JPH0758614B2 - Hydrogen storage alloy electrode and manufacturing method thereof - Google Patents
Hydrogen storage alloy electrode and manufacturing method thereofInfo
- Publication number
- JPH0758614B2 JPH0758614B2 JP63291159A JP29115988A JPH0758614B2 JP H0758614 B2 JPH0758614 B2 JP H0758614B2 JP 63291159 A JP63291159 A JP 63291159A JP 29115988 A JP29115988 A JP 29115988A JP H0758614 B2 JPH0758614 B2 JP H0758614B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- storage alloy
- electrode
- battery
- fluororesin
- 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
- 229910045601 alloy Inorganic materials 0.000 title claims description 56
- 239000000956 alloy Substances 0.000 title claims description 56
- 238000003860 storage Methods 0.000 title claims description 52
- 239000001257 hydrogen Substances 0.000 title claims description 50
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 7
- PEVRKKOYEFPFMN-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene;1,1,2,2-tetrafluoroethene Chemical group FC(F)=C(F)F.FC(F)=C(F)C(F)(F)F PEVRKKOYEFPFMN-UHFFFAOYSA-N 0.000 claims description 6
- 229920006026 co-polymeric resin Polymers 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- 229910018007 MmNi Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/242—Hydrogen storage electrodes
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、水素を可逆的に吸蔵・放出する水素吸蔵合金
電極及びその製造方法に関するものであり、特に密閉形
アルカリ蓄電池の負極などに使用できるものである。Description: TECHNICAL FIELD The present invention relates to a hydrogen storage alloy electrode that reversibly stores and releases hydrogen, and a method for producing the same, which can be used particularly as a negative electrode of a sealed alkaline storage battery. Is.
従来の技術 各種電源のうち蓄電池としては、鉛蓄電池とニッケルカ
ドミウム蓄電池に代表されるアルカリ蓄電池とが広く使
われている。2. Description of the Related Art Lead storage batteries and alkaline storage batteries represented by nickel-cadmium storage batteries are widely used as storage batteries among various power sources.
近年、高エネルギー密度に対する期待が高まっており、
そこで注目されてきたのは水素を可逆的に吸蔵・放出す
る水素吸蔵合金を用いたアルカリ蓄電池である。In recent years, expectations for high energy density have increased,
Therefore, what has been attracting attention is an alkaline storage battery using a hydrogen storage alloy that stores and releases hydrogen reversibly.
これに用いる水素吸蔵合金電極は、カドミウムや亜鉛な
どと同じ取り扱いで電池を構成でき、実際の放電可能な
容量密度をカドミウムより大きくできることや亜鉛のよ
うなデンドライトの形成などがないことなどから、高エ
ネルギー密度で長寿命、無公害のアルカリ蓄電池用負極
として有望である。The hydrogen storage alloy electrode used for this can be constructed with the same handling as cadmium and zinc, and the actual dischargeable capacity density can be made larger than that of cadmium, and there is no formation of dendrite such as zinc. It is promising as a negative electrode for alkaline storage batteries with energy density, long life, and pollution-free.
この水素吸蔵合金電極は、水素吸蔵合金を焼結して得る
焼結式と、導電性芯材にパンチングメタルやエキスパン
ドメタル、発泡メタル、金属繊維などを用い、水素吸蔵
合金をペースト状にして塗着したり、充填するペースト
式や、プレスなどで加圧成形する加圧式などの非焼結式
とに大別できる。この中で焼結式は、製造が複雑で高価
になること、焼結過程で水素吸蔵合金が変質しやすく十
分な性能が得られにくいことなどの理由から、非焼結式
が主流になりつつある。This hydrogen storage alloy electrode uses a sintering type obtained by sintering a hydrogen storage alloy, and a conductive core material made of punching metal, expanded metal, foam metal, metal fiber, or the like, and coated with a hydrogen storage alloy in a paste form. It can be roughly divided into a non-sintering type such as a paste type that is worn or filled, and a pressure type that is pressure-molded by pressing. Among them, the non-sintering type is becoming the mainstream because the manufacturing process is complicated and expensive, and the hydrogen storage alloy is likely to deteriorate in the sintering process, and it is difficult to obtain sufficient performance. is there.
非焼結式で電極を作製する場合は、活物質保持材料であ
る水素吸蔵合金を結着材によって結着し電極にするのが
通常の方法である。この結着材は、少量の添加で強い結
着強度を有すること、化学的に安定であること、電池反
応を阻害しないことなどが要求され、これまで水素吸蔵
合金電極には、ポリビニルアルコール、カルボキシメチ
ルセルローズ、ポリエチレン、フッ素樹脂などが知られ
ていた。When manufacturing an electrode by a non-sintering method, it is a usual method to bind a hydrogen storage alloy, which is an active material holding material, with a binder to form an electrode. This binder is required to have a strong binding strength with a small amount of addition, be chemically stable, and not inhibit the battery reaction.So far, hydrogen-absorbing alloy electrodes have been limited to polyvinyl alcohol and carboxy. Methylcellulose, polyethylene, fluororesin, etc. were known.
発明が解決しようとする課題 しかし、これらの結着材を用いた水素吸蔵電極は、結着
材が少量では水素吸蔵合金特有の充放電の繰り返しによ
って合金が微細化し、低い電極強度によって電極性能が
低下することが認められ、逆に多量に用いると長期間使
用の安定性は向上するが、本来の電池反応、例えば電池
内でのガス吸収能や充放電容量（利用率）の低下をもた
らすことが認められる。したがって、使用する結着材の
改善によって長期間にわたって安定に、優れた電池性能
を得ることが重要な課題であった。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention However, in the hydrogen storage electrodes using these binders, when the binder is a small amount, the alloy becomes finer due to repeated charging / discharging specific to the hydrogen storage alloy, and the electrode performance is low due to the low electrode strength. However, if used in a large amount, the stability of long-term use is improved, but the original battery reaction, such as a decrease in gas absorption capacity and charge / discharge capacity (utilization rate) in the battery, may occur. Is recognized. Therefore, it has been an important issue to obtain excellent battery performance stably over a long period of time by improving the binder used.
水素吸蔵合金電極は、充電により合金中に水素を吸蔵
し、放電により合金中の水素を放出する。この水素吸蔵
・放出によって合金の膨張と収縮が認められる。この体
積変化はほぼ10〜20％程度と非常に大きい。この結果と
して合金は微粉化する。これまでの水素吸蔵合金電極用
の結着材ではこのような条件下で優れた性能を有するこ
とに問題があった。The hydrogen storage alloy electrode stores hydrogen in the alloy by charging and releases hydrogen in the alloy by discharging. The expansion and contraction of the alloy are recognized by this hydrogen storage / release. This volume change is very large, about 10 to 20%. As a result of this, the alloy becomes finely divided. The conventional binders for hydrogen storage alloy electrodes have a problem in that they have excellent performance under such conditions.
本発明は上記従来技術の課題に鑑み、高性能で長寿命の
水素吸蔵合金電極を提供することを目的とする。The present invention has been made in view of the above problems of the prior art, and an object thereof is to provide a hydrogen storage alloy electrode having high performance and long life.
課題を解決するための手段 本発明は、水素吸蔵合金を所定の粒度に粉砕後、少なく
ともフッ素樹脂および熱可塑性エラストマーの両方の結
着剤を用いて電極を構成することを特徴とする水素吸蔵
合金電極、および水素吸蔵合金を所定の粒度に粉砕後、
その水素吸蔵合金粉末の表面にフッ素樹脂を介在させ、
その後さらに熱可塑性エラストマーによって電極を構成
することを特徴とする水素吸蔵合金電極の製造法であ
る。Means for Solving the Problems The present invention is a hydrogen storage alloy, characterized in that, after pulverizing a hydrogen storage alloy into a predetermined particle size, an electrode is constituted by using at least a binder of both a fluororesin and a thermoplastic elastomer. After crushing the electrode and the hydrogen storage alloy to a specified particle size,
Fluorine resin is interposed on the surface of the hydrogen storage alloy powder,
Thereafter, the electrode is made of a thermoplastic elastomer, which is a method for producing a hydrogen storage alloy electrode.
そして本発明において、好ましくはフッ素樹脂が特に四
フッ化エチレン樹脂、もしくは四フッ化エチレン−六フ
ッ化プロピレン共重合樹脂であり、熱可塑性エラストマ
ーが特にスチレン−ブタジエン系共重合体であり、電極
が特に非焼結式によって製造される水素吸蔵合金電極お
よびその製造法である。And in the present invention, preferably the fluororesin is particularly a tetrafluoroethylene resin, or a tetrafluoroethylene-hexafluoropropylene copolymer resin, the thermoplastic elastomer is particularly a styrene-butadiene copolymer, and the electrode is In particular, it is a hydrogen storage alloy electrode manufactured by a non-sintering method and a manufacturing method thereof.
作用 水素吸蔵合金電極は充電時に水素を合金中に吸蔵する
が、この場合に合金粉末の表面が電解液によって完全に
濡れた状態より、適度に乾いた部分が存在する方がむし
ろ電気化学反応と水素ガスによる通常の化学反応の両方
で充電を進められる点で有効なことがわかった。そのた
めに水素吸蔵合金粉末の表面を吸水性がきわめて小さい
結着材で適当に覆うことが重要である。この結着材とし
ては四フッ化エチレン樹脂、もしくは四フッ化エチレン
−六フッ化プロピレン共重合樹脂などのフッ素樹脂が良
好である。Action Hydrogen storage alloy electrodes store hydrogen in the alloy during charging.In this case, it is more likely that the surface of the alloy powder is not completely wet by the electrolytic solution, but rather an appropriately dry portion is present as an electrochemical reaction. It was found to be effective in that charging can be promoted by both normal chemical reactions using hydrogen gas. Therefore, it is important to properly cover the surface of the hydrogen storage alloy powder with a binder having extremely low water absorption. As this binder, a fluororesin such as tetrafluoroethylene resin or tetrafluoroethylene-hexafluoropropylene copolymer resin is preferable.
また、充放電により合金が膨張・収縮する体積変化をう
まく緩和して電極としての機能を向上させるためには弾
性の著しい熱可塑性エラストマーを結着材として用いる
ことが効果的であることが明らかになった。スチレン−
ブタジエン共重合体、スチレン−イソプレン共重合体な
どの熱可塑性エラストマーにより優れた特性を長期間に
わたり維持できることがわかった。この電極の製造法と
しては、まず水素吸蔵合金を所定の粒度に粉砕後、その
水素吸蔵合金粉末の表面にフッ素樹脂を介在させ、その
後さらに熱可塑性エラストマーによって電極を構成する
ことが性能上効果的である。In addition, it is clear that it is effective to use a thermoplastic elastomer with remarkable elasticity as a binder in order to properly alleviate the volume change in which the alloy expands and contracts due to charge and discharge and improve the function as an electrode. became. Styrene
It has been found that thermoplastic elastomers such as butadiene copolymer and styrene-isoprene copolymer can maintain excellent properties for a long period of time. As a method for producing this electrode, it is effective in terms of performance to first pulverize the hydrogen storage alloy to a predetermined particle size, then interpose a fluororesin on the surface of the hydrogen storage alloy powder, and then further configure the electrode with a thermoplastic elastomer. Is.
実施例 以下、本発明の実施例である水素吸蔵合金電極について
説明する。Example Hereinafter, a hydrogen storage alloy electrode which is an example of the present invention will be described.
水素吸蔵合金として市販のMm（ミッシュメタル）,Ni,C
o,Mn,Alの各原材料を一定の組成比に秤量し、アルゴン
アーク溶解炉によってMmNi3.8Co0.5Mn0.4Al0.3合金を製
造した。ついでこの合金を真空中で熱処理し、その後40
0メッシュ以下の粒径になるように粉砕した。このよう
にして得た合金粉末に３重量％の四フッ化エチレン−六
フッ化プロピレン共重合樹脂粉末を混合し、さらに乳鉢
中で練合して水素吸蔵合金粉末の表面にフッ素樹脂を介
在させた。そしてこのフッ素樹脂添加の水素吸蔵合金粉
末をスチレン−ブタジエン共重合体のトルエン溶液と混
合、ペースト化し平均ポアサイズ150ミクロン、多孔度9
5％、厚さ1.2mmのシート状発泡ニッケルに充填した。こ
れを100℃で乾燥して水素吸蔵合金電極とした。この電
極を本発明の電極として電極Ａとする。この電極の特性
を比較するために他の方法による電極も合わせて作製し
た。すなわち、結着材としてフッ素樹脂のみで前述のよ
うに構成した電極を電極Ｂ、同様にスチレン−ブタジエ
ン共重合体のトルエン溶液のみで構成した電極を電極Ｃ
として作製した。これらの電極をまず、対極に過剰の容
量を持つニッケル極を配し、電解液に比重1.30の水酸化
カリウム水溶液を用い、電解液が豊富な条件下で水素吸
蔵合金負極で容量規制を行なった開放系での一定条件下
での充放電試験に供した。Commercially available Mm (Misch metal), Ni, C as hydrogen storage alloy
Raw materials of o, Mn, and Al were weighed to have a constant composition ratio, and an MmNi 3.8 Co 0.5 Mn 0.4 Al 0.3 alloy was manufactured by an argon arc melting furnace. The alloy is then heat treated in vacuum, then 40
It was pulverized to have a particle size of 0 mesh or less. The alloy powder thus obtained was mixed with 3% by weight of tetrafluoroethylene-hexafluoropropylene copolymer resin powder and further kneaded in a mortar to interpose the fluororesin on the surface of the hydrogen storage alloy powder. It was Then, the hydrogen storage alloy powder containing the fluororesin was mixed with a toluene solution of styrene-butadiene copolymer to form a paste, and the average pore size was 150 microns and the porosity was 9
5%, 1.2 mm thick sheet-like foamed nickel was filled. This was dried at 100 ° C. to obtain a hydrogen storage alloy electrode. This electrode is referred to as electrode A as the electrode of the present invention. In order to compare the characteristics of this electrode, electrodes made by other methods were also prepared. That is, the electrode configured as described above with only the fluororesin as the binder is the electrode B, and the electrode similarly configured with only the toluene solution of the styrene-butadiene copolymer is the electrode C.
Was prepared as. With these electrodes, first, a nickel electrode having an excessive capacity was placed on the counter electrode, and an aqueous solution of potassium hydroxide having a specific gravity of 1.30 was used as the electrolytic solution, and the capacity was regulated by the hydrogen storage alloy negative electrode under the condition that the electrolytic solution was abundant. It was subjected to a charge / discharge test under a constant condition in an open system.
その結果、電極Ａ、Ｃは長期の充放電試験にもかかわら
ずほとんど一定した放電容量を維持しており、優れた性
能の安定性を確認した。一方フッ素樹脂だけで構成した
電極Ｂは、20〜100サイクルの比較的早い充放電サイク
ルで放電容量の低下が認められ、この容量低下は合金の
電極からの脱落によることが確認できた。As a result, the electrodes A and C maintained almost constant discharge capacity despite the long-term charge / discharge test, and confirmed excellent stability of performance. On the other hand, in the electrode B composed only of fluororesin, the discharge capacity was found to decrease in a relatively fast charge / discharge cycle of 20 to 100 cycles, and it was confirmed that this decrease in capacity was due to the alloy falling off from the electrode.
つぎにこれらの電極を用いて密閉形ニッケル−水素蓄電
池を構成した結果について説明する。先の電極A,B,Cを
それぞれ幅3.9cm、長さ26cm、厚さ0.52mmに調整し、リ
ード板を所定の２カ所に取り付けた。そして、正極、セ
パレータと組み合わせてＣサイズの電槽に収納した。こ
のときの正極は、公知の発泡式ニッケル極を選び、幅3.
9cm、長さ22cmとして用いた。この場合もリート板を２
カ所に取り付けた。またセパレータは、ポリアミド不織
布を用いた。電解液としては、比重1.20の水酸化カリウ
ム水溶液に水酸化リチウムを30g/l溶解して用いた。こ
れを封口して密閉形電池とした。この電池は、正極容量
規制で公称容量は3.0Ahである。この密閉形電池で水素
吸蔵合金電極の電極Ａで構成した電池を電池Ａ、同様に
電極B,Cで構成した電池をそれぞれ電池B,Cとする。Next, the results of constructing a sealed nickel-hydrogen storage battery using these electrodes will be described. The electrodes A, B, and C were adjusted to have a width of 3.9 cm, a length of 26 cm, and a thickness of 0.52 mm, and lead plates were attached at two predetermined places. Then, it was stored in a C size battery case in combination with the positive electrode and the separator. For the positive electrode at this time, a well-known foamed nickel electrode is selected, and the width is 3.
It was used as 9 cm and 22 cm in length. Also in this case, 2 REIT boards
I attached it to the place. A polyamide non-woven fabric was used for the separator. As an electrolytic solution, 30 g / l of lithium hydroxide was dissolved in an aqueous potassium hydroxide solution having a specific gravity of 1.20 and used. This was sealed to form a sealed battery. This battery has a nominal capacity of 3.0 Ah according to the positive electrode capacity regulation. In this sealed battery, a battery composed of the hydrogen storage alloy electrode A is referred to as battery A, and batteries composed of electrodes B and C are referred to as batteries B and C, respectively.
これらの電池を電池の内圧を測定しつつ通常の充放電サ
イクル試験によって評価した結果を説明する。The results of evaluating these batteries by a normal charge / discharge cycle test while measuring the internal pressure of the battery will be described.
充電は、1/3C（３時間率）で130％まで、放電は0.5C
（２時間率）で終止電圧1.0Vとし20℃での充放電サイク
ルを繰り返した。その結果A,B,Cいずれの電池も20サイ
クル程度の初期は、ほぼ3.0Ahの放電容量が得られた。
この時の充電時の電池最高内圧は、電池Ａが2.3kg/c
m2、電池Ｂが2.1kg/cm2、電池Ｃが4.4kg/cm2であり、電
池Ｃがやや高い内圧を示した。さらに充放電サイクルを
進めるに従って次第にこれらの電池に差異が見られた。
まず電池Ｃは、250サイクル前後で急激な容量低下を示
した。この時の電池内圧はサイクルの経過とともに上昇
し、15kg/cm2以上の高い値を示した。これに対し電池A,
Bは、400サイクル経過後も比較的安定しており、電池内
圧は２〜3kg/cm2で3.0〜3.1Ahの放電容量を示した。し
かし、電池Ｂの一部は400サイクルまでに10コ中２コが
内部ショート不良を生じた。Charging up to 130% at 1 / 3C (3 hour rate), discharging 0.5C
The final voltage was 1.0 V at (2 hour rate) and the charge / discharge cycle at 20 ° C. was repeated. As a result, in each of the batteries A, B, and C, a discharge capacity of approximately 3.0 Ah was obtained at the initial stage of about 20 cycles.
The maximum battery internal pressure during charging at this time is 2.3 kg / c for Battery A.
m 2 and battery B were 2.1 kg / cm 2 and battery C were 4.4 kg / cm 2 , respectively, and battery C showed a slightly higher internal pressure. As the charge / discharge cycle was further advanced, differences gradually appeared in these batteries.
First, the battery C showed a rapid decrease in capacity around 250 cycles. At this time, the internal pressure of the battery increased with the lapse of cycles and showed a high value of 15 kg / cm 2 or more. In contrast, battery A,
B was relatively stable even after 400 cycles, and showed a discharge capacity of 3.0 to 3.1 Ah at a battery internal pressure of 2 to 3 kg / cm 2 . However, in 400 parts of battery B, 2 out of 10 batteries had internal short circuit failure.
つぎにこれらの電池A,B,Cの急速充電特性を調べた。ま
ず先の通常充放電サイクル条件で30サイクル経過後、充
電は、1C（１時間率）で130％まで充電レートを上げ、
放電は0.5C（２時間率）で終止電圧1.0Vとし20℃での充
放電サイクルを繰り返した。その結果A,B,Cいずれの電
池もほぼ3.0Ahの放電容量が得られたが、この時の充電
時の電池最高内圧は、電池Ａが6.1kg/cm2、電池Ｂが5.6
kg/cm2、電池Ｃが9.8kg/cm2であった。Next, the rapid charging characteristics of these batteries A, B, C were examined. First of all, after 30 cycles under the normal charge / discharge cycle conditions, the charge rate is increased to 130% at 1C (1 hour rate),
The discharge was 0.5 C (2 hour rate), the final voltage was 1.0 V, and the charge / discharge cycle at 20 ° C. was repeated. As a result, the discharge capacities of almost 3.0 Ah were obtained for all the batteries A, B, and C, but the maximum battery internal pressure during charging at this time was 6.1 kg / cm 2 for battery A and 5.6 for battery B.
kg / cm 2 and Battery C had 9.8 kg / cm 2 .
以上の結果から電池Ｂはかなり良好な性能を示すもの
の、電極中の合金粉末の脱落と予想される内部ショート
の発生に問題があり、電池Ｃは電池内の圧力が高いこと
から充電時のガス吸収能力に問題があった。これに対し
電池Ａは、性能が良好で長寿命であることが明らかにな
った。From the above results, although the battery B shows considerably good performance, there is a problem in that the alloy powder in the electrode may fall off and an internal short circuit may occur, and the battery C has a high pressure inside the battery. There was a problem with the absorption capacity. On the other hand, it was revealed that the battery A had good performance and a long life.
なお、本実施例では、電極支持体として発泡メタルを用
いた例を示したが、最も低廉な電極が得られるパンチン
グメタルやエキスパンドメタルを用いた場合、さらに金
属繊維などを用いた場合にも有効である。また、結着材
としてフッ素樹脂の場合には四フッ化エチレン−六フッ
化プロピレン共重合樹脂粉末、熱可塑性エラストマーの
場合にはスチレン−ブタジエン共重合体のトルエン溶液
を例に示したが、この他にも例えば、フッ素樹脂のディ
スパージョンやスチレン−ブタジエン共重合体のラテッ
クスなども同様に優れた効果を発揮できる。In this example, a foamed metal is used as the electrode support, but it is also effective when a punching metal or an expanded metal that can obtain the cheapest electrode is used, or when a metal fiber is used. Is. Further, in the case of a fluororesin as a binder, tetrafluoroethylene-hexafluoropropylene copolymer resin powder was shown as an example, and in the case of a thermoplastic elastomer, a toluene solution of styrene-butadiene copolymer was shown as an example. In addition, for example, a dispersion of a fluororesin or a latex of a styrene-butadiene copolymer can similarly exhibit excellent effects.
また、本実施例では水素吸蔵合金を所定の粒度に粉砕
後、その水素吸蔵合金粉末の表面にフッ素樹脂を介在さ
せ、その後さらに熱可塑性エラストマーによって電極を
構成したが、熱可塑性エラストマーを先に、その後フッ
素樹脂で構成する方法や、フッ素樹脂と熱可塑性エラス
トマーを同時に用いて構成する電極は特にガス吸収能力
の点でやや劣っていることがわかった。Further, in this example, after crushing the hydrogen storage alloy to a predetermined particle size, the fluororesin is interposed on the surface of the hydrogen storage alloy powder, and then the electrode is constituted by the thermoplastic elastomer, but the thermoplastic elastomer is first. After that, it was found that the method of using a fluororesin and the electrode using a fluororesin and a thermoplastic elastomer at the same time were slightly inferior in terms of gas absorption capacity.
発明の効果 以上のように本発明の水素吸蔵合金電極およびその製造
法は、優れた性能を長期間安定に発揮することができ
る。EFFECTS OF THE INVENTION As described above, the hydrogen storage alloy electrode of the present invention and the method for producing the same can exhibit excellent performance stably for a long period of time.
Claims (6)
くともフッ素樹脂および熱可塑性エラストマーの両方の
結着剤を用いて電極が構成されたことを特徴とする水素
吸蔵合金電極。1. A hydrogen storage alloy electrode, characterized in that after crushing the hydrogen storage alloy to a predetermined particle size, the electrode is constituted by using at least binders of both fluororesin and thermoplastic elastomer.
水素吸蔵合金粉末の表面にフッ素樹脂を介在させ、その
後さらに熱可塑性エラストマーによって電極を構成する
ことを特徴とする水素吸蔵合金電極の製造法。2. A hydrogen storage alloy electrode, characterized by crushing a hydrogen storage alloy to a predetermined particle size, interposing a fluororesin on the surface of the hydrogen storage alloy powder, and then forming the electrode with a thermoplastic elastomer. Manufacturing method.
もしくは四フッ化エチレン−六フッ化プロピレン共重合
樹脂である請求項１記載の水素吸蔵合金電極。3. A fluororesin, especially a tetrafluoroethylene resin,
Alternatively, the hydrogen storage alloy electrode according to claim 1, which is a tetrafluoroethylene-hexafluoropropylene copolymer resin.
もしくは四フッ化エチレン−六フッ化プロピレン共重合
樹脂である請求項２記載の水素吸蔵合金電極の製造法。4. The fluororesin is particularly a tetrafluoroethylene resin,
Alternatively, the method for producing a hydrogen storage alloy electrode according to claim 2, which is a tetrafluoroethylene-hexafluoropropylene copolymer resin.
タジエン系共重合体である請求項１記載の水素吸蔵合金
電極。5. The hydrogen storage alloy electrode according to claim 1, wherein the thermoplastic elastomer is particularly a styrene-butadiene copolymer.
タジエン系共重合体である請求項２記載の水素吸蔵合金
電極の製造法。6. The method for producing a hydrogen storage alloy electrode according to claim 2, wherein the thermoplastic elastomer is particularly a styrene-butadiene copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63291159A JPH0758614B2 (en) | 1988-11-17 | 1988-11-17 | Hydrogen storage alloy electrode and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63291159A JPH0758614B2 (en) | 1988-11-17 | 1988-11-17 | Hydrogen storage alloy electrode and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02135665A JPH02135665A (en) | 1990-05-24 |
| JPH0758614B2 true JPH0758614B2 (en) | 1995-06-21 |
Family
ID=17765210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63291159A Expired - Lifetime JPH0758614B2 (en) | 1988-11-17 | 1988-11-17 | Hydrogen storage alloy electrode and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0758614B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5527638A (en) * | 1993-06-30 | 1996-06-18 | Matsushita Electric Industrial Co., Ltd. | Hydrogen storage alloy electrode and sealed-type nickel-metal hydride storage battery using the same |
| WO1999008335A1 (en) * | 1997-08-11 | 1999-02-18 | Sony Corporation | Nonaqueous electrolyte secondary battery |
| JP3573964B2 (en) | 1998-06-17 | 2004-10-06 | 三洋電機株式会社 | Method of manufacturing hydrogen storage alloy electrode for alkaline battery and hydrogen storage alloy electrode for alkaline storage battery |
| JP4790207B2 (en) * | 2003-05-29 | 2011-10-12 | パナソニック株式会社 | Method for producing positive electrode for alkaline storage battery |
| JP2009076430A (en) * | 2007-08-28 | 2009-04-09 | Sanyo Electric Co Ltd | Negative electrode for alkaline storage battery, and alkaline storage battery |
-
1988
- 1988-11-17 JP JP63291159A patent/JPH0758614B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02135665A (en) | 1990-05-24 |
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