JPH0564419B2 - - Google Patents
Info
- Publication number
- JPH0564419B2 JPH0564419B2 JP60172752A JP17275285A JPH0564419B2 JP H0564419 B2 JPH0564419 B2 JP H0564419B2 JP 60172752 A JP60172752 A JP 60172752A JP 17275285 A JP17275285 A JP 17275285A JP H0564419 B2 JPH0564419 B2 JP H0564419B2
- Authority
- JP
- Japan
- Prior art keywords
- wetting agent
- layer
- zinc
- surface layer
- active material
- 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
- 229910052725 zinc Inorganic materials 0.000 claims description 60
- 239000011701 zinc Substances 0.000 claims description 60
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 58
- 239000010410 layer Substances 0.000 claims description 39
- 239000000080 wetting agent Substances 0.000 claims description 38
- 239000002344 surface layer Substances 0.000 claims description 34
- 239000011149 active material Substances 0.000 claims description 22
- 238000003860 storage Methods 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 11
- 238000007599 discharging Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- 238000000034 method Methods 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- -1 zincate ions Chemical class 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010294 electrolyte impregnation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
(イ) 産業上の利用分野
本発明はニツケル−亜鉛蓄電池、銀−亜鉛蓄電
池のように負極活物質として亜鉛を用いるアルカ
リ亜鉛蓄積電池に関する。
(ロ) 従来の技術
アルカリ蓄電池の負極活物質としての亜鉛は単
位重量あたりのエネルギー密度が大きく且つ安価
である反面、亜鉛が放電時に電解液中に溶解して
亜鉛酸イオンとなり、充電時にこの亜鉛酸イオン
が海綿状あるいは樹枝状に電析するため、充放電
サイクルを繰り返すと、それら電析亜鉛が生長し
てセパレータを貫通し内部短絡を引き起してサイ
クル寿命が低下する問題を有していた。
このような問題を解決するために一般に電解液
量を規制し、遊離の電解液をなくし、亜鉛酸イオ
ンの溶出を抑制する方法が採用されている。
ところが電解液量を規制した電池では高率放電
や低温での放電に於いて亜鉛活物質の充放電反応
が円滑に進行しない。これは高率放電では反応速
度が速く同時に多量の電解液を必要とするため電
解液の供給不足となるからであり、低温ではイオ
ンの移動が遅いため実質的に電解液不足となつて
いるからである。また電解液が不足した状態で放
電反応が進むと、亜鉛極の活物質層表面が放電生
成物である緻密な酸化亜鉛に覆われ、活物質層内
部への電解液の拡散が阻害されると共に、前記酸
化亜鉛は電子伝導性の低い不活性なものであるの
で、亜鉛極の反応性が極端に低下する。
このような不活性な酸化亜鉛の生成を抑制する
方法として活物質層中の電解液保持量を増大させ
ることが考えられる。例えば特開昭58−163162号
公報では湿潤剤として酸化チタンを活物質層中に
含有させた亜鉛極が提案されており、これによつ
て、亜鉛極の電解液の含液性が向上し、電解液不
足による不活性な酸化亜鉛の生成が抑制される。
(ハ) 発明が解決しようとする問題点
ところが、湿潤剤を添加した亜鉛極であつて
も、特開昭58−163162号公報で示されるような湿
潤剤が活物質層に均一に添加された亜鉛極では、
湿潤剤の添加量が少ないと、高率放電などを行な
つた場合に、亜鉛極表面の不活性化を充分に抑制
することができなかつた。また湿潤剤の添加量を
増すことにより亜鉛極表面の不活性化を防止する
ことも可能であるが、この場合、活物質量の減少
が多くなるため極板容量が低下すると共に、亜鉛
極の含液性が大きくなり過ぎ活物質が電解液に溶
出するという問題点があつた。
(ニ) 問題点を解決するための手段
本発明はアルカリ亜鉛蓄電池に於ける亜鉛極の
不活性化が亜鉛極表面近傍で著しいことに鑑み、
亜鉛極の集電体表面に形設する活物質層を表面層
と内部層から構成し、表面層及び内部層の何れに
もチタンやジルコニウムなどの酸化物または水酸
化物びカーボンなどの湿潤剤を含有させると共に
湿潤剤の含有割合を内部層より表面層の方を大と
し、上記問題点を解決するものである。
また上記湿潤剤の含有割合は前記表面層で表面
層の５乃至50重量％、前記内部層で内部層の５重
量％以下とするとより一層有効である。
(ホ) 作用
上記手段により、電解液不足が生じ不活性化が
生じ易い亜鉛極表面近傍の電解液の含液性を向上
させることができ、且つ湿潤剤含有割合が大であ
ることによる亜鉛極内部の活物質量の減少及び多
量の電解液を含有することによる活物質の溶出を
防止することができる。
(ヘ) 実施例
以下に本発明の実施例を説明する。
酸化亜鉛粉末45重量％、金属亜鉛粉末45重量
％、添加剤としての酸化水銀４重量％、湿潤剤と
しての酸化ケイ素１重量％及び結着剤としてのフ
ツ素樹脂粉末５重量％よりなる混合粉末に水を加
えて混練し、ローラで圧延してシートＡを作製し
た。またシートＡと同様にして湿潤剤の含有割合
を表１に示すように種々変化させて増量し、その
増量分だけ前記酸化亜鉛及び金属亜鉛からなる活
物質量を減少させてシートＢを作製した。
(a) Industrial Application Field The present invention relates to an alkaline zinc storage battery that uses zinc as a negative electrode active material, such as a nickel-zinc storage battery or a silver-zinc storage battery. (b) Conventional technology Zinc, which is used as a negative electrode active material in alkaline storage batteries, has a high energy density per unit weight and is inexpensive, but on the other hand, zinc dissolves in the electrolyte during discharge and becomes zincate ions, and during charging, this zinc Since acid ions are deposited in a spongy or dendritic shape, when charge and discharge cycles are repeated, the deposited zinc grows and penetrates the separator, causing an internal short circuit and shortening the cycle life. Ta. In order to solve such problems, a method is generally adopted in which the amount of electrolyte is regulated, free electrolyte is eliminated, and elution of zincate ions is suppressed. However, in batteries in which the amount of electrolyte is regulated, the charging and discharging reactions of the zinc active material do not proceed smoothly during high rate discharge or low temperature discharge. This is because in high rate discharge, the reaction speed is fast and a large amount of electrolyte is required at the same time, resulting in a shortage of electrolyte supply, and at low temperatures, the movement of ions is slow, resulting in an actual shortage of electrolyte. It is. In addition, when the discharge reaction progresses in a state where the electrolyte is insufficient, the surface of the active material layer of the zinc electrode is covered with dense zinc oxide, which is a discharge product, and the diffusion of the electrolyte into the active material layer is inhibited. Since the zinc oxide is inert and has low electronic conductivity, the reactivity of the zinc electrode is extremely reduced. One possible method for suppressing the formation of such inert zinc oxide is to increase the amount of electrolyte retained in the active material layer. For example, JP-A-58-163162 proposes a zinc electrode containing titanium oxide as a wetting agent in the active material layer, which improves the electrolyte receptivity of the zinc electrode. The production of inert zinc oxide due to electrolyte shortage is suppressed. (c) Problems to be solved by the invention However, even in the case of a zinc electrode with a wetting agent added, the wetting agent is uniformly added to the active material layer as shown in JP-A-58-163162. At the zinc electrode,
When the amount of the wetting agent added is small, inactivation of the zinc electrode surface cannot be sufficiently suppressed when high rate discharge is performed. It is also possible to prevent the zinc electrode surface from becoming inactivated by increasing the amount of wetting agent added, but in this case, the amount of active material decreases, resulting in a decrease in the electrode plate capacity and the loss of the zinc electrode surface. There was a problem that the liquid-containing property became too large and the active material was eluted into the electrolyte. (d) Means for solving the problems In view of the fact that the zinc electrode in an alkaline zinc storage battery is significantly deactivated near the surface of the zinc electrode, the present invention
The active material layer formed on the current collector surface of the zinc electrode is composed of a surface layer and an internal layer, and both the surface layer and the internal layer contain a wetting agent such as oxide or hydroxide such as titanium or zirconium or carbon. The above-mentioned problems are solved by containing a wetting agent in the surface layer and making the content of the wetting agent larger in the surface layer than in the inner layer. It is even more effective if the content of the wetting agent is 5 to 50% by weight of the surface layer in the surface layer and 5% by weight or less of the inner layer in the inner layer. (E) Effect By the above means, it is possible to improve the electrolyte impregnation near the surface of the zinc electrode where deactivation is likely to occur due to electrolyte shortage, and the zinc electrode is improved due to the large wetting agent content. It is possible to prevent the elution of the active material due to a decrease in the amount of internal active material and the inclusion of a large amount of electrolyte. (f) Examples Examples of the present invention will be described below. Mixed powder consisting of 45% by weight zinc oxide powder, 45% by weight zinc metal powder, 4% by weight mercury oxide as an additive, 1% by weight silicon oxide as a wetting agent, and 5% by weight fluororesin powder as a binder. Water was added and kneaded, and sheet A was prepared by rolling with rollers. Further, in the same manner as sheet A, the content ratio of the wetting agent was varied and increased as shown in Table 1, and the amount of the active material consisting of zinc oxide and metal zinc was decreased by the increased amount to prepare sheet B. .
【表】
こうして作製したシートＡ，Ｂを銅などよりな
る集電体の両面にシートＡ、シートＢの順で重ね
て付着し、加圧成型後乾燥して、集電体の表面に
シートＡからなる内部層と、シートＢからなる表
面層とを備え、且つ内部層と表面層の厚みが１対
１である亜鉛極を得る。この亜鉛極と公知の焼結
式ニツケル極とを組み合わせてニツケル−亜鉛蓄
電池ａ乃至ｈを作製した。尚電池に付した符号は
用いた亜鉛極の表面層の酸化ケイ素の含有割合に
よつて表１に示したａ乃至ｈの符号を対応させて
いる。
第１図にこのニツケル−亜鉛畜電池の断面図を
示す。図中１は亜鉛極であり、２が内部層、３が
表面層、４が集電体である。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。
また比較のために集電体の両面に前記シートＡ
を倍の厚みで付着し、加圧成型及び乾燥して、表
面部及び内部の活物質層に湿潤剤が均一に添加さ
れた亜鉛極を得、この亜鉛極を用いたことを除
き、他は前記実施例と同一の比較電池ｉを作製し
た。
これら電池ａ乃至ｉを用い、0.2Cの電流で５時
間充電した後、0.2Cの電流で電池電圧が1.0Vに
なるまで放電するサイクル条件で充放電を繰り返
し行ない、電池容量が初期容量の50％に達した時
点でサイクル寿命とする方法でサイクル寿命を測
定した。この結果を第２図に示す。また、亜鉛極
に添加する湿潤剤をアセチレンブラツクに替え、
その他は同一で同じ測定を行なつた結果を第３図
に示す。
第２図及び第３図から明らかなように、亜鉛極
の表面層の湿潤剤含有割合が表面層の５〜60重量
％であるときに、湿潤剤が均一に添加され表面層
の湿潤剤含有割合が表面層と１重量％であるもの
よりサイクル寿命が向上し、特に表面層の湿潤剤
含有割合が表面層の５〜50重量％であるときに良
好なサイクル特性が得られていることがわかる。
これは表面層の湿潤剤含有割合が５重量％未満で
あると亜鉛極表面部の含液性があまり向上せず活
物質の不動態化を抑制することができず、また表
面層の湿潤剤含有割合が60重量％を越えると亜鉛
極表面近傍の含液性は大幅に向上するが、活物質
量が減少することとなり、亜鉛極の有効活物質量
が減少し劣化が早まると考えられる。活物質層を
内部層と表面層から構成し内部層の表面に表面層
を形成したこの種亜鉛極では、充放電により表面
層中の亜鉛が内部層に電着し内部層と表面層の密
着性が向上するが、湿潤剤を多量に添加するなど
して表面層中の亜鉛の含有量が減少すると、内部
層に電着する亜鉛が少くなり内部層と表面層の密
着性が低くなり湿潤性の添加効果を充分に発揮す
ることができない。
次いで、電池ｄと同様に湿潤剤含有割合を亜鉛
極の内部層で１重量％、外部層で30重量％とし、
その他の構成は同じで湿潤剤のみ種々変化させて
電池を作製し、表２に示すように用いた湿潤剤に
よつて電池ｊ乃至ｓとする。[Table] Sheets A and B produced in this way are stacked and adhered to both sides of a current collector made of copper or the like in the order of Sheet A and Sheet B, and then dried after pressure molding, and sheet A is placed on the surface of the current collector. A zinc electrode is obtained which includes an inner layer made of the sheet B and a surface layer made of the sheet B, and in which the thickness of the inner layer and the surface layer is 1:1. Nickel-zinc storage batteries a to h were prepared by combining this zinc electrode with a known sintered nickel electrode. The symbols given to the batteries correspond to the symbols a to h shown in Table 1 depending on the content of silicon oxide in the surface layer of the zinc electrode used. FIG. 1 shows a sectional view of this nickel-zinc storage battery. In the figure, 1 is a zinc electrode, 2 is an inner layer, 3 is a surface layer, and 4 is a current collector. 5 is nickel pole, 6
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. For comparison, the sheet A was placed on both sides of the current collector.
was adhered to twice the thickness, pressure-molded, and dried to obtain a zinc electrode with a wetting agent uniformly added to the surface and internal active material layer. Comparative battery i, which is the same as the example described above, was produced. Using these batteries a to i, after charging with a current of 0.2C for 5 hours, charging and discharging were repeated under cycle conditions of discharging with a current of 0.2C until the battery voltage reached 1.0V, and the battery capacity was 50% of the initial capacity. The cycle life was measured by a method in which the cycle life was determined as the cycle life reached the point at which % was reached. The results are shown in FIG. In addition, the wetting agent added to the zinc electrode was replaced with acetylene black,
Figure 3 shows the results obtained by performing the same measurements with the other components being the same. As is clear from Figures 2 and 3, when the wetting agent content in the surface layer of the zinc electrode is 5 to 60% by weight of the surface layer, the wetting agent is uniformly added and the surface layer contains the wetting agent. The cycle life is improved compared to those in which the proportion of the wetting agent in the surface layer is 1% by weight, and particularly good cycle characteristics are obtained when the content of the wetting agent in the surface layer is 5 to 50% by weight of the surface layer. Recognize.
This is because if the wetting agent content in the surface layer is less than 5% by weight, the liquid impregnation of the zinc electrode surface will not improve much and passivation of the active material cannot be suppressed. If the content exceeds 60% by weight, the liquid impregnation near the surface of the zinc electrode will be greatly improved, but the amount of active material will decrease, and it is thought that the effective amount of active material in the zinc electrode will decrease and deterioration will be accelerated. In this type of zinc electrode, where the active material layer is composed of an inner layer and a surface layer, and the surface layer is formed on the surface of the inner layer, the zinc in the surface layer is electrodeposited on the inner layer by charging and discharging, causing close contact between the inner layer and the surface layer. However, if the zinc content in the surface layer is reduced by adding a large amount of wetting agent, less zinc will be electrodeposited on the inner layer, reducing the adhesion between the inner layer and the surface layer, resulting in less moisture. It is not possible to fully demonstrate the effect of adding sex. Next, as in battery d, the wetting agent content was 1% by weight in the inner layer of the zinc electrode and 30% by weight in the outer layer.
Batteries were prepared with the other configurations being the same, but with various wetting agents, and as shown in Table 2, batteries j to s were used depending on the wetting agent used.
【表】
こうして作製した本発明電池ｊ乃至ｓ及びｄと
前記比較電池ｉを用いてサイクル特性を測定し
た。第４図は前述したサイクル条件で充放電を繰
り返し行なつたときのサイクル特性図であり、第
５図は0.2Cの電流で５時間充電した後、2Cの電
流で電池電圧が1.0Vになるまで放電するサイク
ル条件で充放電を繰り返し行なつたときのサイク
ル特性図である。尚、第４図及び第５図中の斜線
部分は、この範囲内に電池ｉ乃至ｓ及びｄの特性
が集中したことを示している。
第４図及び第５図から明らかなように本発明電
池ｉ乃至ｓ及びｄは比較電池ｉよりサイクル寿命
が向上している。これは本発明電池では亜鉛極の
表面層の湿潤剤含有割合が適度に増加したため亜
鉛極表面の電解液の含液性が向上すると共に亜鉛
極の内部層に添加した湿潤剤により亜鉛極の内部
に含液された電解液が放電時に亜鉛極表面に供給
されるので、亜鉛極表面近傍に於ける電解液不足
による不活性化が防止でき、且つ亜鉛極の含液性
が大きすぎることによる活物質の溶出を、亜鉛極
内部の湿潤剤の含有割合を抑えることで効果的に
抑制できたためと考えられる。
また第４図及び第５図では明らかではないが、
本発明電池のうち特性が一番優れたのは電池ｋで
あり、ほとんど差がなく次に電池ｊが、またその
次に電池ｎが優れた特性を示していた。このよう
に電池ｋ及びｉが優れるのは酸化ジルコニウム及
び酸化チタンが他の湿潤剤に比べイオン伝導性が
優れるためと考えられ、電池ｎが優れたのはアセ
チレンブラツクが高い含液性を有するのに加え電
子伝導性が良好であるため、亜鉛極内での亜鉛の
酸化還元反応が円滑に行なわれたからと考えられ
る。
尚、本発明に用いる湿潤剤としては上記実施例
に於いて示したものの他、ストロンチウム、バリ
ウム、イツトリウム、ゲルマニウム及び錫の酸化
物または水酸化物などが有効である。
(ト) 発明の効果
本発明のアルカリ亜鉛蓄電池は、集電体の表面
に活物質層を形設してなる亜鉛極を備えるもので
あり、前記活物質層を表面層と内部層とから構成
し、表面層及び内部層の何れにも湿潤剤を含有さ
せ、且つ湿潤剤の含有割合を内部層より表面層の
方を大としたものであるから、高率放電時などに
於ける亜鉛極表面近傍の電解液不足による不活性
化が抑制されると共に、亜鉛極の含液性が向上し
過ぎることによる活物質の溶出を抑えることがで
き、サイクル寿命を向上させることができる。[Table] Cycle characteristics were measured using the batteries j to s and d of the present invention thus prepared and the comparative battery i. Figure 4 is a cycle characteristic diagram when charging and discharging are repeated under the above-mentioned cycle conditions, and Figure 5 shows that after 5 hours of charging at a current of 0.2C, the battery voltage becomes 1.0V at a current of 2C. FIG. 3 is a cycle characteristic diagram when charging and discharging are repeatedly performed under cycle conditions of discharging up to 100 Ω. Note that the shaded areas in FIGS. 4 and 5 indicate that the characteristics of batteries i to s and d are concentrated within this range. As is clear from FIGS. 4 and 5, batteries i to s and d of the present invention have improved cycle life than comparative battery i. This is because in the battery of the present invention, the content of the wetting agent in the surface layer of the zinc electrode has been appropriately increased, which improves the electrolyte receptivity on the surface of the zinc electrode. Since the electrolyte contained in the zinc electrode is supplied to the surface of the zinc electrode during discharge, inactivation due to lack of electrolyte near the surface of the zinc electrode can be prevented, and activation due to excessive liquid impregnation of the zinc electrode can be prevented. This is thought to be because the elution of the substance could be effectively suppressed by suppressing the content of the wetting agent inside the zinc electrode. Also, although it is not clear in Figures 4 and 5,
Among the batteries of the present invention, battery k had the best characteristics, followed by battery j with almost no difference, and then battery n. The reason why batteries k and i are superior is thought to be because zirconium oxide and titanium oxide have superior ionic conductivity compared to other wetting agents, and the reason battery n is superior is because acetylene black has high liquid-retaining properties. This is thought to be due to the fact that the zinc oxidation-reduction reaction within the zinc electrode was carried out smoothly due to the good electron conductivity. In addition to the wetting agents shown in the above examples, oxides or hydroxides of strontium, barium, yttrium, germanium, and tin are also effective as wetting agents used in the present invention. (G) Effects of the Invention The alkaline zinc storage battery of the present invention includes a zinc electrode formed by forming an active material layer on the surface of a current collector, and the active material layer is composed of a surface layer and an inner layer. However, since both the surface layer and the internal layer contain a wetting agent, and the content of the wetting agent is greater in the surface layer than in the internal layer, the zinc electrode is Inactivation due to insufficient electrolyte near the surface can be suppressed, and elution of the active material due to excessive improvement in liquid impregnation of the zinc electrode can be suppressed, and cycle life can be improved.
第１図は本発明電池の断面図、第２図及び第３
図は亜鉛極の表面層の湿潤剤含有割合とサイクル
寿命との関係を示す図面、第４図及び第５図は本
発明電池と比較電池のサイクル特性図である。
１……亜鉛極、２……内部層、３……表面層、
５……ニツケル極、６……セパレータ、７……保
液層、８……電槽、９……電槽蓋、１０，１１…
…正、負極端子。
Figure 1 is a sectional view of the battery of the present invention, Figures 2 and 3.
The figure shows the relationship between the wetting agent content in the surface layer of the zinc electrode and the cycle life, and FIGS. 4 and 5 are cycle characteristic diagrams of the battery of the present invention and the comparative battery. 1...Zinc electrode, 2...Inner layer, 3...Surface layer,
5... Nickel electrode, 6... Separator, 7... Liquid retaining layer, 8... Battery container, 9... Battery container lid, 10, 11...
...Positive and negative terminals.
Claims (1)
極を備えた電池であつて、前記活物質層は表面層
と内部層とから構成され、表面層及び内部層は何
れも湿潤剤を含有し、且つ湿潤剤の含有割合が内
部層より表面層の方が大であることを特徴とする
アルカリ亜鉛蓄電池。 ２ 前記表面層は表面層の５乃至50重量％の湿潤
剤を含有し、前記内部層は内部層の５重量％以下
の湿潤剤を含有することを特徴とする特許請求の
範囲第１項記載のアルカリ亜鉛蓄電池。 ３ 前記湿潤剤はケイ素、ジルコニウム、チタ
ン、マグネシウム、ストロンチウム、バリウム、
アルミニウム、イツトリウム、ゲルマニウム及び
錫からなる群から選ばれた少なくとも一種の酸化
物または水酸化物であることを特徴とする特許請
求の範囲第１項記載のアルカリ亜鉛蓄電池。 ４ 前記湿潤剤はカーボンであることを特徴とす
る特許請求の範囲第１項記載のアルカリ亜鉛蓄電
池。[Scope of Claims] 1. A battery equipped with a zinc electrode formed with an active material layer formed on the surface of a current collector, wherein the active material layer is composed of a surface layer and an internal layer, and the surface layer and An alkaline zinc storage battery characterized in that each of the internal layers contains a wetting agent, and the content of the wetting agent is greater in the surface layer than in the internal layer. 2. The surface layer contains a wetting agent in an amount of 5 to 50% by weight of the surface layer, and the inner layer contains a wetting agent in an amount of 5% by weight or less of the inner layer. alkaline zinc storage battery. 3 The wetting agent is silicon, zirconium, titanium, magnesium, strontium, barium,
The alkaline zinc storage battery according to claim 1, wherein the alkaline zinc storage battery is at least one oxide or hydroxide selected from the group consisting of aluminum, yttrium, germanium, and tin. 4. The alkaline zinc storage battery according to claim 1, wherein the wetting agent is carbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60172752A JPS6235453A (en) | 1985-08-06 | 1985-08-06 | Alkaline-zinc storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60172752A JPS6235453A (en) | 1985-08-06 | 1985-08-06 | Alkaline-zinc storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6235453A JPS6235453A (en) | 1987-02-16 |
| JPH0564419B2 true JPH0564419B2 (en) | 1993-09-14 |
Family
ID=15947663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60172752A Granted JPS6235453A (en) | 1985-08-06 | 1985-08-06 | Alkaline-zinc storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6235453A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004522256A (en) * | 2000-11-10 | 2004-07-22 | パワージェニックス システムズ インク | Zinc negative electrode formulation for rechargeable cells with alkaline electrolyte |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7550230B2 (en) | 2001-03-15 | 2009-06-23 | Powergenix Systems, Inc. | Electrolyte composition for nickel-zinc batteries |
-
1985
- 1985-08-06 JP JP60172752A patent/JPS6235453A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004522256A (en) * | 2000-11-10 | 2004-07-22 | パワージェニックス システムズ インク | Zinc negative electrode formulation for rechargeable cells with alkaline electrolyte |
| JP4807923B2 (en) * | 2000-11-10 | 2011-11-02 | パワージェニックス システムズ， インコーポレーテッド | Zinc negative electrode formulation for rechargeable cells with alkaline electrolyte |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6235453A (en) | 1987-02-16 |
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