JP2000294236A - Nickel electrode and its manufacture - Google Patents
Nickel electrode and its manufactureInfo
- Publication number
- JP2000294236A JP2000294236A JP11099834A JP9983499A JP2000294236A JP 2000294236 A JP2000294236 A JP 2000294236A JP 11099834 A JP11099834 A JP 11099834A JP 9983499 A JP9983499 A JP 9983499A JP 2000294236 A JP2000294236 A JP 2000294236A
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- resin
- plating film
- electrode
- thermoplastic resin
- 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
Classifications
-
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、アルカリ二次電池
用のニッケル電極およびその製造方法に関するものであ
る。TECHNICAL FIELD The present invention relates to a nickel electrode for an alkaline secondary battery and a method for producing the same.
【０００２】[0002]
【従来の技術】ニッケル電極は、ニッケル・カドミウム
電池、ニッケル・水素化物電池をはじめ、ニッケル・亜
鉛電池、ニッケル・鉄電池など多くのアルカリ電池に共
通の正極として用いられている。このうち、近年、急速
に発展してきたニッケル・水素化物電池は、携帯電話な
どの小型ポータブル機器用から大型電気自動車用まで多
機種の電源として使用されている。従来の焼結式水酸化
ニッケル電極は、カルボニルニッケルをパンチングメタ
ル上に焼結させた三次元多孔体基板に、ニッケル塩溶融
液を含浸させて化学的または電気化学的に水酸化ニッケ
ルに変換する方法がとられてきた。しかし、焼結式三次
元多孔体基板の多孔度が約８０％であることからエネル
ギー密度が低くなること、製造工程が複雑であることな
どの問題があった。一方、ペースト式ニッケル電極は、
水酸化ニッケル粉末とコバルト化合物の粉末などを混合
したものか、もしくは、水酸化ニッケル表面にコバルト
化合物をコーティングした粉末を多孔度が９５％以上の
三次元多孔体基板に充填して作製される。これにより、
高エネルギー密度の電極が得られるようになった。しか
し、高率放電特性は燒結式ニッケル電極よりも低い。電
気自動車用途などの電池においては、さらなる高エネル
ギー密度化、高出力密度化が要求されているのに加え
て、コバルト化合物使用などによるコスト高が問題とな
っている。2. Description of the Related Art Nickel electrodes are used as a common positive electrode in many alkaline batteries such as nickel-cadmium batteries, nickel-hydride batteries, nickel-zinc batteries, nickel-iron batteries. Of these, nickel / hydride batteries, which have been rapidly developing in recent years, are used as power sources for various types of devices from small portable devices such as mobile phones to large electric vehicles. Conventional sintered nickel hydroxide electrodes are chemically or electrochemically converted into nickel hydroxide by impregnating a three-dimensional porous substrate obtained by sintering carbonyl nickel on a punching metal with a nickel salt melt. The way has been taken. However, since the porosity of the sintered three-dimensional porous substrate is about 80%, there are problems such as a low energy density and a complicated manufacturing process. On the other hand, paste-type nickel electrodes
It is prepared by mixing a nickel hydroxide powder and a cobalt compound powder or a powder obtained by coating a nickel compound surface with a cobalt compound into a three-dimensional porous substrate having a porosity of 95% or more. This allows
High energy density electrodes can now be obtained. However, the high rate discharge characteristics are lower than those of sintered nickel electrodes. Batteries for use in electric vehicles and the like are required to have higher energy density and higher output density, and also have a problem of high cost due to the use of a cobalt compound.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、上記問題点
に鑑みてなされたものであり、ペースト式電極、焼結式
電極のそれぞれの長所である高エネルギー密度、高出力
密度特性を兼ね備え、さらに低コストタイプの水酸化ニ
ッケル粉末を用いたニッケル電極を提供しようとするも
のである。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has both high energy density and high output density characteristics which are advantages of a paste type electrode and a sintered type electrode. It is another object of the present invention to provide a nickel electrode using a low-cost type nickel hydroxide powder.
【０００４】[0004]
【課題を解決するための手段】本発明のニッケル電極
は、表面に熱可塑性樹脂の微粒子を包含した金属メッキ
被膜を有する水酸化ニッケル粉末を含むことを特徴とす
る。本発明は、表面に熱可塑性樹脂の微粒子を包含した
金属メッキ被膜を有する水酸化ニッケル粉末を前記熱可
塑性樹脂の熱分解温度未満の温度下で加圧成型すること
により多孔性のニッケル電極を得るものである。また、
本発明は、前記表面に熱可塑性樹脂の微粒子を包含した
金属メッキ被膜を有する水酸化ニッケル粉末を用いて作
製するペースト式電極にも関する。水酸化ニッケルは、
本来絶縁性物質であるが、本発明においては導電性を確
保するためにその表面に金属メッキを施し、成型性を高
めるために金属メッキ被膜が熱可塑性樹脂の微粒子を包
含している。According to the present invention, there is provided a nickel electrode comprising a nickel hydroxide powder having a metal plating film containing fine particles of a thermoplastic resin on the surface. The present invention provides a porous nickel electrode by pressure molding a nickel hydroxide powder having a metal plating film containing thermoplastic resin fine particles on the surface thereof at a temperature lower than the thermal decomposition temperature of the thermoplastic resin. Things. Also,
The present invention also relates to a paste electrode manufactured using a nickel hydroxide powder having a metal plating film containing thermoplastic resin fine particles on the surface. Nickel hydroxide is
Although it is originally an insulating substance, in the present invention, its surface is plated with metal to secure conductivity, and the metal plating film contains fine particles of a thermoplastic resin in order to enhance moldability.
【０００５】従って、本発明によれば、表面に熱可塑性
樹脂の微粒子を包含した金属メッキ被膜を有する水酸化
ニッケル粉末を前記熱可塑性樹脂の熱分解温度未満の温
度下で加圧成型することにより多孔性の水酸化ニッケル
電極を得ることができる。また、前記表面に熱可塑性樹
脂の微粒子を包含した金属メッキ被膜を有する水酸化ニ
ッケル粉末を用いてペースト式電極を作製することもで
きる。前記金属メッキ被膜は、水分子及び水酸化物イオ
ンの拡散を許容する多孔質被膜である。多孔質被膜であ
れば、充電反応または放電反応に必要な物質種またはイ
オン種を水酸化ニッケル粒子表面または内部に供給する
際の妨げにはならない。また、前記金属メッキ被膜は、
エネルギー密度を低下させないため、水酸化ニッケル量
に対し２０重量％以下、好ましくは５〜１７％が適当で
ある。Therefore, according to the present invention, a nickel hydroxide powder having a metal plating film containing fine particles of a thermoplastic resin on its surface is molded under pressure at a temperature lower than the thermal decomposition temperature of the thermoplastic resin. A porous nickel hydroxide electrode can be obtained. Also, a paste-type electrode can be manufactured using nickel hydroxide powder having a metal plating film containing thermoplastic resin fine particles on the surface. The metal plating film is a porous film that allows diffusion of water molecules and hydroxide ions. The porous coating does not hinder the supply of the substance species or ionic species necessary for the charge or discharge reaction to the surface or inside of the nickel hydroxide particles. Further, the metal plating film,
In order not to lower the energy density, the amount is suitably 20% by weight or less, preferably 5 to 17% based on the amount of nickel hydroxide.
【０００６】本発明は、表面に熱可塑性樹脂の微粒子を
包含した金属メッキ被膜を有する水酸化ニッケル粉末を
前記熱可塑性樹脂の熱分解温度未満の温度下で加圧成型
することにより、前記水酸化ニッケル粉末が前記熱可塑
性樹脂により結合された多孔体を得るニッケル電極の製
造方法を提供する。さらに、本発明は、表面に熱可塑性
樹脂の微粒子を包含した金属メッキ被膜を有する水酸化
ニッケル粉末を金属支持体の片面または両面に配し、前
記熱可塑性樹脂の熱分解温度未満の温度下で加圧成型す
ることにより、前記水酸化ニッケル粉末が前記熱可塑性
樹脂により結合され、かつ前記金属支持体を一体に結合
した多孔体を得るニッケル電極の製造方法を提供する。[0006] The present invention provides a method for producing a hydration resin by press-molding a nickel hydroxide powder having a metal plating film containing fine particles of a thermoplastic resin on the surface thereof at a temperature lower than the thermal decomposition temperature of the thermoplastic resin. A method for producing a nickel electrode for obtaining a porous body in which nickel powder is bound by the thermoplastic resin. Furthermore, the present invention arranges nickel hydroxide powder having a metal plating film containing thermoplastic resin fine particles on one or both surfaces of a metal support, and at a temperature lower than the thermal decomposition temperature of the thermoplastic resin. The present invention provides a method for producing a nickel electrode, in which the nickel hydroxide powder is bonded by the thermoplastic resin by pressure molding to obtain a porous body in which the metal support is integrally bonded.
【０００７】[0007]
【発明の実施の形態】水酸化ニッケル粉末を被覆するメ
ッキ被膜の金属としては、Ｎｉ、Ｃｏ、Ｎｉ−Ｃｏ、Ｎ
ｉ−Ｐ、Ｎｉ−Ｂ、Ｃｏ−ＰおよびＣｏ−Ｂからなる群
より選んだものが好適に用いられる。メッキ被膜の膜厚
は、０．０１〜５０μｍ、好ましくは１〜１０μｍが適
当である。前記メッキ被膜に包含させる可塑性樹脂粉末
としては、ポリテトラフルオロエチレン、ポリエチレ
ン、ＡＢＳ樹脂、ポリアミド、ポリスルフォン、ＡＳ樹
脂、ポリスチレン、塩化ビニリビデン樹脂、ポリフェニ
レンエーテル、メチルペンテン樹脂、およびメタクリル
酸樹脂からなる群より選ばれる樹脂の粒子が適当であ
る。樹脂粒子の粒径は、０．０１〜５０μｍ、好ましく
は１〜５μｍが適当である。BEST MODE FOR CARRYING OUT THE INVENTION Ni, Co, Ni-Co, N
Those selected from the group consisting of i-P, Ni-B, Co-P and Co-B are preferably used. The thickness of the plating film is suitably 0.01 to 50 μm, preferably 1 to 10 μm. Examples of the plastic resin powder included in the plating film include a group consisting of polytetrafluoroethylene, polyethylene, ABS resin, polyamide, polysulfone, AS resin, polystyrene, vinylidene chloride resin, polyphenylene ether, methylpentene resin, and methacrylic acid resin. Resin particles selected from the above are appropriate. The particle size of the resin particles is suitably from 0.01 to 50 μm, preferably from 1 to 5 μm.
【０００８】[0008]
【実施例】以下、実施例により本発明を説明する。The present invention will be described below with reference to examples.
【０００９】固溶体添加量が水酸化亜鉛６重量％、水酸
化コバルト７重量％の球状水酸化ニッケル粉末粒子を用
意し、以下に示す方法で無電解複合ニッケルメッキし
た。まず、前記球状水酸化ニッケル粉末粒子１００ｇを
イオン交換水で洗浄した後、奥野製薬株式会社製ＯＰ−
１１３の名で販売されている脱脂剤の水溶液（６０ｇ／
ｌ）からなる浴に６０℃で１０分間浸漬し、次いで水洗
する脱脂工程を行った。次に、３０ｇ／ｌの塩化第一ス
ズおよび１５ｍｌ／ｌの塩酸を含むセンシタイザー液に
脱脂後の水酸化ニッケル粒子を２５℃で３分間浸漬した
後に水洗する工程と、０．２ｇ／ｌの塩化パラジウムお
よび４ｍｌ／ｌの塩酸を含むアクチベイター液に水酸化
ニッケル粒子を２５℃で３分間浸漬した後に水洗する活
性化処理工程を行った。この活性化処理工程は２回繰り
返した。[0009] Spherical nickel hydroxide powder particles having a solid solution addition amount of 6% by weight of zinc hydroxide and 7% by weight of cobalt hydroxide were prepared, and electroless composite nickel plating was performed by the following method. First, after washing 100 g of the spherical nickel hydroxide powder particles with ion-exchanged water, OP-OPO manufactured by Okuno Pharmaceutical Co., Ltd.
An aqueous solution of a degreasing agent sold under the name of 113 (60 g /
A degreasing step of immersing in the bath consisting of 1) at 60 ° C. for 10 minutes and then washing with water was performed. Next, the degreased nickel hydroxide particles are immersed in a sensitizer solution containing 30 g / l of stannous chloride and 15 ml / l of hydrochloric acid at 25 ° C. for 3 minutes, and then washed with water. An activation treatment step of immersing nickel hydroxide particles in an activator solution containing palladium chloride and 4 ml / l hydrochloric acid at 25 ° C. for 3 minutes and then washing with water was performed. This activation step was repeated twice.
【００１０】次に、８０℃の２０ｇ／ｌのグリシンと３
ｇ／ｌの粒径０．３μｍのポリテトラフルオロエチレン
（以下ＰＴＦＥで表す）粒子と界面活性剤とを含む混合
液１リットル中に活性化処理後の水酸化ニッケル粒子を
投入して分散させた。この分散液を攪拌しながら、３０
０ｇ／ｌの硫酸ニッケル水溶液１５９ｍｌと、２８２ｇ
／１の次亜リン酸ナトリウムと１５０ｇ／ｌの水酸化ナ
トリウムを含む混合水溶液１５９ｍｌをそれぞれ１０ｍ
ｌ／分の滴下速度で添加した。水素ガスの発生が終了す
るまで攪拌を続けた後、水洗、濾過、乾燥して、Ｎｉ−
ＰＴＦＥ複合メッキ被膜を有する水酸化ニッケル粉末試
料を得た。なお、濾液は無色であったので、供給したニ
ッケルイオンは全て水酸化ニッケル粒子表面に還元析出
された。Next, 20 g / l glycine at 80 ° C. and 3 g
The activated nickel hydroxide particles were put into 1 liter of a mixed solution containing polytetrafluoroethylene (hereinafter, referred to as PTFE) particles having a particle size of 0.3 μm and a surfactant and dispersed therein. . While stirring this dispersion, 30
159 ml of 0 g / l nickel sulfate aqueous solution and 282 g
159 ml of a mixed aqueous solution containing 150 g / l sodium hydroxide and 150 g / l sodium hypophosphite each in 10 m
It was added at a dropping rate of 1 / min. After stirring was continued until the generation of hydrogen gas was completed, the mixture was washed with water, filtered and dried to obtain Ni-
A nickel hydroxide powder sample having a PTFE composite plating film was obtained. Since the filtrate was colorless, all the supplied nickel ions were reduced and precipitated on the surface of the nickel hydroxide particles.
【００１１】このようにして得た試料の一部を走査型電
子顕微鏡で観察したところ、水酸化ニッケル粒子はＰＴ
ＦＥを包含した金属ニッケル皮膜で覆われていることが
わかった。メッキ皮膜は水酸化ニッケル粒子全体を覆う
のではなく、部分的に水酸化ニッケル粒子の表面が見え
る箇所が観察された。このような部分が存在するため
に、水分子や水酸化物イオンの水酸化ニッケル粒子への
拡散が可能となる。また、ＩＣＰによるメッキ量分析の
結果、メッキ量は水酸化ニッケルの１０．８重量％相当
であることがわかった。さらに、メッキ被膜には、ニッ
ケルの他にリンが存在することが確認された。When a part of the sample thus obtained was observed with a scanning electron microscope, the nickel hydroxide particles were found to be PT
It was found that it was covered with a metallic nickel film containing FE. The plating film did not cover the entire nickel hydroxide particles, but was partially observed where the surface of the nickel hydroxide particles was visible. The presence of such a portion enables diffusion of water molecules and hydroxide ions into the nickel hydroxide particles. Further, as a result of plating amount analysis by ICP, it was found that the plating amount was equivalent to 10.8% by weight of nickel hydroxide. Further, it was confirmed that phosphorus was present in the plating film in addition to nickel.
【００１２】次に、得られたＮｉ−ＰＴＦＥ複合メッキ
被膜を有する水酸化ニッケル粉末試料１．５ｇを厚さ
０．０６ｍｍのパンチングメタル（穴あきの鉄板にニッ
ケルメッキしたもの）集電基板の両側に配し、２００℃
において４００ｋｇ／ｃｍ2の成型圧で加圧成型し、直
径２３ｍｍ、厚さ１ｍｍの成型体を得た。この成型体を
ニッケル網で包み込んで周囲をスポット溶接し、ニッケ
ルのリード線を設けてニッケル電極を得た。これを電極
Ａとする。次に、複合メッキ被膜を有する水酸化ニッケ
ル粉末試料の代わりに、同じ固溶体組成のメッキをして
いない水酸化ニッケル粉末試料を用いること以外は電極
Ａと同様の方法でニッケル電極を作製した。これを比較
電極Ｂとする。さらに、比較電極Ｂで用いた水酸化ニッ
ケル粉末試料に、一酸化コバルト粉末を１０重量％混
合、分散させた試料を用いること、および加圧成型を常
温で行うこと以外は電極Ａと同様の方法でニッケル電極
を作製した（高温で加圧すると一酸化コバルトが酸化さ
れて四三酸化コバルトに変化してしまうため）。これを
比較電極Ｃとする。電極Ａ、比較電極Ｂおよび比較電極
Ｃの成型体の多孔度は、いずれも約３０％であった。Next, 1.5 g of the obtained nickel hydroxide powder sample having the Ni-PTFE composite plating film was punched on a current collector substrate having a thickness of 0.06 mm by punching metal (a nickel plate on a perforated iron plate). 200 ° C
Was molded under pressure at a molding pressure of 400 kg / cm 2 to obtain a molded body having a diameter of 23 mm and a thickness of 1 mm. The molded body was wrapped in a nickel net and the periphery was spot-welded, and a nickel lead wire was provided to obtain a nickel electrode. This is electrode A. Next, a nickel electrode was produced in the same manner as for the electrode A, except that a nickel hydroxide powder sample having the same solid solution composition but not plated was used instead of the nickel hydroxide powder sample having the composite plating film. This is designated as Comparative electrode B. Further, the same method as that of the electrode A except that the nickel hydroxide powder sample used in the comparative electrode B was mixed and dispersed with 10% by weight of cobalt monoxide powder, and the pressure molding was performed at room temperature. To produce a nickel electrode (since cobalt monoxide is oxidized and turned into cobalt trioxide when pressurized at high temperature). This is referred to as reference electrode C. The porosity of the molded articles of the electrode A, the comparative electrode B and the comparative electrode C was about 30%.
【００１３】また、Ｎｉ−ＰＴＦＥ複合メッキ被膜を有
する水酸化ニッケル粉末試料に増粘剤を加えてペースト
状にし、三次元多孔体基板に充填して乾燥、プレスして
ニッケル電極を得た。これを電極Ｄとする。さらに、比
較電極Ｂで用いた水酸化ニッケル粉末試料に一酸化コバ
ルト粉末を１０重量％混合、分散させた試料を用いるこ
と以外は電極Ｄと同様の方法でニッケル電極を作製し
た。これを従来電極Ｅとする。A thickener was added to a nickel hydroxide powder sample having a Ni-PTFE composite plating film to form a paste, which was filled in a three-dimensional porous substrate, dried and pressed to obtain a nickel electrode. This is electrode D. Further, a nickel electrode was prepared in the same manner as for the electrode D except that a sample in which 10% by weight of cobalt monoxide powder was mixed and dispersed in the nickel hydroxide powder sample used for the comparative electrode B was used. This is referred to as a conventional electrode E.
【００１４】これらの電極と水素吸蔵合金電極を組み合
わせて開放型電池を作製し、２０℃で充放電試験を行っ
た。充電は０．１Ｃで１５０％、放電は０．２Ｃで終止
電圧を１．０Ｖとし、充放電を１０サイクル行った。い
ずれの電極も放電容量が安定したので、１０サイクル目
の電極重量および電極体積あたりの放電容量と活物質利
用率を表１に示す。An open-type battery was manufactured by combining these electrodes and a hydrogen storage alloy electrode, and a charge / discharge test was performed at 20 ° C. Charging was performed at 0.1 C at 150%, discharging was performed at 0.2 C at a final voltage of 1.0 V, and charging and discharging were performed for 10 cycles. Since the discharge capacity was stable for all the electrodes, Table 1 shows the discharge capacity per unit electrode volume and the discharge capacity per 10 electrode cycles and the active material utilization rate.
【００１５】[0015]
【表１】 [Table 1]
【００１６】表１から明らかなとおり、比較電極Ｂ以外
は、電極重量および電極体積あたりの放電容量が従来電
極Ｅよりも向上した。これは活物質利用率による影響が
大きい。活物質利用率とは、放電容量の実測値と計算値
の比を表したものである。本発明による電極Ａおよび電
極Ｄは、活物質利用率が向上したため、電極重量および
電極体積あたりの放電容量が増大した。また、比較電極
Ｃは、活物質利用率の向上は見られなかったが、電極に
三次元多孔体を用いていないので、見かけの電極重量お
よび電極体積あたりの放電容量が増大した。本発明の電
極Ａが最大容量を示しているのは、これらの相乗効果に
よる。一方、比較電極Ｂは、金属メッキ被膜やコバルト
化合物が存在しないので、反応性が悪くなり、活物質利
用率が極端に低下した。As is clear from Table 1, except for the comparative electrode B, the discharge capacity per electrode weight and electrode volume was improved as compared with the conventional electrode E. This is largely affected by the active material utilization. The active material utilization expresses a ratio between a measured value and a calculated value of the discharge capacity. In the electrodes A and D according to the present invention, since the active material utilization rate was improved, the discharge capacity per electrode weight and electrode volume was increased. In Comparative electrode C, no improvement in the active material utilization was observed, but the apparent electrode weight and discharge capacity per electrode volume increased because no three-dimensional porous body was used for the electrode. The electrode A of the present invention exhibits the maximum capacity due to these synergistic effects. On the other hand, since the comparative electrode B did not have a metal plating film or a cobalt compound, the reactivity was deteriorated and the active material utilization rate was extremely reduced.
【００１７】次に、前記開放型電池を用いて高率放電試
験を行った。放電のレートは１Ｃ〜２０Ｃまでさまざま
に行った。それぞれの放電レートにおいて、放電開始か
ら１０秒目の電池電圧を測定し、横軸に放電レート、縦
軸に電池電圧をプロットした結果を図１に示す。図１か
ら明らかなとおり、本発明による電極Ａおよび電極Ｄ
は、良好な導電性ネットワークを持つため、従来電極Ｅ
に比べ優れた高率放電特性を示した。比較電極Ｂは、導
電性ネットワークを全く持たないので、粒子間接触抵抗
が大きく、いずれの放電レートでも大きな電圧降下を示
した。また、比較電極Ｃは、コバルト化合物からなる導
電性ネットワークを持つが、ニッケルの三次元多孔体を
用いていないので、大電流放電時には導電性が不十分と
なるため、電圧降下が著しくなる。Next, a high-rate discharge test was performed using the open-type battery. The discharge rate was varied from 1C to 20C. At each discharge rate, the battery voltage at 10 seconds after the start of discharge was measured, and the discharge rate was plotted on the horizontal axis and the battery voltage was plotted on the vertical axis, and the results are shown in FIG. As is evident from FIG. 1, electrode A and electrode D according to the invention
Has a good conductive network, so that the conventional electrode E
It exhibited excellent high-rate discharge characteristics as compared to Since the comparative electrode B had no conductive network at all, the contact resistance between particles was large, and a large voltage drop was shown at any discharge rate. Further, although the comparative electrode C has a conductive network made of a cobalt compound, it does not use a three-dimensional porous body of nickel, and therefore has insufficient conductivity at the time of large current discharge, so that the voltage drop becomes remarkable.
【００１８】図２に１５Ｃ放電時の放電曲線を示す。終
止電圧は０．８Ｖとした。従来電極Ｅの２８秒（利用率
１１．７％）に対し、本発明の電極Ａは５２秒（利用率
２１．７％）、電極Ｄは６２秒（利用率２５．８％）の
放電が可能であった。終止電圧を０．８Ｖより低く設定
すれば、さらに大きな放電容量を得ることもできる。特
に、電極Ａにおいては、個々の水酸化ニッケル粒子表面
に備えた導電性金属メッキ被膜が大電流に耐えうる三次
元的な導電性ネットワークを形成しているので、高価な
三次元多孔体、コバルト化合物などの材料を用いる必要
がなく、大幅なコスト削減効果も兼ね備えている。FIG. 2 shows a discharge curve at the time of 15C discharge. The end voltage was set to 0.8V. In contrast to the conventional electrode E of 28 seconds (utilization rate of 11.7%), the electrode A of the present invention discharges for 52 seconds (utilization rate of 21.7%) and the electrode D discharges for 62 seconds (utilization rate of 25.8%). It was possible. If the cutoff voltage is set lower than 0.8 V, a larger discharge capacity can be obtained. Particularly, in the electrode A, since the conductive metal plating film provided on the surface of each nickel hydroxide particle forms a three-dimensional conductive network capable of withstanding a large current, an expensive three-dimensional porous material, cobalt There is no need to use materials such as compounds, and a significant cost reduction effect is also achieved.
【００１９】[0019]
【発明の効果】上記のように本発明は、粒子表面に熱可
塑性樹脂を包含した金属メッキ皮膜を有する水酸化ニッ
ケル粉末を用いるので、高エネルギー密度、高出力密度
を有し、かつ、安価なニッケル電極を提供することが可
能となった。As described above, the present invention uses a nickel hydroxide powder having a metal plating film containing a thermoplastic resin on the surface of the particles, so that it has a high energy density, a high output density and is inexpensive. It has become possible to provide nickel electrodes.
【図１】各種ニッケル電極と水素吸蔵合金電極を組み合
わせた開放型電池の放電レートと電池電圧の関係を示す
図である。FIG. 1 is a diagram showing a relationship between a discharge rate and a battery voltage of an open battery in which various nickel electrodes and a hydrogen storage alloy electrode are combined.
【図２】同電池の放電時間と電池電圧の関係を示す図で
ある。FIG. 2 is a diagram showing a relationship between a discharge time and a battery voltage of the battery.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 5H003 AA08 BA05 BB04 BB11 BB14 BC01 BC05 BD01 BD04 5H016 AA02 AA05 BB05 CC03 EE01 EE05 EE09 HH01 HH11 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 5H003 AA08 BA05 BB04 BB11 BB14 BC01 BC05 BD01 BD04 5H016 AA02 AA05 BB05 CC03 EE01 EE05 EE09 HH01 HH11
Claims (11)
金属メッキ被膜を有する水酸化ニッケル粉末を含むこと
を特徴とするニッケル電極。1. A nickel electrode comprising a nickel hydroxide powder having a metal plating film containing thermoplastic resin fine particles on the surface.
イオンの拡散を許容する多孔質被膜である請求項１記載
のニッケル電極。2. The nickel electrode according to claim 1, wherein the plating film is a porous film that allows diffusion of water molecules and hydroxide ions.
２０重量％以下である請求項１記載のニッケル電極。3. The nickel electrode according to claim 1, wherein the amount of the plating film is not more than 20% by weight of the amount of nickel hydroxide.
−Ｃｏ、Ｎｉ−Ｐ、Ｎｉ−Ｂ、Ｃｏ−ＰおよびＣｏ−Ｂ
からなる群より選ばれる請求項１記載のニッケル電極。4. The method according to claim 1, wherein the metal plating film is made of Ni, Co, Ni.
-Co, Ni-P, Ni-B, Co-P and Co-B
The nickel electrode according to claim 1, which is selected from the group consisting of:
エチレン、ポリエチレン、ＡＢＳ樹脂、ポリアミド、ポ
リスルフォン、ＡＳ樹脂、ポリスチレン、塩化ビニリビ
デン樹脂、ポリフェニレンエーテル、メチルペンテン樹
脂、およびメタクリル酸樹脂からなる群より選ばれる請
求項１記載のニッケル電極。5. The plastic resin is selected from the group consisting of polytetrafluoroethylene, polyethylene, ABS resin, polyamide, polysulfone, AS resin, polystyrene, vinylidene chloride resin, polyphenylene ether, methylpentene resin, and methacrylic resin. The nickel electrode according to claim 1, wherein
金属メッキ被膜を有する水酸化ニッケル粉末を前記熱可
塑性樹脂の熱分解温度未満の温度下で加圧成型すること
により、前記水酸化ニッケル粉末が前記熱可塑性樹脂に
より結合された多孔体を得ることを特徴とするニッケル
電極の製造方法。6. The nickel hydroxide powder having a metal plating film containing fine particles of a thermoplastic resin on its surface under pressure at a temperature lower than the thermal decomposition temperature of the thermoplastic resin. Obtaining a porous body bonded by the thermoplastic resin.
金属メッキ被膜を有する水酸化ニッケル粉末を金属支持
体の片面または両面に配し、前記熱可塑性樹脂の熱分解
温度未満の温度下で加圧成型することにより、前記水酸
化ニッケル粉末が前記熱可塑性樹脂により結合され、か
つ前記金属支持体を一体に結合した多孔体を得ることを
特徴とするニッケル電極の製造方法。7. A nickel hydroxide powder having a metal plating film containing thermoplastic resin fine particles on one surface or both surfaces of a metal support, and heated at a temperature lower than the thermal decomposition temperature of the thermoplastic resin. A method for producing a nickel electrode, comprising: pressing to obtain a porous body in which the nickel hydroxide powder is bonded by the thermoplastic resin and the metal support is integrally bonded.
イオンの拡散を許容する多孔質被膜である請求項６また
は７記載のニッケル電極の製造方法。8. The method for producing a nickel electrode according to claim 6, wherein the plating film is a porous film that allows diffusion of water molecules and hydroxide ions.
２０重量％以下である請求項６または７記載のニッケル
電極の製造方法。9. The method for producing a nickel electrode according to claim 6, wherein the amount of the plating film is 20% by weight or less of the amount of nickel hydroxide.
ｉ−Ｐ、Ｎｉ−Ｂ、Ｃｏ−Ｐ、およびＣｏ−Ｂからなる
群より選ばれる請求項６または７記載のニッケル電極の
製造方法。10. The metal plating film is made of Ni, Co, N
8. The method for producing a nickel electrode according to claim 6, wherein the method is selected from the group consisting of i-P, Ni-B, Co-P, and Co-B.
ロエチレン、ポリエチレン、ＡＢＳ樹脂、ポリアミド、
ポリスルフォン、ＡＳ樹脂、ポリスチレン、塩化ビニリ
デン樹脂、ポリフェニレンエーテル、メチルペンテン樹
脂、およびメタクリル酸樹脂からなる群より選ばれる請
求項６または７記載のニッケル電極の製造方法。11. The plastic resin is polytetrafluoroethylene, polyethylene, ABS resin, polyamide,
The method for producing a nickel electrode according to claim 6 or 7, wherein the method is selected from the group consisting of polysulfone, AS resin, polystyrene, vinylidene chloride resin, polyphenylene ether, methylpentene resin, and methacrylic acid resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09983499A JP3553816B2 (en) | 1999-04-07 | 1999-04-07 | Nickel electrode and method of manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09983499A JP3553816B2 (en) | 1999-04-07 | 1999-04-07 | Nickel electrode and method of manufacturing the same |
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| Publication Number | Publication Date |
|---|---|
| JP2000294236A true JP2000294236A (en) | 2000-10-20 |
| JP3553816B2 JP3553816B2 (en) | 2004-08-11 |
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ID=14257855
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|---|---|---|---|
| JP09983499A Expired - Fee Related JP3553816B2 (en) | 1999-04-07 | 1999-04-07 | Nickel electrode and method of manufacturing the same |
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| Country | Link |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004035860A1 (en) * | 2002-10-21 | 2004-04-29 | Kiyokawa Plating Industry Co., Ltd. | Metal resin composite and process for producing the same |
| US7338686B2 (en) | 2003-04-18 | 2008-03-04 | Kiyokawa Plating Industry Co., Ltd. | Method for producing conductive particles |
| CN105659416A (en) * | 2013-12-10 | 2016-06-08 | 松下知识产权经营株式会社 | Positive electrode for alkali storage battery, and alkali storage battery |
| WO2019181787A1 (en) * | 2018-03-20 | 2019-09-26 | 株式会社田中化学研究所 | Compound for positive electrode |
| WO2019181788A1 (en) * | 2018-03-20 | 2019-09-26 | 株式会社田中化学研究所 | Compound for positive electrode |
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1999
- 1999-04-07 JP JP09983499A patent/JP3553816B2/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004035860A1 (en) * | 2002-10-21 | 2004-04-29 | Kiyokawa Plating Industry Co., Ltd. | Metal resin composite and process for producing the same |
| US7338686B2 (en) | 2003-04-18 | 2008-03-04 | Kiyokawa Plating Industry Co., Ltd. | Method for producing conductive particles |
| CN105659416A (en) * | 2013-12-10 | 2016-06-08 | 松下知识产权经营株式会社 | Positive electrode for alkali storage battery, and alkali storage battery |
| WO2019181787A1 (en) * | 2018-03-20 | 2019-09-26 | 株式会社田中化学研究所 | Compound for positive electrode |
| WO2019181788A1 (en) * | 2018-03-20 | 2019-09-26 | 株式会社田中化学研究所 | Compound for positive electrode |
| CN111868976A (en) * | 2018-03-20 | 2020-10-30 | 株式会社田中化学研究所 | Compound for positive electrode |
| CN111868975A (en) * | 2018-03-20 | 2020-10-30 | 株式会社田中化学研究所 | Compound for positive electrode |
| JPWO2019181788A1 (en) * | 2018-03-20 | 2021-03-25 | 株式会社田中化学研究所 | Compound for positive electrode |
| JPWO2019181787A1 (en) * | 2018-03-20 | 2021-04-08 | 株式会社田中化学研究所 | Compound for positive electrode |
| JP7290625B2 (en) | 2018-03-20 | 2023-06-13 | 株式会社田中化学研究所 | Positive electrode compound and method for producing positive electrode active material |
| JP7290626B2 (en) | 2018-03-20 | 2023-06-13 | 株式会社田中化学研究所 | Positive electrode compound and method for producing positive electrode active material |
| CN111868976B (en) * | 2018-03-20 | 2023-08-15 | 株式会社田中化学研究所 | Positive electrode compound |
| CN111868975B (en) * | 2018-03-20 | 2023-11-17 | 株式会社田中化学研究所 | Positive electrode compound |
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|---|---|
| JP3553816B2 (en) | 2004-08-11 |
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