JPH04206468A - Sealed alkali-zinc storage battery - Google Patents
Sealed alkali-zinc storage batteryInfo
- Publication number
- JPH04206468A JPH04206468A JP2338702A JP33870290A JPH04206468A JP H04206468 A JPH04206468 A JP H04206468A JP 2338702 A JP2338702 A JP 2338702A JP 33870290 A JP33870290 A JP 33870290A JP H04206468 A JPH04206468 A JP H04206468A
- Authority
- JP
- Japan
- Prior art keywords
- electrode plate
- bulkheads
- negative electrode
- oxygen gas
- 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.)
- Pending
Links
- 239000011701 zinc Substances 0.000 title claims abstract description 21
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011149 active material Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 239000011347 resin Substances 0.000 claims abstract description 6
- 229920005989 resin Polymers 0.000 claims abstract description 6
- 239000011787 zinc oxide Substances 0.000 claims abstract description 4
- 230000002093 peripheral effect Effects 0.000 claims abstract 3
- 238000005192 partition Methods 0.000 claims description 19
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 12
- 238000010521 absorption reaction Methods 0.000 abstract description 10
- 239000004809 Teflon Substances 0.000 abstract description 4
- 229920006362 Teflon® Polymers 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- -1 zincate ions Chemical class 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 239000010949 copper Substances 0.000 abstract description 2
- 238000004080 punching Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は密閉型アルカリ亜鉛蓄電池の亜鉛極及び亜鉛極
に接する保液層の構造に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to the structure of a zinc electrode and a liquid retaining layer in contact with the zinc electrode of a sealed alkaline zinc storage battery.
従来の技術
辺土特に電気自動車、産業用ロホ・・トこと・“−用七
較的大容量電池を、必要とする機器か普及し始ｙ・ごい
る。これら機器の高性能化、軽量化か進むｒ ＋＋′い
、電池もより軽量化、小型化、高エネルギー密度化か要
求されている。Conventional technology is beginning to spread, especially in electric vehicles and industrial devices, which require relatively high-capacity batteries. As the world advances, batteries are required to be lighter, smaller, and have higher energy density.
密閉型アルカリ亜鉛蓄電池は、高エネルキコ 密度、
高出力特性、メンテナンスのＩ′１１↓ろさに優れてい
る。しかし、従来のアルカリ亜鉛蓄電／ｌｉ！の曲１；
）極は、充放電によってデンドライトショート、Ｊｌ状
変化、酸素ガスの不均一吸収なとの現象δ′１ユ（ると
いう欠点を持っていた。特に、比較釣人ヤ（の電池にお
いては、酸素ガスの不均一吸収（てよ−２て充放電サイ
クル初期に於て電池の放電容量カベ低「゛するという欠
点を持っていた。Sealed alkaline zinc storage batteries have high energy density,
Excellent high output characteristics and low maintenance I'11↓. However, conventional alkaline zinc storage/li! song 1;
) electrodes had the disadvantages of dendrite short-circuiting, Jl-like changes, and uneven absorption of oxygen gas due to charging and discharging. It has the disadvantage that the discharge capacity of the battery decreases at the beginning of the charge/discharge cycle.
これに対し、寅開昭６１−４８６５５号公報に於て、亜
鉛電極基盤にペースト状亜鉛を学年すく・過程で、ペー
スト不塗布部を設けることによって電解液透通部を形成
することか提案されている。On the other hand, in Torakai Publication No. 61-48655, it was proposed to form an electrolyte permeable part by providing a paste-uncoated part in the process of applying paste zinc to a zinc electrode base. ing.
発明か解決しようとする課題
従来の技術で述へた考案は、電解液、もしくはイオンの
透通を自在にすることて、電解液の濃度及び活物質濃度
を均一にすることを目的としているもので、ジンケート
イオンの拡散による形状変化を防止できずサイクル寿命
性能を高めることか出来なかった。又、酸素ガスの不均
一吸収を防止し、充放電サイクル初期に於ける電池の放
電容量の低下を抑制することはてきないという問題点か
あった。Problems to be Solved by the Invention The inventions described in the prior art are aimed at making the concentration of the electrolytic solution and the concentration of the active material uniform by allowing the electrolytic solution or ions to freely pass through. However, it was not possible to prevent shape changes due to diffusion of zincate ions, and it was not possible to improve cycle life performance. Further, there is a problem in that it is impossible to prevent uneven absorption of oxygen gas and suppress a decrease in the discharge capacity of the battery at the beginning of the charge/discharge cycle.
本発明は、上記問題点に鑑みてなされたものであって、
その目的とするところは、酸素ガスの均一吸収を容易に
して充放電サイクル初期における電池の放電容量低下の
防止を可能にし、かつ、形状変化を抑制し５て亜鉛極容
量の減少を防止することであり、その結果電池容量及び
サイクル寿命性能に優れた密閉型アルカリ亜鉛蓄電池を
提供することである。The present invention has been made in view of the above problems, and includes:
The purpose of this is to facilitate uniform absorption of oxygen gas to prevent a decrease in the discharge capacity of the battery at the beginning of the charge/discharge cycle, and to prevent a decrease in zinc electrode capacity by suppressing shape changes5. As a result, it is an object of the present invention to provide a sealed alkaline zinc storage battery that has excellent battery capacity and cycle life performance.
課題を解決するだめの手段
そのような課題を解決するものとして、この発明に係る
密閉型アルカリ亜鉛蓄電池は次のよう１″；ものとした
。すなわち、耐アルカリ性樹脂によ１て負極板の活物質
を同一極板上で分割して、分割された各部分か完全に分
離されたものとした。そして、負極板周辺部にも耐アル
カリ性樹脂の隔壁を設け、さらにこの隔壁と接触する保
液層か隔壁に溶着または圧着されていることか好ましい
。Means for Solving the Problems In order to solve such problems, the sealed alkaline zinc storage battery according to the present invention has the following structure.That is, the negative electrode plate is activated by an alkali-resistant resin. The material was divided on the same electrode plate, and each divided part was completely separated.Also, a partition wall made of alkali-resistant resin was provided around the negative electrode plate, and a liquid retaining layer was placed in contact with this partition wall. Preferably, the layer is welded or crimped to the partition wall.
作 用
１枚の負極を耐アルカリ性樹脂からなる隔壁で分割し、
さらに隔壁に接触する保液層を隔壁に溶着又は圧着して
各部分の活物質を完全に分離することによってジンケー
トイオンの拡散による形状変化を防止し、かつ、極板周
辺部に設けた隔壁により極板周辺部のみにおける酸素ガ
スの吸収を抑制することか可能となり、かつ、隔壁を通
して酸素ガスか極板中央部へ拡散するため、酸素ガスの
不均一吸収か防止される。Function: A single negative electrode is divided by partition walls made of alkali-resistant resin.
Furthermore, by welding or press-bonding the liquid retaining layer that contacts the partition wall to the partition wall and completely separating the active material in each part, shape change due to diffusion of zincate ions is prevented, and the partition wall provided around the electrode plate It is possible to suppress the absorption of oxygen gas only in the periphery of the electrode plate, and since the oxygen gas diffuses into the center of the electrode plate through the partition wall, uneven absorption of oxygen gas is prevented.
実施例
以下に本発明の実施例について図面を参照して説明する
。Embodiments Below, embodiments of the present invention will be described with reference to the drawings.
第１図（Ａ）および（Ｂ）は、本発明の一実施例に係る
負極板を示す斜視図および断面図であり、１か銅パシチ
ングメタル製の集電体、２はテフロン製の隔壁で、格子
形状をなし、内面か９分割されている。３は亜鉛と酸化
亜鉛を主成分とする活物質、４は端子である。このよな
負極板５は以下の方法で作製した。すなわち、金属亜鉛
と酸化亜鉛およびバインダーとしてのテフロンを混合し
、溶剤としてアルコールを用いてペースト状活物質３を
作製し、これを厚み０．１ｍｍ、開孔率５０％の銅パン
チングメタル集電体１の両面に幅１ ＋ｌｌＩｎ。FIGS. 1(A) and 1(B) are a perspective view and a sectional view showing a negative electrode plate according to an embodiment of the present invention, in which 1 is a current collector made of a copper-pasting metal, and 2 is a partition wall made of Teflon. It has a lattice shape, and the inner surface is divided into nine parts. 3 is an active material whose main components are zinc and zinc oxide, and 4 is a terminal. Such a negative electrode plate 5 was produced by the following method. That is, a paste-like active material 3 is prepared by mixing metal zinc, zinc oxide, and Teflon as a binder, and using alcohol as a solvent, and this is made into a copper punching metal current collector with a thickness of 0.1 mm and a porosity of 50%. Width 1 +llIn on both sides of 1.
厚み１ｍｍのテフロンからなる格子状の隔壁２を配置し
たものに塗布した後切断し、縦６０ｍｍＸ横６５ｍｍＸ
厚み１ｍｍの亜鉛極を得た。第２図は、この負極板５を
用いた密閉型ニッケル亜鉛電池Ｉの断面図である。第２
図で６は負極板５と同寸法の焼結式ニッケルからなる正
極板である。正極板２枚と負極板１枚とは、微孔性フィ
ルムとセロファン膜なとのセパレータ７並びにナイロン
不織布なとの保液層８からなるセパレータ層を介して交
互に積み重ねられている。負極板５に接する保液層８は
隔壁２に接触する部分か隔壁２に溶着されている。９は
電槽である。電解液は水酸化リチウムを添加した、比重
１゜３５の水酸化カリウム水溶液であり、正極板６、負
極板５、セパレータ層７゜８の全空隙の８０〜９５％に
注入されている。この本発明電池１の電池容量は１０Ａ
ｈであった。It was coated on a lattice-like partition wall 2 made of Teflon with a thickness of 1 mm, and then cut to a size of 60 mm long x 65 mm wide.
A zinc electrode with a thickness of 1 mm was obtained. FIG. 2 is a sectional view of a sealed nickel-zinc battery I using this negative electrode plate 5. Second
In the figure, 6 is a positive electrode plate made of sintered nickel and having the same dimensions as the negative electrode plate 5. Two positive electrode plates and one negative electrode plate are stacked alternately with separator layers made of a separator 7 made of a microporous film and a cellophane membrane, and a liquid retaining layer 8 made of a nylon nonwoven fabric. The liquid retaining layer 8 in contact with the negative electrode plate 5 is welded to the partition wall 2 at a portion thereof in contact with the partition wall 2 . 9 is a battery case. The electrolytic solution is a potassium hydroxide aqueous solution having a specific gravity of 1.35 to which lithium hydroxide has been added, and is injected into 80 to 95% of the total voids in the positive electrode plate 6, the negative electrode plate 5, and the separator layer 7.8. The battery capacity of this invention battery 1 is 10A
It was h.
実施例２として、第１図（Ｃ）に示した同寸法で見かけ
上１６分割した負極板を用いた本発明電池■も作製した
。また、比較例として、同寸法で見かけ上の分割を行っ
ていない従来型の負極板を用い、その他の条件は同一の
比較電池■も作製した。As Example 2, a battery (2) of the present invention was also fabricated using a negative electrode plate having the same dimensions as shown in FIG. 1(C) but apparently divided into 16 parts. As a comparative example, a comparative battery (2) was also produced using a conventional negative electrode plate with the same dimensions and no apparent division, and under the same conditions as above.
第３図は、本発明型／ｌ！２Ｉ、ＩＩと比較電池ｍを用
いてサイクル寿命試験を行った結果である。この試験は
ＩＡて１０．５時間充電し、１セル当り１゜２■迄放電
するいわゆる放電深度１００％のサイクル寿命試験であ
る。この図から分かるように、１０サイクル程度のサイ
クル充放電初期において、比較電池■に対し、本発明電
池Ｉ、■は、放電容量の低下か少なく、かつ、サイクル
寿命も比較電池ｍか１２０サイクル程度の寿命であるの
に対し、本発明電池Ｉは１６０サイクル、■は１８０サ
イクル程度と良好な結果を示している。また表１は、本
発明電池１．ＩＩと比較電池■の負極板のサイクル充放
電による形状変化を求めた結果であり、表中の割合（％
）は負極板の形状変化していない面積を０サイクル時の
負極板の面積で割ったものである。FIG. 3 shows the present invention type/l! These are the results of a cycle life test using 2I, 2I and comparative battery m. This test is a so-called 100% depth of discharge cycle life test in which the battery is charged at IA for 10.5 hours and then discharged to 1°2mm per cell. As can be seen from this figure, in the initial stage of cycle charging and discharging of about 10 cycles, inventive batteries I and (2) had a smaller decrease in discharge capacity than comparative battery (2), and their cycle life was also about 120 cycles compared to comparative battery (M). In contrast, the battery I of the present invention had a life of 160 cycles, and the battery II had a life of about 180 cycles, showing good results. Table 1 also shows the battery 1 of the present invention. These are the results of determining the shape changes due to cycle charging and discharging of the negative electrode plates of II and comparison battery ■, and the percentages (%) in the table are
) is the area of the negative electrode plate whose shape has not changed divided by the area of the negative electrode plate at 0 cycles.
表 １
これらの結果から、負極板の活物質か分割さイー、さら
に隔壁に接触する保液層か溶着された二とにより、シン
ケルトイオンの拡散か抑制され、′３Ｉ−状変化か減少
し、又、極板周辺部に配置した隔壁及び分割用隔壁によ
り、酸素カス吸収か７８極面の広い範囲で起こっている
と考えられる。また、そ（ニ）結果によって対向する正
極板の活物質のｇ仕度か失われることか防止されるため
、サイクル寿命の向上かみられたと考えられる。Table 1 From these results, it can be seen that the active material of the negative electrode plate is divided, and the liquid retaining layer that contacts the partition wall or the welded layer suppresses the diffusion of sinkelt ions and reduces the '3I-like change. In addition, it is considered that oxygen gas absorption occurs over a wide range of the 78 electrode surfaces due to the partition walls and dividing partition walls placed around the electrode plate. In addition, as a result of this, it is thought that the cycle life was improved because the active material of the opposing positive electrode plate was prevented from being lost.
発明の効果
本発明は、酸素ガスの不均一吸収、形状変化なとを防止
し、さらに初期放電容量の低下を抑制し、サイクル寿命
性能を大幅に向上させることかできる。Effects of the Invention The present invention can prevent non-uniform absorption of oxygen gas and change in shape, suppress a decrease in initial discharge capacity, and significantly improve cycle life performance.
−第１図（Ａ）および（Ｂ）は本発明の１実施例に係る
負極板の斜視図および断面図、第１図＜Ｃ＞は本発明の
他の実施例に係る負極板の斜視図１第２図は本発明の密
閉型アルカリ亜鉛蓄電池の断面図、第３図は本発明電池
Ｉ、ＩＩと比較電池■を用いてサイクル寿命試験を行っ
た結果を示した図である。
２ ・・ 隔壁
３ ・・ 活物質
５ ・ 負極板
６ ・ 正極板
８ ・・ 保液層- FIGS. 1(A) and (B) are a perspective view and a sectional view of a negative electrode plate according to one embodiment of the present invention, and FIG. 1 <C> is a perspective view of a negative electrode plate according to another embodiment of the present invention. 1. FIG. 2 is a sectional view of a sealed alkaline zinc storage battery of the present invention, and FIG. 3 is a diagram showing the results of a cycle life test using Batteries I and II of the present invention and Comparative Battery ■. 2.. Partition wall 3.. Active material 5. Negative electrode plate 6. Positive electrode plate 8.. Liquid retaining layer
Claims (3)
する負極板と、正極板と、これら両電極板に接する保液
層とからなる密閉型アルカリ亜鉛蓄電池において、前記
負極板の活物質は、耐アルカリ性樹脂からなる気体透過
性の隔壁を用いて分割されていることを特徴とする、 密閉型アルカリ亜鉛蓄電池。(1) In a sealed alkaline zinc storage battery comprising a negative electrode plate containing at least one of zinc or zinc oxide as a main component, a positive electrode plate, and a liquid retaining layer in contact with both electrode plates, the active material of the negative electrode plate is A sealed alkaline zinc storage battery characterized by being divided using gas-permeable partition walls made of alkali-resistant resin.
ことを特徴とする、 請求項１記載の密閉型アルカリ亜鉛蓄電池。(2) The sealed alkaline zinc storage battery according to claim 1, wherein the negative electrode plate has a peripheral portion formed by the partition wall.
ることを特徴とする、 請求項１または請求項２記載の密閉型アルカリ亜鉛蓄電
池。(3) The sealed alkaline zinc storage battery according to claim 1 or 2, wherein the liquid retaining layer is welded or crimped to the partition wall.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2338702A JPH04206468A (en) | 1990-11-30 | 1990-11-30 | Sealed alkali-zinc storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2338702A JPH04206468A (en) | 1990-11-30 | 1990-11-30 | Sealed alkali-zinc storage battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04206468A true JPH04206468A (en) | 1992-07-28 |
Family
ID=18320663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2338702A Pending JPH04206468A (en) | 1990-11-30 | 1990-11-30 | Sealed alkali-zinc storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04206468A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2760896A1 (en) * | 1997-03-14 | 1998-09-18 | Sorapec Lab | Cylindrical sealed nickel@-zinc@ battery |
| JP2015005493A (en) * | 2013-05-23 | 2015-01-08 | 株式会社日本触媒 | Electrode precursor, electrode, and battery |
| WO2016178184A1 (en) * | 2015-05-06 | 2016-11-10 | Suren Martirosyan | Partitioned zinc electrode |
| US10573927B2 (en) | 2013-02-01 | 2020-02-25 | Nippon Shokubai Co., Ltd. | Electrode precursor, electrode, and cell |
| WO2022050367A1 (en) * | 2020-09-04 | 2022-03-10 | 日本碍子株式会社 | Secondary battery and manufacturing method therefor |
| WO2024014304A1 (en) * | 2022-07-11 | 2024-01-18 | 日本碍子株式会社 | Negative electrode plate and zinc secondary battery |
| WO2024029364A1 (en) * | 2022-08-02 | 2024-02-08 | 日本碍子株式会社 | Negative electrode plate and zinc secondary battery comprising same |
-
1990
- 1990-11-30 JP JP2338702A patent/JPH04206468A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2760896A1 (en) * | 1997-03-14 | 1998-09-18 | Sorapec Lab | Cylindrical sealed nickel@-zinc@ battery |
| US10573927B2 (en) | 2013-02-01 | 2020-02-25 | Nippon Shokubai Co., Ltd. | Electrode precursor, electrode, and cell |
| JP2015005493A (en) * | 2013-05-23 | 2015-01-08 | 株式会社日本触媒 | Electrode precursor, electrode, and battery |
| WO2016178184A1 (en) * | 2015-05-06 | 2016-11-10 | Suren Martirosyan | Partitioned zinc electrode |
| WO2022050367A1 (en) * | 2020-09-04 | 2022-03-10 | 日本碍子株式会社 | Secondary battery and manufacturing method therefor |
| WO2024014304A1 (en) * | 2022-07-11 | 2024-01-18 | 日本碍子株式会社 | Negative electrode plate and zinc secondary battery |
| WO2024029364A1 (en) * | 2022-08-02 | 2024-02-08 | 日本碍子株式会社 | Negative electrode plate and zinc secondary battery comprising same |
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