JPH0546662B2 - - Google Patents
Info
- Publication number
- JPH0546662B2 JPH0546662B2 JP61284715A JP28471586A JPH0546662B2 JP H0546662 B2 JPH0546662 B2 JP H0546662B2 JP 61284715 A JP61284715 A JP 61284715A JP 28471586 A JP28471586 A JP 28471586A JP H0546662 B2 JPH0546662 B2 JP H0546662B2
- Authority
- JP
- Japan
- Prior art keywords
- cadmium
- negative electrode
- layer
- paste
- oxygen gas
- 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 - Lifetime
Links
- 229910052793 cadmium Inorganic materials 0.000 claims description 29
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- 239000011149 active material Substances 0.000 claims description 9
- 239000011162 core material Substances 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 6
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical compound [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 claims description 5
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 2
- 230000000149 penetrating effect Effects 0.000 claims 1
- 239000010410 layer Substances 0.000 description 33
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 22
- 229910001882 dioxygen Inorganic materials 0.000 description 22
- 238000010521 absorption reaction Methods 0.000 description 20
- 239000000126 substance Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000003487 electrochemical reaction Methods 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229940065285 cadmium compound Drugs 0.000 description 1
- 150000001662 cadmium compounds Chemical class 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—Alloys
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
- H01M10/526—Removing gases inside the secondary cell, e.g. by absorption by gas recombination on the electrode surface or by structuring the electrode surface to improve gas recombination
-
- 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)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、アルカリ蓄電池用ペースト式カドミ
ウム負極に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a paste-type cadmium negative electrode for alkaline storage batteries.
従来の技術
アルカリ蓄電池用ペースト式カドミウム負極
は、一般に酸化カドミウムあるいは水酸化カドミ
ウムを主体とし、これにカーボニルニツケル、グ
ラフアイト等の導電性粉末、ポリビニルアルコー
ル、カルボキシメチルセルロース等の結着剤及び
水やエチレングリコール等の溶媒を加え、混練し
て調整したペーストをニツケルメツキした開孔鋼
板等の導電性芯材に塗着し、乾燥後、アルカリ溶
液中で化成することによつて製造される。Conventional technology Paste-type cadmium negative electrodes for alkaline storage batteries generally consist of cadmium oxide or cadmium hydroxide as a main ingredient, and conductive powders such as carbonyl nickel and graphite, binders such as polyvinyl alcohol and carboxymethyl cellulose, and water and ethylene. It is manufactured by adding a solvent such as glycol and kneading the prepared paste, applying it to a conductive core material such as a nickel-plated perforated steel plate, drying it, and then chemically converting it in an alkaline solution.
前記の化成工程の目的は、活物質材料に用いる
酸化カドミウム、水酸化カドミウムなどの放電状
態のカドミウム化合物の一部または全部を充電状
態の金属カドミウムに変換し、負極内に予備充電
部分を付与することにある。 The purpose of the above chemical conversion step is to convert part or all of the cadmium compound in a discharged state, such as cadmium oxide or cadmium hydroxide, used for the active material into metallic cadmium in a charged state, and to provide a pre-charged portion within the negative electrode. There is a particular thing.
また、予備充電部分を付与する化成工程を省略
するために、酸化カドミウムあるいは水酸化カド
ミウムとともに金属カドミウムを混合して用いる
場合もある。 Further, in order to omit the chemical conversion step for providing a pre-charged portion, metal cadmium may be used in combination with cadmium oxide or cadmium hydroxide.
発明が解決しようとする問題点
このようにペースト式カドミウム負極は、焼結
式に比べて製造が容易で、高い容量密度が得られ
る利点を有する。しかし焼結式負極のように基板
兼骨格をなす導電性マトリクスが存在しないた
め、電池充電時に生成する金属カドミウムの成長
は主に芯材近傍で起こり、極板表面層までその成
長は達しにくい。このため過充電時に正極から発
生する酸素ガスと金属カドミウムとの反応が効率
的に行われず、密閉形電池に使用すると、電池の
内圧が高くなるという欠点がある。Problems to be Solved by the Invention As described above, the paste type cadmium negative electrode has the advantage that it is easier to manufacture and can provide a higher capacity density than the sintered type. However, unlike sintered negative electrodes, there is no conductive matrix that serves as a substrate and skeleton, so the growth of metallic cadmium produced during battery charging occurs mainly near the core material, making it difficult for the growth to reach the surface layer of the electrode plate. For this reason, the reaction between the oxygen gas generated from the positive electrode and metal cadmium during overcharging does not occur efficiently, and when used in a sealed battery, there is a drawback that the internal pressure of the battery increases.
本発明は、このようなペースト式カドミウム負
極における酸素ガス吸収能力の向上をはかり、大
電流充電（短時間充電）を可能にするものであ
る。 The present invention aims to improve the oxygen gas absorption capacity of such a paste-type cadmium negative electrode, thereby enabling large current charging (short-time charging).
問題点を解決するための手段
本発明は酸素カドミウムあるいは水酸化カドミ
ウムを主体とするか又はこれに金属カドミウムを
混入したペースト状活物質を芯材に塗着し、その
層表面に、フツ素樹脂粉末層と、このフツ素樹脂
粉末層表面にこの樹脂粉末層を部分的に貫通して
ペースト状活物質層と電気的に接触する耐アルカ
リ性で導電性を有する物質の多孔層とを形成した
ものであり、負極での酸素ガス吸収能力の向上を
はかるものである。Means for Solving the Problems The present invention applies a paste-like active material mainly composed of oxygen cadmium or cadmium hydroxide or mixed with metal cadmium to a core material, and then coats the layer surface with a fluorine resin. A powder layer and a porous layer of an alkali-resistant and electrically conductive material formed on the surface of the fluororesin powder layer, which partially penetrates the resin powder layer and makes electrical contact with the paste active material layer. This is intended to improve the oxygen gas absorption ability of the negative electrode.
作 用
カドミウム負極上での酸素ガス吸収機構におい
ては、つぎの(1)および(2)式の化学的または電気化
学的反応が生じる。Action In the oxygen gas absorption mechanism on the cadmium negative electrode, the following chemical or electrochemical reactions (1) and (2) occur.
O2＋2H2Ｏ＋2Cd→Cd（OH）2 ……(1)
O2＋2H2Ｏ＋4e-→4OH- ……(2)
化成工程あるいは電池充電時に生成される金属
カドミウムは、通常導電性芯体の近傍に形成され
る。しかし、本発明のように極板表面に導電性の
多孔層が形成されている場合は、極板表面の導電
性層側からも金属カドミウムの成長は進行し、極
板表面に金属カドミウムの層が形成される。この
極板表面側からも充電が進行し、極板表面に金属
カドミウムの層を形成するためには、極板表面に
設けられた導電層が導電層全体にわたつて通電性
を確保している必要があり、連続層を形成してい
ることが必要である。 O 2 +2H 2 O+2Cd→Cd(OH) 2 ...(1) O 2 +2H 2 O+4e - →4OH - ...(2) Metallic cadmium produced during the chemical formation process or during battery charging is usually located near the conductive core. is formed. However, when a conductive porous layer is formed on the surface of the electrode plate as in the present invention, the growth of metal cadmium also progresses from the conductive layer side on the surface of the electrode plate, resulting in a layer of metal cadmium on the surface of the electrode plate. is formed. In order for charging to proceed from the surface side of the electrode plate and to form a layer of metal cadmium on the surface of the electrode plate, the conductive layer provided on the surface of the electrode plate must ensure electrical conductivity across the entire conductive layer. It is necessary to form a continuous layer.
また、導電層から負極内部への通電は、上記導
電層が部分的にペースト状活物質層と接触してい
ればよく、充電時には、この負極活物質と部分的
に接触した導電層から充電が進行し、金属カドミ
ウムは、ここを中心として負極表面を覆うように
生成する。 In addition, the conduction of current from the conductive layer to the inside of the negative electrode only requires that the conductive layer is partially in contact with the paste-like active material layer, and during charging, charging is carried out from the conductive layer that is partially in contact with the negative electrode active material. As the process progresses, metallic cadmium is generated to cover the surface of the negative electrode centering on this point.
密閉形電池では、過充電時に正極より発生する
酸素ガスの負極での吸収反応が重要である。この
負極での酸素ガス吸収が悪いと、過充電時に電池
内圧が上昇するので、大電流での充電ができな
い。言い換えると、短時間充電ができない。酸素
ガスの一部は前記(1)式により化学的に負極の金属
カドミウムにより吸収されるものであるから、本
発明によるもののように金属カドミウムが極板表
面に多く分布している方がガスとの接触が多くな
り有利である。 In sealed batteries, the absorption reaction at the negative electrode of oxygen gas generated from the positive electrode during overcharging is important. If this negative electrode absorbs oxygen gas poorly, the internal pressure of the battery will rise during overcharging, making it impossible to charge with a large current. In other words, it cannot be charged for a short period of time. A part of the oxygen gas is chemically absorbed by the metal cadmium of the negative electrode according to the above equation (1), so it is better to have a large amount of metal cadmium distributed on the electrode plate surface as in the case of the present invention. This is advantageous because there will be more contact.
また、負極での化学的な酸素ガスの吸収は、負
極の金属カドミウムにより行なわれるが、この
際、金属カドミウムと、電解液と、酸素ガスとの
三相界面の存在が重要となる。三相界面の形成度
合いが大きいほど酸素ガスの導入と吸収は効率よ
く進行する。周知のごとくフツ素樹脂は、撥水性
が大きいため、本発明によるフツ素樹脂粉末層は
活物質表面層での前記の三相界面の形成を容易と
し、金属カドミウム上での酸素ガス吸収効率はさ
らに向上する。 Further, chemical absorption of oxygen gas at the negative electrode is carried out by the metal cadmium of the negative electrode, and in this case, the existence of a three-phase interface between the metal cadmium, the electrolyte, and the oxygen gas is important. The greater the degree of formation of the three-phase interface, the more efficiently the introduction and absorption of oxygen gas proceeds. As is well known, fluororesin has high water repellency, so the fluororesin powder layer according to the present invention facilitates the formation of the above-mentioned three-phase interface on the active material surface layer, and the oxygen gas absorption efficiency on metal cadmium is Further improvement.
また、酸素ガスの吸収は、前記(2)式の電気化学
反応によつても進行する。電気化学反応による酸
素ガスの吸収は、導電体の表面の三相界面で進行
する。本発明による負極では、極板の表面に設け
た導電層下側とフツ素樹脂粉末層との界面に形成
される三相界面において電気化学反応による酸素
ガス吸収が進行し、前記の化学反応による酸素ガ
スの吸収と相まつてガス吸収効率はさらに向上す
る。 Further, the absorption of oxygen gas also proceeds by the electrochemical reaction of formula (2) above. Absorption of oxygen gas by electrochemical reaction proceeds at the three-phase interface on the surface of the conductor. In the negative electrode according to the present invention, oxygen gas absorption due to an electrochemical reaction progresses at the three-phase interface formed at the interface between the lower side of the conductive layer provided on the surface of the electrode plate and the fluororesin powder layer, and the absorption of oxygen gas due to the above chemical reaction proceeds. Together with the absorption of oxygen gas, the gas absorption efficiency is further improved.
以上のように本発明によるカドミウム負極の構
成を用いれば、化学的な酸素吸収の主体をなす金
属カドミウムを酸素吸収が効率よく行なわれる負
極の活物質層表面に生成させ、さらに撥水層の存
在により酸素吸収が加速されるとともに、負極表
面積と同等程度の面接を有する撥水層と電位のか
かつた固層としての導電層との界面で撥水層を透
過した酸素ガスが電気化学的に吸収されるため、
負極の酸素吸収性は非常に優れたものになる。 As described above, if the configuration of the cadmium negative electrode according to the present invention is used, metal cadmium, which is the main component of chemical oxygen absorption, can be generated on the surface of the active material layer of the negative electrode where oxygen absorption is efficiently performed, and the presence of a water-repellent layer can also be achieved. This accelerates oxygen absorption, and oxygen gas that has passed through the water-repellent layer is electrochemically absorbed at the interface between the water-repellent layer, which has a surface area comparable to the surface area of the negative electrode, and the conductive layer, which is a solid layer with a high potential. In order to be
The oxygen absorbency of the negative electrode is extremely excellent.
実施例 以下本発明の実施例を説明する。Example Examples of the present invention will be described below.
平均粒径約1μmの酸化カドミウム粉末をポリビ
ニルアルコールのエチレングリコール溶液で練合
してペースト１とし、これをニツケルメツキした
開孔鉄板からなる芯材２に塗着し、次に、この極
板をフツ素樹脂を分散させた溶液に浸漬し、乾燥
を行ないフツ素樹脂粉末層３を形成した。次にポ
リビニルアルコールを結着剤として用いたカーボ
ンペーストを塗布してフツ素樹脂粉末表面上に導
電性の多孔層４を形成した。なお、カーボン粒子
は部分的にフツ素樹脂粉末相互間に入り込み、こ
の層を貫通するため、ペースト状活物質層との電
気的接触が得られる。 Cadmium oxide powder with an average particle size of approximately 1 μm is kneaded with a polyvinyl alcohol ethylene glycol solution to form a paste 1, which is applied to a core material 2 made of a nickel-plated perforated iron plate. A fluororesin powder layer 3 was formed by immersing it in a solution containing a base resin dispersed therein and drying it. Next, a carbon paste using polyvinyl alcohol as a binder was applied to form a conductive porous layer 4 on the surface of the fluororesin powder. Note that the carbon particles partially penetrate between the fluororesin powders and penetrate this layer, so that electrical contact with the paste-like active material layer can be obtained.
第１図は、本発明による負極の断面概略図であ
る。 FIG. 1 is a schematic cross-sectional view of a negative electrode according to the present invention.
この極板を比重1.20の水酸化ナトリウム水溶液
中で陰電解し、金属カドミウムを付与する化成を
行い、水洗、乾燥した。 This electrode plate was subjected to negative electrolysis in an aqueous sodium hydroxide solution with a specific gravity of 1.20, chemically formed to impart metal cadmium, washed with water, and dried.
この極板を所定の寸法に切断し、焼結式ニツケ
ル正極と組み合わせて1200mAh相当の密閉型蓄
電池を構成し、電池特性を試験した。 This electrode plate was cut into predetermined dimensions and combined with a sintered nickel positive electrode to construct a sealed storage battery equivalent to 1200mAh, and the battery characteristics were tested.
試験は、負極の酸素ガス吸収性を評価するため
の過充電時の電池内圧試験を行つた。電池内圧試
験は、20℃において、１〜3C相当（1.2〜3.6A）
の電流で充電したときの電池内圧のピークで評価
した。 The test was a battery internal pressure test during overcharging to evaluate the oxygen gas absorption ability of the negative electrode. Battery internal pressure test is equivalent to 1-3C (1.2-3.6A) at 20℃
The evaluation was based on the peak of the battery internal pressure when charging with a current of .
第２図は充電レートと電池内圧力のピークとの
関係を示す。ａは上記実施例の負極を用いた電
池、ｂは従来の化成工程までを行つた比較例の負
極を用いた電池を示す。本発明による負極は、充
電時に金属カドミウムが極板表面に分布しやす
く、また、フツ素樹脂粉末の存在による三相界面
の形成により、金属カドミウム上での化学反応に
よる酸素ガス吸収能力が向上するとともに、極板
表面の導電層とフツ素樹脂粉末層との界面での電
気化学的酸素ガス吸収が同時に機能して酸素ガス
吸収能力は極めて高い。従つて電池ａは電池内圧
が低く、大電流による高率充電が可能である。 FIG. 2 shows the relationship between the charging rate and the peak of the battery internal pressure. A shows a battery using the negative electrode of the above example, and b shows a battery using a negative electrode of a comparative example, which was subjected to the conventional chemical formation process. In the negative electrode according to the present invention, metal cadmium is easily distributed on the electrode plate surface during charging, and the formation of a three-phase interface due to the presence of fluorine resin powder improves the ability to absorb oxygen gas through a chemical reaction on the metal cadmium. At the same time, electrochemical oxygen gas absorption at the interface between the conductive layer on the surface of the electrode plate and the fluorine resin powder layer functions at the same time, and the oxygen gas absorption capacity is extremely high. Therefore, battery a has a low internal pressure and can be charged at a high rate with a large current.
発明の効果
以上のように本発明によれば、ペースト式カド
ミウム負極の酸素ガス吸収特性を大幅に改良する
ことができる。Effects of the Invention As described above, according to the present invention, the oxygen gas absorption characteristics of a paste-type cadmium negative electrode can be significantly improved.
第１図は本発明による負極の断面概略図、第２
図は本発明による負極を用いたニツケルカドミウ
ム蓄電池と、従来法によるものとの電池内圧と充
電電流との関係を示す図である。
１……ペースト、２……芯材、３……フツ素樹
脂粉末層、４……カーボンペースト。
FIG. 1 is a schematic cross-sectional view of a negative electrode according to the present invention, and FIG.
The figure is a diagram showing the relationship between battery internal pressure and charging current for a nickel-cadmium storage battery using a negative electrode according to the present invention and one using a conventional method. 1... Paste, 2... Core material, 3... Fluorine resin powder layer, 4... Carbon paste.
Claims (1)
は水酸化カドミウムを主体とするかは又はこれに
金属カドミウムを混入したペースト状活物質層の
表面にフツ素樹脂粉末層と、このフツ素樹脂粉末
層の表面に部分的にこの樹脂粉末層を貫通して前
記活物質層と電気的に接触する耐アルカリ性で導
電性を持つた多孔層とを設けたことを特徴とする
ペースト式カドミウム負極。1 A fluororesin powder layer is formed on the surface of a paste-like active material layer mainly composed of cadmium oxide or cadmium hydroxide or mixed with metal cadmium, which is coated on a conductive core material, and this fluororesin powder layer is coated on a conductive core material. A paste-type cadmium negative electrode characterized in that an alkali-resistant and conductive porous layer is provided on the surface of the paste-type cadmium negative electrode, partially penetrating the resin powder layer and electrically contacting the active material layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61284715A JPS63138651A (en) | 1986-11-28 | 1986-11-28 | Paste type cadmium negative electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61284715A JPS63138651A (en) | 1986-11-28 | 1986-11-28 | Paste type cadmium negative electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63138651A JPS63138651A (en) | 1988-06-10 |
| JPH0546662B2 true JPH0546662B2 (en) | 1993-07-14 |
Family
ID=17682042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61284715A Granted JPS63138651A (en) | 1986-11-28 | 1986-11-28 | Paste type cadmium negative electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63138651A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5796463A (en) * | 1980-12-05 | 1982-06-15 | Matsushita Electric Ind Co Ltd | Manufacture of cadmium electrode for sealed alkaline storage battery |
| JPS6081765A (en) * | 1983-10-12 | 1985-05-09 | Sanyo Electric Co Ltd | Manufacturing method for paste type cadmium negative electrode plate |
| JPS60202666A (en) * | 1984-03-26 | 1985-10-14 | Sanyo Electric Co Ltd | Paste type cadmium anode plate for alkaline storage battery |
-
1986
- 1986-11-28 JP JP61284715A patent/JPS63138651A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5796463A (en) * | 1980-12-05 | 1982-06-15 | Matsushita Electric Ind Co Ltd | Manufacture of cadmium electrode for sealed alkaline storage battery |
| JPS6081765A (en) * | 1983-10-12 | 1985-05-09 | Sanyo Electric Co Ltd | Manufacturing method for paste type cadmium negative electrode plate |
| JPS60202666A (en) * | 1984-03-26 | 1985-10-14 | Sanyo Electric Co Ltd | Paste type cadmium anode plate for alkaline storage battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63138651A (en) | 1988-06-10 |
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| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |