JPH01134861A - Manufacture of hydrogen absorption alloy electrode - Google Patents
Manufacture of hydrogen absorption alloy electrodeInfo
- Publication number
- JPH01134861A JPH01134861A JP62294332A JP29433287A JPH01134861A JP H01134861 A JPH01134861 A JP H01134861A JP 62294332 A JP62294332 A JP 62294332A JP 29433287 A JP29433287 A JP 29433287A JP H01134861 A JPH01134861 A JP H01134861A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- storage alloy
- chloride
- manufacturing
- porous body
- 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.)
- Pending
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 83
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 83
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 82
- 239000000956 alloy Substances 0.000 title claims abstract description 82
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 238000010521 absorption reaction Methods 0.000 title abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 23
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 17
- -1 nitric acid compound Chemical class 0.000 claims abstract description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims abstract description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 3
- 239000001110 calcium chloride Substances 0.000 claims abstract description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 3
- 239000011777 magnesium Substances 0.000 claims abstract description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 3
- 238000003860 storage Methods 0.000 claims description 78
- 238000000034 method Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910020851 La(NO3)3.6H2O Inorganic materials 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 abstract description 2
- 230000001476 alcoholic effect Effects 0.000 abstract 2
- 229910017604 nitric acid Inorganic materials 0.000 abstract 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract 1
- 229910052746 lanthanum Inorganic materials 0.000 abstract 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract 1
- 229910052749 magnesium Inorganic materials 0.000 abstract 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Substances OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 101100229939 Mus musculus Gpsm1 gene Proteins 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 230000002747 voluntary effect Effects 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
-
- 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
【発明の詳細な説明】
主星上■■■分団
本発明は金属酸化物から成る正極活物質を備えた正極と
、水素吸蔵合金を備えた負極とを有する金属−水素アル
カリ蓄電池の水素吸蔵合金電極の製造方法に関するもの
である。Detailed Description of the Invention The present invention provides a hydrogen storage alloy electrode for a metal-hydrogen alkaline storage battery having a positive electrode having a positive electrode active material made of a metal oxide and a negative electrode having a hydrogen storage alloy. The present invention relates to a manufacturing method.
従来■肢歪
従来より、蓄電池としては鉛電池及びニッケルーカドミ
ウム電池がよく用いられているが、近年、これらの電池
より軽量で且つ高容量化が可能な金属−水素アルカリ蓄
電池の開発が盛んに行われている。この金属−水素アル
カリ蓄電池は、特に低圧で水素を可逆的に吸蔵及び放出
することのできる水素吸蔵合金を負極に備えると共に、
水酸化ニッケル等の金属酸化物からなる正極活物質を正
極に備えるような構造である。Conventional ■ Limb strain Traditionally, lead batteries and nickel-cadmium batteries have been commonly used as storage batteries, but in recent years, metal-hydrogen alkaline storage batteries, which are lighter than these batteries and can have higher capacities, have been actively developed. It is being done. This metal-hydrogen alkaline storage battery is equipped with a hydrogen storage alloy in the negative electrode that can reversibly store and release hydrogen especially at low pressure, and
It has a structure in which the positive electrode is equipped with a positive electrode active material made of a metal oxide such as nickel hydroxide.
ところで、上記金属−水素アルカリ蓄電池の負極に用い
られる水素吸蔵合金としては、特公昭５９−３１８２９
号公報に示すように、チタンとコバルトとからなるよう
なものが提案されている。By the way, as a hydrogen storage alloy used for the negative electrode of the above-mentioned metal-hydrogen alkaline storage battery, Japanese Patent Publication No. 59-31829
As shown in the publication, a material made of titanium and cobalt has been proposed.
しかし、この水素吸蔵合金は粉体の形で用いられている
ため、水素ガスを繰り返し吸蔵、放出すると徐々に破砕
されて微粉化する。このため、水素吸蔵合金が電極から
剥離、脱落し、負極の容量が低下するという問題点を有
していた。However, since this hydrogen-absorbing alloy is used in the form of a powder, if it repeatedly absorbs and releases hydrogen gas, it will gradually be crushed into fine powder. Therefore, there was a problem in that the hydrogen storage alloy peeled off and fell off from the electrode, resulting in a decrease in the capacity of the negative electrode.
そこで、特開昭５８−２７９７６号公報に示すように、
フラッシュ蒸着法により希土類金属−Ｎｉ系合金から成
る水素吸蔵合金薄膜を基板上に形成するようなものが提
案されている。Therefore, as shown in Japanese Patent Application Laid-open No. 58-27976,
A method has been proposed in which a hydrogen storage alloy thin film made of a rare earth metal-Ni alloy is formed on a substrate by a flash vapor deposition method.
■ く”しよ゛と−る。 占
しかしながら、上記製造方法で作製した水素吸蔵合金は
結晶状であるため、水素吸蔵合金が電極から剥離すると
いう問題を完全に解決するには到らない。更に、水素吸
蔵合金作製工程を経た後に薄膜工程が必要となるため製
造工程が複雑化し、電池の製造コストが高くなり、加え
て、水素吸蔵合金の膜厚を大きくすることができないた
め、水素吸蔵合金の高容量化を図ることができない等の
問題点を有していた。■ It is possible to do so. However, since the hydrogen storage alloy produced by the above manufacturing method is crystalline, it is not possible to completely solve the problem of the hydrogen storage alloy peeling off from the electrode. Furthermore, a thin film process is required after the hydrogen storage alloy manufacturing process, which complicates the manufacturing process and increases the manufacturing cost of the battery.In addition, since the film thickness of the hydrogen storage alloy cannot be increased, There were problems such as the inability to increase the capacity of the alloy.
本発明は従来のこのような問題点を解決して、水素ガス
の吸蔵、放出を繰り返し行った場合であっても水素吸蔵
合金が電極から剥離するのを完全に防止して電池容量が
低下するのを防ぎ、且つ製造工程を簡素化し、加えて水
素吸蔵合金の高容量化を図ることにより、高品質、高性
能且つ安価な水素吸蔵合金電極の製造方法の提供を目的
とするものである。The present invention solves these conventional problems and completely prevents the hydrogen storage alloy from peeling off from the electrode even when hydrogen gas is stored and released repeatedly, resulting in a decrease in battery capacity. The purpose of the present invention is to provide a method for manufacturing a high-quality, high-performance, and inexpensive hydrogen-absorbing alloy electrode by preventing this, simplifying the manufacturing process, and increasing the capacity of the hydrogen-absorbing alloy.
１、 占 ２ るための
本発明は上記の目的を達成するために、２種以上の金属
化合物をアルコール溶液に溶解させる第１ステップと、
上記アルコール溶液に多孔体を浸漬した後、この多孔体
を乾燥させる第２ステップと、前記金属化合物を還元さ
せて上記多孔体上に水素吸蔵合金を形成して正極を作成
する第３ステップとを有することを特徴とするものであ
る。1. In order to achieve the above object, the present invention includes a first step of dissolving two or more metal compounds in an alcohol solution;
After immersing the porous body in the alcohol solution, a second step of drying the porous body; and a third step of reducing the metal compound to form a hydrogen storage alloy on the porous body to create a positive electrode. It is characterized by having.
作二−−−月−
本発明は上記のように、多孔体の表面に付着した２種以
上の金属化合物を還元させて、多孔体の表面に水素吸蔵
合金を形成している。このように、多孔体の表面にて水
素吸蔵合金を形成しているので、多孔体と水素吸蔵合金
との密着性が向上する。As described above, the present invention reduces two or more metal compounds attached to the surface of a porous body to form a hydrogen storage alloy on the surface of the porous body. In this way, since the hydrogen storage alloy is formed on the surface of the porous body, the adhesion between the porous body and the hydrogen storage alloy is improved.
この結果、水素ガスの吸蔵、放出を繰り返し行っても水
素吸蔵合金は破砕されず、水素吸蔵合金が微粉化するの
を防ぐことができるので、負極から水素吸蔵合金が剥離
、脱落するのを防止しうる。As a result, even if hydrogen gas is repeatedly absorbed and released, the hydrogen-absorbing alloy will not be crushed, and the hydrogen-absorbing alloy will be prevented from becoming pulverized, thereby preventing the hydrogen-absorbing alloy from peeling off or falling off from the negative electrode. I can do it.
また、上記製造方法で作製された水素吸蔵合金はアモル
ファス化しているということによっても、水素吸蔵合金
が微粉化するのを防ぐことができ、負極から水素吸蔵合
金が剥離、脱落するのを防止しろる。Furthermore, since the hydrogen storage alloy produced by the above manufacturing method is amorphous, it is possible to prevent the hydrogen storage alloy from becoming pulverized, and to prevent the hydrogen storage alloy from peeling off or falling off from the negative electrode. Ru.
更に、上記の如く多孔体と水素吸蔵合金との密着性は良
好であるため、多孔体の表面に厚い水素吸蔵層を形成す
ることができ、負極の水素吸蔵量を多くすることができ
る。Furthermore, since the adhesion between the porous body and the hydrogen storage alloy is good as described above, a thick hydrogen storage layer can be formed on the surface of the porous body, and the amount of hydrogen storage in the negative electrode can be increased.
加えて、水素吸蔵合金を別途作製する工程が不要となる
ので、製造工程を簡素化することができる。In addition, since a separate process for producing a hydrogen storage alloy is not necessary, the manufacturing process can be simplified.
実−」Ｌ−桝 以下、本発明の実施例について述べる。Fruit-”L-masu Examples of the present invention will be described below.
〔第１実施例〕
先ず初めに、ランタン塩化物（Ｌ ａ ＣＩ！３ ・
８Ｈ，０）４００ｇと、ニッケル塩化物（Ｎ ｉ Ｃ１
２・６８２Ｏ）１２Ｏ０ｇとをアルコール溶解させる。[First Example] First, lanthanum chloride (L a CI!3 ・
8H,0) and 400 g of nickel chloride (N i C1
2.682O) 12O0g is dissolved in alcohol.
次に、このアルコール溶液に焼結式ニッケル板を浸漬し
た後、この焼結式ニッケル板を乾燥させる。そして、こ
れら浸漬、乾燥工程を数回繰り返した後、上記焼結式ニ
ッケル板を金属リチウムの蒸気中（温度１１００℃）で
１時間加熱し、上記両温化物を還元させる。しかる後、
焼結式ニッケル板を冷却し、更にこの焼結式ニッケル板
をアルコール溶液に浸漬して未反応の前記塩化物をアル
コール溶液に溶出させて、焼結式ニッケル板上から未反
応の塩化物を除去する。これによって、焼結式ニッケル
板の表面には［、 ａ Ｎ ｉ ｓという組成の水素吸
蔵合金が形成される。Next, after immersing the sintered nickel plate in this alcohol solution, the sintered nickel plate is dried. After repeating these immersion and drying steps several times, the sintered nickel plate is heated in metallic lithium vapor (temperature 1100° C.) for one hour to reduce the two warmed products. After that,
The sintered nickel plate is cooled, and the sintered nickel plate is immersed in an alcohol solution to dissolve the unreacted chloride into the alcohol solution, and the unreacted chloride is removed from the sintered nickel plate. Remove. As a result, a hydrogen storage alloy having a composition of [, aN i s is formed on the surface of the sintered nickel plate.
（第２実施例〕
金属化合物として、チタン塩化物（ＴｉＣ６ｇ＞２Ｏ０
ｇと、ニッケル塩化物（ＮｉｃＩｌｚ ・６Ｈ．０）
２Ｏ０ｇとを用い、且つ加熱温度を１０００℃で行った
以外は第１実施例と同様にして作成した。これにより、
焼結式ニッケル板の表面にはＴｉ．Ｎｉという組成の水
素吸蔵合金が形成される。(Second Example) Titanium chloride (TiC6g>2O0
g and nickel chloride (NicIlz ・6H.0)
It was prepared in the same manner as in Example 1, except that 2O0g was used and the heating temperature was 1000°C. This results in
The surface of the sintered nickel plate contains Ti. A hydrogen storage alloy having a composition of Ni is formed.
〔第３実施例〕
金属化合物として、ランタン塩化物（Ｌ ａ Ｃ Ｉ！
、・８ＨｔＯ）４００ｇと、ニッケル塩化物（ＮｉｃＩ
ｌｚ ・６Ｈｚ Ｏ）５００ｇと、コバルト塩化物（
ＣｏＣ＆！ｚ ）４００ｇとを用い、且つ加熱温度を１
３００℃で行った以外は第１実施例と同様にして作成し
た。これにより、焼結式ニッケル板の表面には、ＬａＮ
ｉ，Ｃｏ３という組成を有する水素吸蔵合金が形成され
る。[Third Example] As a metal compound, lanthanum chloride (L a C I!
, 400 g of 8HtO) and 400 g of nickel chloride (NicI
lz ・6Hz O) 500g and cobalt chloride (
CoC&! z) 400g, and the heating temperature was 1
It was prepared in the same manner as in the first example except that the temperature was 300°C. As a result, the surface of the sintered nickel plate has LaN
A hydrogen storage alloy having the composition i,Co3 is formed.
〔第４実施例〕
金属化合物として、マグネシウム塩化物（ＭｇＣｌｔ
・６ Ｈ□Ｏ）４００ｇと、ニッケル塩化物（ＮＩＣ
１ｚ ・６Ｈｚ Ｏ）２５０ｇとを用い、且つ加熱温
度を１３００℃で行った以外は第１実施例と同様にして
作成した。これにより、焼結式ニッケル板の表面にはＭ
ｇｚＮｉという組成の水素吸蔵合金が形成される。[Fourth Example] As a metal compound, magnesium chloride (MgClt
・6H□O) 400g and nickel chloride (NIC
It was prepared in the same manner as in Example 1, except that 250 g of 1z 6 Hz O) was used and the heating temperature was 1300°C. As a result, the surface of the sintered nickel plate has M
A hydrogen storage alloy having the composition gzNi is formed.
〔第５実施例〕
金属化合物として、カルシウム塩化物（ＣａＣｌ，・６
Ｈ．Ｏ）２Ｏ０ｇと、ニッケル塩化物（Ｎｉ（１！，
・６ＨｇＯ）１０００ｇとを用い、且つ加熱温度を１
３００℃で行った以外は第１実施例と同様にして作成し
た。これにより、焼結式ニッケル板の表面にはＣ ａ
Ｎ ｉ ｓという組成の水素吸蔵合金が形成される。[Fifth Example] As a metal compound, calcium chloride (CaCl, 6
H. O)2O0g and nickel chloride (Ni(1!,
・6HgO) 1000g and heating temperature 1
It was prepared in the same manner as in the first example except that the temperature was 300°C. As a result, the surface of the sintered nickel plate has C a
A hydrogen storage alloy having a composition of N i s is formed.
〔第６実施例〕
金属化合物として、ランタン硝酸化合物（Ｌａ（Ｎｏｉ
ｚ ・６Ｈｚ Ｏ）１００ｇと、ニッケル硝酸化合物
［Ｎ ｉ （Ｎ ０３ ） ｚ ・６Ｈ２Ｏ）１４
００ｇと用いた以外は第１実施例と同様にして作成した
。これにより、焼結式ニッケル板の表面にはＬａＮｉ、
という組成の水素吸蔵合金が形成される。[Sixth Example] As a metal compound, a lanthanum nitrate compound (La (Noi
z ・6Hz O) 100 g and nickel nitrate compound [N i (N 03 ) z ・6H2O) 14
It was prepared in the same manner as in the first example except that 00g was used. As a result, the surface of the sintered nickel plate has LaNi,
A hydrogen storage alloy with the following composition is formed.
〔第７実施例〕
金属化合物として、マグネシウム過塩素酸化合物（Ｍｇ
（Ｃ１０ａ ）ｚ ）２Ｏ０ｇと、ニッケル塩化′Ｊ
ｊ！ｙＪ（Ｎｉｃｌ、 ・６Ｈ２Ｏ）４００ｇとを用
い、且つ加熱温度を１３００℃で行った以外は第１実施
例と同様にして作成した。これにより、焼結式ニッケル
板の表面にはＭｇｚＮｉという組成の水素吸蔵合金が形
成される。[Seventh Example] Magnesium perchlorate compound (Mg
(C10a)z)2O0g and nickel chloride'J
j! It was prepared in the same manner as in Example 1, except that 400 g of yJ (NiCl, .6H2O) was used and the heating temperature was 1300°C. As a result, a hydrogen storage alloy having a composition of MgzNi is formed on the surface of the sintered nickel plate.
尚、上記第１実施例乃至第７実施例においては水素吸蔵
合金の製造方法について説明したが、これら水素吸蔵合
金を電極として使用できることは実験により確認済であ
る。In addition, in the first to seventh embodiments described above, the method of manufacturing hydrogen storage alloys has been described, but it has been confirmed through experiments that these hydrogen storage alloys can be used as electrodes.
ここで、第１実施例、第２実施例、第４実施例、及び第
５実施例で作製した水素吸蔵多孔体をそれぞれ圧力容器
に充填し、水素ガスを吸蔵させたときの水素吸蔵量を以
下の表１に示す。尚、実験条件は４０℃の温度雰囲気で
、水素ガス圧は２Ｏ気圧で行った。Here, the hydrogen storage amount when the hydrogen storage porous bodies produced in the first example, the second example, the fourth example, and the fifth example are filled into a pressure vessel and stored hydrogen gas is calculated. It is shown in Table 1 below. The experimental conditions were a temperature atmosphere of 40° C. and a hydrogen gas pressure of 20 atm.
上記表１から明らかなように、第１実施例の水素吸蔵合
金（ＬａＮｉ、）では水素吸蔵量が１．３ｉ％であり、
第２実施例の水素吸蔵合金（Ｔｊ。As is clear from Table 1 above, the hydrogen storage alloy (LaNi) of the first example has a hydrogen storage capacity of 1.3i%,
Hydrogen storage alloy (Tj.
Ｎｉ）では水素吸蔵量が１．２ｈｔ％であり、第４実施
例の水素吸蔵合金（ＭｇｚＮｉ）では水素吸蔵量が３．
５ｗｔ％であり、第５実施例の水素吸蔵合金（ＣａＮｉ
、）では水素吸蔵量が１．１ｗｔ％であることが認めら
れる。この結果、熔解法により作製した合金と同程度の
水素吸蔵量を有していることが伺える。Ni) has a hydrogen storage capacity of 1.2ht%, and the hydrogen storage alloy (MgzNi) of the fourth example has a hydrogen storage capacity of 3.2ht%.
5 wt%, and the hydrogen storage alloy of the fifth example (CaNi
, ), it is recognized that the hydrogen storage amount is 1.1 wt%. As a result, it can be seen that the alloy has a hydrogen storage capacity comparable to that of the alloy produced by the melting method.
〔第８実施例〕
前記第３実施例の方法を用いて、焼結式ニッケル板の表
面に厚み２５〜３０μｍの１ａＮｉｚｃ０、膜を形成し
た水素吸蔵多孔体から成る負極と、理論界ＩＪ ５００
ｍＡｈの公知の焼結式ニッケル極から成る正極と、６規
定の水酸化カリウム水溶液から成る電解液とを用いてニ
ッケル水素電池を作製した。[Eighth Example] Using the method of the third example, a negative electrode consisting of a hydrogen storage porous body with a 25-30 μm thick 1aNizc0 film formed on the surface of a sintered nickel plate, and a theoretical IJ 500
A nickel-metal hydride battery was fabricated using a positive electrode consisting of a known sintered nickel electrode of mAh and an electrolyte consisting of a 6N potassium hydroxide aqueous solution.
以下、この電池を（Ａ）電池と称する。Hereinafter, this battery will be referred to as the (A) battery.
ＬａＮｉ、Ｃｏ、合金粉末とＮｉ粉末とをＮｉ網で覆っ
た後これを加圧形成して作成した負極を用いる他は上記
第８実施例と同様の方法で製造した。It was manufactured in the same manner as in Example 8, except that a negative electrode was prepared by covering LaNi, Co, alloy powder, and Ni powder with a Ni net and then forming the same under pressure.
以下、この電池を（Ｂ）電池と称する。Hereinafter, this battery will be referred to as the (B) battery.
ここで、上記第８実施例の（Ａ）電池と、比較例の（Ｂ
）電池とのサイクル特性試験を行ったので、その結果を
第１図に示す。Here, the (A) battery of the eighth example and the (B) battery of the comparative example are compared.
) A cycle characteristic test was conducted with the battery, and the results are shown in Figure 1.
尚、試験条件は１１５ Ｃの電流値で５時間充電した後
、１／２Ｃの電流値で放電電圧が１．ＯＶに低下するま
で放電を行なった。The test conditions were: after charging for 5 hours at a current value of 115C, the discharge voltage was 1.5C at a current value of 1/2C. Discharge was continued until the voltage dropped to OV.
第１図より、比較例の（Ｂ）電池では約２２Ｏ０サイク
ル経過後に急激に電池容量が低下するのに対して、本発
明の（Ａ）電池では３０００サイクル経過後であっても
電池容量の急激な低下は認められない。したがって、本
発明の（Ａ）電池は、比較例の（Ｂ）電池に比べ、サイ
クル寿命が飛躍的に向上していることが伺える。From FIG. 1, it can be seen that in the battery (B) of the comparative example, the battery capacity rapidly decreases after approximately 2200 cycles, whereas in the battery (A) of the present invention, the battery capacity rapidly decreases even after 3000 cycles. No significant decrease was observed. Therefore, it can be seen that the cycle life of the battery (A) of the present invention is dramatically improved compared to the battery (B) of the comparative example.
これは以下に示す理由によるものと考えられる。This is considered to be due to the following reasons.
即ち、比較例の（Ｂ）電池の負極では合金は粉末状態で
あるため、充放電が繰り返されるにしたがって合金が微
粉化し、これにより、合金が負極から剥離、脱落するの
に対し、本発明の（Ａ）電池では、焼結式ニッケル板の
表面で合金を作製しているため、合金と焼結式ニッケル
板の密着性が良好となり、合金が負極から剥離、脱落す
るのを防止しうるからである。特に、第８実施例の如く
合金の一部に多孔体の金属（本実施例ではニッケル）と
同一の金属が含まれていれば、合金と多孔体との密着性
をより向上させることができる。更に、（Ａ）電池の水
素吸蔵合金はアモルファス化しているため、−層微粉化
し難くなる。That is, in the negative electrode of the battery (B) of the comparative example, the alloy is in a powder state, so as charging and discharging are repeated, the alloy becomes fine powder, and as a result, the alloy peels off and falls off from the negative electrode, whereas in the present invention, the alloy is in a powder state. (A) In batteries, since the alloy is made on the surface of the sintered nickel plate, the adhesion between the alloy and the sintered nickel plate is good, which prevents the alloy from peeling off or falling off the negative electrode. It is. In particular, if part of the alloy contains the same metal as the metal of the porous body (nickel in this example) as in the eighth embodiment, the adhesion between the alloy and the porous body can be further improved. . Furthermore, since the hydrogen storage alloy of the battery (A) is amorphous, it becomes difficult to pulverize the -layer.
皇皿圓羞来
本発明の水素吸蔵合金電極の製造方法は以上のように、
多孔体の表面にて水素吸蔵合金を形成しているので、多
孔体と水素吸蔵合金との密着性が向上する。従って、水
素ガスの吸蔵、放出を繰り返し行っても水素吸蔵合金は
破砕されず、水素吸蔵合金が微粉化するのを防ぐことが
できるので、負極から水素吸蔵合金が剥離、脱落するの
を防止できる。また、上記製造方法で作製された水素吸
蔵合金はアモルファス化しているということによっても
、水素吸蔵合金が微粉化するのを防ぐことができ、負極
から合金が剥離、脱落するのを防止しうる。これらのこ
とから、充放電を繰り返し行っても電池容量は低下しな
いので、金属−水素アルカリ蓄電池の品質を飛躍的に向
上させることができる。The method for manufacturing the hydrogen storage alloy electrode of the present invention is as described above.
Since the hydrogen storage alloy is formed on the surface of the porous body, the adhesion between the porous body and the hydrogen storage alloy is improved. Therefore, even if hydrogen gas is stored and released repeatedly, the hydrogen storage alloy will not be crushed, and the hydrogen storage alloy will be prevented from being pulverized, which will prevent the hydrogen storage alloy from peeling off or falling off from the negative electrode. . Furthermore, since the hydrogen storage alloy produced by the above manufacturing method is amorphous, it is possible to prevent the hydrogen storage alloy from becoming pulverized, and it is possible to prevent the alloy from exfoliating or falling off from the negative electrode. For these reasons, the battery capacity does not decrease even after repeated charging and discharging, so the quality of the metal-hydrogen alkaline storage battery can be dramatically improved.
更に、上記の如く多孔体と水素吸蔵合金との密着性は良
いため、多孔体の表面に厚い水素吸蔵層を形成しうるの
で、負極の水素Ｗ＆藏量を多くすることができる。これ
により、金属−水素アルカリ蓄電池の性能を著しく向上
させることが可能となる。Furthermore, since the adhesion between the porous body and the hydrogen storage alloy is good as described above, a thick hydrogen storage layer can be formed on the surface of the porous body, so that the amount of hydrogen W and hydrogen in the negative electrode can be increased. This makes it possible to significantly improve the performance of metal-hydrogen alkaline storage batteries.
加えて、水素吸蔵合金を別途作製する工程が不要となる
ので、製造工程を簡素化することができ、低コストで金
属−水素アルカリ蓄電池を作製しうる等の効果を奏する
。In addition, since a separate process for producing a hydrogen storage alloy is not necessary, the production process can be simplified, and a metal-hydrogen alkaline storage battery can be produced at low cost.
第１図は本発明の（Ａ）電池と比較例の（Ｂ）電池との
サイクル特性を示すグラフである。
特許出願人 ： 三洋電機 株式会社
代理人 ： 弁理士 中隔 司朗
手 続 補 正 書（自発）FIG. 1 is a graph showing the cycle characteristics of the battery (A) of the present invention and the battery (B) of the comparative example. Patent applicant: Sanyo Electric Co., Ltd. Agent: Patent attorney Shiro Nakagaki Procedural amendment (voluntary)
Claims (13)
せる第１ステップと、 上記アルコール溶液に多孔体を浸積した後、この多孔体
を乾燥させる第２ステップと、 前記金属化合物を還元させて上記多孔体上に水素吸蔵合
金を形成して正極を作成する第３ステップとを有するこ
とを特徴とする水素吸蔵合金電極の製造方法。(1) A first step of dissolving two or more metal compounds in an alcohol solution; A second step of immersing the porous body in the alcohol solution and then drying the porous body; and reducing the metal compound. A method for manufacturing a hydrogen storage alloy electrode, comprising a third step of forming a hydrogen storage alloy on the porous body to create a positive electrode.
ン塩化物（ＬａＣｌ＿３・８Ｈ＿２Ｏ）と、ニッケル塩
化物（ＮｉＣｌ＿２・６Ｈ＿２Ｏ）とから成ることを特
徴とする特許請求の範囲第１項記載の水素吸蔵合金電極
の製造方法。(2) The hydrogen storage alloy according to claim 1, wherein the metal compound in the first step is composed of lanthanum chloride (LaCl_3.8H_2O) and nickel chloride (NiCl_2.6H_2O). Method of manufacturing electrodes.
塩化物（ＴｉＣｌ＿２）と、ニッケル塩化物（ＮｉＣｌ
＿２・６Ｈ＿２Ｏ）とから成ることを特徴とする特許請
求の範囲第１項記載の水素吸蔵合金電極の製造方法。(3) The metal compounds in the first step include titanium chloride (TiCl_2) and nickel chloride (NiCl_2).
_2.6H_2O). The method for manufacturing a hydrogen storage alloy electrode according to claim 1.
ン塩化物（ＬａＣｌ＿３・８Ｈ＿２Ｏ）と、ニッケル塩
化物（ＮｉＣｌ＿２・６Ｈ＿２Ｏ）と、コバルト塩化物
（ＣｏＣｌ＿２）とから成ることを特徴とする特許請求
の範囲第１項記載の水素吸蔵合金電極の製造方法。(4) Claims characterized in that the metal compound in the first step consists of lanthanum chloride (LaCl_3.8H_2O), nickel chloride (NiCl_2.6H_2O), and cobalt chloride (CoCl_2). 2. A method for producing a hydrogen storage alloy electrode according to item 1.
シウム塩化物（ＭｇＣｌ＿２・６Ｈ＿２Ｏ）と、ニッケ
ル塩化物（ＮｉＣｌ＿２・６Ｈ＿２Ｏ）とから成ること
を特徴とする特許請求の範囲第１項記載の水素吸蔵合金
電極の製造方法。(5) The hydrogen storage alloy according to claim 1, wherein the metal compound in the first step is composed of magnesium chloride (MgCl_2.6H_2O) and nickel chloride (NiCl_2.6H_2O). Method of manufacturing electrodes.
ウム塩化物（ＣａＣｌ＿２・６Ｈ＿２Ｏ）と、ニッケル
塩化物（ＮｉＣｌ＿２・６Ｈ＿２Ｏ）とから成ることを
特徴とする特許請求の範囲第１項記載の水素吸蔵合金電
極の製造方法。(6) The hydrogen storage alloy according to claim 1, wherein the metal compound in the first step is composed of calcium chloride (CaCl_2.6H_2O) and nickel chloride (NiCl_2.6H_2O). Method of manufacturing electrodes.
ン硝酸化合物〔Ｌａ（Ｎｏ＿３）＿３・６Ｈ＿２Ｏ〕と
、ニッケル硝酸化合物〔Ｎｉ（Ｎｏ＿３）＿２・６Ｈ＿
２Ｏ〕とから成ることを特徴とする特許請求の範囲第１
項記載の水素吸蔵合金電極の製造方法。(7) The metal compounds in the first step are a lanthanum nitrate compound [La(No_3)_3.6H_2O] and a nickel nitrate compound [Ni(No_3)_2.6H_
2O]
A method for producing a hydrogen storage alloy electrode as described in Section 1.
シウム過塩素酸化合物〔Ｍｇ（ＣｌＯ＿４）＿２〕と、
ニッケル塩化物（ＮｉＣｌ＿２・６Ｈ＿２Ｏ）とから成
ることを特徴とする特許請求の範囲第１項記載の水素吸
蔵合金電極の製造方法。(8) The metal compound in the first step is a magnesium perchlorate compound [Mg(ClO_4)_2],
The method for manufacturing a hydrogen storage alloy electrode according to claim 1, characterized in that the electrode is made of nickel chloride (NiCl_2.6H_2O).
リチウム蒸気中で行なうことを特徴とする特許請求の範
囲第１項記載の水素吸蔵合金電極の製造方法。(9) The method for manufacturing a hydrogen storage alloy electrode according to claim 1, wherein in the second step, the reduction of the metal compound is carried out in lithium vapor.
際に、１０００℃〜１３００℃の温度範囲で行なうこと
を特徴とする特許請求の範囲第９項記載の水素吸蔵合金
電極の製造方法。(10) The method for producing a hydrogen storage alloy electrode according to claim 9, wherein the reduction of the metal compound in the lithium vapor is carried out at a temperature range of 1000°C to 1300°C.
ッケルから成ることを特徴とする特許請求の範囲第１項
記載の水素吸蔵合金電極の製造方法。(11) The method for manufacturing a hydrogen storage alloy electrode according to claim 1, wherein the porous body in the second step is made of sintered nickel.
ステップにて作成される水素吸蔵合金成分の金属の成分
のうち少なくとも一種の成分と同一成分の金属から成る
ことを特徴とする特許請求の範囲第１項記載の水素吸蔵
合金電極の製造方法。(12) The porous body in the second step is
The method for manufacturing a hydrogen storage alloy electrode according to claim 1, characterized in that the electrode is made of a metal having the same composition as at least one of the metal components of the hydrogen storage alloy component prepared in the step.
複数回繰り返すことを特徴とする特許請求の範囲第１項
記載の水素吸蔵合金電極の製造方法。(13) The method for manufacturing a hydrogen storage alloy electrode according to claim 1, wherein in the second step, the dipping and drying steps are repeated multiple times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62294332A JPH01134861A (en) | 1987-11-20 | 1987-11-20 | Manufacture of hydrogen absorption alloy electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62294332A JPH01134861A (en) | 1987-11-20 | 1987-11-20 | Manufacture of hydrogen absorption alloy electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01134861A true JPH01134861A (en) | 1989-05-26 |
Family
ID=17806331
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62294332A Pending JPH01134861A (en) | 1987-11-20 | 1987-11-20 | Manufacture of hydrogen absorption alloy electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01134861A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044175C (en) * | 1994-10-20 | 1999-07-14 | 浙江大学 | Magnesium base hydrogen-storing alloy electrode |
-
1987
- 1987-11-20 JP JP62294332A patent/JPH01134861A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044175C (en) * | 1994-10-20 | 1999-07-14 | 浙江大学 | Magnesium base hydrogen-storing alloy electrode |
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