JPS6352745B2 - - Google Patents
Info
- Publication number
- JPS6352745B2 JPS6352745B2 JP55108642A JP10864280A JPS6352745B2 JP S6352745 B2 JPS6352745 B2 JP S6352745B2 JP 55108642 A JP55108642 A JP 55108642A JP 10864280 A JP10864280 A JP 10864280A JP S6352745 B2 JPS6352745 B2 JP S6352745B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- calcium hydroxide
- layer
- active material
- tin compound
- 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
Links
- 239000011701 zinc Substances 0.000 claims description 41
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 40
- 229910052725 zinc Inorganic materials 0.000 claims description 40
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 18
- 239000000920 calcium hydroxide Substances 0.000 claims description 18
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 18
- 150000003606 tin compounds Chemical class 0.000 claims description 16
- 239000011149 active material Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 8
- 239000010410 layer Substances 0.000 description 28
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- -1 zincate ions Chemical class 0.000 description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 229910004860 CaZn Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical class [Zn].[Sn] GZCWPZJOEIAXRU-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
- H01M4/244—Zinc 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
Description
【発明の詳細な説明】
本発明はニツケル―亜鉛電池、銀―亜鉛電池の
ように陰極活物質として亜鉛を用いるアルカリ亜
鉛二次電池に係り、特に亜鉛陰極の改良に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to alkaline zinc secondary batteries that use zinc as a cathode active material, such as nickel-zinc batteries and silver-zinc batteries, and particularly relates to improvements in zinc cathodes.
この種の電池において亜鉛は単位重量当りのエ
ネルギー密度が大きく、且低価格であるという利
点を有するが、放電生成物である亜鉛酸イオンが
電解液中に遊離し、充電の際に金属亜鉛が樹枝状
に電着する形態をとり、充放電の繰返しにより電
着亜鉛が生長して対極に接し内部短絡を引起すと
いう問題があつた。 In this type of battery, zinc has the advantage of high energy density per unit weight and low price, but zincate ions, which are discharge products, are liberated in the electrolyte, and metal zinc is released during charging. There was a problem in that the electrodeposited zinc was formed in a dendritic form, and as a result of repeated charging and discharging, the electrodeposited zinc grew and came into contact with the counter electrode, causing an internal short circuit.
このような問題に対処するために従来では亜鉛
活物質層の表面に水酸化カルシウム層を形成し、
下記の反応式に基づきCaZz（OH）4の形体で固定
する方法が提案されている。 In order to deal with such problems, conventionally a calcium hydroxide layer is formed on the surface of the zinc active material layer.
A method of fixing in the form of CaZz(OH) 4 has been proposed based on the reaction formula below.
Ca（OH）＋Zn（OH）2- 4→CaZn（OH）4＋20H-
しかしながら、水酸化カルシウム層のみでは遊
離した亜鉛酸イオンを完全に固定することは不可
能である。何故なら上述の反応式で明らかなよう
に亜鉛酸イオン１モルに対して水酸化カルシウム
１モルが必要となる。従つて放電時に溶解してく
る亜鉛酸イオンを全て固定するためには少くとも
等モルの水酸化カルシウムを必要とし、悪鉛陰極
における水酸化カルシウム量が増大して電極活物
質の利用率の低下を招くことになる。 Ca(OH) + Zn(OH) 2- 4 →CaZn(OH) 4 +20H - However, it is impossible to completely fix the liberated zincate ions with only a calcium hydroxide layer. This is because, as is clear from the above reaction formula, 1 mol of calcium hydroxide is required for 1 mol of zincate ion. Therefore, at least an equimolar amount of calcium hydroxide is required to fix all the zincate ions that dissolve during discharge, which increases the amount of calcium hydroxide in the bad lead cathode and reduces the utilization rate of the electrode active material. will be invited.
又、CaZn（OH）4の形で固定されたはずの亜鉛
の一部については充放電反応に関与することがあ
り、その結果金属亜鉛亜鉛酸イオンの反応を繰
返し金属亜鉛が樹枝状に生長する懸念がある。 In addition, some of the zinc that should have been fixed in the form of CaZn(OH) 4 may be involved in charge/discharge reactions, and as a result, the reaction of zinc metal zincate ions is repeated and metal zinc grows in a dendritic shape. There are concerns.
このため、一方では水酸化カルシウム層と併用
してアルカリ電解液中にスズ化合物を添加するこ
とが、例えば特公昭48―27100号公報に記載され
ている。この方法は亜鉛酸イオンが金属亜鉛とし
て電着する際に亜鉛―スズの共析物の形態で電着
させることにより金属亜鉛の樹枝状生長を阻止す
ることを目的とするものであるが、この方法にお
いては添加するスズ化合物の有効量は電解液に対
して10-3〜10-2重量％という微量であるため、長
期の充放電繰返しを行うとその効果が得られなく
なる。即ち充電により亜鉛と共に電着したスズが
亜鉛陰極の下部に沈積してしまい、充放電反応に
関与するスズ化合物がほとんどなくなつてしまう
からである。 For this reason, on the one hand, adding a tin compound to an alkaline electrolyte in combination with a calcium hydroxide layer is described, for example, in Japanese Patent Publication No. 48-27100. The purpose of this method is to prevent the dendritic growth of metallic zinc by electrodepositing zincate ions in the form of a zinc-tin eutectoid. In this method, the effective amount of the tin compound added is as small as 10 -3 to 10 -2 % by weight based on the electrolytic solution, so if repeated charging and discharging are performed for a long period of time, the effect will no longer be obtained. That is, the tin electrodeposited together with zinc during charging is deposited under the zinc cathode, and the tin compound involved in the charging/discharging reaction is almost completely eliminated.
本発明は斯る点に鑑みてなされたものであり、
その要旨とするところは亜鉛活物質層の表面に水
酸化カルシウムとスズ化合物とを混合して得た混
合物層を形成する点にあり、水酸化カルシウムに
より亜鉛酸イオンが溶出するのを抑えて金属亜鉛
が樹枝状に生長することを抑制する。更に、前記
水酸化カルシウムによつて阻止できずに生長した
樹枝状金属亜鉛を、スズ化合物と接触させること
により、金属亜鉛を酸化させて酸化亜鉛とし、も
つて樹枝状金属亜鉛の生長を因とする内部短絡の
阻止を計るものである。ここでスズ化合物が金属
亜鉛を酸化させるという挙動は、樹枝状金属亜鉛
が生長しやすい亜鉛活物質表面において観察され
る固有の現象であり、本願特有の構成に基づくも
のである。そして、スズ化合物を導電性の低い水
酸化カルシウムの導電性の低い層中に存在させて
いるので、スズ化合物は単なる充放電サイクル中
においては金属スズに還元され難く、その添加効
果の維持が可能である。 The present invention has been made in view of these points,
The gist of this method is to form a mixture layer obtained by mixing calcium hydroxide and a tin compound on the surface of the zinc active material layer, and the calcium hydroxide suppresses the elution of zincate ions and Prevents zinc from growing like a tree. Furthermore, by bringing the dendritic metal zinc that has grown uninhibited by the calcium hydroxide into contact with a tin compound, the metal zinc is oxidized to zinc oxide, thereby causing the growth of the dendritic metal zinc. This is intended to prevent internal short circuits. The behavior in which the tin compound oxidizes metallic zinc is a unique phenomenon observed on the surface of the zinc active material where dendritic metallic zinc tends to grow, and is based on the unique structure of the present application. In addition, since the tin compound is present in the low conductivity layer of calcium hydroxide, the tin compound is difficult to reduce to metal tin during simple charge/discharge cycles, and the effect of its addition can be maintained. It is.
尚、亜鉛活物質層表面にスズ化合物層、次に水
酸化カルシウム層とした場合には、スズ化合物は
導電性の高い亜鉛活物質層表面に接しているの
で、充放電サイクル中において、金属スズに還元
されてしまい、その添加効果を発揮できない。 In addition, when a tin compound layer is formed on the surface of the zinc active material layer and then a calcium hydroxide layer, the tin compound is in contact with the surface of the highly conductive zinc active material layer, so during the charge/discharge cycle, the metal tin The effect of the addition cannot be achieved.
更に、亜鉛活物質層表面に水酸化カルシウム
層、次にスズ化合物層とした場合には、水酸化カ
ルシウム層中で生長した樹枝状金属亜鉛により、
スズ化合物層と亜鉛活物質層とが電気的に接続さ
れ、前記同様、充放電サイクル中においてスズ化
合物層中では加速度的に金属スズが生じ、ここか
ら樹枝状亜鉛が発生しやすい。 Furthermore, when a calcium hydroxide layer and then a tin compound layer are formed on the surface of the zinc active material layer, the dendritic metal zinc grown in the calcium hydroxide layer causes
The tin compound layer and the zinc active material layer are electrically connected, and as described above, metallic tin is generated at an accelerated rate in the tin compound layer during charge and discharge cycles, and dendritic zinc is likely to be generated therefrom.
以下本発明の実施例を図面に基づき説明する
に、１は亜鉛活物質層２とその表面に形成した混
合物層３よりなる亜鉛陰極であつて、前記亜鉛活
物質層２は酸化亜鉛活物質粉末にポリテトラフル
オロエチレン分散液を５〜10％加え水で希釈し混
練した後、数回ロール掛けして所定厚みの亜鉛シ
ートを作成し、これを陰極集電板４の両面に圧着
してなる。又前記混合物層３は水酸化カルシウム
10部、酸化スズ２部を十分混合した混合物にポリ
テトラフルオロエチレン分散液を10部加え水で希
釈し混練した後、ロール掛けしてシート状とな
し、これを亜鉛活物質層２の表面に圧着して形成
されている。 Embodiments of the present invention will be described below with reference to the drawings. Reference numeral 1 denotes a zinc cathode consisting of a zinc active material layer 2 and a mixture layer 3 formed on the surface thereof, and the zinc active material layer 2 is zinc oxide active material powder. After adding 5 to 10% polytetrafluoroethylene dispersion and diluting it with water and kneading it, roll it several times to create a zinc sheet of a predetermined thickness, which is then crimped onto both sides of the cathode current collector plate 4. . Further, the mixture layer 3 is made of calcium hydroxide.
Add 10 parts of polytetrafluoroethylene dispersion to a mixture of 10 parts of tin oxide and 2 parts of tin oxide, dilute with water, knead, roll to form a sheet, and apply this to the surface of zinc active material layer 2. It is formed by crimping.
５はニツケル陽極、６はアルカリ電解液を含浸
させたセパレータ、７及び８は陰、陽極外部端子
である。 5 is a nickel anode, 6 is a separator impregnated with an alkaline electrolyte, and 7 and 8 are negative and anode external terminals.
上記構成の本発明によるニツケル―亜鉛電池と
比較のため混合物層がスズ化合物を含有しない水
酸化カルシウムのみの単独層で、且電解液中に酸
化スズを0.01重量％溶解させた比較電池を作成し
た。尚、容量はいづれも4AHである。 For comparison with the nickel-zinc battery according to the present invention having the above configuration, a comparative battery was prepared in which the mixture layer was a single layer of only calcium hydroxide containing no tin compound, and in which 0.01% by weight of tin oxide was dissolved in the electrolyte. . In addition, the capacity of each is 4AH.
そしてこれら電池を0.25Cで４時間充電、0.25C
で３時間放電という条件で充放電を繰返したとこ
ろ、比較電池では50サイクル経過後、内部短絡す
るものがあつたが、本発明電池では100サイクル
経過してもそのような現象は認められなかつた。 Then charge these batteries at 0.25C for 4 hours, 0.25C
When charging and discharging were repeated under the condition of discharging for 3 hours, some internal short circuits occurred in the comparison battery after 50 cycles, but no such phenomenon was observed in the battery of the present invention even after 100 cycles. .
上述した如く、本発明電池に依れば亜鉛活物質
層の表面に、水酸化カルシウムとスズ化合物とを
混合して得た混合物層を形成したので、水酸化カ
ルシウムで阻止できなかつた樹枝状に生長する金
属亜鉛をスズと接触させて生長を阻止するという
両者の相乗効果によつて内部短絡現象を極端に抑
制しうるものであり、この種電池においてその工
業的価値は極めて大である。 As described above, according to the battery of the present invention, a mixture layer obtained by mixing calcium hydroxide and a tin compound is formed on the surface of the zinc active material layer, so that dendritic formation that could not be prevented by calcium hydroxide is prevented. The synergistic effect of bringing the growing metallic zinc into contact with the tin and inhibiting its growth makes it possible to extremely suppress internal short circuit phenomena, and its industrial value in this type of battery is extremely large.
図面は本発明電池の縦断面図を示す。
１…亜鉛陰極、２…亜鉛活物質層、３…混合物
層、４…陰極集電板、５…ニツケル陽極、６…セ
パレータ、７，８…陰、陽極外部端子。
The drawing shows a longitudinal cross-sectional view of the battery of the invention. DESCRIPTION OF SYMBOLS 1... Zinc cathode, 2... Zinc active material layer, 3... Mixture layer, 4... Cathode current collector plate, 5... Nickel anode, 6... Separator, 7, 8... Anode, anode external terminal.
Claims (1)
スズ化合物とを混合して得た混合物層を形成せる
亜鉛陰極を備えたアルカリ亜鉛二次電池。1. An alkaline zinc secondary battery equipped with a zinc cathode that forms a mixture layer obtained by mixing calcium hydroxide and a tin compound on the surface of a zinc active material layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10864280A JPS5732570A (en) | 1980-08-06 | 1980-08-06 | Alkali zinc secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10864280A JPS5732570A (en) | 1980-08-06 | 1980-08-06 | Alkali zinc secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5732570A JPS5732570A (en) | 1982-02-22 |
| JPS6352745B2 true JPS6352745B2 (en) | 1988-10-20 |
Family
ID=14489967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10864280A Granted JPS5732570A (en) | 1980-08-06 | 1980-08-06 | Alkali zinc secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5732570A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60166923U (en) * | 1984-04-13 | 1985-11-06 | 東神電気株式会社 | wire bondage section |
-
1980
- 1980-08-06 JP JP10864280A patent/JPS5732570A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5732570A (en) | 1982-02-22 |
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