JPS63241861A - Nickel positive electrode - Google Patents
Nickel positive electrodeInfo
- Publication number
- JPS63241861A JPS63241861A JP62073983A JP7398387A JPS63241861A JP S63241861 A JPS63241861 A JP S63241861A JP 62073983 A JP62073983 A JP 62073983A JP 7398387 A JP7398387 A JP 7398387A JP S63241861 A JPS63241861 A JP S63241861A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- nickel
- paste
- porosity
- hydroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 67
- 229910052759 nickel Inorganic materials 0.000 title claims description 33
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 12
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 10
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims description 10
- 239000011149 active material Substances 0.000 claims description 9
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical compound [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 238000007599 discharging Methods 0.000 abstract description 9
- 230000008961 swelling Effects 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 208000028659 discharge Diseases 0.000 abstract description 4
- 238000011049 filling Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 3
- 239000013543 active substance Substances 0.000 abstract 4
- 230000007423 decrease Effects 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 4
- 150000002815 nickel Chemical class 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process 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
- 229940065285 cadmium compound Drugs 0.000 description 1
- 150000001662 cadmium compounds Chemical class 0.000 description 1
- 239000006229 carbon black Substances 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
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/32—Nickel oxide or hydroxide 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- 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)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
［発明の目的］
（産業上の利用分野）
本発明はニッケル正極に関し、更に詳しくは、充放電に
おける活物質を含むペーストが導電性芯体から脱落する
ことはなく、しかも電池に組込まれた場合、その電池の
エネルギー密度すなわち容量を大たちしめ′るに有効な
ニッケル正極に関する。[Detailed Description of the Invention] [Object of the Invention] (Industrial Application Field) The present invention relates to a nickel positive electrode, and more specifically, the present invention relates to a nickel positive electrode, and more specifically, a paste containing an active material during charging and discharging does not fall off from a conductive core, and Moreover, the present invention relates to a nickel positive electrode that is effective in increasing the energy density, that is, the capacity, of the battery when incorporated into the battery.
（従来の技術）
代表的なアルカリニ次電池には、正極としてニッケルを
、負極としてカドミウム、亜鉛若しくは水素を使用する
ものがある。このようなアルカリニ次電池のニッケル正
極としては、従来から、例えばカルボニルニッケルを所
定形状に成形φ焼結して得られた多孔質の基板にニッケ
ル塩の水溶液を含浸せしめ、ついでアルカリ水溶液中で
このニッケル塩を水酸化ニッケルに転化せしめて製造す
るいわゆる焼結式ニッケル正極が知られている。(Prior Art) Some typical alkaline secondary batteries use nickel as a positive electrode and cadmium, zinc, or hydrogen as a negative electrode. Conventionally, the nickel positive electrode of such an alkaline secondary battery has been made by impregnating a porous substrate obtained by molding carbonyl nickel into a predetermined shape and sintering it with an aqueous solution of nickel salt, and then soaking the porous substrate in an aqueous alkaline solution. A so-called sintered nickel positive electrode manufactured by converting nickel salt into nickel hydroxide is known.
しかしながら、この焼結式ニッケル正極は、基板の製造
、ニッケル塩の水溶液の含浸、その水酸化ニッケルへの
転化など繁雑な操作を経て製造されるため、量産性が劣
るという問題がある。However, since this sintered nickel positive electrode is manufactured through complicated operations such as manufacturing a substrate, impregnating it with an aqueous solution of nickel salt, and converting it into nickel hydroxide, it has a problem of poor mass productivity.
このため、上記正極に代るものとして、活物質である水
酸化ニッケルの粉末と、ニッケル粉末。Therefore, as an alternative to the above-mentioned positive electrode, nickel hydroxide powder and nickel powder, which are active materials, are used.
カーボンブラックのような導電材の粉末と、カルボキシ
メチルセルロース、ポリテトラフルオロエチレンのよう
な結着材とから、水またはエチレングリコールのような
有機溶媒を媒体としてペーストを調製し、このペースト
を各種の導電性芯体に直接塗着・充電したのち、これを
乾燥するペースト式ニッケル正極が提案されている。A paste is prepared from powder of a conductive material such as carbon black and a binder such as carboxymethyl cellulose or polytetrafluoroethylene using water or an organic solvent such as ethylene glycol as a medium, and this paste is used for various conductive materials. A paste-type nickel positive electrode has been proposed, which is applied directly to the core body, charged, and then dried.
ただし、ペーストを導電性芯体に塗着・充填しただけで
は、乾燥後にあって乾燥ペーストの空隙率が大きくその
充填密度は高まらず、水酸化ニッケル粉末の結着度合も
小さく利用率を高められないので、通常は正極の厚み方
向に所定圧で加圧して空隙率を小たちしめるという処理
が施されている。However, simply applying and filling the conductive core with the paste will result in a large porosity of the dried paste after drying, and the packing density will not increase, and the degree of binding of the nickel hydroxide powder will also be small, making it difficult to increase the utilization rate. Since this is not the case, a process is usually performed in which a predetermined pressure is applied in the thickness direction of the positive electrode to reduce the porosity.
（発明が解決しようとする問題点）
しかしながら上記方法を適用して過度に空隙率を減少せ
しめると、充放電時に電解液はこのニッケル正極内で均
一かつ円滑に拡散されず、また、充電時のガス発生によ
りニッケル正極内のガス圧が上昇し、充填されている水
酸化ニッケルの脱落や正極それ自体の膨潤現象が起こる
。(Problem to be solved by the invention) However, if the above method is applied to reduce the porosity excessively, the electrolyte will not be uniformly and smoothly diffused within this nickel positive electrode during charging and discharging. Gas generation increases the gas pressure within the nickel positive electrode, causing the filled nickel hydroxide to fall off and the positive electrode to swell.
このような現象を抑制するために、ペーストに酸化カド
ミウムのようなカドミウム化合物を適量配合する方法が
知られている。しかしながら、酸化カドミウムなどはそ
の活性が大きく、これを配合するとペースト調製が困難
となり導電性芯体への塗着作業、充填作業に難をきたす
。In order to suppress such a phenomenon, a method is known in which an appropriate amount of a cadmium compound such as cadmium oxide is added to the paste. However, cadmium oxide and the like have high activity, and when they are added, it becomes difficult to prepare a paste, which makes it difficult to apply the paste to the conductive core and to fill it.
本発明は、ペースト式ニッケルを正極の上記したような
問題点を解消し、活物質（水酸化ニッケル）の脱落や正
極の膨潤を阻止し、あわせてそのエネルギー密度が大き
いニッケル正極の提供を目的とする。The purpose of the present invention is to solve the above-mentioned problems of paste-type nickel positive electrodes, prevent the active material (nickel hydroxide) from falling off and swelling of the positive electrode, and provide a nickel positive electrode with high energy density. shall be.
［発明の構成］
（問題点を解決す°るための手段・作用）本発明者らは
上記目的を達成すべく鋭意研究を重ねた結果、活物質の
脱落、正極の膨潤への抑制効果を有する酸化カドミウム
をペーストに配合する場合、その表面に水酸化カドミウ
ム層を形成したものを用いるとペースト調製は良好であ
り、また充放電処理後の空隙率を所定の範囲に制御する
とエネルギー密度を一層大たちしめることができるとの
知見を得、この知見に基づいて本発明のニッケル正極を
開発するに到った。[Structure of the invention] (Means and effects for solving the problems) The present inventors have conducted intensive research to achieve the above object, and as a result, have found that the effect of suppressing the falling off of the active material and the swelling of the positive electrode has been found. When blending cadmium oxide with a hydroxide layer into a paste, the paste preparation is good if a cadmium hydroxide layer is formed on the surface, and the energy density can be further improved by controlling the porosity within a predetermined range after charge/discharge treatment. Based on this knowledge, we have developed the nickel positive electrode of the present invention.
すなわち、本発明のニッケル正極は、活物質が水酸化ニ
ッケルであるペーストを導電性芯体に充填して成るニッ
ケル正極において、該ペーストには、表面に水酸化カド
ミウム層を形成せしめた酸化カドミウムが該水酸化ニッ
ケルに対し２〜１５重量％配合されており、かつ該ニッ
ケル正極を電池に組込み、充放電を行なったのちの該ニ
ッケル正極の空隙率が１８〜３５容積％であることを特
徴とする。That is, the nickel positive electrode of the present invention is a nickel positive electrode in which a conductive core is filled with a paste whose active material is nickel hydroxide, and the paste contains cadmium oxide with a cadmium hydroxide layer formed on the surface. The nickel positive electrode contains 2 to 15% by weight of the nickel hydroxide, and the nickel positive electrode has a porosity of 18 to 35% by volume after the nickel positive electrode is incorporated into a battery and charged and discharged. do.
本発明のニッケル正極の製造に用いるペーストは、前述
した従来の成分の外に、表面に水酸化カドミウム層が形
成されている酸化カドミウムを配合して構成されている
。The paste used for manufacturing the nickel positive electrode of the present invention is composed of, in addition to the conventional components described above, cadmium oxide on which a cadmium hydroxide layer is formed on the surface.
その配合量は、活物質である水酸化ニッケルに対し２〜
１５ｉ１％に相当する量である。この量が多すぎても少
なすぎても、得られたニッケル正極のエネルギー密度は
満足のいく水準にならないからである。The blending amount is 2 to 2 to 2 to 2
This amount corresponds to 1% of 15i. This is because if this amount is too large or too small, the energy density of the obtained nickel positive electrode will not reach a satisfactory level.
酸化カドミウム表面への水酸化カドミウム層の形成は１
例えば酸化カドミウムを水中に適宜な時間浸漬しておく
ことにより容易に行なうことができる。また水酸化カド
ミウムの層厚は格別限定されるものではない。Formation of cadmium hydroxide layer on cadmium oxide surface is 1
For example, this can be easily carried out by soaking cadmium oxide in water for an appropriate period of time. Further, the layer thickness of cadmium hydroxide is not particularly limited.
また１本発明のニッケル正極は、これを電池に組込んだ
のち充放電を行ない、その結果、正極の空隙率が１８〜
３５容植％となるように導電性芯体にペーストが充填さ
れているものである。In addition, the nickel positive electrode of the present invention is charged and discharged after being incorporated into a battery, and as a result, the porosity of the positive electrode is 18 to 18.
The conductive core is filled with paste so that the paste becomes 35%.
このときの空隙率が１８容積％未膚の場合にはいわば過
度に充填された状態であって、活物質の脱落や正極それ
自体のｉｌｌが顕著になり、また３５容積％より大きい
場合はそもそちが活物質の充填量が少なくエネルギー密
度を低水準にしてしまう。好ましくは２４〜３２容積％
である。If the porosity at this time is less than 18% by volume, it is in a so-called overfilled state, and drop-off of the active material and illumination of the positive electrode itself become noticeable, and if the porosity is more than 35% by volume, then However, the filling amount of active material is small and the energy density is at a low level. Preferably 24-32% by volume
It is.
この空隙率は、充放電条件によって調整することができ
る０例えば、１８容積％の場合は１／１５Ｃ１３５容積
％の場合はＩｃの電流で充放電すればよい。また２０容
積％ではｌ／１０Ｃ１３０容積％では１／２Ｃ１３５容
積％ではＩＣの電流で充放電する。この条件を適宜に設
定することにより、空隙率を上記範囲に調節する。This porosity can be adjusted depending on the charging and discharging conditions. For example, in the case of 18 volume %, 1/15C and 135 volume % may be charged and discharged with a current of Ic. Further, when the battery is 20 volume %, 1/10C is 130 volume %, and 1/2C is 135 volume %, charging and discharging is performed by the IC current. By appropriately setting these conditions, the porosity is adjusted within the above range.
なお、本発明のニッケル正極の製造時に用いる導電性芯
体としては、従来から用いられている芯体であれば何で
あってもよいが、例えば、スポンジ状若しくはフェルト
状の金属多孔体または金属繊維不織布の焼結体は好適で
ある。The conductive core used in manufacturing the nickel positive electrode of the present invention may be any conventionally used core, such as a sponge-like or felt-like porous metal body or a metal fiber. A sintered body of non-woven fabric is preferred.
（発明の実施例）
実施例１〜３、比較例１，２
粒径２−未満の酸化カドミウム粉末を１昼夜水に浸漬し
たのちとりだし、８０℃で乾燥して表面に水酸化カドミ
ウム層を形成した。(Examples of the invention) Examples 1 to 3, Comparative Examples 1 and 2 Cadmium oxide powder with a particle size of less than 2-2 was immersed in water for one day and night, then taken out and dried at 80°C to form a cadmium hydroxide layer on the surface. did.
水酸化ニッケル粉末９０重量部、カーポンプラック６重
量部、ポリテトラフルオロエチレン４重量部を用意し、
また上記酸化カドミウム粉末を水酸化ニッケル粉末に対
し、０，２，５゜１５．２０ｆｉ１％量の５水準で用意
し、これらを３０重量部の純水で混練して５種類のペー
ストを調製した。Prepare 90 parts by weight of nickel hydroxide powder, 6 parts by weight of carpon rack, and 4 parts by weight of polytetrafluoroethylene.
In addition, the above cadmium oxide powder was prepared in 5 levels of 0, 2, 5° and 15.20fi 1% amount relative to the nickel hydroxide powder, and these were kneaded with 30 parts by weight of pure water to prepare 5 types of pastes. .
これらの各ペーストを焼結ニッケルａｍに塗着番充填し
８０℃で乾燥したのち５００ ｋｇ／ ｃｒａ２でロー
ラ加圧した。Each of these pastes was coated onto a sintered nickel am, dried at 80°C, and then pressed with a roller at 500 kg/cra2.
得られた各シートを電池に組込み、１／４０Ｃ〜３Ｃの
範囲で充放電電流を条件設定して各種空隙率の正極たら
しめた。なお、１７４０Ｃではｉｏ容積％、４０容積％
は２Ｃ，５０容積％は３Ｃの充放電電流の場合である。Each of the obtained sheets was assembled into a battery, and charging/discharging current conditions were set in the range of 1/40C to 3C to form positive electrodes with various porosity. In addition, for 1740C, io volume%, 40 volume%
is for a charging/discharging current of 2C, and 50% by volume is a charging/discharging current of 3C.
これらの電池につき放電容量を測定し、空隙率とエネル
ギー密度（■Ａ／ｃｃ）の関係を求め、その結果を図に
示した。The discharge capacity of these batteries was measured, and the relationship between porosity and energy density (■A/cc) was determined, and the results are shown in the figure.
［発明の効果］
以上の説明で明らかなように、本発明のニッケル正極は
、充放電時にあっても活物質の脱落、正極の膨潤を起す
ことなく、大きなエネルギー密度を有しており、その工
業的価値は大である。[Effects of the Invention] As is clear from the above explanation, the nickel positive electrode of the present invention does not cause shedding of the active material or swelling of the positive electrode even during charging and discharging, and has a high energy density. The industrial value is great.
図は、ニッケル正極の空隙率とエネルギー密度との関係
図である。The figure is a diagram showing the relationship between porosity and energy density of a nickel positive electrode.
Claims (2)
芯体に充填して成るニッケル正極において、該ペースト
には、表面に水酸化カドミウム層を形成せしめた酸化カ
ドミウムが該水酸化ニッケルに対し２〜１５重量％配合
されており、かつ該ニッケル正極を電池に組込み、充放
電を行なったのちの該ニッケル正極の空隙率が１８〜３
５容積％であることを特徴とするニッケル正極。(1) In a nickel positive electrode in which a conductive core is filled with a paste whose active material is nickel hydroxide, the paste contains cadmium oxide, which forms a cadmium hydroxide layer on the surface, with respect to the nickel hydroxide. The nickel positive electrode contains 2 to 15% by weight, and after the nickel positive electrode is incorporated into a battery and charged and discharged, the porosity of the nickel positive electrode is 18 to 3.
A nickel positive electrode characterized by having a nickel content of 5% by volume.
金属多孔体または金属繊維不織布の焼結体である特許請
求の範囲第１項記載のニッケル正極。(2) The nickel positive electrode according to claim 1, wherein the conductive core is a porous metal body in the form of a sponge or felt, or a sintered body of a metal fiber nonwoven fabric.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62073983A JPS63241861A (en) | 1987-03-30 | 1987-03-30 | Nickel positive electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62073983A JPS63241861A (en) | 1987-03-30 | 1987-03-30 | Nickel positive electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63241861A true JPS63241861A (en) | 1988-10-07 |
Family
ID=13533847
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62073983A Pending JPS63241861A (en) | 1987-03-30 | 1987-03-30 | Nickel positive electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63241861A (en) |
-
1987
- 1987-03-30 JP JP62073983A patent/JPS63241861A/en active Pending
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