JPH0252386B2 - - Google Patents
Info
- Publication number
- JPH0252386B2 JPH0252386B2 JP57020559A JP2055982A JPH0252386B2 JP H0252386 B2 JPH0252386 B2 JP H0252386B2 JP 57020559 A JP57020559 A JP 57020559A JP 2055982 A JP2055982 A JP 2055982A JP H0252386 B2 JPH0252386 B2 JP H0252386B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- cadmium
- active material
- compound
- electrode
- 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
- 239000011701 zinc Substances 0.000 claims description 61
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 59
- 229910052725 zinc Inorganic materials 0.000 claims description 58
- 239000011149 active material Substances 0.000 claims description 18
- 229940065285 cadmium compound Drugs 0.000 claims description 15
- 150000001662 cadmium compounds Chemical class 0.000 claims description 15
- 150000002472 indium compounds Chemical class 0.000 claims description 9
- -1 zincate ions Chemical class 0.000 description 8
- 229910052793 cadmium Inorganic materials 0.000 description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 7
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 6
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000011787 zinc oxide 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
- H01M4/244—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
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】
本発明はニツケル−亜鉛電池、銀−亜鉛蓄電池
のように陰極活物質として亜鉛を用いるアルカリ
亜鉛蓄電池に関し、特に亜鉛極の改良に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to alkaline zinc storage batteries that use zinc as a cathode active material, such as nickel-zinc batteries and silver-zinc storage batteries, and particularly relates to improvements in zinc electrodes.
この種電池において、負極活物質としての亜鉛
は、単位重量当りのエネルギー密度が大きく、且
安価である利点を有する反面、次のような欠点が
ある。即ち、亜鉛極の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
樹枝状あるいは海綿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セパレー
タを貫通し、対極に接して内部短絡を引起す。ま
た亜鉛極は通常亜鉛活物質に結着剤を加え、混練
したペーストを芯体（集電体）に塗着乾燥して作
成されているが、放電時に亜鉛極表面の亜鉛が亜
鉛酸イオンとなつて溶出するため、充放電を繰返
すと亜鉛極表面と亜鉛極内部とでは、亜鉛濃度に
差が生じ、亜鉛極表面の結着剤の割合が増大して
電導性及び含液性が低下することになり、亜鉛極
内部における反応が起り難くなり電池容量が低下
する。 In this type of battery, zinc as the negative electrode active material has the advantages of high energy density per unit weight and low cost, but has the following drawbacks. That is, zincate ions, which are the discharge products of the zinc electrode, are liberated in the electrolytic solution, and during charging, metallic zinc is electrodeposited in a dendritic or spongy form, and as the charging and discharging are repeated, the electrodeposited zinc is It grows through the separator and contacts the opposite electrode, causing an internal short circuit. Zinc electrodes are usually made by adding a binder to zinc active material and applying the kneaded paste to a core (current collector) and drying it, but during discharge, the zinc on the surface of the zinc electrode turns into zincate ions. Therefore, when charging and discharging are repeated, there will be a difference in zinc concentration between the surface of the zinc electrode and the inside of the electrode, and the proportion of binder on the surface of the zinc electrode will increase, resulting in a decrease in conductivity and liquid impregnation. This makes it difficult for reactions to occur inside the zinc electrode, resulting in a decrease in battery capacity.
これらの現象が生じる原因を詳細に考察する
と、放電時において亜鉛極は下記の反応が生じて
いる。 If we consider in detail the causes of these phenomena, the following reactions occur in the zinc electrode during discharge.
Zn＋2OH-→ZnO＋H2O＋2e ……
Zn＋4OH-→Zn（OH）-- 4＋2e ……
式が主反応として生じるが式の反応が同時
に進行し、亜鉛酸イオンとして電解液中に溶解す
る。この亜鉛酸イオンが充電時に樹枝状或いは海
綿状に電着するものであり、又亜鉛酸イオンとし
て溶解するために亜鉛極表面の亜鉛濃度が低下す
るのである。 Zn+2OH - →ZnO+H 2 O+2e ... Zn+4OH - →Zn(OH) -- 4 +2e ... The formula occurs as the main reaction, but the reaction of the formula proceeds simultaneously and dissolves in the electrolyte as zincate ions. These zincate ions are electrodeposited in a dendritic or spongy form during charging, and because they are dissolved as zincate ions, the zinc concentration on the surface of the zinc electrode decreases.
従つて、放電時に生成される亜鉛酸イオンが電
解液中に溶出するのを抑えることによりこの種電
池のサイクル特性を改善しうることがわかる。 Therefore, it can be seen that the cycle characteristics of this type of battery can be improved by suppressing the elution of zincate ions generated during discharge into the electrolytic solution.
そこでカドミウム化合物を添加せる亜鉛活物質
層の表面に、カドミウム化合物層を形成してなる
亜鉛極を備えたアルカリ亜鉛蓄電池を先に提案し
た。この提案によれば、亜鉛活物質層の表面のカ
ドミウム化合物層は、初期充電により金属カドミ
ウム層を形成し、亜鉛活物質層が電解液の保持体
であるセパレータもしくは電解液自体と直接接し
ていないので、放電反応により生成する亜鉛酸イ
オンが非常に少なくなる。このため充電反応によ
り生ずる樹枝状あるいは海綿状の電着亜鉛の生成
が少く、また亜鉛活物質層の表面部における亜鉛
濃度の低下が抑制されるので、サイクル特性が向
上するものである。 Therefore, we have previously proposed an alkaline zinc storage battery that has a zinc electrode formed by forming a cadmium compound layer on the surface of a zinc active material layer to which a cadmium compound is added. According to this proposal, the cadmium compound layer on the surface of the zinc active material layer forms a metal cadmium layer upon initial charging, and the zinc active material layer is not in direct contact with the separator that holds the electrolyte or with the electrolyte itself. Therefore, the amount of zincate ions generated by the discharge reaction is extremely small. Therefore, the formation of dendritic or spongy electrodeposited zinc caused by the charging reaction is reduced, and a decrease in zinc concentration at the surface of the zinc active material layer is suppressed, resulting in improved cycle characteristics.
ところがその後の研究によれば、表面のカドミ
ウム化合物層は、サイクルが進むにつれて不働態
化現象がみられ、不働態膜カドミウム層が抵抗と
なり、電池性能を劣下させることが判明した。 However, subsequent research revealed that the cadmium compound layer on the surface becomes passivated as the cycle progresses, and the passive cadmium layer acts as resistance, degrading battery performance.
本発明はかかる点に鑑み発明されたものにし
て、カドミウム化合物とインジウム化合物を添加
せる亜鉛活物質層の表面に、カドミウム化合物と
インジウム化合物の混合層を形成してなる亜鉛極
を備えたアルカリ亜鉛蓄電池を提供せんとするも
のであり、カドミウム化合物とインジウム化合物
とを使用することにより、カドミウムの不働態化
を防止するものである。 The present invention was invented in view of the above, and provides an alkali zinc electrode comprising a zinc electrode formed by forming a mixed layer of a cadmium compound and an indium compound on the surface of a zinc active material layer to which a cadmium compound and an indium compound are added. The present invention aims to provide a storage battery, and uses a cadmium compound and an indium compound to prevent cadmium from becoming passivated.
以下本発明の実施例を説明する。 Examples of the present invention will be described below.
実施例 １
酸化亜鉛粉末80重量％、金属亜鉛粉末８重量
％、添加剤として酸化カドミウム５重量％及び水
酸化インジウム２重量％を十分混合し、この混合
粉末にフツ素樹脂（PTFE）デスパージヨン（濃
度60％）５重量％と水50重量％を加え、混練して
ペースト状となし、このペーストを銅又は鉄より
なる集電体に塗着・乾燥して亜鉛活物質層を形成
する。ついで酸化カドミウム80重量％、金属カド
ミウム10重量％及び水酸化インジウム５重量％を
十分混合し、この混合粉末にフツ素樹脂デスパー
ジヨン（濃度60％）５重量％と水を加え、混練し
てペースト状にする。このペーストを亜鉛活物質
層の表面に塗着し、乾燥させてカドミウム化合物
の薄層を形成した後圧着して亜鉛極とする。Example 1 80% by weight of zinc oxide powder, 8% by weight of metal zinc powder, 5% by weight of cadmium oxide and 2% by weight of indium hydroxide as additives were thoroughly mixed, and fluororesin (PTFE) despersion (PTFE) was added to this mixed powder. 5% by weight (concentration 60%) and 50% by weight of water are added, kneaded to form a paste, and this paste is applied to a current collector made of copper or iron and dried to form a zinc active material layer. Next, 80% by weight of cadmium oxide, 10% by weight of metal cadmium, and 5% by weight of indium hydroxide are thoroughly mixed, and 5% by weight of fluororesin despersion (concentration 60%) and water are added to this mixed powder and kneaded to form a paste. make it into a shape. This paste is applied to the surface of the zinc active material layer, dried to form a thin layer of cadmium compound, and then pressed to form a zinc electrode.
このように形成した亜鉛極の断面図を第１図に
示す。この図面において、亜鉛極１は、カドミウ
ム化合物とインジウム化合物を添加した亜鉛活物
質層２と、カドミウム化合物とインジウム化合物
の混合層３とからなり、該混合層の厚みは亜鉛活
物質層２の厚みの約1/6〜1/10程度である。４は
集電体である。 A cross-sectional view of the zinc electrode formed in this manner is shown in FIG. In this drawing, a zinc electrode 1 consists of a zinc active material layer 2 to which a cadmium compound and an indium compound are added, and a mixed layer 3 of a cadmium compound and an indium compound, and the thickness of the mixed layer is equal to the thickness of the zinc active material layer 2. It is about 1/6 to 1/10 of that. 4 is a current collector.
第２図は上記亜鉛極１と公知のニツケル極を組
合せて形成したニツケル−亜鉛蓄電池Ａの断面図
である。この図面において、５はニツケル極、６
はセパレータ、７は保液層、８は電槽、９は電槽
蓋、１０，１１は正負極端子である。 FIG. 2 is a sectional view of a nickel-zinc storage battery A formed by combining the zinc electrode 1 and a known nickel electrode. In this drawing, 5 is a nickel pole, 6 is a nickel pole,
7 is a separator, 7 is a liquid retaining layer, 8 is a battery case, 9 is a battery cover, and 10 and 11 are positive and negative electrode terminals.
実施例 ２
実施例１における亜鉛活物質層１の表面に、酸
化カドミウム、金属カドミウム及び水酸化インジ
ウムとの混合粉末を均一に分散配置して後圧着し
たものを亜鉛極とし、他は実施例１と同様にアル
カリ亜鉛蓄電池Ｂを作成した。Example 2 A zinc electrode was obtained by uniformly dispersing a mixed powder of cadmium oxide, metal cadmium, and indium hydroxide on the surface of the zinc active material layer 1 in Example 1 and then pressing it. Alkaline zinc storage battery B was prepared in the same manner as above.
そして比較のため、実施例１において亜鉛活物
質層２及び混合層３に夫々水酸化インジウムを含
まない亜鉛極を備え、他の点は実施例１と同様の
比較電池Ｃを作成した。尚この比較電池において
水酸化インジウムの含有量に等しい分だけ、亜鉛
活物質層２及び混合層３における酸化カドミウム
を増量した。 For comparison, a comparative battery C was prepared in the same manner as in Example 1 except that the zinc active material layer 2 and the mixed layer 3 in Example 1 were each provided with a zinc electrode that did not contain indium hydroxide. In this comparative battery, the amount of cadmium oxide in the zinc active material layer 2 and the mixed layer 3 was increased by an amount equal to the content of indium hydroxide.
第３図はこれらの蓄電池のサイクル特性比較図
であり、特性Ａ乃至Ｃは同一符号を付した蓄電池
のサイクル特性である。充放電条件は、容量
800mAHの蓄電池を150mAで６時間充電した後、
150mAで放電し、蓄電池電圧が1.0Vに達すると
き、放電を停止するものである。このサイクル特
性比較図から明らかなように、本発明による蓄電
池Ａ又はＢは比較電池Ｃに比し、サイクル特性が
向上する。 FIG. 3 is a comparison diagram of the cycle characteristics of these storage batteries, and characteristics A to C are the cycle characteristics of the storage batteries with the same reference numerals. Charge/discharge conditions are capacity
After charging the 800mAH storage battery at 150mA for 6 hours,
It discharges at 150mA and stops discharging when the storage battery voltage reaches 1.0V. As is clear from this cycle characteristic comparison diagram, the cycle characteristics of storage battery A or B according to the present invention are improved compared to comparative battery C.
この理由を考察するに、亜鉛活物質層２及びそ
の表面の混合層３におけるカドミウム化合物の不
働態化を、インジウムが防止しているためと考え
られる。即ち、混合層３に添加した水酸化インジ
ウムは、カドミウムが充放電する際、その表面で
水酸イオン（OH-）と反応して生成する複雑な
カドミウム酸化物あるいは水酸化物を結晶化学的
に歪を持つた半導体的性質の組成物に変えて、固
相内におけるカドミウムイオンの輸送や遊離した
電子の移動を容易にし、抵抗となる表面カドミウ
ムの不働態膜形成を防止する。また亜鉛活物質層
２に添加した水酸化インジウムは、添加剤の酸化
カドミウムの不働態化を防止すると共に亜鉛の金
属格子中にインジウムが電析し、これが次の亜鉛
電析の核となり、均一な亜鉛の電析が行なわれ
る。 The reason for this is considered to be that indium prevents the cadmium compound in the zinc active material layer 2 and the mixed layer 3 on its surface from becoming passivated. In other words, the indium hydroxide added to the mixed layer 3 crystal-chemically converts the complex cadmium oxide or hydroxide that is generated by reacting with hydroxide ions (OH - ) on the surface when cadmium charges and discharges. By changing the composition to a strained composition with semiconducting properties, it facilitates the transport of cadmium ions and the movement of free electrons within the solid phase, and prevents the formation of a passive film of surface cadmium that becomes a resistance. In addition, indium hydroxide added to the zinc active material layer 2 prevents the additive cadmium oxide from becoming passivated, and indium is electrodeposited in the zinc metal lattice, which becomes the nucleus for the next zinc electrodeposition and is uniform. Electrodeposition of zinc is carried out.
以上の如く本発明は、カドミウム化合物とイン
ジウム化合物を添加せる亜鉛活物質層の表面に、
カドミウム化合物とインジウム化合物の混合層を
形成してなる亜鉛極を用いるものであるから、ア
ルカリ亜鉛蓄電池のサイクル特性を改善すること
ができ、その工業的価値大なるものである。 As described above, in the present invention, on the surface of a zinc active material layer to which a cadmium compound and an indium compound are added,
Since it uses a zinc electrode formed of a mixed layer of a cadmium compound and an indium compound, the cycle characteristics of the alkaline zinc storage battery can be improved, and its industrial value is great.
第１図は本発明による亜鉛極の断面図、第２図
は同亜鉛極を用いたニツケル−亜鉛蓄電池の断面
図、第３図は本発明による蓄電池と比較電池のサ
イクル特性比較図である。
２……亜鉛活物質層、３……混合層、１……亜
鉛極。
FIG. 1 is a sectional view of a zinc electrode according to the present invention, FIG. 2 is a sectional view of a nickel-zinc storage battery using the same zinc electrode, and FIG. 3 is a comparison diagram of cycle characteristics of a storage battery according to the invention and a comparative battery. 2... Zinc active material layer, 3... Mixed layer, 1... Zinc electrode.
Claims (1)
せる亜鉛活物質層の表面に、カドミウム化合物と
インジウム化合物の混合層を形成してなる亜鉛極
を備えたアルカリ亜鉛蓄電池。1. An alkaline zinc storage battery equipped with a zinc electrode formed by forming a mixed layer of a cadmium compound and an indium compound on the surface of a zinc active material layer to which a cadmium compound and an indium compound are added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57020559A JPS58137964A (en) | 1982-02-09 | 1982-02-09 | Alkaline zinc storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57020559A JPS58137964A (en) | 1982-02-09 | 1982-02-09 | Alkaline zinc storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58137964A JPS58137964A (en) | 1983-08-16 |
| JPH0252386B2 true JPH0252386B2 (en) | 1990-11-13 |
Family
ID=12030511
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57020559A Granted JPS58137964A (en) | 1982-02-09 | 1982-02-09 | Alkaline zinc storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58137964A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5626988A (en) * | 1994-05-06 | 1997-05-06 | Battery Technologies Inc. | Sealed rechargeable cells containing mercury-free zinc anodes, and a method of manufacture |
-
1982
- 1982-02-09 JP JP57020559A patent/JPS58137964A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58137964A (en) | 1983-08-16 |
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