≦0.9) That is, the present inventors found that among the gas diffusion type oxygen electrodes proposed by the previous application, Lad-CaxCo0z (however, 0.05≦x≦0.9) A gas diffusion electrode using 05≦x≦0.9) as an oxide catalyst has excellent oxygen reduction properties and can obtain a higher current density than conventional electrodes, and also has remarkable properties as an oxygen generation electrode. The present invention was completed based on the discovery that high-speed charging is possible.
以下に本発明を図面を参照して詳細に説明する。The present invention will be explained in detail below with reference to the drawings.
第１図は本発明の金属−空気２次電池の一実施例に係る
亜鉛−空気２次電池１の一部切欠き斜視図である。FIG. 1 is a partially cutaway perspective view of a zinc-air secondary battery 1 according to an embodiment of the metal-air secondary battery of the present invention.
第１図において、２はセルケース、３は金属極（例えば
、亜鉛板）、４はセパレーター ５は電解液（例えば、
３０重量％ＫＯＨ）、６はリード線、７は集電体（例え
ば、Ｎｉメツシュ）、１０はガス拡散電極である。In Fig. 1, 2 is a cell case, 3 is a metal electrode (for example, a zinc plate), 4 is a separator, and 5 is an electrolyte (for example,
30% by weight KOH), 6 is a lead wire, 7 is a current collector (for example, Ni mesh), and 10 is a gas diffusion electrode.
本発明の金属−空気２次電池は、空気電極として、第２
図に示すような反応層の酸化物触媒として、
Ｌ ａ １−ｘ Ｃａ 、 Ｃｏ Ｏｓ（ただし、
０．０５≦ｘ≦０．９）
で示されるペロブスカイト型酸化物触媒を用いたガス拡
散電極１０を用いること以外は、従来の金属−空気２次
電池と同様の構成を有する。The metal-air secondary battery of the present invention uses a second air electrode as an air electrode.
As oxide catalysts in the reaction layer as shown in the figure, L a 1-x Ca, CoOs (however,
0.05≦x≦0.9) It has the same structure as a conventional metal-air secondary battery except for using the gas diffusion electrode 10 using a perovskite type oxide catalyst.
以下に、本発明で空気電極として採用されるガス拡散電
極１０について説明する。The gas diffusion electrode 10 employed as an air electrode in the present invention will be described below.
本発明に係るガス拡散電極１０に用いられる上記酸化物
触媒のＣａ置換率は、得られる電池性能に影響を及ぼし
、
０．３≦ｘ≦０．５
であることが好ましい。The Ca substitution rate of the oxide catalyst used in the gas diffusion electrode 10 according to the present invention affects the resulting battery performance, and is preferably 0.3≦x≦0.5.
ガス拡散電極１０の反応層１３中の上記酸化物触媒の含
有量は、少な過ぎると十分な触媒効果が得られず、また
所定量を超えて用いてもそれに見合う電極抵抗の改善効
果が得られない上に、過度に多量の酸化物触媒を用いた
場合には電極内部の微細構造に変化が生じ、電極抵抗が
悪化する場合がある。このようなことから、酸化物触媒
の含有量は１０〜６０重量％、特に２０〜３０重量％の
範囲とするのが好ましい。If the content of the oxide catalyst in the reaction layer 13 of the gas diffusion electrode 10 is too small, a sufficient catalytic effect cannot be obtained, and even if it is used in excess of a predetermined amount, a commensurate improvement in electrode resistance cannot be obtained. Moreover, if an excessively large amount of oxide catalyst is used, the fine structure inside the electrode may change, and the electrode resistance may deteriorate. For this reason, the content of the oxide catalyst is preferably in the range of 10 to 60% by weight, particularly 20 to 30% by weight.
反応層１３及びガス拡散層１２中のポリテトラフルオロ
エチレン（以下ｒＰＴＦＥＪと略記する。・）の含有量
は、少な過ぎると電極の結着性が悪くなり、反対に多く
なると電極の抵抗が高くなったり、ガス拡散性が悪くな
る。従りて、ＰＴＦＥ含有量は１０〜４０重量％、特に
反応層１３では２０〜３Ｏｆｉ量％、ガス拡散Ｎ１２で
は１８〜２８重量％の範囲とするのが好ましい。If the content of polytetrafluoroethylene (hereinafter abbreviated as rPTFEJ) in the reaction layer 13 and gas diffusion layer 12 is too small, the binding properties of the electrode will deteriorate, and on the other hand, if it is too large, the resistance of the electrode will increase. or gas diffusion becomes worse. Therefore, the PTFE content is preferably in the range of 10 to 40% by weight, particularly 20 to 3% by weight in the reaction layer 13, and 18 to 28% by weight in the gas diffusion N12.
本発明に係るガス拡散電極１０は、ガス拡散層１２とし
て炭素及びＰ Ｔ Ｆ Ｅ、反応層１３として炭素、Ｐ
ＴＦＥ及び酸化物触媒を混合した原料粉末を用い、これ
ら２層を例えばＮＬメツシュと共にホットプレスするな
どの方法により容易に作製することができる。The gas diffusion electrode 10 according to the present invention includes carbon and P T F E as the gas diffusion layer 12 and carbon and P TFE as the reaction layer 13 .
These two layers can be easily produced by using a raw material powder containing a mixture of TFE and an oxide catalyst, for example, by hot pressing them together with an NL mesh.
なお、各層の原料粉末は、例えば次のようにして調製す
ることができる。Note that the raw material powder for each layer can be prepared, for example, as follows.
■ ガス拡散層用原料粉末
ブタノール水溶液にカーボンブラックを添加して混合す
る。これにＰＴＦＥを分散させた後、濾過、乾燥して微
粉化する（ブタノール分散）。あるいは、混合系として
トライトン水溶液を用いて行なうこともできる。この場
合には、微粉化後、熱処理を施してトライトンを十分に
飛ばすことが必要である。■ Add carbon black to the butanol aqueous solution of raw material powder for the gas diffusion layer and mix. After dispersing PTFE therein, it is filtered, dried and pulverized (butanol dispersion). Alternatively, a Triton aqueous solution can be used as a mixed system. In this case, after pulverization, it is necessary to perform heat treatment to sufficiently remove the Triton.
■ 反応層用原料粉末
カーボンと酸化物触媒をメノウ乳鉢で十分混合したもの
に、■の方法で得られたカーボンブラック−ＰＴＦＥ混
合粉末を加え、ブタノールを分散剤として液相混合、濾
過、乾燥した後、微粉化する。■ The raw carbon powder for the reaction layer and the oxide catalyst were thoroughly mixed in an agate mortar, and the carbon black-PTFE mixed powder obtained by the method (■) was added, mixed in a liquid phase using butanol as a dispersant, filtered, and dried. After that, it is pulverized.
本発明に係るガス拡散電極１０の厚さについては特に制
限はないが、その厚さは薄いほど電極抵抗が低くなるた
め性能が良くなる傾向にある。厚さがあまり薄くなり過
ぎるとガス漏れ、液漏れが発生するため性能が低下する
こととなる。従って、電極の反応層１３、ガス拡散層１
２のそれぞれにおいて、ホットプレスに用いた原料粉末
の量が単位面積当り５〜１５ｍｇ／ｃｒｎ’程度、特に
反応層１３においては約１０〜１２ｍｇ／ｃゴ、ガス拡
散層１２では約９〜Ｓｉｎｇ／ｃｍ’とするのが好まし
い。There is no particular restriction on the thickness of the gas diffusion electrode 10 according to the present invention, but the thinner the electrode, the lower the electrode resistance and the better the performance tends to be. If the thickness becomes too thin, gas leakage and liquid leakage will occur, resulting in a decrease in performance. Therefore, the reaction layer 13 of the electrode, the gas diffusion layer 1
2, the amount of raw material powder used for hot pressing is about 5 to 15 mg/crn' per unit area, particularly about 10 to 12 mg/crn' in the reaction layer 13, and about 9 to Sing/crn' in the gas diffusion layer 12. It is preferable to set it as cm'.
このようなガス拡散電極１０に用いられる酸化物触媒の
製造方法としては、特に制限はないが、後述の［実施例
］の項における製造例１で挙げる酢酸塩分解法（ＡＤ法
）又はアモルフ・アスクエン酸前駆体法（ＡＣＰ法）に
より製造することができる。There are no particular restrictions on the method for producing the oxide catalyst used in the gas diffusion electrode 10, but the method may be the acetate decomposition method (AD method) or the amorphous asquene method mentioned in Production Example 1 in the Examples section below. It can be produced by an acid precursor method (ACP method).
特に、本発明においては、ＡＣＰ法により調製したペロ
ブスカイト型酸化物触媒を用いることにより、著しく優
れた電流密度の向上効果が得られる。これは、ＡＣＰ法
で調製した触媒はその焼成温度がＡＤ法よりも約２００
℃低いため、表面積が大きくなっていることから、触媒
活性が高いためと考えられる。In particular, in the present invention, by using a perovskite-type oxide catalyst prepared by the ACP method, a remarkable effect of improving current density can be obtained. This means that the calcination temperature of the catalyst prepared by the ACP method is approximately 200° higher than that of the AD method.
This is thought to be due to the high catalytic activity due to the large surface area due to the low temperature.
なお、本発明において、金属−空気２次電池の金属極３
としては、亜鉛、鉄等の金属板又は金属粉末を用いるこ
とができる。これらのうち、特に、亜鉛板又は亜鉛粉末
が一般的である。特に、亜鉛粉末を用いた場合には、よ
り高い電流を流せるという効果が奏され、極めて有利で
ある。In addition, in the present invention, the metal electrode 3 of the metal-air secondary battery
As the material, a metal plate or metal powder such as zinc or iron can be used. Among these, zinc plates or zinc powder are particularly common. In particular, when zinc powder is used, it is extremely advantageous because it allows higher current to flow.
リード線６としては、Ａｕ線、Ｃｕ線、Ａｆｌ線等を用
いることができるが、Ａｕ線を用いることにより、副反
応が起こり難くなり、高い放電容量を得ることができる
という効果が奏され、極めて有利である。As the lead wire 6, an Au wire, a Cu wire, an Afl wire, etc. can be used, but by using an Au wire, side reactions are less likely to occur, and a high discharge capacity can be obtained. Extremely advantageous.
集電体７としては、Ｎｉメツシュ、カーボン紙、Ａｕメ
ツシュ等を用いることができるが、特に、安価で高電流
密度が得られることがらＮｉメツシュが好適である。As the current collector 7, Ni mesh, carbon paper, Au mesh, etc. can be used, but Ni mesh is particularly suitable because it is inexpensive and can provide a high current density.
電解液５としては、通常、３０重量％のＫＯＨ水溶液が
用いられるが、その他ＮａＯＨ水溶液、ＺｎＣλ２水溶
液等を用いることもできる。As the electrolytic solution 5, a 30% by weight KOH aqueous solution is usually used, but other NaOH aqueous solutions, ZnCλ2 aqueous solutions, etc. can also be used.
セパレーター４としては、ジュラガート（ポリプロピレ
ンフィルム）、シリコンファイバー濾紙等を用いること
ができる。As the separator 4, Duragart (polypropylene film), silicone fiber filter paper, etc. can be used.
［作用］
１、ａｌ−ＸＣａＸＣｏｏ３
（ただし、０．０５≦ｘ≦０．９）
なる組成を有するベロブストカイト型酸化物触媒は、酸
素の電気化学的還元用電極触媒として非常に有効である
上に、酸素発生に対しても極めて高活性である。このた
め、このベロブストカイト型酸化物触媒を用いたガス拡
散電極は、耐酸化性に優れ、酸素還元のみならず、酸素
発生用電極としても高い電流密度を得ることができる。[Function] 1. The belobstite-type oxide catalyst having the composition al-XCaXCoo3 (0.05≦x≦0.9) is very effective as an electrode catalyst for electrochemical reduction of oxygen. Furthermore, it has extremely high activity against oxygen generation. Therefore, a gas diffusion electrode using this belobustokite type oxide catalyst has excellent oxidation resistance and can obtain a high current density not only as an oxygen reduction electrode but also as an oxygen generation electrode.
従って、このようなガス拡散電極を用いることにより、
高出力放電及び高速充電が可能な金属−空気２次電池が
提供される。Therefore, by using such a gas diffusion electrode,
A metal-air secondary battery capable of high-output discharge and high-speed charging is provided.
［実施例］
以下に製造例及び実験例を挙げて本発明をより具体的に
説明する。[Example] The present invention will be described in more detail below with reference to production examples and experimental examples.
製造例１：触媒の調製
酢酸塩分解（ＡＤ）法及びアモルファスクエン酸前駆体
（ＡＣＰ）法により、ベロブストカイト型酸化物触媒Ｌ
ａ ａｊＣａ ６．４ Ｃｏ Ｏ３を調製した。Production Example 1: Preparation of Catalyst Belobstite-type oxide catalyst L was prepared by acetate decomposition (AD) method and amorphous citric acid precursor (ACP) method.
a ajCa 6.4 Co O3 was prepared.
■ 酢酸塩分解（ＡＤ）法
所定のモル組成の金属酢酸塩を秤量しく調製した酸化物
の金属組成としては、仕込の組成をそのまま用いた。）
、蒸留水を加えてホットプレート上で加熱（約８０℃）
し、完全に溶解させた後、混合水溶液とした。これを攪
拌しながら、濃縮、蒸発乾固させ、更に約３５０’ｅで
加熱して、酢酸塩を完全に分解させた。分解物は、メノ
ウ乳鉢で粉砕した後に、８５０℃で１０時間焼成してベ
ロブストカイト型酸化物を得た。(2) Acetate decomposition (AD) method Metal acetate having a predetermined molar composition was weighed and prepared. As the metal composition of the oxide, the composition used as it was was used as it was. )
, add distilled water and heat on a hot plate (approximately 80℃)
After completely dissolving the mixture, a mixed aqueous solution was prepared. This was concentrated and evaporated to dryness with stirring, and further heated at about 350'e to completely decompose the acetate. The decomposed product was crushed in an agate mortar and then calcined at 850° C. for 10 hours to obtain a belobustocite-type oxide.
■ アモルファスクエン酸前駆体（Ａｃｐ）法所定モル
組成の金属硝酸塩とクエン酸を掻く少量の蒸留水にそれ
ぞれ別々に完全に溶解させ、これらの溶液を混合した後
、ロータリーエバポレーターに移し７０℃で脱水した。■ Amorphous citric acid precursor (Acp) method: Completely dissolve metal nitrate and citric acid of a given molar composition in a small amount of distilled water separately, mix these solutions, and then transfer to a rotary evaporator and dehydrate at 70°C. did.
大部分が脱水したら、真空乾燥器に移し８０℃で、５時
間乾燥した。この乾燥した前駆体を少量ルツボに採取し
、約２００’ｅで仮焼した。この後、メノウ乳鉢で粉砕
した後、６５０ｔで２時間焼成しベロブストカイト型酸
化物を得た。Once most of the water had been dehydrated, it was transferred to a vacuum dryer and dried at 80°C for 5 hours. A small amount of this dried precursor was collected in a crucible and calcined at about 200'e. Thereafter, it was crushed in an agate mortar and then fired at 650 tons for 2 hours to obtain a belobustocite type oxide.
製造例２：ガス拡散層用原料粉末の製造界面活性剤（ト
ライトン）分散法及びブタノール分散法により、ＰＴＦ
Ｅ含有率１８重量％のガス拡散層用粉末を作製した。Production Example 2: Production of raw material powder for gas diffusion layer By surfactant (Triton) dispersion method and butanol dispersion method, PTF
A powder for a gas diffusion layer with an E content of 18% by weight was produced.
■ 界面活性剤（トライトン）分散法
カーボンブラック、界面活性剤（トライトン）及び水を
１：１：３０（重量比）の割合で混合し、これにＰＴＦ
Ｅディスバージョンを添加し、ミキサーで５分間攪拌し
た。この溶液を凍結、解凍した後に吸引濾過させ、１０
０℃で１２時間乾燥させた。これをミキサーで攪拌する
ことにより微粉化し、２８０℃で３時間空気中で熱処理
を行った（これは、トライトンを十分に飛ばすためであ
る。）。得られた粉末をミキサー又はミルによりもう一
度微粉化して、ガス拡散層用粉末を得た。■ Surfactant (Triton) dispersion method Carbon black, surfactant (Triton) and water are mixed in a ratio of 1:1:30 (weight ratio), and PTF is added to this.
E-disversion was added and stirred with a mixer for 5 minutes. This solution was frozen, thawed, filtered with suction,
It was dried at 0°C for 12 hours. This was pulverized by stirring with a mixer, and heat treated in air at 280° C. for 3 hours (this was to sufficiently blow off Triton). The obtained powder was once again pulverized using a mixer or a mill to obtain a powder for a gas diffusion layer.
■ ブタノール分散法
カーボンブラック、ブタノール及び水を１：１：３０（
重量比）の割合で混合し、これに、ＰＴＦＥディスバー
ジョンを添加し、スターテで６０分間攪拌した。この溶
液を吸引濾過させ、１２０℃で１２時間乾燥させた。こ
れをミルで微粉化し、ガス拡散層用粉末を得た。■ Butanol dispersion method Carbon black, butanol and water are mixed in a ratio of 1:1:30 (
PTFE dispersion was added thereto and stirred for 60 minutes using a starter. The solution was filtered with suction and dried at 120° C. for 12 hours. This was pulverized using a mill to obtain a powder for a gas diffusion layer.
製造例３：反応層用粉末の製造
カーボンと製造例１の■ＡＣＰ法で得られた酸化物触媒
をメノウ乳鉢にて十分に混合粉砕し、これに上記製造例
２の■の方法により調製したガス拡散層用粉末（ＰＴＦ
Ｅ処理カーボン）を混合し、分散媒としてブタノールを
加えて十分攪拌したのち、濾過、乾燥（１２０℃、１２
時間）した後、ミルで微粉化して、ＰＴＦＥ含有率１５
重量％、酸化物触媒含有率２５重量％の反応層用粉末を
得た。Production Example 3: Production of powder for reaction layer Carbon and the oxide catalyst obtained by the ACP method in Production Example 1 were thoroughly mixed and ground in an agate mortar, and the powder was prepared by the method in Production Example 2 above. Powder for gas diffusion layer (PTF
E-treated carbon) was mixed, butanol was added as a dispersion medium and stirred thoroughly, then filtered and dried (120°C, 12°C).
time), it is pulverized in a mill and the PTFE content is 15%.
A reaction layer powder having an oxide catalyst content of 25% by weight was obtained.
製造例４：ホットプレス法によるガス拡散電極の作製
第４図に示すホットプレス用金型３０（第４図中の数値
の単位はｍｍ）にアルミホイル（アセトンで脱脂）をの
せ、その上にＮｉメツシュを挟み込み、製造例２で得ら
れたガス拡散層粉末を３０ｍｇ充填し、金型Ｂにより冷
間ブレス（１６ＭＰａ）する０次に、その上に金型Ｃを
入れ、製造例３で得られた反応層粉末を２５ｍｇ充填し
、金型Ａを用いて、反応層粉末を指圧程度の圧力で押え
、金型Ａ、Ｃを取り除き、さらに金型Ｂを使用して冷間
ブレス（１６ＭＰａ）Ｌ／た。その後、電極表面にアル
ミホイルをのせたのち、約６００℃に保った電気炉の中
に投入し、３７０℃まで昇温し、ホットプレス（６４Ｍ
Ｐａ ： １〜６０秒）した。このあと、金型ごと水冷
し、第２図に示すようなガス拡散電極を得た。Production example 4: Preparation of gas diffusion electrode by hot press method Place aluminum foil (degreased with acetone) on the hot press mold 30 shown in Fig. 4 (units of numerical values in Fig. 4 are mm), and place aluminum foil (degreased with acetone) on top of it. A Ni mesh was sandwiched, 30 mg of the gas diffusion layer powder obtained in Production Example 2 was filled, and the powder was cold pressed (16 MPa) using mold B.Next, mold C was placed on top of the powder obtained in Production Example 3. Fill 25 mg of the reaction layer powder, press the reaction layer powder with finger pressure using mold A, remove molds A and C, and cold press (16 MPa) using mold B. L/ta. After that, aluminum foil was placed on the electrode surface, and the electrode was placed in an electric furnace kept at about 600℃, heated to 370℃, and hot pressed (64M
Pa: 1 to 60 seconds). Thereafter, the mold was cooled with water to obtain a gas diffusion electrode as shown in FIG.
なお、用いた金型ＡＮＣの寸法は次の通りである。The dimensions of the mold ANC used are as follows.
金型Ａ：１５ｍｒｎφＸ１０ｍｍｔ
金型Ｂ：２０ｍｍφＸ７ｍｍｔ
金型Ｃ：２０ｍｍφ（１５ｍｍφ）ｘ７ｍｍｔ得られた
ガス拡散電極１０は、第２図に示す如く、Ｎｉメツシュ
１４を備えるガス拡散層１２及び反応層１３の２層構造
を有し、ガス拡散層１２の厚さは０．２ｍｍ、反応層１
３の厚さは０．２ｍｍ、全厚さｔは０．４ｍｍ、長さ１
は１５ｍｍである。Mold A: 15 mrnφ x 10 mmt Mold B: 20 mmφ x 7 mmt Mold C: 20 mmφ (15 mmφ) x 7 mmt As shown in FIG. The gas diffusion layer 12 has a thickness of 0.2 mm, and the reaction layer 1 has a layered structure.
The thickness of 3 is 0.2 mm, the total thickness t is 0.4 mm, and the length 1
is 15 mm.
製造例５：金属−空気２次電池の作製
製造例４で得られたガス拡散電極を陽極として用いて、
第１図に示す亜鉛−空気電池（電池Ｄ）を作製した。陰
極活物質である金属極３には亜鉛板、電解液５には３０
重量％ＫＯ）Ｉ、集電体７にはＮｉメツシュ、リード線
６としてはＣｕ線、セパレーター４としてはシリコンフ
ァイバー濾紙を用いた。Production Example 5: Preparation of metal-air secondary battery Using the gas diffusion electrode obtained in Production Example 4 as an anode,
A zinc-air battery (Battery D) shown in FIG. 1 was manufactured. A zinc plate is used for the metal electrode 3, which is the cathode active material, and a 30% zinc plate is used for the electrolyte 5.
Weight% KO)I, Ni mesh was used as the current collector 7, Cu wire was used as the lead wire 6, and silicon fiber filter paper was used as the separator 4.
また、陰極活物質、集電体、リード線として、後掲の第
１表に示すものを用いて、同様に電池ＡＮＣを作製した
。In addition, a battery ANC was similarly produced using the cathode active material, current collector, and lead wire shown in Table 1 below.
製造例６：ガス拡散電極ユニットの作製製造例４で得ら
れた電極を、第３図に示すようにセットして、ガス拡散
電極ユニットを作製した。第３図中、２０はガス拡散電
極、２１．２２はテフロン製のホルダ、２３．２４は０
リング、２５は銅線である。Production Example 6: Production of Gas Diffusion Electrode Unit The electrodes obtained in Production Example 4 were set as shown in FIG. 3 to produce a gas diffusion electrode unit. In Figure 3, 20 is a gas diffusion electrode, 21.22 is a Teflon holder, and 23.24 is 0
The ring 25 is a copper wire.
実験例１：亜鉛−空気２次電池の放電特性製造例５で得
られた電池りについて、放電特性とその時の電力を調べ
、結果を第Ｓ図に示した。Experimental Example 1: Discharge characteristics of zinc-air secondary battery Regarding the battery obtained in Production Example 5, the discharge characteristics and the electric power at that time were investigated, and the results are shown in Figure S.
なお、以下の実験例において、ガス拡散電極の酸素還元
及び酸素発生試験は、２５℃、３０重量％ＫＯＨ溶液中
で、裏面から酸素、空気又はヘリウムガスを流しながら
、ボテンシ日スタットにより行ない、亜鉛−空気電池の
充放電試験は、大気中、室温（１５〜ｂ
た。In the following experimental examples, the oxygen reduction and oxygen generation tests of the gas diffusion electrode were performed using a potency diode in a 30% by weight KOH solution at 25°C while flowing oxygen, air, or helium gas from the back side. - The charge/discharge test of the air battery was carried out in the atmosphere at room temperature (15 to 15°C).
第５図より、この亜鉛−空気電池りによれば、電池起電
力１．ＯＶ時に約２００ｍＡ／ｃｒｒｌ’もの高電流密
度が得られることが明らかである。この時の電池出力は
、約２６０ｍＷ／ｃｒｒ？であり、従来の電池に比べ、
約５〜１５倍の非常に高性能なものである。From FIG. 5, according to this zinc-air battery, the battery electromotive force is 1. It is clear that current densities as high as about 200 mA/crrl' can be obtained during OV. The battery output at this time is approximately 260mW/crr? , compared to conventional batteries,
The performance is approximately 5 to 15 times higher.
実験例２：各種電池の放電特性
実験例１の結果からも明らかなように、亜鉛板を用いて
高性能電池が得られたが、陽極活物質には亜鉛板よりも
亜鉛粉末を用いる方が高電流を流せるという利点がある
。そこで、製造例５において、亜鉛粉末を用いて作製し
た３つのタイプの電池Ａ、Ｂ、Ｃについて、電池性能を
調べ、亜鉛板を用いた電池りのものと共に第１表に示し
た。Experimental Example 2: Discharge characteristics of various batteries As is clear from the results of Experimental Example 1, a high-performance battery was obtained using a zinc plate, but it is better to use zinc powder as the anode active material than a zinc plate. It has the advantage of being able to flow high current. Therefore, in Production Example 5, the battery performance of three types of batteries A, B, and C produced using zinc powder was investigated, and the results are shown in Table 1 along with batteries using zinc plates.
第１表より、いずれの場合も、亜鉛粉末を用いると亜鉛
板よりも電流密度が小さくなることがわかる。これは、
粉末系の方は、亜鉛板に比べ集電効果が劣っているため
と思われる。しかし、亜鉛粉末を用いた電池は高電流（
約８００ｍＡ／ｃ ｒｒｉ’ ）が流せるが、亜鉛板で
は３００ｍＡ／ｃｎｆで頭打ちになる。また、リード線
としてＡｕを用いると放電容量が大きくなることがわか
った。これは、副反応が起こりにくくなるためと思われ
る。また、集電体としてはＮｉメツシュを用いる方が、
カーボンベーパーよりも電流密度がよく、集電体として
通していることがわかる。亜鉛粉末系では、亜鉛板に比
べて端子電圧はやや低くなるが、Ｎｉメツシュ集電体と
Ａｕリード線を用いることにより、放電容量６９９ ｍ
Ｗ −Ａ／ｇ（亜鉛利用率８３．３％：放電電流密度１
２ｍＡ／ ｃ ｒｎ” ）ものロングライフ電池が得ら
れることがわかった。From Table 1, it can be seen that in all cases, when zinc powder is used, the current density is smaller than when a zinc plate is used. this is,
This seems to be because the powder type has a poorer current collecting effect than the zinc plate. However, batteries using zinc powder have high current (
Approximately 800 mA/cnf can flow, but the zinc plate reaches a ceiling at 300 mA/cnf. It was also found that the discharge capacity increases when Au is used as the lead wire. This seems to be because side reactions are less likely to occur. Also, it is better to use Ni mesh as the current collector.
It can be seen that the current density is higher than that of carbon vapor, and it can be passed as a current collector. With the zinc powder system, the terminal voltage is slightly lower than that with the zinc plate, but by using the Ni mesh current collector and Au lead wire, the discharge capacity can be increased to 699 m.
W -A/g (zinc utilization rate 83.3%: discharge current density 1
It was found that a long-life battery of as much as 2 mA/c rn'' could be obtained.
第 １
表
※ セル電圧１．０■
実験例３ニガス拡散電極のカソード特性製造例６で得ら
れた、電極触媒としてＬ ａ ａｓＣａ １１．４ Ｃ
ＯＯ３を用い、空気流通下における最適条件下で作製し
たガス拡散電極ユニット（反応層；テフロン１５重量％
、ガス拡散層：テフロン１８重量％）を用いて、そのカ
ソード特性を調べ、結果を亜鉛のアノード特性と共に第
６図に示した。Table 1 * Cell voltage 1.0 ■ Experimental Example 3 Cathode characteristics of nitrogen gas diffusion electrode L a asCa 11.4 C as an electrode catalyst obtained in Production Example 6
A gas diffusion electrode unit (reaction layer; Teflon 15% by weight) manufactured using OO3 under optimal conditions under air circulation.
, gas diffusion layer: Teflon (18% by weight)), the cathode characteristics were investigated, and the results are shown in FIG. 6 together with the anode characteristics of zinc.
第６図より、通常、分極が小さいと言われている亜鉛極
に対しても本発明に係る空気極の特性は遜色がなく、亜
鉛−空気電池として、十分な性能を持つことが明らかで
ある。From FIG. 6, it is clear that the characteristics of the air electrode according to the present invention are comparable to those of zinc electrodes, which are usually said to have low polarization, and that they have sufficient performance as a zinc-air battery. .
実験例４：ガス拡散電極の酸素発生特性製造例６で得ら
れた、ＡＣＰ法で作製したＬ ａ ａｓ Ｃａ ６．４
Ｃｏ Ｏｓを用いたガス拡散電極ユニットを用いて、
その酸素発生特性を調べ、結果を第７図に示した。Experimental Example 4: Oxygen generation characteristics of gas diffusion electrode L a as Ca 6.4 produced by ACP method obtained in Production Example 6
Using a gas diffusion electrode unit using CoOs,
The oxygen generation characteristics were investigated and the results are shown in FIG.
第７図より、０．７０Ｖ（対極Ｈｇ／Ｈｇ０）の時に約
１０１００Ｏ／ｃｒｎ’もの高電流密度が得られており
、このガス拡散電極は、従来のものに比較して非常に高
性能であることが明らかである。しかも、高電流下にお
いても使用できるため、高速充電が可能であることが推
測される。From Figure 7, a high current density of about 10100 O/crn' is obtained at 0.70 V (counter electrode Hg/Hg0), and this gas diffusion electrode has extremely high performance compared to conventional ones. That is clear. Moreover, since it can be used even under high current conditions, it is presumed that high-speed charging is possible.
実験例５：ガス拡散電極の酸素還元酸素発生のサイクル
試験
従来の酸素還元、酸素発生のいわゆる「２元機能」を持
った電極は、比較的電流密度が低いところで用いられて
いた。しかし、実験例４に示す如く、本発明に係るガス
拡散電極は、酸素還元においても高電流密度が得られる
だけでなく、酸素発生用電極として用いても比較的高電
流が得られた。そこで、一定電流（２００ｍ Ａ ／
ｃ ｍ’ ）のもとで１時間ごとに、酸素還元及び酸素
発生を繰り返すサイクル試験を行った。電解液としては
３０重量％ＫＯＨ，参照極（対極）としてはＨｇ／Ｈｇ
Ｏを用い、２５℃において測定した。Experimental Example 5: Oxygen Reduction Oxygen Generation Cycle Test of Gas Diffusion Electrode Conventional electrodes with so-called "dual functions" of oxygen reduction and oxygen generation have been used where the current density is relatively low. However, as shown in Experimental Example 4, the gas diffusion electrode according to the present invention not only obtained a high current density in oxygen reduction, but also obtained a relatively high current when used as an oxygen generation electrode. Therefore, a constant current (200mA/
A cycle test was carried out in which oxygen reduction and oxygen generation were repeated every hour under the following conditions: cm'). 30 wt% KOH as electrolyte, Hg/Hg as reference electrode (counter electrode)
Measurements were made using O at 25°C.
６０サイクルまでの結果を第８図に示す。The results up to 60 cycles are shown in FIG.
第８図より明らかなように、１サイクル目の酸素還元に
おいて、時間の経過と共に酸素還元電位が責になってお
り、電極性能が向上している。また、１サイクル目の酸
素発生においても時間の経通と共に酸素発生電位が卑に
なっており、酸素発生に、おいても電極性能が向上した
。１回目の酸素還元反応後の酸素発生時の電極電位は、
第７図における電位よりも約０．３５Ｖも卑になってお
り電極性能がかなり良くなる。また、この傾向はいずれ
のサイクル反応後においても見られた。約１５サイクル
までは酸素還元及び酸素発生の両反応に対する電極性能
はやや低下したが、その後は試験を行なった６０サイク
ル目までは安定に作動した。As is clear from FIG. 8, in the oxygen reduction in the first cycle, the oxygen reduction potential becomes more responsible as time passes, and the electrode performance improves. In addition, even in the first cycle of oxygen generation, the oxygen generation potential became less noble as time progressed, and the electrode performance improved in oxygen generation as well. The electrode potential at the time of oxygen generation after the first oxygen reduction reaction is:
The potential is less noble by about 0.35 V than the potential in FIG. 7, and the electrode performance is considerably improved. Moreover, this tendency was observed after any cycle reaction. The electrode performance for both oxygen reduction and oxygen generation reactions decreased slightly up to about 15 cycles, but after that it operated stably until the 60th cycle when the test was conducted.
従って、Ｌａ＠、ａｃａ・、嘔Ｃｏｏｓを用いることに
より、高い酸素還元活性及び酸素発生活性、耐酸化性に
優れたガス拡散電極を作製でき、高出力放電及び高速充
電ができる金属−空気２次電池を得ることができること
が明らかである。Therefore, by using La@, aca, and Coos, a gas diffusion electrode with high oxygen reduction activity, oxygen generation activity, and excellent oxidation resistance can be produced, and a metal-air secondary electrode capable of high-output discharge and high-speed charging can be fabricated. It is clear that batteries can be obtained.
実験例６：亜鉛−空気２次電池の充放電特性製造例５で
作製した電池Ｃの金属−空気２次電池（亜鉛粉未使用、
集電体：Ｎｉメツシュ、リード線＝Ａｕ線）を用いて、
その放電特性を調べ、結果を第９図に示した。第９図よ
り明らかなように、電流密度１００ｍＡ／ｅｒｒ？にお
いても約１、Ｏｖの電圧が得られ、３００ ｍ Ａ ／
ｃ ｒｄにおける電力は２００ｍＷ−ｈ／Ｃｒｒ？に
達した。Experimental Example 6: Charge/discharge characteristics of zinc-air secondary battery Metal-air secondary battery of battery C prepared in Production Example 5 (no zinc powder used,
Using current collector: Ni mesh, lead wire = Au wire),
The discharge characteristics were investigated and the results are shown in FIG. As is clear from Figure 9, the current density is 100mA/err? A voltage of approximately 1.0V was obtained at 300 mA/
The power at crd is 200mW-h/Crr? reached.
また、この電池を用い、まず３０Ωの抵抗を用いて５時
間定負荷放電（３５〜４０ｍＡ）を全電池容量の約’６
０％までとさせた時の電圧の経時変化を第１０図に示す
。第１０図より明らかなように、約１．２ｖの電圧が安
定に得られた。その後、４０ｍＡで５時間定電流充電す
るという充放電サイクル試験を行ない、結果を第１１図
（ａ）〜（ｄ）に示した。第１１図より明らかなように
、可逆的に放電、充電を繰り返すことが可能であり、２
次電池として作動していることがわかる。In addition, using this battery, first constant load discharge (35 to 40mA) for 5 hours using a 30Ω resistor was performed to approximately 6'6 of the total battery capacity.
FIG. 10 shows the change in voltage over time when the voltage is reduced to 0%. As is clear from FIG. 10, a voltage of approximately 1.2 V was stably obtained. Thereafter, a charge/discharge cycle test was conducted in which constant current charging was performed at 40 mA for 5 hours, and the results are shown in FIGS. 11(a) to (d). As is clear from Figure 11, it is possible to repeat reversibly discharging and charging, and 2
It can be seen that it is operating as a secondary battery.
［発明の効果］
以上詳述した通り、本発明の金属−空気２次電池によれ
ば、充電用電極（酸素発生電極）として第３の電極を設
ける必要のない、金属−空気２次電池であって、高出力
放電及び高速充電が可能な高特性金属−空気２次電池が
提供される。[Effects of the Invention] As detailed above, according to the metal-air secondary battery of the present invention, the metal-air secondary battery does not require a third electrode as a charging electrode (oxygen generating electrode). Therefore, a high-performance metal-air secondary battery capable of high-output discharge and high-speed charging is provided.
第１図は本発明の金属−空気２次電池の一実施例に係る
亜鉛−空気２次電池を示す一部切欠き斜視図、第２図は
ガス拡散電極の断面図、第３図は製造例６で作製したガ
ス拡散電極ユニットの断面図、第４図は製造例４で用い
た金型を示す正面図、第５図は実験例１の結果を示すグ
ラフ、第６図は実験例３の結果を示すグラフ、第７図は
実験例４の結果を示すグラフ、第８図は実験例５の結果
を示すグラフ、第９図、第１０図は実験例６で得られた
放電特性試験の結果を示すグラフ、第１１図は実験例６
で得られた充放電特性試験の結果を示すグラフである。
１・・・亜鉛−空気２次電池、２・・・セルケース、３
・・・金属極（亜鉛板）、 ４・・・セパレーター５・
・・電解液、 ６・・・リード線、１０・
・・ガス拡散電極、 １２・・・ガス拡散層、１３
・・・反応層。
第１図
第２図
代理人 弁理士 重 野 剛
第５図
電流密度（ｍＡ／ｃｍ２）
第６図
電流密度（Ａ／ｃｍ）
第７図
電流密度（Ａ／ｃｒｒ１２）
第９図
電流密度（ｍＡ／ａｍ２）
第１０図
第１１図（ｂ）
時間（分）
時間（分）
手続補正書
平成１年５月１５日
平成１年特許願第７９８４６号
発明の名称
金属−空気２次電池
補正をする者
事件との関係 特許出願人Fig. 1 is a partially cutaway perspective view showing a zinc-air secondary battery according to an embodiment of the metal-air secondary battery of the present invention, Fig. 2 is a cross-sectional view of a gas diffusion electrode, and Fig. 3 is a manufactured one. A cross-sectional view of the gas diffusion electrode unit manufactured in Example 6, Figure 4 is a front view showing the mold used in Manufacturing Example 4, Figure 5 is a graph showing the results of Experimental Example 1, and Figure 6 is Experimental Example 3. Figure 7 is a graph showing the results of Experimental Example 4, Figure 8 is a graph showing the results of Experimental Example 5, Figures 9 and 10 are discharge characteristic tests obtained in Experimental Example 6. A graph showing the results of , Figure 11 is Experimental Example 6.
2 is a graph showing the results of a charge-discharge characteristic test obtained in FIG. 1... Zinc-air secondary battery, 2... Cell case, 3
...Metal electrode (zinc plate), 4...Separator 5.
... Electrolyte, 6... Lead wire, 10.
...Gas diffusion electrode, 12...Gas diffusion layer, 13
...Reaction layer. Figure 1 Figure 2 Agent Patent Attorney Tsuyoshi Shigeno Figure 5 Current density (mA/cm2) Figure 6 Current density (A/cm) Figure 7 Current density (A/crr12) Figure 9 Current density (mA /am2) Figure 10 Figure 11 (b) Time (minutes) Time (minutes) Procedural amendment May 15, 1999 Patent application No. 79846, 1999 Name of the invention Metal-air secondary battery Make an amendment Relationship with patent case Patent applicant
Claims (1)
チレンを含むガス拡散層と、炭素、ポリテトラフルオロ
エチレン及び酸化物触媒を含む反応層とを備えるガス拡
散電極であって、酸化物触媒として下記組成を有するペ
ロブスカイト型酸化物触媒を用いたガス拡散電極を備え
てなることを特徴とする金属−空気２次電池。 Ｌａ＿１＿−＿ｘＣａ＿ｘＣｏＯ＿３ （ただし、０．０５≦ｘ≦０．９）(1) A gas diffusion electrode comprising, as an air electrode, a gas diffusion layer containing carbon and polytetrafluoroethylene and a reaction layer containing carbon, polytetrafluoroethylene and an oxide catalyst, the oxide catalyst having the following composition: 1. A metal-air secondary battery comprising a gas diffusion electrode using a perovskite oxide catalyst. La_1_−_xCa_xCoO_3 (however, 0.05≦x≦0.9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1079846A JPH02257577A (en) | 1989-03-30 | 1989-03-30 | Metal-air secondary cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1079846A JPH02257577A (en) | 1989-03-30 | 1989-03-30 | Metal-air secondary cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02257577A true JPH02257577A (en) | 1990-10-18 |
| JPH0587950B2 JPH0587950B2 (en) | 1993-12-20 |
Family
ID=13701566
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1079846A Granted JPH02257577A (en) | 1989-03-30 | 1989-03-30 | Metal-air secondary cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02257577A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7566388B2 (en) | 2002-12-17 | 2009-07-28 | Asahi Kasei Chemicals Corporation | Electrode catalyst for oxygen reduction and gas diffusion electrode |
| JP2011014478A (en) * | 2009-07-06 | 2011-01-20 | Nippon Telegr & Teleph Corp <Ntt> | Lithium air battery |
| JP2011108512A (en) * | 2009-11-18 | 2011-06-02 | Nippon Telegr & Teleph Corp <Ntt> | Lithium air secondary battery and manufacturing method for the same |
| JP2015046403A (en) * | 2014-10-24 | 2015-03-12 | トヨタ自動車株式会社 | Air electrode for air batteries, and air battery |
| WO2015115592A1 (en) * | 2014-01-31 | 2015-08-06 | 国立大学法人北海道大学 | Catalyst for air electrode for metal/air secondary battery, and air electrode |
| US9236641B2 (en) | 2009-03-18 | 2016-01-12 | Showa Denko K.K. | Air battery catalyst and air battery using the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080083112A (en) * | 2005-12-06 | 2008-09-16 | 리볼트 테크놀로지 리미티드 | Bifunctional air electrode |
-
1989
- 1989-03-30 JP JP1079846A patent/JPH02257577A/en active Granted
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7566388B2 (en) | 2002-12-17 | 2009-07-28 | Asahi Kasei Chemicals Corporation | Electrode catalyst for oxygen reduction and gas diffusion electrode |
| US9236641B2 (en) | 2009-03-18 | 2016-01-12 | Showa Denko K.K. | Air battery catalyst and air battery using the same |
| JP2011014478A (en) * | 2009-07-06 | 2011-01-20 | Nippon Telegr & Teleph Corp <Ntt> | Lithium air battery |
| JP2011108512A (en) * | 2009-11-18 | 2011-06-02 | Nippon Telegr & Teleph Corp <Ntt> | Lithium air secondary battery and manufacturing method for the same |
| WO2015115592A1 (en) * | 2014-01-31 | 2015-08-06 | 国立大学法人北海道大学 | Catalyst for air electrode for metal/air secondary battery, and air electrode |
| JPWO2015115592A1 (en) * | 2014-01-31 | 2017-03-23 | 国立大学法人北海道大学 | Zinc-air secondary battery air electrode catalyst, Brown mirror light type transition metal oxide as zinc-air secondary battery air electrode catalyst, zinc-air secondary battery air electrode, zinc-air secondary Secondary battery, electrode catalyst for electrolysis, electrode for electrolysis and electrolysis method |
| US10693145B2 (en) | 2014-01-31 | 2020-06-23 | National University Corporation Hokkaid University | Catalyst for air electrode for metal-air secondary battery and air electrode |
| JP2015046403A (en) * | 2014-10-24 | 2015-03-12 | トヨタ自動車株式会社 | Air electrode for air batteries, and air battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0587950B2 (en) | 1993-12-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101795845B1 (en) | Positive electrode active material for sodium batteries and method for producing same | |
| JP4161382B2 (en) | Process for producing two-layer structured particulate composition | |
| JP4568124B2 (en) | Air electrode and air secondary battery using the air electrode | |
| JP4152618B2 (en) | Method for producing positive electrode active material for layered oxide battery | |
| Shen et al. | Co 3 O 4 nanorods–graphene composites as catalysts for rechargeable zinc-air battery | |
| Vanags et al. | Membrane-less amphoteric decoupled water electrolysis using WO 3 and Ni (OH) 2 auxiliary electrodes | |
| JPH02257577A (en) | Metal-air secondary cell | |
| KR101586403B1 (en) | Cathode Catalyst for Metal-Air Battery, Method of Manufacturing the Same, and Metal-Air Battery Comprising the Same | |
| US3808052A (en) | Organic electrolyte cell employing molybdenum oxide cathodic electrode | |
| JPH04133264A (en) | Fuel electrode of solid electrolyte cell and its manufacture | |
| Wang et al. | Effects of Ca doping on the electrochemical properties of LiNi0. 8Co0. 2O2 cathode material | |
| JP4441678B2 (en) | Method for producing orthorhombic lithium manganese composite oxide particulate composition represented by LiMnO 2 | |
| US3791896A (en) | Bi-functional gas electrode | |
| Mohamad et al. | Mechanically alloyed Mg2Ni for metal-hydride–air secondary battery | |
| JPH02288159A (en) | Ceramic electrode and fuel cell having same | |
| JP6310413B2 (en) | Lithium air secondary battery, method for producing catalyst for air electrode, and method for producing lithium air secondary battery | |
| JPWO2019093441A1 (en) | Amorphous transition metal oxides and their uses | |
| JPH10321228A (en) | Positive electrode active material for lithium battery, its manufacture, and lithium battery using it | |
| JP6688210B2 (en) | Separator and lithium-air secondary battery | |
| JPH10255832A (en) | Composite air electrode material for solid fuel cell for low temperature operation | |
| KR20160038833A (en) | Electrolyte membrane, fuel cell comprising the same, battery module comprising the fuel cell and method for manufacturing the electrolyte membrane | |
| JPH04192261A (en) | Fuel electrode and its manufacture for solid electrolyte type fuel cell | |
| JP3451602B2 (en) | Non-aqueous electrolyte battery | |
| JP7327798B2 (en) | Cathode catalyst for metal-air battery, positive electrode for metal-air battery and metal-air battery | |
| WO2022190322A1 (en) | Positive electrode catalyst for metal-air battery, positive electrode for metal-air battery, and metal-air battery |