JPH0715814B2 - Paste type cadmium cathode plate for alkaline storage battery - Google Patents
Paste type cadmium cathode plate for alkaline storage batteryInfo
- Publication number
- JPH0715814B2 JPH0715814B2 JP62167294A JP16729487A JPH0715814B2 JP H0715814 B2 JPH0715814 B2 JP H0715814B2 JP 62167294 A JP62167294 A JP 62167294A JP 16729487 A JP16729487 A JP 16729487A JP H0715814 B2 JPH0715814 B2 JP H0715814B2
- Authority
- JP
- Japan
- Prior art keywords
- cathode plate
- cadmium
- battery
- paste
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims description 25
- 229910052793 cadmium Inorganic materials 0.000 title claims description 24
- 238000003860 storage Methods 0.000 title claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 239000011149 active material Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 5
- 239000010410 layer Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 16
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 13
- 229910001882 dioxygen Inorganic materials 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 11
- 239000002002 slurry Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 6
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 5
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000003411 electrode reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical compound [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 description 3
- 239000006182 cathode active material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical group [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000009736 wetting Methods 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- 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
-
- 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
- H01M4/246—Cadmium electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/74—Meshes or woven material; Expanded metal
- H01M4/742—Meshes or woven material; Expanded metal perforated material
-
- 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
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0014—Alkaline electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
- H01M6/10—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with wound or folded 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】 （イ）産業上の利用分野 本発明は、ニッケル−カドミウム電池等のアルカリ蓄電
池に用いられるペースト式カドミウム陰極板に関するも
のである。The present invention relates to a paste type cadmium cathode plate used in an alkaline storage battery such as a nickel-cadmium battery.
（ロ）従来の技術 ペースト式カドミウム陰極板は、製造工程が簡単であ
り、製造コストが安く、高エネルギー密度が得られる
等、焼結式カドミウム陰極板に比し優れた利点を有する
反面、電子伝導性に劣るため、過充電により陽極から発
生した場合の酸素ガスの吸収能力が悪く、密閉型電池に
使用すると内部ガス圧が上昇し易いという欠点があっ
た。その為、化成を行ない導電性を付与する方法が取ら
れているが、この方法ではペースト式カドミウム陰極板
の製造工程が簡単で製造コストが安いというメリットが
失なわれてしまうことになる。その為、特開昭60−6387
5号公報では、ペースト状活物質の表層に炭素粉末より
なる導電層を形成することにより、酸素ガス吸収能力に
優れたペースト式カドミウム陰極板を得られることが提
案されている。即ち酸化カドミウムを主体とするペース
ト状活物質層の表面にポリビニルアルコール（PVA）等
の親水性糊料の水溶液に炭素粉末を分散させたスラリー
をコーティング、乾燥して強固な炭素層を形成する。こ
の炭素は導電性を有しており、電池充電時、表層の活物
質が優先的に充電され、次式に基づく化学的酸素ガス吸
収速度を向上せしめる。(B) Conventional technology The paste-type cadmium cathode plate has advantages over the sintered cadmium cathode plate, such as simple manufacturing process, low manufacturing cost, and high energy density. Since it has poor conductivity, it has a drawback in that it has a poor ability to absorb oxygen gas generated from the anode due to overcharging, and the internal gas pressure tends to rise when used in a sealed battery. For this reason, a method of forming a conductive material to give conductivity is taken, but this method loses the merit that the manufacturing process of the paste type cadmium cathode plate is simple and the manufacturing cost is low. Therefore, JP-A-60-6387
Japanese Patent Laid-Open No. 5 (1994) proposes that a paste-type cadmium cathode plate having excellent oxygen gas absorption ability can be obtained by forming a conductive layer made of carbon powder on the surface layer of the paste-like active material. That is, the surface of the paste-like active material layer mainly containing cadmium oxide is coated with a slurry prepared by dispersing carbon powder in an aqueous solution of a hydrophilic paste such as polyvinyl alcohol (PVA), and dried to form a strong carbon layer. This carbon has conductivity, and when the battery is charged, the active material in the surface layer is preferentially charged, and the chemical oxygen gas absorption rate based on the following formula is improved.
Cd＋1/2O2＋H2O→Cd(OH)2 しかしこの方法においても全く問題がない訳ではない。
炭素粉末の固定に親水性糊料を用いている為、陰極板表
面が電解液で濡れ易く、電池内の電解液量を増大させた
場合、酸素ガス吸収に於て、化成方式より劣るといった
問題点がある。一方、電池の放電特性、サイクル寿命の
点からいえば、電解液量はできる限り多い方が望まし
い。Cd + 1 / 2O 2 + H 2 O → Cd (OH) 2 However, this method is not completely free of problems.
Since a hydrophilic paste is used to fix the carbon powder, the surface of the cathode plate is easily wetted by the electrolytic solution, and when the amount of electrolytic solution in the battery is increased, oxygen gas absorption is inferior to that of the chemical conversion method. There is a point. On the other hand, in terms of the discharge characteristics and cycle life of the battery, it is desirable that the amount of the electrolytic solution be as large as possible.
また一方、電極表面を撥水処理して濡れ特性を低下さ
せ、酸素ガス吸収能力を、他の特性を低下させずに向上
せしめんとする提案が種々知られている。代表的な例と
して、特開昭57−96463号公報に記載されているよう
に、酸化カドミウム粉末を主体とし、親水性糊料を含む
活物質ペーストを導電芯体に塗着し、乾燥した後、加圧
し、ついでフッ素樹脂ディスパージョンを含浸する方法
が挙げられる。この方法では活物質表層部に重点的とし
ながら、一部は活物質内部に迄、フッ素樹脂の微粒子を
くいこませ併せて極板の強度向上を図っている。確かに
この方法によれば、極板表面に撥水性を附与する事は可
能である。しかしながら、やはり問題がない訳ではな
い。即ち活物質層を事前にプレスした程度では極板の残
孔度は50％以上有り、どうしても不用のフッ素樹脂の微
粒子が活物質層細孔内に迄かなり侵入し、フッ素樹脂は
絶縁物質であるから電極反応を阻害し易く、現実的には
採用し難い。又、フッ素樹脂の水性ディスパージョンを
酸化カドミウムを主体とする活物質層に直接含浸する
為、酸化カドミウムが水和して一部水酸化カドミウムに
転化し、極板の膨化が起こる。この際生成した水酸化カ
ドミウムは電池初回充電時における水素ガス発生をひき
起こし易く、問題となる。尚、電池系外で水和して生成
した水酸化カドミウムは特に導電性が悪く、充電初期か
ら水素ガスが発生しやすい事が知得されている。On the other hand, various proposals have been made to improve the oxygen gas absorption capacity without lowering other characteristics by treating the surface of the electrode with water repellency to lower the wetting characteristics. As a typical example, as described in JP-A-57-96463, an active material paste containing a cadmium oxide powder as a main component and a hydrophilic paste is applied to a conductive core and then dried. A method of pressurizing and then impregnating with a fluororesin dispersion can be mentioned. In this method, while focusing on the surface layer of the active material, a part of the fluororesin is incorporated into the inside of the active material to improve the strength of the electrode plate. Certainly, according to this method, it is possible to impart water repellency to the surface of the electrode plate. However, it is not without problems. That is, the residual porosity of the electrode plate is 50% or more when the active material layer is pressed in advance, and unnecessary fine particles of fluororesin infiltrate into the pores of the active material layer, and the fluororesin is an insulating material. Therefore, the electrode reaction is liable to be hindered, and it is practically difficult to adopt. Further, since the aqueous dispersion of fluororesin is directly impregnated into the active material layer mainly composed of cadmium oxide, the cadmium oxide is hydrated and partially converted into cadmium hydroxide, resulting in swelling of the electrode plate. The cadmium hydroxide generated at this time is apt to cause generation of hydrogen gas during the initial charging of the battery, which is a problem. It has been known that cadmium hydroxide produced by hydration outside the battery system has particularly poor conductivity and is likely to generate hydrogen gas from the beginning of charging.
（ハ）発明が解決しようとする問題点 本発明は、前記問題点に鑑みなされたものであって電極
表面に、炭素粉末よりなる導電性を有する炭素層を有し
たペースト式カドミウム陰極板の更なる酸素ガス吸収性
能の向上を計るものである。(C) Problems to be Solved by the Invention The present invention has been made in view of the above problems, and further includes a paste type cadmium cathode plate having a conductive carbon layer made of carbon powder on the electrode surface. It is intended to improve the oxygen gas absorption performance.
（ニ）問題点を解決するための手段 本発明のアルカリ蓄電池用ペースト式カドミウム陰極板
は、導電芯体にカドミウム活物質よりなるペーストを塗
着したカドミウム電極の表面に、炭素粉末層を介してフ
ッ素樹脂粉末が存在する導電性を有する炭素層を設けた
ことを特徴とするものである。(D) Means for solving the problem The paste type cadmium cathode plate for alkaline storage batteries of the present invention is a surface of a cadmium electrode having a conductive core coated with a paste made of a cadmium active material, through a carbon powder layer. It is characterized in that a conductive carbon layer in which the fluororesin powder is present is provided.
（ホ）作用 従来の炭素粉末よりなる導電層には、炭素粒子を活物質
層表面に結着させるべくPVA等の親水性糊料の薄膜が存
在している為、特に電池内電解液を増大せしめた場合、
陰極板表面が電解液で濡れ易くなる。(E) Action In the conventional conductive layer made of carbon powder, a thin film of hydrophilic glue such as PVA is present to bind the carbon particles to the surface of the active material layer, so that the electrolyte solution inside the battery is increased. If you do
The surface of the cathode plate is easily wet with the electrolytic solution.
しかし本発明の陰極板は、炭素薄層にフッ素樹脂の微粒
子が存在する為、陰極板表面の炭素層内に、微視的な撥
水点を均一かつ無数に形成する事ができる。これらの撥
水点の形成により、陰極板表面の炭素粉末薄層に、たと
え電池内の電解液量を多くしても陽極から発生する酸素
ガスが容易に接近できる為、炭素粉末薄層直下に形成さ
れる金属カドミウムと酸素との反応がすみやかに起こ
る。また、フッ素樹脂は陰極活物質と直接接することが
なく、電極反応を阻害することはない。またフッ素樹脂
が存在しない炭素層の二次元的な面が、カドミウム電極
表面上に存在するので、炭素層の導電性において有意に
作用すると考えられる。その結果、酸素ガス吸収性能が
大幅に向上する。However, in the cathode plate of the present invention, since the fine particles of the fluororesin are present in the carbon thin layer, it is possible to form an infinite number of microscopic water repellent points in the carbon layer on the surface of the cathode plate. By forming these water repellent points, the oxygen gas generated from the anode can easily approach the carbon powder thin layer on the surface of the cathode plate even if the amount of electrolyte in the battery is increased. The reaction between the formed metal cadmium and oxygen occurs promptly. Further, the fluororesin does not come into direct contact with the cathode active material and does not interfere with the electrode reaction. Further, since the two-dimensional surface of the carbon layer in which the fluororesin is not present is present on the surface of the cadmium electrode, it is considered that the conductivity of the carbon layer is significantly affected. As a result, the oxygen gas absorption performance is significantly improved.
（ヘ）実施例 以下に本発明の実施例と比較例との対比に言及し、詳述
する。(F) Example Hereinafter, the comparison between the example of the present invention and the comparative example will be described in detail.
〔実施例１〕 水100重量部、炭素粉末10重量部、PVA10重量部よりなる
スラリー（以下スラリーＩとする）に、テフロンディス
パージョン41−Ｊ（三井デュポンフロロケミカル（株）
製）を純水にて10重量％溶液に希釈したもの100重量部
を混合し、スラリー（以下スラリーIIとする）を調整す
る。Example 1 A slurry of 100 parts by weight of water, 10 parts by weight of carbon powder, and 10 parts by weight of PVA (hereinafter referred to as slurry I) was added to Teflon Dispersion 41-J (Mitsui DuPont Fluorochemical Co., Ltd.).
100 parts by weight of a solution prepared by diluting the above) into a 10% by weight solution with pure water is mixed to prepare a slurry (hereinafter referred to as slurry II).
一方、酸化カドミウム粉末900gと金属カドミウム粉末10
0gよりなる活物質と、デンドライト防止剤としての酸化
マグネシウム20gと、結着剤としてのヒドロキシプロピ
ルセルロース6gと、補強剤としてのナイロン繊維10g
と、水和防止剤としてのリン酸ナトリウム水溶液300cc
とを混練して、活物質シートを得た。該シートをパンチ
ングメタルよりなる導電芯体の両表面に塗着し、乾燥を
行ないカドミウム電極を得、この表面に前述のスラリー
Ｉをコーティング、乾燥させた後、更にスラリーIIをコ
ーティング、乾燥させて本発明陰極板ａを得た。On the other hand, 900 g of cadmium oxide powder and 10 g of metal cadmium powder
Active material consisting of 0 g, magnesium oxide 20 g as dendrite inhibitor, hydroxypropyl cellulose 6 g as binder, nylon fiber 10 g as reinforcing agent
And 300cc aqueous solution of sodium phosphate as anti-hydration agent
And were kneaded to obtain an active material sheet. The sheet is applied to both surfaces of a conductive core made of punching metal and dried to obtain a cadmium electrode. The surface is coated with the slurry I and dried, and then the slurry II is further coated and dried. The cathode plate a of the present invention was obtained.
〔比較例１〕 前記実施例１で用いたカドミウム電極に、前記スラリー
IIのみをコーティング、乾燥したものを比較陰極板ｂを
得た。Comparative Example 1 The slurry was added to the cadmium electrode used in Example 1 above.
Comparative cathode plate b was obtained by coating and drying II only.
〔比較例２〕 前記実施例１で用いたカドミウム電極に前記スラリーＩ
のみをコーティング、乾燥したものを比較陰極板ｃとし
た。Comparative Example 2 The slurry I was added to the cadmium electrode used in Example 1 above.
Comparative cathode plate c was obtained by coating and drying only.
〔比較例３〕 前記実施例１で用いたカドミウム電極表面に、テフロン
ディスパージョン41−Ｊを純水にて２重量％に希釈した
ものを吹き付け、乾燥させて、比較陰極板ｄを得た。[Comparative Example 3] A teflon dispersion 41-J diluted with pure water to 2% by weight was sprayed onto the surface of the cadmium electrode used in Example 1 and dried to obtain a comparative cathode plate d.
〔比較例４〕 前記実施例で用いたカドミウム電極を何の処理も施さず
そのまま用いたものを、比較陰極板ｅとした。[Comparative Example 4] A comparative cathode plate e was prepared by using the cadmium electrode used in the above example without any treatment.
このようにして作製されたペースト式カドミウム陰極板
a,b,c,d,eをそれぞれセパレータを介して公知のニッケ
ル陽極板と組み合わせて捲回し、電池ケースに収納し
て、公称容量1.3AHのSCサイズの密閉型ニッケル−カド
ミウム蓄電池を作製し、それぞれ本発明電池A,比較電池
B,比較電池C,比較電池D,比較電池Ｅを得た。Paste type cadmium cathode plate produced in this way
Each of a, b, c, d, and e is wound via a separator in combination with a known nickel anode plate, housed in a battery case, and an SC size sealed nickel-cadmium storage battery with a nominal capacity of 1.3 AH is manufactured. , Battery A of the present invention, Comparative battery
B, comparative battery C, comparative battery D, and comparative battery E were obtained.
〔実験１〕 これらの電池Ａ〜Ｅを用いて、25℃で1.3A（1C）の電流
で充電を行った時の、電池内部圧の比較を行った。この
結果を、第１図に示す。[Experiment 1] Using these batteries A to E, the internal pressures of the batteries were compared when charged at a current of 1.3 A (1 C) at 25 ° C. The results are shown in FIG.
これより本発明電池Ａは、比較電池に比べ極めて内部圧
が低くなっている。これは本発明陰極板表面の炭素層内
に微視的な撥水点が均一かつ無数に形成された事、及び
炭素層の導電性が向上した事により、陽極から発生する
酸素ガスが容易に接近でき、消費できることに起因して
いる。一方、比較電池Ｂは、フッ素樹脂粉末を含んだ炭
素層がカドミウム電極上に存在している陰極板ｂを有
し、この陰極板ｂは炭素単独層を有した本発明陰極板Ａ
より導電性が低いので、酸素ガス吸収性能が劣るもので
ある。As a result, the battery A of the present invention has an extremely lower internal pressure than the comparative battery. This is because the microscopic water repellency points were formed uniformly and innumerably in the carbon layer on the surface of the cathode plate of the present invention, and the conductivity of the carbon layer was improved, so that the oxygen gas generated from the anode was easily generated. It comes from being able to approach and consume. On the other hand, the comparative battery B has a cathode plate b in which a carbon layer containing a fluororesin powder is present on a cadmium electrode, and this cathode plate b is a cathode plate A of the present invention having a carbon single layer.
Since the conductivity is lower, the oxygen gas absorption performance is inferior.
〔実験２〕 前記陰極板ａ〜ｅを用いて、25℃にて1.3Aの電流で90分
間充電した後、1.3Aの電流で放電を行い、放電容量の比
較を行った。このときの結果を、第２図に示す。[Experiment 2] Using the cathode plates a to e, after charging at 25 ° C. with a current of 1.3 A for 90 minutes, discharging was performed with a current of 1.3 A to compare the discharge capacities. The result at this time is shown in FIG.
この結果より、本発明陰極板ａはフッ素樹脂を含有した
炭素層の下に、フッ素樹脂を含有していない炭素単独層
があるため、フッ素樹脂と陰極活物質とが直接接触する
ことがなく、電極反応を阻害しないので、放電容量が大
きくなる。From this result, in the cathode plate a of the present invention, since the carbon layer containing no fluororesin is present below the carbon layer containing the fluororesin, the fluororesin does not come into direct contact with the cathode active material. Since the electrode reaction is not hindered, the discharge capacity becomes large.
以上の実験結果より、以下の事が判明した。From the above experimental results, the following facts were revealed.
ペースト式カドミウム陰極板の酸素ガス吸収能力が
大幅に向上するため、急速充電耐性の優れた電池を得る
ことができる。Since the oxygen gas absorption capacity of the paste type cadmium cathode plate is significantly improved, it is possible to obtain a battery having excellent quick charge resistance.
陰極板のガス吸収能力が向上する為、従来より電池
電解液を多量に設定することが可能となり、電池の諸特
性（特にハイレトート放電特性、サイクル寿命）が向上
する。Since the gas absorption capacity of the cathode plate is improved, it becomes possible to set a large amount of battery electrolyte solution as compared with the conventional case, and various characteristics of the battery (particularly high retort discharge characteristics and cycle life) are improved.
フッ素樹脂は糊料により陰極板表面に固定されてい
る為、充放電サイクルを繰り返し行なっても層内に固定
され続け、酸素ガス吸収能力を維持し続けることがで
き、しかもフッ素樹脂の微粒子は極めて微細な炭素粒子
により回りを取り囲まれた状態であって、更に炭素粉末
の単独層が存在している為、陰極活物質と接触すること
がなく、電極反応を阻害することもない。Since the fluororesin is fixed on the surface of the cathode plate with a paste, it can be kept fixed in the layer even after repeated charge and discharge cycles, and the oxygen gas absorption capacity can be maintained. Since it is surrounded by fine carbon particles and has a single layer of carbon powder, it does not come into contact with the cathode active material and does not hinder the electrode reaction.
（ト）発明の効果 本発明によれば、酸素ガス吸収性能の優れたペースト式
カドミウム陰極板を提供することができ、かかる陰極板
を用いた電池の諸特性を向上させることが可能となるの
で、その工業的価値はきわめて大きい。(G) Effect of the Invention According to the present invention, it is possible to provide a paste type cadmium cathode plate having excellent oxygen gas absorption performance, and it is possible to improve various characteristics of a battery using such a cathode plate. , Its industrial value is extremely large.
第１図は電池の内部圧変化を示した図、第２図は陰極板
の放電特性を示した図である。 Ａ…本発明電池、B,C,D,E…比較電池。FIG. 1 is a diagram showing changes in internal pressure of the battery, and FIG. 2 is a diagram showing discharge characteristics of the cathode plate. A ... Battery of the present invention, B, C, D, E ... Comparative battery.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 伊藤 束 大阪府守口市京阪本通２丁目18番地 三洋 電機株式会社内 (72)発明者 盛岡 勇次 大阪府守口市京阪本通２丁目18番地 三洋 電機株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tsukasa Ito 2-18 Keihan Hondori, Moriguchi City, Osaka Sanyo Electric Co., Ltd. (72) Inventor Yuji Morioka 2-18 Keihan Hondori, Moriguchi City, Osaka Sanyo Denki Within the corporation
Claims (1)
ストを塗着したカドミウム電極の表面に、炭素粉末層を
介してフッ素樹脂粉末が存在する導電性を有する炭素層
を設けたことを特徴とするアルカリ蓄電池用ペースト式
カドミウム陰極板。1. A conductive carbon layer, in which fluororesin powder is present, is provided on the surface of a cadmium electrode having a conductive core coated with a paste containing a cadmium active material through a carbon powder layer. Paste type cadmium cathode plate for alkaline storage batteries.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62167294A JPH0715814B2 (en) | 1987-07-03 | 1987-07-03 | Paste type cadmium cathode plate for alkaline storage battery |
| KR1019880001509A KR920007380B1 (en) | 1987-02-17 | 1988-02-15 | Making method of alkali battery |
| US07/156,154 US4826744A (en) | 1987-02-17 | 1988-02-16 | Alkaline storage cell |
| DE3804932A DE3804932C3 (en) | 1987-02-17 | 1988-02-17 | Alkaline storage cell |
| FR8801869A FR2611087A1 (en) | 1987-02-17 | 1988-02-17 | ALKALINE BATTERY WITH NEGATIVE ELECTRODE TO CADMIUM |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62167294A JPH0715814B2 (en) | 1987-07-03 | 1987-07-03 | Paste type cadmium cathode plate for alkaline storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6412460A JPS6412460A (en) | 1989-01-17 |
| JPH0715814B2 true JPH0715814B2 (en) | 1995-02-22 |
Family
ID=15847086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62167294A Expired - Fee Related JPH0715814B2 (en) | 1987-02-17 | 1987-07-03 | Paste type cadmium cathode plate for alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0715814B2 (en) |
-
1987
- 1987-07-03 JP JP62167294A patent/JPH0715814B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6412460A (en) | 1989-01-17 |
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