JPH0722022B2 - Method for manufacturing sealed alkaline zinc storage battery - Google Patents
Method for manufacturing sealed alkaline zinc storage batteryInfo
- Publication number
- JPH0722022B2 JPH0722022B2 JP61220357A JP22035786A JPH0722022B2 JP H0722022 B2 JPH0722022 B2 JP H0722022B2 JP 61220357 A JP61220357 A JP 61220357A JP 22035786 A JP22035786 A JP 22035786A JP H0722022 B2 JPH0722022 B2 JP H0722022B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- zinc
- anode
- capacity
- cathode
- 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 63
- 239000011701 zinc Substances 0.000 title claims description 60
- 229910052725 zinc Inorganic materials 0.000 title claims description 58
- 238000003860 storage Methods 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000000034 method Methods 0.000 title claims description 5
- 238000007789 sealing Methods 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 10
- 229910001882 dioxygen Inorganic materials 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 8
- 239000011149 active material Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 2
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- -1 zincate ions Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/34—Gastight accumulators
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Description
【発明の詳細な説明】 〈産業上の利用分野〉 この発明は、陰極に亜鉛極を用いる密閉型アルカリ亜鉛
蓄電池の製造方法に関するものである。TECHNICAL FIELD The present invention relates to a method for manufacturing a sealed alkaline zinc storage battery using a zinc electrode as a cathode.
〈従来の技術〉 ニッケル‐亜鉛蓄電池や銀‐亜鉛蓄電池などのアルカリ
亜鉛蓄電池は、エネルギー密度が大きくて無公害の電池
としての期待が高く、その実用化のための開発が進めら
れている。特に、最近、電気機器のコードレス化に伴
い、軽量で高エネルギー密度の蓄電池が要求されている
なかで、この要求を満たしうるものとして注目されてい
る。<Prior Art> Alkaline zinc storage batteries such as nickel-zinc storage batteries and silver-zinc storage batteries have high energy density and are highly expected as pollution-free batteries, and development for practical use thereof is underway. In particular, with the recent trend toward cordless electric devices, lightweight and high-energy-density storage batteries have been demanded, and attention has been paid to satisfying these demands.
このアルカリ亜鉛蓄電池では、放電時に亜鉛極から電解
液中に溶出して生じた亜鉛酸イオンが充電時には亜鉛極
表面に樹枝状あるいは海綿状に電析しまたセパレータを
通って対極に向って漸次生長することから、充放電を何
回も繰弁返すと、この電析亜鉛がセパレータを貫通して
内部短絡を引き起こし、サイクル寿命を低下させるとい
う不都合がある。そこで、従来より、電解液量を制限し
て亜鉛酸イオンの拡散を防止するなどして上記電析亜鉛
の成長に起因する内部短絡の抑制を図るなどの構成が採
られている。In this alkaline zinc storage battery, zincate ions generated by elution from the zinc electrode into the electrolytic solution during discharge are deposited on the surface of the zinc electrode in a dendritic or spongy manner, and gradually grow toward the counter electrode through the separator. Therefore, if charging and discharging are repeated many times, this electrodeposited zinc penetrates the separator and causes an internal short circuit, which disadvantageously shortens the cycle life. Therefore, conventionally, a structure has been adopted in which the amount of the electrolytic solution is limited to prevent the diffusion of zincate ions, thereby suppressing an internal short circuit caused by the growth of the above-described zinc deposit.
また、この種の蓄電池、例えばニッケル‐亜鉛蓄電池で
は、満充電に達するとニッケル陽極からは酸素ガスが、
亜鉛極からは水素ガスがそれぞれ発生する。そして、上
記の酸素ガスは亜鉛極においてその充電生成物の金属亜
鉛と反応させて消費しうるが、亜鉛極で発生する水素ガ
スは電池内で消費されることなく電池内に蓄積され、こ
のため、過充電状態が長く続いた場合、水素ガス蓄積量
の増大によって電池内圧上昇を招くという不都合があ
り、電池の密閉化が非常に困難となってしまう。そこ
で、現用の密閉型アルカリ亜鉛蓄電池では、亜鉛極の容
量を陽極容量よりも実質的に大きくする所謂陽極支配と
し、過充電状態にあっても陽極からの酸素ガスを優先的
に発生させ、亜鉛極からの水素ガス発生を抑制するよう
にしている。Further, in this type of storage battery, for example, a nickel-zinc storage battery, when the battery reaches full charge, oxygen gas is emitted from the nickel anode.
Hydrogen gas is generated from the zinc electrode. The above oxygen gas can be consumed by reacting with the charge product metal zinc at the zinc electrode, but the hydrogen gas generated at the zinc electrode is accumulated in the battery without being consumed in the battery. However, if the overcharged state continues for a long time, there is a disadvantage that the internal pressure of the battery rises due to an increase in the hydrogen gas storage amount, and it becomes very difficult to hermetically seal the battery. Therefore, in the current sealed alkaline zinc storage battery, the capacity of the zinc electrode is so-called anode-dominated so that the capacity of the zinc electrode is substantially larger than the capacity of the anode, and oxygen gas is preferentially generated from the anode even in an overcharged state. The generation of hydrogen gas from the electrodes is suppressed.
ところで、上記のように密閉型アルカリ亜鉛蓄電池を陽
極支配で構成した場合、充電末期に陽極で発生する酸素
ガスを陰極である亜鉛極で速やかに吸収・消費させなけ
れば電池内圧の上昇により漏液や電池缶の膨れの原因と
なり、また電池のサイクル寿命低下を招く。このため、
従来技術では、電池作製時、陰極活物質中に金属亜鉛を
粉末で添加して放電リザーブを持たしておくようにした
構成が知られている。この構成とすれば、酸素ガスの還
元剤として機能する金属亜鉛が陰極中に多量に存在する
ようになり、酸化ガス吸収速度が高まって電池内圧上昇
を大幅に抑制することが可能となる。また、このように
亜鉛極中に金属亜鉛を添加して放電リザーブを持たせて
おくことで、少量の亜鉛活物質が電解液中に溶解し逸散
した場合でもこれによる容量低下が抑えられるという効
果を併せ持つ。By the way, when the sealed alkaline zinc storage battery is configured by controlling the anode as described above, oxygen gas generated at the anode at the end of charging must be promptly absorbed and consumed by the zinc electrode, which is the cathode. It also causes swelling of the battery can and shortens the cycle life of the battery. For this reason,
In the prior art, a structure is known in which metallic zinc is added as a powder to a cathode active material so as to have a discharge reserve at the time of manufacturing a battery. With this configuration, a large amount of metallic zinc, which functions as a reducing agent for oxygen gas, is present in the cathode, the oxidizing gas absorption rate is increased, and the increase in battery internal pressure can be significantly suppressed. In addition, by adding metallic zinc to the zinc electrode in this way so as to have a discharge reserve, even if a small amount of the zinc active material dissolves in the electrolyte and dissipates, the capacity decrease due to this is suppressed. It also has an effect.
〈発明が解決しようとする問題点〉 しかしながら、上記で添加される金属亜鉛粉末は、亜鉛
極において酸化亜鉛から充電されてできる金属亜鉛に較
べてその粒径が非常に大きい。このため、放電時、上記
充電されてできる金属亜鉛に較べて完全放電しにくく、
電池の放電が終了した段階でも亜鉛極表面に粒子として
残る。そして、次の充電時にはここから前記樹枝状の電
析亜鉛が生長し易くなり、結果的に電池内部短絡を引き
起こす度合が高まるという問題がある。<Problems to be Solved by the Invention> However, the particle size of the above-mentioned metallic zinc powder added is much larger than that of metallic zinc formed by charging zinc oxide at the zinc electrode. Therefore, during discharge, it is less likely to be completely discharged as compared with the metallic zinc that can be charged.
Even when the battery is completely discharged, it remains as particles on the zinc electrode surface. Then, during the next charging, there is a problem that the dendritic zinc is likely to grow from here, and as a result, the degree of causing a battery internal short circuit increases.
〈問題点を解決するための手段〉 この発明の密閉型アルカリ亜鉛蓄電池の製造方法は、陰
極容量を陽極容量より実質的に大きくし、且つ陰極と陽
極との理論容量比が約４以上である陽極支配の密閉型ア
ルカリ亜鉛蓄電池の製造工程において、陽極と陰極とを
組合せ、陽極容量に対して120〜300％の充電を行なった
後に、電池封口をすることを要旨とする。<Means for Solving Problems> In the method for manufacturing the sealed alkaline zinc storage battery of the present invention, the cathode capacity is substantially larger than the anode capacity, and the theoretical capacity ratio between the cathode and the anode is about 4 or more. In the process of manufacturing a sealed alkaline zinc storage battery dominated by an anode, the gist is to combine the anode and the cathode, charge the battery to 120 to 300% of the anode capacity, and then seal the battery.
上記充電が陽極容量に対して120％未満であると、亜鉛
極中に放電リザーブ用として十分な量の金属亜鉛が生成
できないのでサイクル時の電池内圧の上昇が大きくな
る。一方、充電量が300％を超えた場合、金属亜鉛の生
成量が過多になり、電池内圧上昇の抑制効果の顕著な向
上はみられず、かえって樹枝状亜鉛によるショートが発
生してしまう。If the charge is less than 120% of the anode capacity, a sufficient amount of metallic zinc for the discharge reserve cannot be generated in the zinc electrode, and the internal pressure of the battery during cycling will increase significantly. On the other hand, when the charge amount exceeds 300%, the amount of metallic zinc produced becomes excessive, and the effect of suppressing the rise in battery internal pressure is not significantly improved, but rather a short circuit due to dendritic zinc occurs.
〈作用〉 例えば陽極支配のニッケル‐亜鉛蓄電池では、充電時に
は （陽極）2Ni（OH）２＋2OH-→2NiOOH＋2H2O＋2e- …
（陰極）ZnO＋H2O＋2e-→Zn＋2OH- … という反応が進行する。そして、陽極の充電が完了した
後も充電を行なった場合、陽極では、 2OH-→1/2O2＋H2O＋2e- … なる反応によって酸素ガスが発生する。この時、陰極で
は上記式の反応が続いており、結局、電池内では式
と式とを合せた ZnO→Zn＋1/2O2 … という反応、即ち、陰極では酸化亜鉛が金属亜鉛に変わ
る反応が進行している。<Action> For example anode domination of nickel - in the zinc battery, at the time of charging (anode) 2Ni (OH) 2 + 2OH - → 2NiOOH + 2H 2 O + 2e - ...
(Cathode) The reaction of ZnO + H 2 O + 2e − → Zn + 2OH − . When the anode is charged even after the charging is completed, oxygen gas is generated in the anode due to the reaction of 2OH − → 1 / 2O 2 + H 2 O + 2e − . At this time, the reaction of the above formula continues at the cathode, and in the end, the reaction of ZnO → Zn + 1 / 2O 2 …, which combines the formulas in the battery, that is, the reaction of converting zinc oxide to metallic zinc at the cathode progresses is doing.
従って、上記手段のように充電を陽極容量に対して120
〜300％行なった場合、この充電によって陰極中では酸
化亜鉛から金属亜鉛が生成し、陰極中に前記放電リザー
ブを作ることができる。このようにして電池化学的に生
成された金属亜鉛はその粒径が微細で、前記金属亜鉛粉
末のような電池内部短絡を引き起こす原因となることは
ない。そして、このような操作を電池封口前に行なえ
ば、上記式により発生する酸素ガスを電池系外に放出
させることができる。Therefore, as in the above-mentioned means, charging is performed with respect to the anode capacity of 120
In the case of ~ 300%, metallic zinc is produced from zinc oxide in the cathode by this charging, and the discharge reserve can be formed in the cathode. The metal zinc thus chemically generated in the battery has a fine particle size and does not cause a short circuit inside the battery like the metal zinc powder. If such an operation is performed before the battery is sealed, the oxygen gas generated by the above formula can be released to the outside of the battery system.
〈実施例〉 酸化亜鉛90重量部、金属亜鉛５重量部、及び添加剤とし
て酸化カドミウム５重量部とからなる活物質粉末を混合
し、更に水とフッ素樹脂とを加え混練して活物質ペース
トを作製した。この活物質ペーストを銅メッシュに圧着
して亜鉛極を作り、この亜鉛極と公知の焼結式ニッケル
極とを組合せ、円筒の電池缶内に収納し、電解液には酸
化亜鉛を飽和させた35重量％水酸化カリウムを用いて、
円筒密閉型のニッケル‐亜鉛蓄電池を構成した。尚、陰
極と陽極との理論容量比（陰極容量／陽極容量）は約４
とした。<Example> An active material powder consisting of 90 parts by weight of zinc oxide, 5 parts by weight of metallic zinc, and 5 parts by weight of cadmium oxide as an additive is mixed, and water and a fluororesin are further added and kneaded to form an active material paste. It was made. This active material paste was pressed onto a copper mesh to form a zinc electrode, and this zinc electrode and a known sintered nickel electrode were combined and housed in a cylindrical battery can, and the electrolytic solution was saturated with zinc oxide. With 35 wt% potassium hydroxide,
A cylindrical sealed nickel-zinc storage battery was constructed. The theoretical capacity ratio of the cathode and the anode (cathode capacity / anode capacity) is about 4
And
以上の構成の池であって、何の処理も行なわずに電池缶
開口部を封口して比較用の電池（比較電池Ａ）を作製し
た。また、亜鉛極とニッケル極とを組合せた後に陽極理
論容量に対して100％相当分の充電をしてから上記封口
を行なって比較用の電池（比較電池Ｂ）を作製した。更
に、上記充電を陽極理論容量に対して120％（本発明電
池Ｃ）、300％（本発明電池Ｄ）行なった後にそれぞれ
封口をして、本発明の電池を作った。一方、酸化亜鉛50
重量部、金属亜鉛45重量部、並びに酸化カドミウム５重
量部からなる活物質粉末を用いた他は上記と同様な活物
質ペーストを作り、このペーストを銅メッシュに圧着し
て得た亜鉛極を用いた他は比較電池Ａと同様にして比較
用の電池（比較電池Ｅ）を作った。尚、電池Ａ〜Ｄにつ
いては封口後に完全放電状態にした。In the pond having the above structure, the battery can opening was sealed without performing any treatment, and a comparative battery (comparative battery A) was produced. Further, a battery for comparison (Comparative Battery B) was prepared by combining a zinc electrode and a nickel electrode, charging 100% of the theoretical theoretical capacity of the anode, and then sealing the battery. Further, after the above charging was carried out to 120% of the theoretical capacity of the anode (Battery C of the present invention) and 300% (Battery D of the present invention), the respective caps were sealed to prepare a battery of the present invention. On the other hand, zinc oxide 50
Parts by weight, 45 parts by weight of metallic zinc, and 5 parts by weight of cadmium oxide were used to prepare an active material paste similar to that described above, and use a zinc electrode obtained by pressing this paste onto a copper mesh. A comparative battery (Comparative Battery E) was made in the same manner as Comparative Battery A except that it was used. The batteries A to D were completely discharged after sealing.
これら電池Ａ〜Ｅについて、充放電電流値を４時間率と
して充放電サイクルを繰返した。その時の電池内圧（Kg
/cm2）の変化を第１図に、また初期放電容量を100％と
した時の電池容量（％）の変化を第２図に夫々示した。
尚、電池内圧は電池缶開口部に設けた封口体に圧力セン
サを取付けて測定した。For these batteries A to E, the charging / discharging cycle was repeated at a charging / discharging current value of 4 hours. Battery internal pressure (Kg
The change in / cm 2 ) is shown in FIG. 1, and the change in battery capacity (%) when the initial discharge capacity is 100% is shown in FIG.
The internal pressure of the battery was measured by attaching a pressure sensor to the sealing body provided at the opening of the battery can.
第１図より、比較電池A,Bは電池内圧の上昇が大きく早
期サイクルで電池内圧が異常に大きくなってしまうこと
がわかる。これは、比較電池A,Bに用いた亜鉛極の酸素
ガス吸収性能が悪いことによることは明らかであり、比
較電池Ｂについて考察すれば、亜鉛極中に十分な放電リ
ザーブ用の金属亜鉛が電池作製時に生成されていないこ
とに起因するものと思われる。From FIG. 1, it is understood that the comparative batteries A and B have a large increase in the battery internal pressure and the battery internal pressure becomes abnormally large in an early cycle. It is clear that this is due to the poor oxygen gas absorption performance of the zinc electrodes used in the comparative batteries A and B. Considering the comparative battery B, sufficient zinc for discharge reserve metal zinc is used in the batteries. It is thought that this is due to the fact that it was not generated during production.
一方、第２図より、比較電池Ｅでは第137サイクルを過
ぎる頃から電池容量の劣化が著しくなり、電池容量が60
％以下になった時点をサイクル寿命とした場合、比較電
池Ｅはサイクル寿命が148サイクルであった。また、比
較電池A,Bのサイクル寿命は夫々293,311であり、サイク
ル寿命は短い。比較電池Ｅのサイクル寿命がこのように
著しく短いのは、この電池に用いた亜鉛極の作製時に放
電リザーブ用として添加された金属亜鉛粉末の粒径が大
きく、放電しにくいので、亜鉛極表面に残って樹枝状の
電析亜鉛の生長の起点となり易く、このために充放電サ
イクルの進行に伴う内部短絡の発生の度合が大きいこと
による。On the other hand, as shown in FIG. 2, in the comparative battery E, the deterioration of the battery capacity became remarkable after about the 137th cycle, and the battery capacity was 60%.
The cycle life of Comparative Battery E was 148 cycles when the time point at which it became less than or equal to% was taken as the cycle life. Further, the cycle lives of the comparative batteries A and B are 293 and 311 respectively, and the cycle lives are short. The comparatively short cycle life of the comparative battery E is because the zinc powder used for the battery has a large particle size of the metal zinc powder added for the discharge reserve when it is manufactured, and is difficult to discharge. This is because the remaining dendritic zinc tends to be a starting point for the growth of the electrodeposited zinc, and for this reason, the degree of occurrence of internal short circuit accompanying the progress of the charge / discharge cycle is large.
これに対して本発明電池C,Dでは、電気化学的に生成さ
せた金属亜鉛を放電リザーブ用として使用した亜鉛極を
用いたので酸素ガス吸収性能もよく、また上記電析亜鉛
の樹枝状の生長が著しく抑えられてサイクル中の内部短
絡の発生の度合が著しく小さく、このため、電池内圧の
上昇が小さく且つ電池容量の劣化の少ない電池が得られ
る。On the other hand, in the batteries C and D of the present invention, since the zinc electrode used was the electrochemically generated metallic zinc used for the discharge reserve, the oxygen gas absorption performance was also good, and the dendritic form of the electrodeposited zinc described above was used. The growth is remarkably suppressed, and the degree of occurrence of internal short circuit during the cycle is remarkably small. Therefore, a battery having a small increase in battery internal pressure and a small deterioration in battery capacity can be obtained.
尚、亜鉛極を構成する陰極活物質中への金属亜鉛粉末の
添加については、本発明C,Dのように少量であればサイ
クル劣化を招くという問題はなく、かえって第１サイク
ル目の充電が円滑に進んで好ましい。しかし、比較電池
Ｅのように金属亜鉛粉末の添加の量が多い場合、上記の
ように内部短絡が生じ易く、サイクル劣化を招く。Regarding the addition of metallic zinc powder into the cathode active material that constitutes the zinc electrode, there is no problem that cycle deterioration will occur as in the case of the present invention C and D, but rather the first cycle charging It is preferable to proceed smoothly. However, when the amount of the metallic zinc powder added is large as in the comparative battery E, the internal short circuit is likely to occur as described above, which causes cycle deterioration.
〈発明の効果〉 以上のように、この発明の製造方法によれば、充放電サ
イクルにおいて酸素ガス吸収性能がよく、また亜鉛極に
おける電析亜鉛に起因する容量低下が少ない、サイクル
特性の良好な密閉型アルカリ亜鉛蓄電池を提供すること
ができる。<Effects of the Invention> As described above, according to the manufacturing method of the present invention, the oxygen gas absorption performance in the charge / discharge cycle is good, the capacity decrease due to the electrodeposited zinc in the zinc electrode is small, and the cycle characteristics are good. A sealed alkaline zinc storage battery can be provided.
第１図は本発明電池並びに比較電池における電池内圧の
サイクル変化を示したグラフ、第２図は同じく電池容量
のサイクル変化を示したグラフである。FIG. 1 is a graph showing cycle changes in battery internal pressure in the present invention battery and comparative battery, and FIG. 2 is a graph showing cycle changes in battery capacity.
Claims (1)
し、且つ陰極と陽極との理論容量比が約４以上である陽
極支配の密閉型アルカリ亜鉛蓄電池の製造工程におい
て、陽極と陰極を組合せ、陽極容量に対して120〜300％
の充電を行った後に、電池封口をすることを特徴とする
密閉型アルカリ亜鉛蓄電池の製造方法。1. A combination of an anode and a cathode in a manufacturing process of an anode-controlled sealed alkaline zinc storage battery in which the cathode capacity is substantially larger than the anode capacity, and the theoretical capacity ratio between the cathode and the anode is about 4 or more. , 120 to 300% of the anode capacity
A method for manufacturing a sealed alkaline zinc storage battery, which comprises charging the battery and then sealing the battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61220357A JPH0722022B2 (en) | 1986-09-18 | 1986-09-18 | Method for manufacturing sealed alkaline zinc storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61220357A JPH0722022B2 (en) | 1986-09-18 | 1986-09-18 | Method for manufacturing sealed alkaline zinc storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6376270A JPS6376270A (en) | 1988-04-06 |
| JPH0722022B2 true JPH0722022B2 (en) | 1995-03-08 |
Family
ID=16749870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61220357A Expired - Lifetime JPH0722022B2 (en) | 1986-09-18 | 1986-09-18 | Method for manufacturing sealed alkaline zinc storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0722022B2 (en) |
-
1986
- 1986-09-18 JP JP61220357A patent/JPH0722022B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6376270A (en) | 1988-04-06 |
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| EXPY | Cancellation because of completion of term |