JPS6166366A - Hydrogen-occlusion electrode - Google Patents
Hydrogen-occlusion electrodeInfo
- Publication number
- JPS6166366A JPS6166366A JP59186878A JP18687884A JPS6166366A JP S6166366 A JPS6166366 A JP S6166366A JP 59186878 A JP59186878 A JP 59186878A JP 18687884 A JP18687884 A JP 18687884A JP S6166366 A JPS6166366 A JP S6166366A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- electrode
- occlusion
- battery
- alloy
- 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
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 42
- 239000001257 hydrogen Substances 0.000 claims abstract description 42
- 239000000956 alloy Substances 0.000 claims abstract description 31
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 4
- 239000000057 synthetic resin Substances 0.000 claims abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 37
- 239000003513 alkali Substances 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 abstract description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 9
- -1 polytetrafluoroethylene Polymers 0.000 abstract description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 abstract description 6
- 230000006866 deterioration Effects 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000010298 pulverizing process Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 2
- 229910002335 LaNi5 Inorganic materials 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 239000004033 plastic Substances 0.000 abstract 1
- 229920003023 plastic Polymers 0.000 abstract 1
- 238000007599 discharging Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- PEVRKKOYEFPFMN-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene;1,1,2,2-tetrafluoroethene Chemical group FC(F)=C(F)F.FC(F)=C(F)C(F)(F)F PEVRKKOYEFPFMN-UHFFFAOYSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- PYVHTIWHNXTVPF-UHFFFAOYSA-N F.F.F.F.C=C Chemical compound F.F.F.F.C=C PYVHTIWHNXTVPF-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel 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
- 229920001778 nylon Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229940032158 sodium silicate Drugs 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229940032147 starch Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/121—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/34—Gastight accumulators
- H01M10/345—Gastight metal hydride accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
- H01M50/1243—Primary casings; Jackets or wrappings characterised by the material having a layered structure characterised by the internal coating on the casing
-
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
本発明は負極活物質として水素を利用するアルカリ蓄電
池の負極、特に水素を可逆的に吸蔵及び放出することの
できるＬ ａ Ｎ ｉｓやＣａＮｉ、などの水素吸蔵合
金粉末を備えた水素吸蔵電極に関する。Detailed Description of the Invention (a) Industrial Field of Application The present invention is directed to negative electrodes of alkaline storage batteries that use hydrogen as negative electrode active materials, particularly L a Ni is or CaNi which can reversibly absorb and release hydrogen. The present invention relates to a hydrogen storage electrode comprising a hydrogen storage alloy powder such as .
（ロ）従来技術
従来からよく用いられる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あるが、近年これら電池より軽
量で且つ高容量となる可能性があるということで、特に
低圧に於いて負極活物質である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備えた電極を負極
に用い、水酸化ニッケル等の金属酸化物を正極活物質と
する電極を正極に用いた金属−水素アルカリ蓄電池が注
目されている。(b) Conventional technology Lead-acid batteries and nickel-cadmium batteries have traditionally been commonly used storage batteries, but in recent years, they have been found to be lighter than these batteries and have the potential to have higher capacities, so negative electrode activation has been developed, especially at low pressures. Metal-hydrogen, in which an electrode equipped with a hydrogen storage alloy that can reversibly absorb and release hydrogen, which is a substance, is used as the negative electrode, and an electrode with a metal oxide such as nickel hydroxide as the positive electrode active material is used as the positive electrode. Alkaline storage batteries are attracting attention.
この水素吸蔵合金である金属水素化物を備えた水素吸蔵
電極は、一般に特公昭５８−４６８２７号公報に於いて
提案されるように、水素吸蔵合金粉末を導電材粉末と共
に焼結して多孔体を作製し、これを水素吸蔵電極とする
方法、あるいはＩ＃開昭５３−３３３３２号公報に於い
て示されるように、水素吸蔵合金粉末を発泡メタル内に
充填し加圧成型した後、充填された金属の融点以下の温
度で真空焼結して水素吸蔵′ｒｔ極とする方法によって
作製されている。Hydrogen storage electrodes equipped with metal hydrides, which are hydrogen storage alloys, are generally produced by sintering hydrogen storage alloy powder together with conductive material powder to form a porous body, as proposed in Japanese Patent Publication No. 58-46827. Alternatively, as shown in I# Publication No. 53-33332, hydrogen-absorbing alloy powder is filled into a foamed metal, pressure-molded, and then filled. It is manufactured by vacuum sintering at a temperature below the melting point of the metal to form a hydrogen storage 'rt' electrode.
しかしながら、これら電極に用いられる水素吸蔵合金は
、従来から負極に活物質として用いられるカドミウム、
亜鉛、鉄などとは異なりアルカリ電解液中で充放電を行
なうと活物質である水素を吸蔵放出するものであり、こ
の水素の吸蔵及び放出によって合金格子が変形し水素吸
蔵合金は微粉化を起こすため、微粉化した合金が電極か
ら脱落して容量低下を招くと共に電極の機械的強度及び
導電性の低下が著しく長期にわたって極板容量を維持す
ることが困難であるという問題点があった。However, the hydrogen storage alloys used in these electrodes contain cadmium, which has traditionally been used as an active material in negative electrodes.
Unlike zinc, iron, etc., when charged and discharged in an alkaline electrolyte, it absorbs and releases the active material hydrogen, and the hydrogen storage and release deforms the alloy lattice, causing the hydrogen storage alloy to become pulverized. Therefore, there is a problem in that the finely powdered alloy falls off from the electrode, resulting in a decrease in capacity, and the mechanical strength and conductivity of the electrode are significantly decreased, making it difficult to maintain the electrode plate capacity over a long period of time.
（ハ）発明が解決しようとする問題点
本発明は充放電を繰り返し行なうことで生じる水素吸蔵
合金の微粉化による脱落を抑制するこ 、とで、極板容
量の劣化を抑えると共に電極の機械的強度及び導電性の
低下を抑え、長期の充放電サイクルにわたり高容量を維
持する水素吸蔵電極を得ようとするものである。(c) Problems to be Solved by the Invention The present invention suppresses the falling off of the hydrogen storage alloy due to pulverization caused by repeated charging and discharging, thereby suppressing the deterioration of the electrode plate capacity and improving the mechanical strength of the electrode. The aim is to obtain a hydrogen storage electrode that suppresses deterioration in strength and conductivity and maintains high capacity over long charge/discharge cycles.
に）問題点を解決するための手段
本発明はかかる問題点を解決するため罠、耐アルカリ性
の合成樹脂結着剤と粘性剤とで水素吸蔵合金粉末を保持
した電極を水素吸蔵電極とするものである。該電極に使
用される結着剤及び粘性剤は電池性能に悪影響を与えな
いものであればよく、例えば結着剤としてはポリテトラ
フルオロエチレン・（ＰＴＦＥ、）、テトラフルオロエ
チレン−ヘキサフルオロプロピレン共重合体（ＦＥＰ）
、４フツ化エチレン及び６７フ化プロピレン等のフッ素
樹脂、クロロプレン系、ニトリルゴム系及びスチレンゴ
ム系の樹脂、ポリスチレン、ナイロン系ポリアミドなど
が使用でき、また粘性剤としてはヒドロキシプロピルセ
ルロース（ＨＰＣ）、ポリエチレンオキサイド（ＰＥＯ
）、不飽和ポリエステル樹脂（エアロジル）、メチルセ
ルロース（ＭＣＬカルボキシメチルセルロース（ＣＭＣ
） 、ポリビニルアルコール（Ｐ ＶＡ ）、 ポリビ
ニルビクリトン、ポリアクリル酸、ポリアクリルアミド
、架橋でんぷん、アクリル酸ソーダ、アルギン酸ソーダ
、ケイ酸ソーダなどが使用できる。B) Means for Solving the Problems The present invention aims to solve these problems by providing an electrode in which a hydrogen-absorbing alloy powder is held with an alkali-resistant synthetic resin binder and a viscosity agent as a hydrogen-absorbing electrode. It is. The binder and viscous agent used in the electrode may be any material as long as it does not adversely affect battery performance. Examples of the binder include polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene, etc. Polymer (FEP)
, fluororesins such as ethylene tetrafluoride and propylene 67 fluoride, chloroprene-based, nitrile rubber-based and styrene rubber-based resins, polystyrene, nylon-based polyamide, etc., and as the viscosity agent, hydroxypropyl cellulose (HPC), Polyethylene oxide (PEO)
), unsaturated polyester resin (Aerosil), methylcellulose (MCL), carboxymethylcellulose (CMC
), polyvinyl alcohol (PVA), polyvinyl vicritone, polyacrylic acid, polyacrylamide, crosslinked starch, sodium acrylate, sodium alginate, sodium silicate, etc. can be used.
（ホ）作 用
上記手段により、水素吸蔵合金粉末は結着剤と粘性剤の
両者によって電極に保持されるため、充放電によって微
粉化を起こしても、粘性剤の粘着力によって微粉化した
水素吸蔵合金が相互に結看され且つ結着剤に強固に支持
されるので水素吸蔵合金の脱落を抑制することができる
。(E) Effect By the above means, the hydrogen storage alloy powder is held on the electrode by both the binder and the viscous agent. Since the hydrogen storage alloys are bound together and firmly supported by the binder, it is possible to suppress the hydrogen storage alloys from falling off.
（へ）実施例
負極に水素吸蔵電極を用い、正極に金属酸化物電極を用
いる代表的な二次電池としてニッケルー水素電池があり
、かかる電池を用りて本発明の一実施例を説明する。(F) Example A nickel-hydrogen battery is a typical secondary battery that uses a hydrogen storage electrode as a negative electrode and a metal oxide electrode as a positive electrode, and an example of the present invention will be described using such a battery.
水素吸蔵能力を有するＬａＮｉ、を機械的に微粉化し、
このＬａＮｉ、粉末に小さなせん断力で粒子が簡単に繊
維化し塑性変形するポリテトラフルオロエチレン（ＰＴ
Ｆ’Ｅ）粉末を結着剤としてＬａＮｉ。Mechanically pulverize LaNi, which has hydrogen storage ability,
This LaNi powder is made of polytetrafluoroethylene (PT), which easily fiberizes and plastically deforms when a small shear force is applied to the powder.
F'E) LaNi powder as a binder.
粉末の重量に対して５９６及びポリエチレンオキサイド
（ＰＥＩ：Ｏ）を粘性剤として１％添加し、均一に混練
すると共にポリテトラフルオロエチレンｔ−ｍ維化させ
る。このポリテトラフルオロエチレンを繊維化させた混
合物を圧延した後集電体の両面に配して圧着を行ない水
素吸蔵電極を得る。596 and polyethylene oxide (PEI:O) are added in an amount of 1% based on the weight of the powder as a viscosity agent, and the mixture is uniformly kneaded and turned into polytetrafluoroethylene t-m fibers. This polytetrafluoroethylene fiber mixture is rolled, placed on both sides of a current collector, and crimped to obtain a hydrogen storage electrode.
次いでこうして得られた水素吸蔵電極を、放電容量２．
ＯＡＨの公知の焼結式ニッケル正極と組み合わせアル
カリ電解液を注液して公称容量２．ＯＡＨのニッケルー
水素電池（Ａ）を作製した。また比較のため水素吸蔵電
極に粘性剤としてのポリエチレンオキサイドを添加せず
、その他は実施例と同一の比較電池（Ｂ）を同時に作製
した。Next, the hydrogen storage electrode obtained in this way was used for a discharge capacity of 2.
Combined with OAH's known sintered nickel positive electrode and injected with alkaline electrolyte, the nominal capacity was 2. An OAH nickel-metal hydride battery (A) was produced. For comparison, a comparative battery (B) was also produced which was the same as the example except that polyethylene oxide as a viscous agent was not added to the hydrogen storage electrode.
図面はこれら電池（Ａ）及び（Ｂ）の充放電サイクル特
性図であり、１０時間率電流にて１５０％充電した後終
止罵圧を１．Ｏｖとして５時間率電流にて放電するサイ
クル条件で充放電を行なったときの結果を各電池の初期
容量を１００９６として表わしている。この図面から明
らかなように本発明の水素吸蔵電極を負極に用いた電池
（Ａ）は、比較電池（Ｂ）に比し充放電サイクルの経過
に伴う電池容量の劣化が小さく抑えられており優れてい
ることがわかる。サイクル試験を終了後の電池を分解し
てみると、特に比較電池（Ｂ）の水素吸蔵電極の変形が
著しく、充放電の繰り返しによって水素吸蔵合金の微粉
化が進行すると細かく繊維化されたポリテトラフルオロ
エチレンからなる結着剤のみでは微粉化した水素吸蔵合
金の脱落を充分に抑制することができないことがわかる
。これに対して電池（Ａ）を前記′を池（Ｂ）と同じサ
イクル経過時点に於いて分解してみると、電池（Ａ）の
水素吸蔵電極の変形は電池（Ｂ）の水素吸蔵電極に比べ
て小さく抑えられていた。これは電池（Ａ）の水素吸蔵
電極にはポリテトラフルオロエチレンからなる結着剤に
加えてポリエチレンオキサイドからなる粘性剤が添加さ
れており、結着剤による抱束力と粘性剤による粘着力に
よって水素吸蔵合金粉末を強固に保持しているため、充
放電の際に水素吸蔵合金粉末が水素を吸蔵、放出して微
粉化を起こしても、粘性剤によって微粉化した水素吸蔵
合金相互及び水素吸蔵合金と集電体との間に良好な結着
性が得られ水素吸蔵合金の脱落が抑制されて充放電サイ
クルの経過に伴う電池容量の劣化が抑えられたものと考
えられる。The figure shows the charge/discharge cycle characteristics of these batteries (A) and (B), in which the batteries were charged to 150% at a rate of 10 hours and then subjected to a final cycle of 1. The results are shown when charging and discharging were performed under cycle conditions of discharging at a 5-hour rate current as Ov, with the initial capacity of each battery being 10096. As is clear from this drawing, the battery (A) using the hydrogen storage electrode of the present invention as a negative electrode is superior to the comparative battery (B) in that the deterioration of battery capacity over the course of charge/discharge cycles is suppressed to a small extent. You can see that When the battery was disassembled after the cycle test, it was found that the hydrogen storage electrode of the comparison battery (B) was significantly deformed, and as the hydrogen storage alloy was pulverized by repeated charging and discharging, finely fibrous polytetra It can be seen that the binder made of fluoroethylene alone cannot sufficiently suppress the falling off of the pulverized hydrogen storage alloy. On the other hand, when battery (A) is disassembled at the same cycle as battery (B), the deformation of the hydrogen storage electrode of battery (A) is the same as that of battery (B). It was kept small in comparison. This is because a viscous agent made of polyethylene oxide is added to the hydrogen storage electrode of battery (A) in addition to a binder made of polytetrafluoroethylene, and the binding force of the binder and the adhesive force of the viscous agent Because the hydrogen-absorbing alloy powder is held firmly, even if the hydrogen-absorbing alloy powder absorbs and releases hydrogen during charging and discharging and becomes pulverized, the pulverized hydrogen-absorbing alloy powder and the hydrogen-absorbing alloy powder are pulverized by the viscous agent. It is considered that good binding properties were obtained between the alloy and the current collector, suppressing the drop-off of the hydrogen storage alloy and suppressing the deterioration of the battery capacity as the charge/discharge cycle progressed.
（ト）発明の効果
本発明の水素吸蔵電極は耐アルカリ性の合成樹脂結着剤
と粘性剤とによって水素吸蔵合金粉末を保持してなるも
のであるから、充放電の繰り返しによって水素吸蔵合金
が微粉化を起こしても、微粉化した水素吸蔵合金が粘性
剤で相互に結着し長期にわたって電極内に保持されるの
で、サイクル寿命が向上する。(G) Effects of the Invention Since the hydrogen storage electrode of the present invention is made by holding hydrogen storage alloy powder with an alkali-resistant synthetic resin binder and a viscous agent, the hydrogen storage alloy becomes fine powder by repeated charging and discharging. Even if oxidation occurs, the pulverized hydrogen storage alloy is bonded to each other by the viscous agent and retained within the electrode for a long period of time, improving cycle life.
図面は充放電サイクル特性図である。
（Ａ）・・・本発明の水素吸蔵電極を用いた電池、（Ｂ
）・・・比較電池。The drawing is a charge/discharge cycle characteristic diagram. (A)...Battery using the hydrogen storage electrode of the present invention, (B
)...Comparison battery.
Claims (1)
水素吸蔵合金粉末を保持してなる水素吸蔵電極。(1) A hydrogen storage electrode formed by holding hydrogen storage alloy powder with an alkali-resistant synthetic resin adhesive and a viscous agent.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59186878A JP2692786B2 (en) | 1984-09-06 | 1984-09-06 | Hydrogen storage electrode |
| FR848418698A FR2569059B1 (en) | 1984-08-10 | 1984-12-07 | ALKALINE METAL / HYDROGEN ACCUMULATOR |
| DE19843444998 DE3444998A1 (en) | 1984-08-10 | 1984-12-10 | METAL / HYDROGEN ALKALI ACCUMULATOR BATTERY |
| GB08431142A GB2162994B (en) | 1984-08-10 | 1984-12-10 | Metal/hydrogen alkaline storage battery |
| US06/841,058 US4636445A (en) | 1984-08-10 | 1986-03-17 | Metal/hydrogen alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59186878A JP2692786B2 (en) | 1984-09-06 | 1984-09-06 | Hydrogen storage electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6166366A true JPS6166366A (en) | 1986-04-05 |
| JP2692786B2 JP2692786B2 (en) | 1997-12-17 |
Family
ID=16196259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59186878A Expired - Lifetime JP2692786B2 (en) | 1984-08-10 | 1984-09-06 | Hydrogen storage electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2692786B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62290066A (en) * | 1986-06-09 | 1987-12-16 | Sanyo Electric Co Ltd | Metal-hydrogen alkaline storage battery |
| JPS64649A (en) * | 1987-03-25 | 1989-01-05 | Toshiba Battery Co Ltd | Hydrogen storage alloy electrode and its manufacture |
| JPH01253159A (en) * | 1988-03-31 | 1989-10-09 | Matsushita Electric Ind Co Ltd | Hydrogen absorbing alloy electrode |
| JPH01267960A (en) * | 1988-04-20 | 1989-10-25 | Matsushita Electric Ind Co Ltd | Hydrogen absorption alloy electrode and its manufacture |
| US5506074A (en) * | 1993-09-30 | 1996-04-09 | Sanyo Electric Co. Ltd. | Metal hydride electrode and nickel-hydrogen alkaline storage cell |
| US6242133B1 (en) | 1998-06-17 | 2001-06-05 | Sanyo Electric Co., Ltd. | Hydrogen-absorbing alloy electrode for alkaline secondary battery and method of manufacture thereof |
| JP2014089879A (en) * | 2012-10-30 | 2014-05-15 | Fdk Twicell Co Ltd | Nickel hydrogen secondary battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5189133A (en) * | 1975-02-03 | 1976-08-04 | ||
| JPS5372138A (en) * | 1976-12-08 | 1978-06-27 | Matsushita Electric Ind Co Ltd | Method of manufacturing zinc electrode for alkaline storage battery |
| JPS60109174A (en) * | 1983-11-18 | 1985-06-14 | Matsushita Electric Ind Co Ltd | Manufacture of hydrogen absorption electrode |
-
1984
- 1984-09-06 JP JP59186878A patent/JP2692786B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5189133A (en) * | 1975-02-03 | 1976-08-04 | ||
| JPS5372138A (en) * | 1976-12-08 | 1978-06-27 | Matsushita Electric Ind Co Ltd | Method of manufacturing zinc electrode for alkaline storage battery |
| JPS60109174A (en) * | 1983-11-18 | 1985-06-14 | Matsushita Electric Ind Co Ltd | Manufacture of hydrogen absorption electrode |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62290066A (en) * | 1986-06-09 | 1987-12-16 | Sanyo Electric Co Ltd | Metal-hydrogen alkaline storage battery |
| JPS64649A (en) * | 1987-03-25 | 1989-01-05 | Toshiba Battery Co Ltd | Hydrogen storage alloy electrode and its manufacture |
| JPH01253159A (en) * | 1988-03-31 | 1989-10-09 | Matsushita Electric Ind Co Ltd | Hydrogen absorbing alloy electrode |
| JPH07105237B2 (en) * | 1988-03-31 | 1995-11-13 | 松下電器産業株式会社 | Hydrogen storage alloy electrode |
| JPH01267960A (en) * | 1988-04-20 | 1989-10-25 | Matsushita Electric Ind Co Ltd | Hydrogen absorption alloy electrode and its manufacture |
| JP2689473B2 (en) * | 1988-04-20 | 1997-12-10 | 松下電器産業株式会社 | Hydrogen storage alloy electrode and its manufacturing method |
| US5506074A (en) * | 1993-09-30 | 1996-04-09 | Sanyo Electric Co. Ltd. | Metal hydride electrode and nickel-hydrogen alkaline storage cell |
| US6242133B1 (en) | 1998-06-17 | 2001-06-05 | Sanyo Electric Co., Ltd. | Hydrogen-absorbing alloy electrode for alkaline secondary battery and method of manufacture thereof |
| JP2014089879A (en) * | 2012-10-30 | 2014-05-15 | Fdk Twicell Co Ltd | Nickel hydrogen secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2692786B2 (en) | 1997-12-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |