JPH0789487B2 - Cadmium electrode for alkaline storage battery and manufacturing method thereof - Google Patents
Cadmium electrode for alkaline storage battery and manufacturing method thereofInfo
- Publication number
- JPH0789487B2 JPH0789487B2 JP61311390A JP31139086A JPH0789487B2 JP H0789487 B2 JPH0789487 B2 JP H0789487B2 JP 61311390 A JP61311390 A JP 61311390A JP 31139086 A JP31139086 A JP 31139086A JP H0789487 B2 JPH0789487 B2 JP H0789487B2
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- battery
- carbon fiber
- electrode
- cadmium
- 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 title claims description 15
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 29
- 239000011149 active material Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 6
- 239000011162 core material Substances 0.000 claims description 4
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 3
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims description 3
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical compound [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 229910001882 dioxygen Inorganic materials 0.000 description 5
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920002972 Acrylic fiber Polymers 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 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
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01M4/246—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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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)
- 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、ニッケル−カドミウム電池などのアルカリ蓄
電池、特に密閉形電池に用いられるカドミウム電極の改
良に関するものである。Description: TECHNICAL FIELD The present invention relates to an improvement of a cadmium electrode used in an alkaline storage battery such as a nickel-cadmium battery, and particularly in a sealed battery.
従来の技術 従来、この種のアルカリ蓄電池用カドミウム電極には、
導電性芯材に活物質と樹脂繊維、結着剤等を混合したペ
ーストを塗着するペースト式電極が一般的である。この
電極は、製造工程の複雑な焼結式電極に比べて製法が簡
単で、製造コストが安価で、かつ高エネルギー密度が得
られる長所を有している。そこで、近年アルカリ蓄電池
の高容量化に伴い、この電極製法が主流になりつつあ
る。しかし、ペースト式電極は、焼結基板に活物質を含
浸した焼結式電極と比較して電子伝導性が低いうえ、過
充電時に正極から発生する酸素ガスのカドミウム負極に
よる吸収が劣る欠点があった。Conventional technology Conventionally, in this type of cadmium electrode for alkaline storage battery,
A paste-type electrode is generally used in which a paste in which an active material, a resin fiber, a binder and the like are mixed is applied to a conductive core material. This electrode has the advantages that the manufacturing method is simple, the manufacturing cost is low, and a high energy density is obtained, as compared with a sintered electrode having a complicated manufacturing process. Therefore, in recent years, with the increase in capacity of alkaline storage batteries, this electrode manufacturing method is becoming mainstream. However, the paste-type electrode has a lower electron conductivity than the sintered-type electrode in which a sintered substrate is impregnated with an active material, and has a drawback that oxygen gas generated from the positive electrode during overcharge is poorly absorbed by the cadmium negative electrode. It was
そこで、電極の電子伝導性を向上させ、かつ同時に電極
の酸素ガスの吸収能力を改善するために、炭素繊維を活
性化した活性炭素繊維（あるいは繊維状活性炭ともい
う）を活物質中に分散させた活物質層を設けることが提
案されている。Therefore, in order to improve the electron conductivity of the electrode and at the same time improve the oxygen gas absorption capacity of the electrode, activated carbon fiber (or fibrous activated carbon) in which carbon fiber is activated is dispersed in the active material. It has been proposed to provide an active material layer.
ここで、活性炭素繊維とは炭素繊維の比表面積500〜120
0m2/gに増大し、触媒活性を有する基を化学的に付与し
たものであり、例えば容易に酸に溶解する無機酸化物、
Al2O3等の微粉末を含むアクリル繊維（直径５〜15μ
ｍ、長さ３〜5mm、平均細孔直径20〜40Å、比表面積50
〜200m2/g）を45℃のIN硫酸溶液に約１時間浸漬して得
たものである。Here, the activated carbon fiber is a specific surface area of the carbon fiber of 500 to 120.
Increased to 0 m 2 / g, a group having a catalytic activity is chemically added, for example, an inorganic oxide that is easily dissolved in an acid,
Acrylic fiber containing fine powder such as Al 2 O 3 (diameter 5 to 15μ
m, length 3-5mm, average pore diameter 20-40Å, specific surface area 50
~ 200 m 2 / g) was obtained by immersing the solution in IN sulfuric acid solution at 45 ° C for about 1 hour.
発明が解決しようとする問題点 しかしながら、このような従来の構成では、アルカリ水
溶液中で充電，放電のサイクルを繰り返すと、活性炭素
繊維の特性が劣化し、一般に考えられているカドミウム
電極によるガス吸収反応の次の２式において、 （１）式の電気化学的ガス吸収反応に関与する活性炭素
繊維の疎水性が低下して、（１）式の反応場と考えられ
る活性炭素繊維における気・液・固の三相界面が不安定
な状態になり、活性炭素繊維による（１）式の触媒効果
が低下する傾向があった。したがって、カドミウム電極
のガス吸収能力が劣化し、電池内圧が上昇するため、電
池のサイクル寿命が短いという問題点があった。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention However, in such a conventional configuration, when the cycle of charging and discharging is repeated in an alkaline aqueous solution, the characteristics of the activated carbon fiber are deteriorated, and the gas absorption by the generally considered cadmium electrode is absorbed. In the next two equations of the reaction, Since the hydrophobicity of the activated carbon fiber involved in the electrochemical gas absorption reaction of the formula (1) decreases, the three-phase interface of gas / liquid / solid in the activated carbon fiber, which is considered to be the reaction field of the formula (1), is not formed. There was a tendency that the catalyst became stable and the catalytic effect of the formula (1) by the activated carbon fiber was lowered. Therefore, the gas absorption capacity of the cadmium electrode deteriorates, and the internal pressure of the battery rises, resulting in a short cycle life of the battery.
本発明は、このような問題点を解決するもので、活性炭
素繊維の充放電サイクルによる特性劣化を防止すること
を目的とするものである。The present invention solves such problems, and an object thereof is to prevent characteristic deterioration of activated carbon fibers due to charge / discharge cycles.
問題点を解決するための手段 この問題点を解決するために本発明は、フッ素樹脂を表
面に付着させた活性炭素繊維と、酸化カドミウムもしく
は水酸化カドミウムを主とする活物質からなる活物質層
と、前記活物質層を表面に形成した導電性芯材からなる
ことを特徴とするものである。Means for Solving the Problems In order to solve this problem, the present invention is directed to an active material layer comprising an activated carbon fiber having a fluororesin adhered to the surface thereof and an active material mainly containing cadmium oxide or cadmium hydroxide. And a conductive core material having the active material layer formed on the surface thereof.
作用 この構成によって、活性炭素繊維の表面にフッ素樹脂の
撥水性が付与されるので、活性炭素繊維の疎水性が向上
し、アルカリ水溶液に対するぬれを適切にコントロール
できる。この構成により前記（１）式の反応場である
気，液，固の三相界面を長期間にわたって安定に保持す
ることが可能となる。つまり、充放電のくり返しにより
アルカリ水溶液で活性炭素繊維表面が被覆されることを
防止し、その触媒能を長期間維持できる。このことから
活性炭素繊維を分散させた活物質層を有するカドミウム
電極のガス吸収能力が、充放電サイクル数とともに劣化
することなく、初期の好ましい状態を長期間にわたって
維持することとなる。Action With this configuration, the surface of the activated carbon fiber is provided with the water repellency of the fluororesin, so that the hydrophobicity of the activated carbon fiber is improved and the wettability with an alkaline aqueous solution can be appropriately controlled. With this configuration, it is possible to stably maintain the three-phase interface of gas, liquid and solid, which is the reaction field of the above formula (1), for a long period of time. That is, it is possible to prevent the surface of the activated carbon fiber from being covered with the alkaline aqueous solution due to repeated charging and discharging, and to maintain its catalytic ability for a long period of time. Therefore, the gas absorption capacity of the cadmium electrode having the active material layer in which the activated carbon fibers are dispersed does not deteriorate with the number of charge / discharge cycles, and the initial preferable state is maintained for a long period of time.
実施例 以下本発明の実施例を詳述する。Examples Examples of the present invention will be described in detail below.
フッ素樹脂をその表面に付着させた活性炭素繊維（以下
フッ素樹脂処理活性炭素繊維という）は次のようにして
作成した。5wt％の四フッ化エチレン懸濁液に活性炭素
繊維（直径５〜15μm,長さ３〜5mm,平均細孔直径20〜40
Å，比表面積500〜1200m2/g,アクリル繊維系活性炭素繊
維）を浸漬し、乾燥してフッ素樹脂処理活性炭素繊維を
得た。An activated carbon fiber having a fluororesin attached to its surface (hereinafter referred to as an activated carbon fiber treated with a fluororesin) was prepared as follows. Activated carbon fiber (diameter 5 to 15 μm, length 3 to 5 mm, average pore diameter 20 to 40) in 5 wt% ethylene tetrafluoride suspension
Å, specific surface area 500 to 1200 m 2 / g, acrylic fiber-based activated carbon fiber) was dipped and dried to obtain fluorocarbon resin-treated activated carbon fiber.
主活物質としての酸化カドミウム粉末100重量部に対
し、前記のフッ素樹脂処理活性炭素繊維を0.6重量部加
えて混合し、これにポリビニルアルコールのエチレング
リコール溶液を適量加えて混練し、ペースト状にする。
このペーストを厚さ0.1mmのニッケルメッキした開孔鉄
板からなる芯材に塗着，乾燥後、公知の方法で化成処理
を行って、厚さ約0.5mmの極板を得た。To 100 parts by weight of cadmium oxide powder as the main active material, 0.6 parts by weight of the fluorocarbon resin-treated activated carbon fiber was added and mixed, and an appropriate amount of an ethylene glycol solution of polyvinyl alcohol was added and kneaded to form a paste. .
This paste was applied to a core material made of a nickel-plated open-hole iron plate having a thickness of 0.1 mm, dried, and then subjected to chemical conversion treatment by a known method to obtain an electrode plate having a thickness of about 0.5 mm.
この本発明品の比較例としてフッ素樹脂処理活性炭素繊
維を通常の活性炭素繊維に置きかえて、前記本発明品の
場合と同様にして、比較用極板を得た。この本発明によ
る電極と比較用電極とを公知の構成方法によって焼結式
ニッケル電極と組み合わせて、本発明のカドミウム電極
を用いた電池Ａと、比較用電極を用いた電池Ｂを作成し
た。このA,Bの密閉形ニッケル−カドミウムアルカリ蓄
電池（公称容量（500mAh,単３サイズ）を用いて、過充
電時の電池内圧のサイクル変化を比較した。As a comparative example of the product of the present invention, a fluorocarbon resin-treated activated carbon fiber was replaced with an ordinary activated carbon fiber, and a comparative electrode plate was obtained in the same manner as in the case of the product of the present invention. The electrode according to the present invention and the comparative electrode were combined with a sintered nickel electrode by a known construction method to prepare a battery A using the cadmium electrode of the present invention and a battery B using the comparative electrode. The sealed nickel-cadmium alkaline storage batteries of A and B (nominal capacity (500 mAh, AA size) were used to compare the cycle changes of the battery internal pressure during overcharge.
図は、0.1C電流で15時間充電し、0.2C電流で放電のサイ
クルを繰り返し、その途中の10サイクル目と50サイクル
目の充電のみを1C電流で２時間行い、前記充電終了後0.
2C電流で放電した時の電池内圧変化を示す。Ａ−１は本
発明電池Ａの10サイクル充電時の内圧で、Ａ−２は50サ
イクル充電時の内圧を示す。同様にＢ−1,B−２は比較
電池Ｂの10サイクル,50サイクル充電時の内圧である。The figure shows that the battery is charged with 0.1C current for 15 hours, and the discharge cycle is repeated with 0.2C current, and only the 10th and 50th cycles in the middle are charged with 1C current for 2 hours.
The change in battery internal pressure when discharged at 2C current is shown. A-1 is the internal pressure of the battery A of the present invention during 10-cycle charging, and A-2 is the internal pressure during 50-cycle charging. Similarly, B-1 and B-2 are internal pressures of the comparative battery B when it is charged for 10 cycles and 50 cycles.
図より明らかなように、充放サイクルの繰り返しによ
り、比較電池Ｂの内圧上昇は著しいが、本発明電池Ａの
内圧上昇はわずかである。図において、電池A,Bの放電
時の圧力は大気圧との差が認められず（すなわち、図中
ではＯに近い内圧値）過充電時の圧力上昇は酸素ガスに
起因すると考えられる。したがって電池A,B間のサイク
ルによる前記圧力上昇の差は、酸素ガス吸収能力のサイ
クル変化に電池A,Bの能力差があることを示している。
つまり、酸素ガス吸収能力の違いは、電池Ａのカドミウ
ム電極の活物質層内に含まれる活性炭素繊維の特性がフ
ッ素樹脂処理により劣化せず、その結果電池Ａのカドミ
ウム電極のガス吸収能力が好ましい初期状態で維持され
ていると考えられる。As is clear from the figure, the internal pressure of the comparative battery B is remarkably increased by the repeated charging and discharging cycles, but the internal pressure of the battery A of the present invention is slightly increased. In the figure, the pressure during discharge of the batteries A and B is not different from the atmospheric pressure (that is, the internal pressure value close to O in the figure), and it is considered that the pressure increase during overcharge is due to oxygen gas. Therefore, the difference in the pressure increase due to the cycle between the batteries A and B indicates that the cycle change of the oxygen gas absorption capacity has the capacity difference between the batteries A and B.
That is, the difference in the oxygen gas absorption capacity is that the characteristics of the activated carbon fiber contained in the active material layer of the cadmium electrode of the battery A are not deteriorated by the fluororesin treatment, and as a result, the gas absorption capacity of the cadmium electrode of the battery A is preferable. It is considered to be maintained in the initial state.
次に、活性炭素繊維の表面に付着させるフッ素樹脂の量
を検討するため、次表に示す４種の濃度の四フッ化エチ
レン懸濁液でフッ素樹脂処理した活性炭素繊維を作成し
た又この４種と無処理の活性炭素繊維を用いて、前記本
発明電池Ａと同様の方法で５種類の電池C,D,E,F,Gを作
成した。Next, in order to study the amount of fluororesin deposited on the surface of the activated carbon fiber, activated carbon fiber treated with the fluororesin was prepared with a tetrafluoroethylene suspension having four concentrations shown in the following table. Five kinds of batteries C, D, E, F, G were prepared in the same manner as the battery A of the present invention using the seeds and the untreated activated carbon fiber.
これらの電池を1C電流で1.5時間充電し、1C電流放電の
サイクル試験にかけて、10サイクルおよび100サイクル
充電時の電池内圧の最大値と、50サイクル放電時の放電
中間電圧を調べた結果を表に示す。表よりフッ素樹脂処
理なしの電池Ｇは50サイクルの放電中間電圧が1.2Vと高
くて電子伝導性は良好であるが、100サイクルの電池内
圧最大値が15kg/cm2と非常に高く、無処理であるのでガ
ス吸収能力が他の４種に比べて著しく劣化したと考えら
れる。一方、高濃度（20wt％）フッ素樹脂懸濁液処理の
電池Ｃは、電池内圧最大値がサイクルを繰り返しても若
干の上昇にとどまり、ガス吸収能力は良好に維持されて
いるが、放電中間電圧が1.05Vと他よりも低くなり、電
圧特性が劣っていた。これは、活性炭素繊維を高濃度の
フッ素樹脂懸濁液で処理したことにより、電極の電子伝
導性が低下したためと考えられる。 These batteries were charged at 1C current for 1.5 hours, subjected to a 1C current discharge cycle test, and the results of examining the maximum value of the battery internal pressure at 10 cycle and 100 cycle charge and the discharge intermediate voltage at 50 cycle discharge are shown in the table. Show. From the table, the battery G without fluororesin treatment has a high discharge intermediate voltage of 1.2 V at 50 cycles and good electron conductivity, but the maximum battery internal pressure at 100 cycles is as high as 15 kg / cm 2, and no treatment is performed. Therefore, it is considered that the gas absorption capacity was significantly deteriorated as compared with the other four types. On the other hand, in the battery C treated with the high concentration (20 wt%) fluororesin suspension, the maximum value of the battery internal pressure was only slightly increased even after repeating the cycle, and the gas absorption capacity was maintained well, but the discharge intermediate voltage was increased. Was 1.05V, which is lower than the others, and the voltage characteristics were inferior. It is considered that this is because the electroconductivity of the electrode was lowered by treating the activated carbon fiber with the high concentration fluororesin suspension.
これら電池G,Cに対して、電池Ｆはフッ素樹脂処理によ
りガス吸収能力が向上して充電時電池内圧の最大値が低
くなり、電池Ｄは処理濃度を低めたことにより電子伝導
性が向上して放電中間電圧が高くなってF,Dいずれも電
池特性が改善されている。しかし、5wt％フッ素樹脂懸
濁液処理の電池Ｅが、ガス吸収能力の長期間維持と、電
子伝導性の両面において最も優れていることは表より明
らかである。したがって、活性炭素繊維のフッ素樹脂量
は、懸濁液濃度が2wt％をこえて、15wt％をこえないフ
ッ素樹脂懸濁液で処理した時に付着する量が、電池特性
上最適であると考えられる。In contrast to these batteries G and C, the battery F has improved gas absorption capacity due to the fluororesin treatment and the maximum value of the battery internal pressure at the time of charging has decreased, and the battery D has improved electron conductivity due to the decreased treatment concentration. As a result, the discharge intermediate voltage becomes higher and the battery characteristics are improved for both F and D. However, it is clear from the table that the battery E treated with the 5 wt% fluororesin suspension is the best in terms of both long-term maintenance of gas absorption capacity and electronic conductivity. Therefore, it is considered that the amount of the fluorocarbon resin of the activated carbon fiber, which is adhered when treated with the fluorocarbon resin suspension having a suspension concentration of more than 2 wt% and not more than 15 wt%, is optimum for the battery characteristics. .
発明の効果 以上のように本発明によれば、フッ素樹脂処理した活性
炭素繊維を用いることにより、良好な電子伝導性が確保
され、ガス吸収能力のサイクル劣化がほとんどないカド
ミウム電極が得られ、サイクル寿命の優れたニッケル−
カドミウムアルカリ蓄電池が提供できるという効果が得
られる。EFFECTS OF THE INVENTION As described above, according to the present invention, by using the activated carbon fiber treated with the fluororesin, good electron conductivity is ensured, and a cadmium electrode having almost no cycle deterioration of the gas absorption capacity is obtained. Nickel with long life
The effect that a cadmium alkaline storage battery can be provided is acquired.
図は、本発明電池と比較電池との充放電サイクルによる
電池内圧の変化を示す図である。The figure is a diagram showing changes in battery internal pressure due to charge / discharge cycles of the battery of the present invention and the comparative battery.
Claims (2)
を主とする活物質層を導電性芯材に支持させてなるカド
ミウム電極であって、前記活物質層は比表面積が500m2/
g以上である活性炭素繊維を含み、前記活性炭素繊維の
表面にはフッ素樹脂が付着したアルカリ蓄電池用カドミ
ウム電極。1. A cadmium electrode in which an active material layer mainly containing cadmium oxide or cadmium hydroxide is supported on a conductive core material, and the active material layer has a specific surface area of 500 m 2 /
A cadmium electrode for an alkaline storage battery, which contains activated carbon fibers of g or more, and a fluororesin is attached to the surface of the activated carbon fibers.
素繊維をフッ素樹脂濃度が２〜15wt％の懸濁液に浸漬し
て付着させ、これを活物質中に混入することを特徴とす
るアルカリ蓄電池用カドミウム電極の製造法。2. The activated carbon fiber to which the fluororesin is attached is characterized in that the activated carbon fiber is immersed in a suspension having a fluororesin concentration of 2 to 15 wt% to be attached, and this is mixed into the active material. Manufacturing method of cadmium electrode for alkaline storage battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61311390A JPH0789487B2 (en) | 1986-12-25 | 1986-12-25 | Cadmium electrode for alkaline storage battery and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61311390A JPH0789487B2 (en) | 1986-12-25 | 1986-12-25 | Cadmium electrode for alkaline storage battery and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63164165A JPS63164165A (en) | 1988-07-07 |
| JPH0789487B2 true JPH0789487B2 (en) | 1995-09-27 |
Family
ID=18016607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61311390A Expired - Lifetime JPH0789487B2 (en) | 1986-12-25 | 1986-12-25 | Cadmium electrode for alkaline storage battery and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0789487B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109411759B (en) * | 2018-10-25 | 2022-04-05 | 江苏海四达电源股份有限公司 | High-temperature lithium ion power battery and pre-formation method thereof |
| EP4209632A4 (en) * | 2020-09-01 | 2025-01-01 | Teijin Limited | RESIN-BONDED FIBER, AND ACTIVE MATERIAL LAYER, ELECTRODE AND NONAQUEOUS ELECTROLYTE SECONDARY BATTERY USING SAME |
-
1986
- 1986-12-25 JP JP61311390A patent/JPH0789487B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63164165A (en) | 1988-07-07 |
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