KR100287123B1 - Alkali-zinc secondary battery - Google Patents

Alkali-zinc secondary battery Download PDF

Info

Publication number
KR100287123B1
KR100287123B1 KR1019940003534A KR19940003534A KR100287123B1 KR 100287123 B1 KR100287123 B1 KR 100287123B1 KR 1019940003534 A KR1019940003534 A KR 1019940003534A KR 19940003534 A KR19940003534 A KR 19940003534A KR 100287123 B1 KR100287123 B1 KR 100287123B1
Authority
KR
South Korea
Prior art keywords
zinc
electrode
secondary battery
alkali
concentration
Prior art date
Application number
KR1019940003534A
Other languages
Korean (ko)
Other versions
KR950026050A (en
Inventor
유영창
Original Assignee
윤종용
삼성전자 주식회사
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 윤종용, 삼성전자 주식회사 filed Critical 윤종용
Priority to KR1019940003534A priority Critical patent/KR100287123B1/en
Publication of KR950026050A publication Critical patent/KR950026050A/en
Application granted granted Critical
Publication of KR100287123B1 publication Critical patent/KR100287123B1/en

Links

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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M10/24—Alkaline accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0014—Alkaline electrolytes
    • 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)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

PURPOSE: Provided is an alkali-zinc secondary battery using a zinc as an anode, which prevents the concentration of electric current, reduces the solubility of the surrounding part of the zinc anode, therefore, can improve charge/discharge cycle time. CONSTITUTION: The alkali-zinc secondary battery contains the zinc anode having zinc and zinc oxides as active material and a cathode using nickel or silver oxide, wherein the metal zinc concentration in the central part(1) of the zinc anode is higher than the metal zinc concentration in the surrounding part(2) of the zinc anode and the thickness of the central part(1) is smaller than the thickness of the surrounding part(2), and a hydrophilic nonwoven fabric is attached to the central part(1).

Description

알카리-아연 2차전지Alkaline-Zinc Rechargeable Batteries

제1도는 본 발명에 따른 아연전극의 정면도이고,1 is a front view of a zinc electrode according to the present invention,

제2도는 본 발명에 따른 아연전극의 단면도이며,2 is a cross-sectional view of a zinc electrode according to the present invention;

제3도는 충방전 사이클에 따른 전지의 방전용량의 변화를 나타낸 그래프이다.3 is a graph showing a change in discharge capacity of a battery according to a charge and discharge cycle.

* 도면의 주요부분에 대한 부호의 설명* Explanation of symbols for main parts of the drawings

1 : 전극 중앙부 2 : 전극 주위부1: center of electrode 2: around electrode

3 : 단자부 4 : 친수성 부직포3: terminal part 4: hydrophilic nonwoven fabric

본 발명은 알카리-아연 2차전지에 관한 것으로, 좀 더 상세하게는 아연을 음전극(anode)으로, 니켈 또는 산화은은 양전극(cathode)으로 하는 알카리-아연 2차전지의 제조시, 아연전극 주위부의 전기전도성을 저하시켜 전류집중을 억제하고 중앙부에 전해액이 유지되도록 전극구조를 변경시키므로써 주위부 활물질의 용해정도를 감소시켜 충방전 사이클수명을 향상시킬 수 있는 알카리-아연 2차전지에 관한 것이다.The present invention relates to an alkali-zinc secondary battery, and more particularly, in the manufacture of an alkaline-zinc secondary battery in which zinc is used as an anode and nickel or silver oxide is used as a cathode. The present invention relates to an alkali-zinc secondary battery capable of reducing charge and discharging current by reducing current conductivity and changing an electrode structure to maintain an electrolyte at a center thereof, thereby reducing a degree of dissolution of a peripheral active material and improving charge and discharge cycle life.

아연을 음전극 활물질로 하는 알카리 2차전지는 에너지 밀도, 출력 밀도가 우수하고 온도특성이 양호할 뿐만 아니라 방전전압이 높은 장점이 있어 전기 자동차용으로서 개발되고 있으며 군사용, 우주개발용 등의 특수용도로 현재 실용화되고 있다.Alkaline secondary batteries that use zinc as a negative electrode active material are developed for electric vehicles because of their excellent energy density, output density, good temperature characteristics, and high discharge voltage. It is put to practical use.

그러나, 아연전극을 사용하는 경우, 충방전이 반복됨에 따라 전해액에 용해되는 아연산(zincate) 이온이 충전시 아연전극 표면에 수지상인 덴드라이트(dendrite)가 석출, 성장하게 되며 이 수지상이 격리판(separator)을 관통하여 전지 내부에서 전극간 단락을 야기시킨다. 또한, 충방전 사이클이 진행되면 아연전극 주위부에 전류가 집중되는 현상인 주변효과(edge effect)에 의해 아연전극 주위부의 활물질이 용해되어 중앙부에 석출되는 현상이 심화된다. 이러한 형상 변화(shape change)현상이 발생됨에 따라 중앙부에 석출되는 활물질이 치밀해져 전극 기공도가 감소되며 아연전극의 이용률 및 용량이 감소되어 사이클 수명이 치명적으로 저하되는 문제점이 있었다.However, in the case of using a zinc electrode, as charging and discharging are repeated, dendrite, which is a resinous phase, precipitates and grows on the surface of the zinc electrode when the zinc acid (zincate) ions dissolved in the electrolyte are charged. It penetrates through a separator and causes an inter-electrode short circuit inside the cell. In addition, when the charge / discharge cycle proceeds, the active material in the peripheral portion of the zinc electrode is dissolved and precipitated in the center due to an edge effect, which is a phenomenon in which current is concentrated in the peripheral portion of the zinc electrode. As the shape change phenomenon occurs, the active material precipitated at the center portion is dense, and thus the electrode porosity is reduced, and the utilization and capacity of the zinc electrode are reduced, thereby causing a seriously low cycle life.

상기와 같은 문제점을 해결하기 위하여 전극 주위부에 아연산화물의 용해를 억제하는 Ca(OH)2다공질층(일본 특공소 제56-19709호(B2)) 또는 다공질 불소층(일본 특개소 제60-14757호(A))을 형성시키는 방법, 결합제의 농도를 크게 하는 방법(일본 특개소 제59-169066호(A))이 제안되었다.In order to solve the above problems, a Ca (OH) 2 porous layer (Japanese Laid-Open Patent Publication No. 56-19709 (B2)) or a porous fluorine layer (Japanese Laid-Open Publication No. 60-) which suppresses the dissolution of zinc oxide in the periphery of the electrode 14757 (A)) and a method of increasing the concentration of the binder (Japanese Patent Laid-Open No. 59-169066 (A)) have been proposed.

그러나, 상기 방법들을 사용할 경우, 아연전극의 주위부 활물질의 용해정도를 감소시켜 덴드라이트 및 형상변화 현상을 억제시킬 수는 있지만, 보다 근본적인 해결책은 되지 못하는 문제점이 있었다.However, in the case of using the above methods, it is possible to reduce the degree of dissolution of the peripheral active material of the zinc electrode to suppress the dendrite and the shape change phenomenon, but there is a problem that cannot be a more fundamental solution.

따라서, 본 발명의 목적은 상기 문제점을 해결할 뿐만 아니라 종래의 것에 비해 충방전 효율이 상당히 향상된 알카리-아연 2차전지를 제공하는 데 있다.Accordingly, an object of the present invention is to provide an alkali-zinc secondary battery which not only solves the above problems but also considerably improves the charge / discharge efficiency as compared with the conventional one.

상기 목적을 달성하기 위한 본 발명의 알카리-아연 2차전지는, 아연 및 아연산화물을 활물질로 하는 아연전극을 구비한 알카리-아연 2차전지에 있어서, 상기 아연전극이 전극 중앙부의 활물질중 금속아연 농도를 전극 주위부의 금속아연 농도보다 크게 하고, 상기 전극 중앙부의 두께를 전극 주위부보다 작게 하고 전극 중앙부에 친수성 부직포가 부착되도록 하여 일체화된 것으로 구성된다.In the alkali-zinc secondary battery of the present invention for achieving the above object, in the alkali-zinc secondary battery having a zinc electrode containing zinc and zinc oxide as an active material, the zinc electrode concentration of metal zinc in the active material in the center of the electrode It is configured to be larger than the metal zinc concentration of the electrode periphery, to make the thickness of the electrode center portion smaller than the electrode periphery, and to attach a hydrophilic nonwoven fabric to the electrode center portion.

이하 본 발명의 구성을 첨부된 도면을 참조하여 좀 더 상세히 설명하면 다음과 같다.Hereinafter, the configuration of the present invention will be described in more detail with reference to the accompanying drawings.

아연을 음전극 활물질로 하는 알카리-아연 2차전지는 에너지밀도, 출력밀도가 우수하고 온도특성이 양호할 뿐만 아니라 방전전압이 높은 장점이 있어 전기자동차용으로서 개발되고 있지만, 충방전이 반복됨에 따라 전지 내부에서 전극간 단락을 야기시키고 전지 싸이클수명을 감소시키는 문제점이 있었다.Alkaline-zinc secondary batteries that use zinc as a negative electrode active material have been developed for electric vehicles because of their excellent energy density, output density, good temperature characteristics, and high discharge voltage. There is a problem that causes short circuit between electrodes and reduces battery cycle life.

본 발명자는 이러한 문제점을 해결하기 위하여 연구를 거듭한 결과, 아연전극 주위부의 전기전도성을 저하시켜 전류집중을 억제하고 중앙부에 전해액이 유지되도록 전극구조를 변경시키므로써 주위부 활물질의 용해정도를 감소시켜 충방전 싸이클수명을 향상시킬 수 있는 본 발명의 알카리-아연 2차전지를 개발한 것이다.The present inventors have conducted a number of studies to solve this problem, reducing the electrical conductivity around the zinc electrode to suppress the current concentration and change the electrode structure so that the electrolyte is maintained in the center to reduce the degree of dissolution of the surrounding active material An alkali-zinc secondary battery of the present invention can improve the charge and discharge cycle life.

제1도 및 제2도는 각각 본 발명에 따른 아연전극의 정면도 및 단면도인데, 상기 도면중 부호 1은 전극 중앙부, 2는 전극 주위부, 3은 단자부, 4는 친수성 부직포이다.1 and 2 are a front view and a cross-sectional view of a zinc electrode according to the present invention, respectively, in which 1 is an electrode center portion, 2 is an electrode periphery portion, 3 is a terminal portion, and 4 is a hydrophilic nonwoven fabric.

제1도 및 제2도에 의하면, 본 발명에 따른 아연전극을 전극 중앙부(1)의 활물질중 금속아연 농도를 전극 주위부(2)의 금속아연 농도보다 크게 하고, 상기 전극 중앙부(1)의 두께를 전극 주위부(2)보다 작게 하고 상기 전극 중앙부(1) 표면에 친수성 부직포(4)가 부착되도록 하여 일체화된 구조로 이루어진다.1 and 2, the zinc electrode according to the present invention has a metal zinc concentration in the active material of the electrode center portion 1 greater than the metal zinc concentration of the electrode peripheral portion 2, The thickness is smaller than the periphery of the electrode 2, and the hydrophilic nonwoven fabric 4 is attached to the surface of the electrode central portion 1 so as to have an integrated structure.

통상, 아연전극은 충방전 반응시 전극 주위부에 전류 집중현상이 발생되므로 중앙부보다 주위부의 아연산화물이 더 많이 전해액에 용해된다. 이때, 아연전극 주위부의 금속아연 농도가 낮으면 주위부의 전기전도성이 저하되어 전류집중이 순화되며 아연전극 표면의 전류분포가 균일화되어 주변효과(edge effect)가 반감된다. 따라서, 본 발명에서는 전극 중앙부의 활물질중 금속아연 농도를 전극 주위부의 금속아연 농도보다 크게 한 것이다.In general, the zinc electrode is more concentrated in the electrolyte than the center part because current concentration occurs in the periphery of the electrode during the charge and discharge reaction. At this time, when the concentration of the metal zinc in the periphery of the zinc electrode is low, the electrical conductivity of the periphery is reduced, the current concentration is smoothed, and the current distribution on the surface of the zinc electrode is uniform, thereby reducing the edge effect. Therefore, in the present invention, the metal zinc concentration in the active material in the electrode center portion is made larger than the metal zinc concentration in the electrode peripheral portion.

또한, 전극 중앙부의 두께를 전극 주위부보다 작게 해주면 주위부는 중앙부에 비해 다른 전극과 더욱 더 밀착되어 주위부 주변의 전해액이 규제되는 효과가 발생되므로 주위부 활물질의 용해를 억제 가능함은 물론, 중앙부에 부착되어 있는 친수성 부직포가 전해액을 함유하게 되어 주위부에 대한 전해액 규제효과가 상승하게 된다. 더욱이, 아연 전극 주위부에 소수성 다공질의 수지 결합제층을 형성시키거나, 또는 부가적으로 소수성 부직포로 봉지하여 아연전극 주위부가 직접 소수성 부직포와 접촉되도록 하는 경우에는 더욱 더 효과가 크다.In addition, if the thickness of the center portion of the electrode is smaller than the periphery of the electrode, the periphery is more closely contacted with other electrodes than the center portion, so that the effect of regulating the electrolyte around the periphery is generated. The adhered hydrophilic nonwoven fabric contains an electrolyte solution, thereby increasing the effect of regulating the electrolyte solution on the periphery. Moreover, it is even more effective when a hydrophobic porous resin binder layer is formed around the zinc electrode, or additionally encapsulated with a hydrophobic nonwoven to allow the zinc electrode periphery to directly contact the hydrophobic nonwoven.

한편, 본 발명의 알카리-아연 2차전지는 각형이지만, 단지 각형에만 제한받지 않고 원통형에도 또한 적용 가능하다.On the other hand, the alkali-zinc secondary battery of the present invention is rectangular, but is not limited to only rectangular, but is also applicable to a cylindrical shape.

이하 실시예를 통하여 본 발명을 좀 더 상세히 설명하지만, 이것이 본 발명의 범주를 안정하는 것은 아니다.The present invention will be described in more detail with reference to the following Examples, which however do not stabilize the scope of the present invention.

[실시예 1]Example 1

산화아연 86중량%, 금속아연 10중량%에 첨가제로 산화납 4중량%를 혼합한 혼합분말에 결합제로서 PTFE(Pely Tetra Flouro Ethylene)와 물을 가하여 혼합, 압연하여 두께 0.6mm, 폭 40mm, 길이 50mm인 활물질 시트를 제조하고 두께 0.2mm인 친수성 부직포의 한쪽 표면에 접착제를 사용하여 부착, 일체화시킨 시트 a를 제조하였다.86% by weight of zinc oxide and 10% by weight of metal zinc were mixed by adding PTFE (Pely Tetra Flouro Ethylene) and water as a binder to the mixed powder mixed with 4% by weight of lead oxide and 0.6 mm in thickness and 40 mm in width. An active material sheet having a thickness of 50 mm was prepared, and a sheet a obtained by attaching and integrating an adhesive onto one surface of a hydrophilic nonwoven fabric having a thickness of 0.2 mm was prepared.

또한, 산화아연 96중량%에 첨가제로서 산화납 4중량%를 혼합한 혼합분말을 사용하여 두께 0.8mm, 폭 5mm의 사각띠 형상의 활물질 시트 b를 제조하고, 폭 50mm, 길이 60mm의 집전체 양면에 상기 시트 a를 부직포를 부착시키지 않은 면이 집전체와 접촉되도록 하여 집전체의 중앙부에 위치시켜 가압성형하고 상기 시트 b를 그 주위부에 위치시켜 가압성형한 후, 건조하여 아연전극을 제조하였다.In addition, using a mixed powder of 96% by weight of zinc oxide and 4% by weight of lead oxide as an additive, a rectangular band-shaped active material sheet b having a thickness of 0.8 mm and a width of 5 mm was prepared, and a current collector having a width of 50 mm and a length of 60 mm on both sides. The sheet a was placed on the center of the current collector to be pressed against the current collector so that the surface on which the non-woven fabric was not attached to the current collector was pressed and placed on the periphery of the sheet b, and dried to prepare a zinc electrode. .

이와같이 제조한 아연전극을 공지의 소결식 Ni(OH)2전극과 조합하여 본 발명에 따른 각형 Ni-Zn 2차전지 A를 제작하였다. 이때, 전극 사이에는 격리판으로서 친수성의 미공성 폴리프로필렌(polypropylene)막과 친수성 부직포를 사용하였으며, 전해액으로는 6M KOH, 1M LiOH의 조성을 사용하였다.The zinc electrode thus prepared was combined with a known sintered Ni (OH) 2 electrode to prepare a rectangular Ni-Zn secondary battery A according to the present invention. At this time, a hydrophilic microporous polypropylene membrane and a hydrophilic nonwoven fabric were used as separators between the electrodes, and 6M KOH and 1M LiOH were used as electrolytes.

[비교예 1]Comparative Example 1

본 발명과의 비교를 위해 도입된 것으로, 실시예 1의 시트 b의 조성을 시트 a의 조성과 동일하게 하였다는 점을 제외하고는 실시예 1과 동일한 방법으로 제조, 조합하여 니켈-아연 2차전지 B를 제작하였다.Introduced for comparison with the present invention, a nickel-zinc secondary battery was prepared and combined in the same manner as in Example 1 except that the composition of Sheet b of Example 1 was the same as that of Sheet a. B was produced.

[비교예 2]Comparative Example 2

본 발명과의 비교를 위해 또한 도입된 것으로, 실시예 1의 시트 a의 두께를 시트 b의 두께와 동일한 0.8mm로 하였고 친수성 부직포를 부착시키지 않았다는 점을 제외하고는 실시예 1과 동일한 방법으로 제조, 조합하여 니켈-아연 2차전지 C를 제작하였다.Also introduced for comparison with the present invention, the thickness of the sheet a of Example 1 was 0.8 mm equal to the thickness of the sheet b, and was prepared in the same manner as in Example 1 except that no hydrophilic nonwoven fabric was attached. In combination, a nickel-zinc secondary battery C was produced.

상기와 같이 제작한 전지 A, B 및 C를 싸이클 초기용량을 100%로 하고 240mA로 5시간 충전시킨 후, 120mA로 방전전압 1.2V까지 방전시켜 전지의 충방전 싸이클 특성을 측정하였으며, 그 결과를 제3도에 나타내었다.After charging the batteries A, B, and C as described above with 100% of the initial cycle of the cycle at 240 mA for 5 hours, the battery was discharged at 120 mA to 1.2 V to measure the charge / discharge cycle characteristics of the battery. 3 is shown.

제3도는 충방전 싸이클에 따른 전지의 방전용량의 변화를 나타낸 그래프인데, 이에 의하면 본 발명의 2차전지 A가 비교전지인 B, C에 비해 싸이클 수명이 개선되었다는 것을 알 수 있다.3 is a graph showing the change in the discharge capacity of the battery according to the charge and discharge cycle, it can be seen that the secondary battery A of the present invention improved the cycle life compared to the comparison battery B, C.

그러므로, 본 발명에 따른 알카리-아연 2차전지의 경우, 아연전극 주위부의 용해정도의 감소로 인해 아연 수지상인 덴드라이트의 발생이 감소되어 전극간 단락이 방지되고, 충전효율의 증가로 인해 방전용량이 향상된다. 또한, 아연전극의 형상변화 현상이 억제되므로 충방전 사이클 수명이 향상되는 잇점이 있다.Therefore, in the case of the alkaline-zinc secondary battery according to the present invention, the generation of dendrites, which are zinc resins, is reduced due to a decrease in the degree of dissolution around the zinc electrode, thereby preventing short-circuits between electrodes, and increasing discharge capacity due to an increase in charging efficiency. This is improved. In addition, since the phenomenon of the shape change of the zinc electrode is suppressed, the charge and discharge cycle life is improved.

Claims (1)

아연 및 아연산화물을 활물질로 하는 아연전극을 구비한 알카리-아연 2차전지에 있어서, 상기 아연전극이 전극 중앙부(1)의 활물질중 금속아연 농도를 전극 주위부(2)의 금속아연 농도보다 크게 하고, 상기 전극 중앙부(1)의 두께를 전극 주위부(2)보다 작게 하고 전극 중앙부(1)에 친수성 부직표(4)가 부착되도록 하여 일체화된 것으로 이루어지는 것을 특징으로 하는 알카리-아연 2차전지.In an alkali-zinc secondary battery having a zinc electrode comprising zinc and zinc oxide as an active material, the zinc electrode has a metal zinc concentration in the active material of the electrode center portion 1 that is greater than the metal zinc concentration in the electrode peripheral portion 2. And the thickness of the electrode center portion 1 is smaller than that of the electrode circumference portion 2 and the hydrophilic non-woven table 4 is attached to the electrode center portion 1 so as to be integrated. .
KR1019940003534A 1994-02-25 1994-02-25 Alkali-zinc secondary battery KR100287123B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1019940003534A KR100287123B1 (en) 1994-02-25 1994-02-25 Alkali-zinc secondary battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1019940003534A KR100287123B1 (en) 1994-02-25 1994-02-25 Alkali-zinc secondary battery

Publications (2)

Publication Number Publication Date
KR950026050A KR950026050A (en) 1995-09-18
KR100287123B1 true KR100287123B1 (en) 2001-11-30

Family

ID=37514933

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1019940003534A KR100287123B1 (en) 1994-02-25 1994-02-25 Alkali-zinc secondary battery

Country Status (1)

Country Link
KR (1) KR100287123B1 (en)

Also Published As

Publication number Publication date
KR950026050A (en) 1995-09-18

Similar Documents

Publication Publication Date Title
WO2011079482A1 (en) Battery
KR20180034660A (en) Lead accumulator
JP3287367B2 (en) Sealed nickel zinc battery
JP4240030B2 (en) Alkaline zinc storage battery
JP3515286B2 (en) Electrodes for secondary batteries
KR100287123B1 (en) Alkali-zinc secondary battery
JP2815566B2 (en) Alkaline zinc secondary battery
JPS62291871A (en) Enclosed type nickel-cadmium storage battery
JPH0787102B2 (en) Sealed nickel-zinc battery
JPS63155552A (en) Enclosed type nickel-cadmium storage battery
JP2001160384A (en) Cylindrical secondary battery
JPH11195410A (en) Lithium secondary battery
CN216563323U (en) Current collector-free battery cell structure
JP2819201B2 (en) Lithium secondary battery
JP2734523B2 (en) Battery separator
JPH01100872A (en) Sealed type nickel-zinc cell
JP2755634B2 (en) Alkaline zinc storage battery
KR100287122B1 (en) Alkali-zinc secondary battery
KR100287124B1 (en) Nickel-zinc secondary battery
JP2762730B2 (en) Nickel-cadmium storage battery
KR860000820B1 (en) Storage battery
JPS59146157A (en) Nonaqueous electrolyte secondary cell
JPH044563A (en) Non-aqueous secondary battery
JP3197658B2 (en) Non-aqueous secondary battery
KR100304826B1 (en) Process for producing alkali battery

Legal Events

Date Code Title Description
A201 Request for examination
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
FPAY Annual fee payment

Payment date: 20121221

Year of fee payment: 13

FPAY Annual fee payment

Payment date: 20131220

Year of fee payment: 14