JPS6324552A - Nickel oxide-hydrogen secondary cell - Google Patents
Nickel oxide-hydrogen secondary cellInfo
- Publication number
- JPS6324552A JPS6324552A JP61166648A JP16664886A JPS6324552A JP S6324552 A JPS6324552 A JP S6324552A JP 61166648 A JP61166648 A JP 61166648A JP 16664886 A JP16664886 A JP 16664886A JP S6324552 A JPS6324552 A JP S6324552A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- electrode
- storage alloy
- alloy
- nickel oxide
- 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
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 68
- 239000001257 hydrogen Substances 0.000 title claims abstract description 67
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title abstract description 14
- 229910052759 nickel Inorganic materials 0.000 title abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 45
- 239000000956 alloy Substances 0.000 claims abstract description 45
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 34
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 12
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 17
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 17
- 239000002253 acid Chemical group 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 125000002560 nitrile group Chemical group 0.000 claims 1
- 230000004913 activation Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 239000005977 Ethylene Substances 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 229940079826 hydrogen sulfite Drugs 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical group O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の目的〕
（産業上の利用分野）
本発明は、ニッケル酸化物・水素二次電池の電極に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to an electrode for a nickel oxide/hydrogen secondary battery.
（従来の技術）
水素を可逆的に吸蔵・放出しうるいわゆる水素吸蔵合金
を用いて作成した二次電池の負極は、従来のニッケル・
カドミウム二次電池や鉛二次電池に使用されているカド
ミウム負極や鉛負極１ご比べて、単位重量当りのエネル
ギー密度が大きく、また、有害金属も含まない、という
長所がある。(Prior technology) The negative electrode of a secondary battery made using a so-called hydrogen storage alloy that can reversibly absorb and release hydrogen is a conventional nickel-based negative electrode.
Compared to the cadmium negative electrode and lead negative electrode 1 used in cadmium secondary batteries and lead secondary batteries, it has the advantage of having a higher energy density per unit weight and not containing any harmful metals.
しかし、この水素吸蔵合金電極は充電状態では、わずか
ながら分子状の水素を放出する。すなわち下に示す電極
反応
の他に、平衡反応
Ｍ−ＨドーＭ ＋ −Ｈ，（２）
も同時に進行する。なお、上記の２つの式中でＭは水素
吸蔵合金を、Ｍ−Ｈは水素吸蔵合金が水素を吸蔵した状
態を示す。通常（２）式で発生する分子状水素は気体と
ならず電極と接した電解液へ、ごくわずか溶屏するのみ
であるが、この溶解水素は正極に達して、これを還元（
放電）する。つまり従来のニッケル・カドミウム二次電
池と比較して、ニッケル酸化物・水素二次電池の自己放
電特性が劣ることは否めない。However, this hydrogen storage alloy electrode releases a small amount of molecular hydrogen in a charged state. That is, in addition to the electrode reaction shown below, the equilibrium reaction M-H (M + -H, (2)) also proceeds simultaneously. In the above two formulas, M represents a hydrogen storage alloy, and MH represents a state in which the hydrogen storage alloy stores hydrogen. Normally, the molecular hydrogen generated in equation (2) does not become a gas and only a small amount dissolves into the electrolyte in contact with the electrode, but this dissolved hydrogen reaches the positive electrode and reduces it (
discharge). In other words, it cannot be denied that nickel oxide/hydrogen secondary batteries have inferior self-discharge characteristics compared to conventional nickel/cadmium secondary batteries.
（本発明が解決しようとする問題点）
本発明は上記したようなニッケル酸化物・水素二次電池
の自己放電特性を改善し、充電電気量を長期に恒って安
定に保ち得るようなニッケル酸化物・水素二次電池を提
供することを目的とする。(Problems to be Solved by the Present Invention) The present invention improves the self-discharge characteristics of the nickel oxide/hydrogen secondary battery as described above, and uses nickel oxide that can maintain a stable charge amount over a long period of time. The purpose is to provide oxide/hydrogen secondary batteries.
（問題点を解決するための手段と作用）本発明のニッケ
ル酸化物・水素二次電池は、水素吸蔵合金粉末の表面、
ないしは水素吸蔵合金を主成分とする負極の表面が、水
媒体中で、該水素吸蔵合金粉末ないしは水素吸蔵合金を
主成分とする負極の存在下でビニルモノマーの重合を行
なうことによりオ得られたビニルポリマーの被覆を有１
することを特徴とする。(Means and effects for solving the problems) The nickel oxide/hydrogen secondary battery of the present invention has a surface of hydrogen storage alloy powder,
Alternatively, the surface of a negative electrode containing a hydrogen storage alloy as a main component is obtained by polymerizing a vinyl monomer in an aqueous medium in the presence of the hydrogen storage alloy powder or a negative electrode containing a hydrogen storage alloy as a main component. Has vinyl polymer coating1
It is characterized by
すなわち本発明は、ニッケル酸化物電極を正極とし、水
素吸蔵合金電極を負極とするニッケル酸化物・水素二次
電池において、
前記水素吸蔵合金電極また、は前記水素吸蔵合金電極を
形成する水素吸蔵合金粉末の表面でビニルモノマーを重
合して形成したとニルポリマーよりなる被覆を有した水
素吸蔵合金電極または水素吸蔵合金粉末よりなる電極を
、負極に用いたことを特徴とするニッケル酸化物・水素
二次電池である。That is, the present invention provides a nickel oxide/hydrogen secondary battery having a nickel oxide electrode as a positive electrode and a hydrogen storage alloy electrode as a negative electrode, which includes: the hydrogen storage alloy electrode or the hydrogen storage alloy forming the hydrogen storage alloy electrode; A nickel oxide/hydrogen secondary, characterized in that a hydrogen storage alloy electrode having a coating made of a vinyl polymer formed by polymerizing a vinyl monomer on the surface of the powder or an electrode made of a hydrogen storage alloy powder is used as a negative electrode. It's a battery.
本発明に使用されるビニルポリマーは、モノマーユニッ
トが次式で示されるポリマーである。The vinyl polymer used in the present invention is a polymer whose monomer units are represented by the following formula.
すなわち、（ＣＨ，＝＝ ＣＲ’Ｒ” ］（式中、Ｒ１
、Ｒ２はそれぞれ同じであっても異なっていてもヨく水
素原子、ハロゲン元素、二） ＩＪル基、炭素数１〜６
のアルキル基を含むアルコキシ基又は酸基の群から選ば
れる。ただし、Ｒ１とＲ２が共に水素原子の場合及びＲ
１とＲ２が同じであって立体障害を起こす場合は除く。That is, (CH,==CR'R''] (where R1
, R2 may be the same or different, hydrogen atom, halogen element, 2) IJ group, carbon number 1-6
selected from the group of alkoxy groups including alkyl groups or acid groups. However, if R1 and R2 are both hydrogen atoms and R
Except when 1 and R2 are the same and cause steric hindrance.
）で示されるモノマーユニットである。) is a monomer unit shown by.
しかしながら、上記モノマーユニットにおいて、几１と
Ｒ２が共に水素原子の場合及びＲ１と几２が共にアルコ
キシ基又は酸基であり側基が立体干渉を起こすような組
合わせの場合は除く。このような場合は、亜鉛又は亜鉛
合金に付着する活性基が生成されないので負極活物質の
表面を被覆することが困難となる。しかしながら、Ｒ１
とＲ２が共にアルコキシ基又は酸基であっても側基が立
体干渉を起こさなければ被覆が可能となる。However, in the above monomer unit, cases in which both R1 and R2 are hydrogen atoms, and combinations in which R1 and R2 are both alkoxy groups or acid groups and the side groups cause steric interference are excluded. In such a case, active groups adhering to zinc or zinc alloy are not generated, making it difficult to coat the surface of the negative electrode active material. However, R1
Even if R2 and R2 are both alkoxy groups or acid groups, coating is possible if the side groups do not cause steric interference.
上式のＲ１，Ｒ２と置換可能なハロゲン元素としては、
例えば、塩素、フッ素、臭素、ヨウ素である。As the halogen element that can be substituted for R1 and R2 in the above formula,
For example, chlorine, fluorine, bromine, and iodine.
同様に、アルコキシ基としては、例えば、メトキシ基、
エトキシ基、プロポキシ基、ブトキシ基、ペンチルオキ
シ基、ヘキシルオキシ基である。Similarly, examples of alkoxy groups include methoxy groups,
These are ethoxy group, propoxy group, butoxy group, pentyloxy group, and hexyloxy group.
酸基さしては、例えば、アセトキシ基、プロピオン酸基
などがある。Examples of acid groups include acetoxy groups and propionic acid groups.
上記のような各種の基、元素を几１．Ｒ２に適用した具
体的なモノマーユニットとしては、例えば、ハロゲン元
素を含む場合では、［ＣＨ，＝ＣＨ−Ｃｔ〕ニリデン、
ＣＣＨ，＝ＣＨ−Ｂ ｒ ］で示される臭化ビニル
などがあげられ、二Ｉ−’Ｊル基を含む場合では、（Ｃ
Ｈ，＝＝ＣＨ−ＣＮ ：ｌで示されるアクリロニトリル
（またはシアン化ビニル）などがあげられる。1. Various groups and elements as mentioned above. Specific monomer units applied to R2 include, for example, when containing a halogen element, [CH,=CH-Ct]nylidene,
Examples include vinyl bromide represented by CCH,=CH-Br], and in cases containing a diI-'J group, (C
Examples include acrylonitrile (or vinyl cyanide) represented by H,==CH-CN:l.
そして、アルコキシ基を含む場合としては、例えば、メ
チルビニルエーテル（ＣＨ，＝ＣＨ−０−ＣＨ，）、エ
チルビニルエーテル（ＣＨ，＝ＣＨ−０−Ｃ！Ｈ，）、
ｎ−ブチルビニルエーテル（ＣＨ２＝ＣＨ−０−（ＣＨ
２）。Examples of cases containing an alkoxy group include methyl vinyl ether (CH,=CH-0-CH,), ethyl vinyl ether (CH,=CH-0-C!H,),
n-Butyl vinyl ether (CH2=CH-0-(CH
2).
ＣＨ３）、インブチルビニルエーテル（ＣＨ２＝ＣＨ−
０−Ｃ（ＣＨ，）３ ）などがあげられる。CH3), inbutyl vinyl ether (CH2=CH-
0-C(CH,)3), etc.
酸基を含む場合としては、例えば、
酸ビニル、［ＣＨ，＝ＣＨ−０−凸−Ｃ，Ｈ，］で示さ
れる安息香酸ビニルなどがあげられる。Examples of the case containing an acid group include vinyl acid and vinyl benzoate represented by [CH,=CH-0-convex-C,H,].
本発明で使用されるビニルポリマーは、上記したモノマ
ー１種からなる場合のほか、上記したモノマー２種以上
からなる共重合体も含む。このような共重合体としては
、例えば、塩化ビニル−酢酸ビニル共重合体、塩化ビニ
ル−塩化ビニリデン共重合体、アクリロニトリル−塩化
ビニル共重合体などがあげられる。The vinyl polymer used in the present invention includes not only one type of monomer described above but also a copolymer consisting of two or more types of monomers described above. Examples of such copolymers include vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinylidene chloride copolymers, and acrylonitrile-vinyl chloride copolymers.
上記したビニルポリマーフィルムは、苛性アルカリ水溶
液中で溶解せず安定でなければならないと同時に電池の
使用時における放電反応を阻害するものであってはなら
ない。The vinyl polymer film described above must be stable and not dissolve in an aqueous caustic solution, and at the same time must not inhibit the discharge reaction during use of the battery.
従って、水素吸蔵合金、または水素吸蔵合金を主成分と
する負極を該ビニルポリマーで被覆する際には、ビニル
ポリマーフィルムの厚さを０．０１〜７０μｍの範囲好
ましくは０．０２〜２０μｍの範囲にする。Therefore, when coating a hydrogen storage alloy or a negative electrode mainly composed of a hydrogen storage alloy with the vinyl polymer, the thickness of the vinyl polymer film should be in the range of 0.01 to 70 μm, preferably in the range of 0.02 to 20 μm. Make it.
フィルムの厚みが０．１μｍ未満の場合には、前記（２
）式で発生する水素がフィルムを通して電解液に溶解す
る程度が大きくなり、また、７０μｍを超えると電池使
用時にも放電反応が阻害されて好ましくない。When the thickness of the film is less than 0.1 μm, the above (2)
) The extent to which the hydrogen generated in the formula is dissolved into the electrolytic solution through the film becomes large, and if the thickness exceeds 70 μm, the discharge reaction is inhibited even when the battery is used, which is not preferable.
ビニルポリマーを上記した厚さで水素吸蔵合金ないしは
、水素吸蔵合金を主成分とする負極に被覆する方法とし
て、本発明の負極活物質の存在下で水媒体中でビニルモ
ノマーの重合を用いる。これより水素吸蔵合金、ないし
は水素吸蔵合金を主成分とする負極の表面に均一に被覆
を施すことができる。As a method for coating a hydrogen storage alloy or a negative electrode mainly composed of a hydrogen storage alloy with a vinyl polymer to the above-mentioned thickness, polymerization of a vinyl monomer in an aqueous medium in the presence of the negative electrode active material of the present invention is used. This makes it possible to uniformly coat the surface of the hydrogen storage alloy or the negative electrode whose main component is the hydrogen storage alloy.
その具体的な方法としては、例えば以下に述べるような
方法が採用される。まず攪拌装置を備えた丸底フラスコ
に電極もしくは電極材料、水、上記したビニルポリマー
のモノマーを加え、３５〜８０℃、好ましくは４０〜７
０℃、さらに好ましくは４５〜６０℃に保ったのち、必
要な場合にはごく微量の反応開始剤（主として亜硫酸イ
オンを生成する物質）を添加し２０分〜５時間程度攪拌
しながらビニルモノマーを重合させる。As a specific method, for example, the following method is adopted. First, add the electrode or electrode material, water, and the above-mentioned vinyl polymer monomer to a round-bottomed flask equipped with a stirring device, and heat the mixture to 35-80°C, preferably 40-70°C.
After maintaining the temperature at 0°C, more preferably at 45 to 60°C, add a very small amount of a reaction initiator (mainly a substance that generates sulfite ions) if necessary, and stir the vinyl monomer for about 20 minutes to 5 hours. Polymerize.
反応終了後、フラスコ底部に沈降した試料を分別し、水
洗し、さらに必要な場合にはエタノール、アセトン等で
洗浄した後、空気中で、好ましくは真空中ないしは窒素
、アルゴン等の不活性雰囲気中で乾燥（降ましくは５〜
１２０℃で）する。こうして得られた被覆の施された電
極もしくは電極材料を走査電子顕微鏡などで観察すると
、その表面がビニルポリマーで均一に被覆されカプセル
化されていることが認められた。After the reaction is complete, the sample settled at the bottom of the flask is separated, washed with water, and if necessary, washed with ethanol, acetone, etc., and then placed in air, preferably in vacuum or in an inert atmosphere such as nitrogen or argon. Dry (preferably 5~
) at 120°C. When the coated electrode or electrode material thus obtained was observed using a scanning electron microscope, it was found that the surface was uniformly coated and encapsulated with vinyl polymer.
なお、ニッケル酸化物・水素二次電池の自己放電は、基
本的には、前述したように、水素吸蔵合金を主成分とす
る負極から脱落した水素が、ニッケル酸化物電極に達し
、これを還元することによって進行するものである。し
たがって本発明で使用するビニルポリマーは、充放電を
休止している期間中、負極表面からの水素の脱離反応を
抑制する働きをしているものと考えられる。As mentioned above, self-discharge in nickel oxide/hydrogen secondary batteries basically occurs when hydrogen that falls off from the negative electrode, which is mainly composed of a hydrogen storage alloy, reaches the nickel oxide electrode and is reduced. It progresses by doing. Therefore, it is considered that the vinyl polymer used in the present invention functions to suppress the hydrogen desorption reaction from the negative electrode surface during the period when charging and discharging are suspended.
これに対し、本発明者らが既に出願したビニルポリマー
をアルカリ電池中の活物質金属の腐食抑制に用いる発明
（特願昭６０−８２５８７号明細書）で記載したのは、
該ビニルポリマーを添加することによってアルカリ溶液
中で卑金属が酸化されることを防止することを目的とし
たものであって、本発明のように、水素が反応媒体とし
て関与する反応とは全く別異のものである。On the other hand, what was described in the invention (Japanese Patent Application No. 82587/1987) in which a vinyl polymer is used to inhibit corrosion of active material metal in an alkaline battery, which the present inventors have already applied for, is as follows.
The purpose of this reaction is to prevent base metals from being oxidized in an alkaline solution by adding the vinyl polymer, and this reaction is completely different from a reaction in which hydrogen is involved as a reaction medium as in the present invention. belongs to.
（実施例）
まず、実施例および比較例で用いる電極系を以下の手順
で作成した。(Example) First, electrode systems used in Examples and Comparative Examples were created according to the following procedure.
水素吸蔵合金Ｌ ａＮ ’ ４．７Ａｔｏ３を耐圧タン
ク中に入れ６０℃で１時間減圧脱気したのち、直ちに１
０℃に冷却して３０ ｋｇ／ｍＡの水素を圧入した。２
時間水素で加圧したのち、これを排気して再び９０℃ま
で加熱しながら３時間減圧脱気を行なった。以上の活性
化処理を施こし、微粉化した合金のうち２００メツシュ
Ｃ目開き寸法７４μｍ）のふるいを通過した粉末に４．
０重量％のＰＴＦＢ粉末を添加し、混練したのち、ロー
ラーを用いて厚さ０．５ ｍのシート状にした。これを
１洲に切断し、線径０．１５ｍｍ、４０メツシユのニッ
ケルネットに重ねて、ｓｏｏ＃／ｄの圧力で圧着し、水
素吸蔵合金電極を作成した。Hydrogen storage alloy L aN ' 4.7 Ato3 was placed in a pressure tank and degassed under reduced pressure at 60°C for 1 hour, and then immediately
It was cooled to 0°C and hydrogen was injected at 30 kg/mA. 2
After pressurizing with hydrogen for an hour, it was evacuated and degassed under reduced pressure for 3 hours while heating to 90°C. After performing the above activation treatment, the powder that passed through a 200 mesh C sieve (opening size: 74 μm) out of the finely powdered alloy was subjected to 4.
After adding 0% by weight of PTFB powder and kneading, it was formed into a sheet with a thickness of 0.5 m using a roller. This was cut into one piece, stacked on a 40-mesh nickel net with a wire diameter of 0.15 mm, and crimped at a pressure of soo#/d to produce a hydrogen storage alloy electrode.
この電極をポリプロピレン製布織布（厚さ０．２■）を
介してニッケル酸化物電極ではさみ、トルク０．５ ＃
αのネジ２本で固定して電極系を構成した。以下これを
基本電極系と呼ぶ。This electrode was sandwiched between nickel oxide electrodes through a polypropylene cloth (thickness: 0.2 mm), and a torque of 0.5 #
An electrode system was constructed by fixing it with two α screws. Hereinafter, this will be referred to as the basic electrode system.
実施例１〜４
攪拌器を備えた、容量１ｔの丸底フラスコに、前記の２
００メツシユの篩を通過した水素吸蔵合金粉末２０ｇ、
水５００ｍｔ１第１表に示したビニルモノマーを加え、
３５〜６０℃に保ったのち、必要に応じて反応開始剤（
主として亜硫酸水素イオンを生成する物質、例えば亜硫
酸）を添加し、約３時間攪拌しながらビニルモノマーを
重合させ、水素吸蔵合金粉末に厚さ約１μＩｎのビニル
ポリマーを被覆した。この粉末を水洗乾燥後、走査形電
子顕微鏡により観察し、該水素吸蔵合金粉末の表面がビ
ニルポリマーにより均一にカプセル化されていることを
確認した。Examples 1 to 4 Into a 1 t capacity round bottom flask equipped with a stirrer, the above 2
20g of hydrogen storage alloy powder passed through a 00 mesh sieve,
Add 500 mt of water and the vinyl monomer shown in Table 1,
After maintaining the temperature at 35 to 60°C, add a reaction initiator (
A substance that mainly generates bisulfite ions, such as sulfite, was added, and the vinyl monomer was polymerized while stirring for about 3 hours, thereby coating the hydrogen storage alloy powder with a vinyl polymer having a thickness of about 1 μIn. After washing and drying this powder, it was observed using a scanning electron microscope, and it was confirmed that the surface of the hydrogen storage alloy powder was uniformly encapsulated with the vinyl polymer.
上記の、表面がビニルポリマーで被覆された水素吸蔵合
金に４．０重量％のＰＴＦＥ粉末を添加し、混練し以下
基本電極系の場合と全く同様にして、水素吸蔵合金電極
を作成し、これを用いて本発明に係る電極系を構成した
。Add 4.0% by weight of PTFE powder to the above hydrogen storage alloy whose surface is coated with vinyl polymer, knead it, and then proceed in exactly the same manner as in the case of the basic electrode system to create a hydrogen storage alloy electrode. An electrode system according to the present invention was constructed using the following.
実施例５〜８
前述した基本電極系に用いたものと全く同様にして水素
吸着合金電極を作成し、攪拌器を備えた容ｉ１ｔの丸底
フラスコ内に、水５００ｍｔ、第１表に示したビニルモ
ノマーと共−に加え、３５〜６０℃に保ったのち、必要
に応じて反応開始剤（主として亜硫酸水素イオンを生成
する物質、例えば亜硫酸）を添加し、約３時間攪拌しな
がらビニルモノマーを重合させ、該水素吸着合金電極の
表面に厚さ約１μｍのビニルポリマーを被覆した。Examples 5 to 8 Hydrogen adsorption alloy electrodes were prepared in exactly the same manner as those used for the basic electrode system described above, and 500 m of water and the amount shown in Table 1 were placed in a round bottom flask with a capacity of 1 t equipped with a stirrer. After adding the vinyl monomer together with the vinyl monomer and keeping it at 35 to 60°C, add a reaction initiator (mainly a substance that generates hydrogen sulfite ions, e.g. sulfite) as necessary, and add the vinyl monomer while stirring for about 3 hours. The surface of the hydrogen adsorption alloy electrode was coated with a vinyl polymer having a thickness of about 1 μm.
上記水素吸蔵合金電極を用い、その他は基本電極系と全
く同様にして電極系を構成した。An electrode system was constructed in exactly the same manner as the basic electrode system except for using the above hydrogen storage alloy electrode.
以上の電極系に対し、充電： ６６ｍＡＸ３０分、放電
：３３ｍＡでＩＶまで、休止時間１０分の条件で充放電
を士数回繰り返したのち、充電状態で３０℃、９５％Ｒ
Ｈの雰囲気に保存した。２週間経過後に、この電池を２
０℃の雰囲気中で放電し、この時の容量と保存前の容量
との比較から次式により自己放電率を算出した。For the above electrode system, charge: 66 mA for 30 minutes, discharge: 33 mA to IV, and after repeating charging and discharging several times under the conditions of resting for 10 minutes, the battery was heated at 30°C and 95% R in the charged state.
It was stored in an atmosphere of H. After 2 weeks, replace this battery with 2
The battery was discharged in an atmosphere at 0° C., and the self-discharge rate was calculated by the following formula from a comparison between the capacity at this time and the capacity before storage.
得られたそれぞれの実施例の電極系の自己放電率を基本
電極系の自己放電率と比較して相対自己放電率を算出し
表中に併記した。The self-discharge rate of the obtained electrode system of each example was compared with the self-discharge rate of the basic electrode system to calculate the relative self-discharge rate, which is also listed in the table.
第 １ 表
〔発明の効果〕
以上の結果から明らかなように、本発明のニッケル酸化
物・水素二次電池は自己放電率に優れ、長期に恒る保存
が可能な二次電池であり、工業的価値が極めて大きいも
のであると考える。Table 1 [Effects of the Invention] As is clear from the above results, the nickel oxide/hydrogen secondary battery of the present invention has an excellent self-discharge rate, can be stored for a long time, and is suitable for industrial use. We believe that this is of extremely great value.
代理人 弁理士 則 近 憲 佑 同 竹 花 喜久男Agent: Patent Attorney Noriyuki Chika Same Bamboo Flower Kikuo
Claims (3)
極を負極とするニッケル酸化物・水素二次電池において
、 前記水素吸蔵合金電極または前記水素吸蔵合金電極を形
成する水素吸蔵合金粉末の表面でビニルモノマーを重合
して形成したビニルポリマーよりなる被覆を有した水素
吸蔵合金電極または水素吸蔵合金粉末よりなる電極を、
負極に用いたことを特徴とするニッケル酸化物・水素二
次電池。(1) In a nickel oxide/hydrogen secondary battery having a nickel oxide electrode as a positive electrode and a hydrogen storage alloy electrode as a negative electrode, on the surface of the hydrogen storage alloy electrode or the hydrogen storage alloy powder forming the hydrogen storage alloy electrode. A hydrogen storage alloy electrode having a coating made of a vinyl polymer formed by polymerizing a vinyl monomer or an electrode made of a hydrogen storage alloy powder,
A nickel oxide/hydrogen secondary battery characterized by its use as a negative electrode.
であることを特徴とする特許請求の範囲第１項記載のニ
ッケル酸化物、水素二次電池。(2) The thickness of the vinyl polymer is 0.01 to 70 μm
The nickel oxide, hydrogen secondary battery according to claim 1, characterized in that:
Ｈ＿２＝ＣＲ＾１Ｒ＾２〕 （式中、Ｒ＾１、Ｒ＾２はそれぞれ同じであっても異な
っていてもよく、水素原子、ハロゲン元素、ニトリル基
、炭素数１〜６のアルキル基を含むアルコキシ基または
酸基の群から選ばれる。ただし、Ｒ＾１、Ｒ＾２が共に
水素原子の場合及びＲ＾１とＲ＾２が同じであって、立
体障害を起こす場合は除く。）で示されることを特徴と
する特許請求の範囲第１項記載のニッケル酸化物・水素
二次電池。(3) The vinyl polymer monomer unit has the following formula [C
H_2=CR^1R^2] (In the formula, R^1 and R^2 may be the same or different, and represent a hydrogen atom, a halogen element, a nitrile group, or an alkyl group having 1 to 6 carbon atoms. selected from the group containing alkoxy groups or acid groups.However, cases where both R^1 and R^2 are hydrogen atoms, or cases where R^1 and R^2 are the same and cause steric hindrance are excluded.) The nickel oxide/hydrogen secondary battery according to claim 1, characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61166648A JPS6324552A (en) | 1986-07-17 | 1986-07-17 | Nickel oxide-hydrogen secondary cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61166648A JPS6324552A (en) | 1986-07-17 | 1986-07-17 | Nickel oxide-hydrogen secondary cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6324552A true JPS6324552A (en) | 1988-02-01 |
Family
ID=15835164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61166648A Pending JPS6324552A (en) | 1986-07-17 | 1986-07-17 | Nickel oxide-hydrogen secondary cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6324552A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1168470A1 (en) * | 2000-06-30 | 2002-01-02 | SANYO ELECTRIC Co., Ltd. | Hydrogen absorbing alloy electrode, method of fabricating the same and alkaline storage battery |
-
1986
- 1986-07-17 JP JP61166648A patent/JPS6324552A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1168470A1 (en) * | 2000-06-30 | 2002-01-02 | SANYO ELECTRIC Co., Ltd. | Hydrogen absorbing alloy electrode, method of fabricating the same and alkaline storage battery |
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