WO2017138742A1 - Secondary battery - Google Patents

Secondary battery Download PDF

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Publication number
WO2017138742A1
WO2017138742A1 PCT/KR2017/001364 KR2017001364W WO2017138742A1 WO 2017138742 A1 WO2017138742 A1 WO 2017138742A1 KR 2017001364 W KR2017001364 W KR 2017001364W WO 2017138742 A1 WO2017138742 A1 WO 2017138742A1
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negative electrode
secondary battery
active material
present
volume
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PCT/KR2017/001364
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French (fr)
Korean (ko)
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류병훈
공재경
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주식회사 이엠따블유에너지
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Publication of WO2017138742A1 publication Critical patent/WO2017138742A1/en

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    • 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
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • 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
    • H01M4/40—Alloys based on alkali metals
    • 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
    • H01M4/42—Alloys based on zinc
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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

Definitions

  • the present invention relates to a secondary battery capable of minimizing the volume change of the negative electrode portion even after repeated charging and discharging.
  • Lithium ion secondary batteries are prepared by reversibly inserting and detaching lithium ions as a positive electrode and a negative electrode, and filling an organic electrolyte or a polymer electrolyte between the positive electrode and the negative electrode, and lithium ions are inserted in the positive electrode and the negative electrode. And electrical energy is generated by the reduction and oxidation reactions upon desorption.
  • the lithium secondary battery greatly depends on the charge and discharge voltage, cycle life characteristics and storage characteristics of the battery according to the material of the electrode active material used, and efforts to improve the active material of both electrodes to improve the characteristics of the battery is steadily It's going on.
  • LiyM (M Al, Si, Sn, Pb, Ge, In, etc.), which is a lithium alloy, has a reaction potential different from that of lithium metal in the range of 0.1 to 1.0 V, and the charging capacity is higher than that of the carbon material. 2 to 10 times higher.
  • the lithium ion secondary battery is not limited to the above, but other types of secondary batteries such as an air-zinc secondary battery and a silicon secondary battery have a degree of difference, but they are a common problem.
  • the present invention was derived to solve the above problems, the object of the present invention is to minimize the volume change of the entire negative electrode portion of the secondary battery even if the volume expansion of the negative electrode active material as the charge and discharge of the secondary battery is repeated. It is to provide a secondary battery that can be.
  • the present invention relates to a secondary battery, more specifically, a positive electrode portion; And a negative electrode part, wherein the negative electrode active material of the negative electrode part includes expanded graphite powder.
  • the negative electrode active material of the negative electrode part includes expanded graphite in which volume expansion and contraction are elastic
  • the expanded graphite is expanded by the volume that expands even when volume expansion of the negative electrode active material occurs due to repeated charging and discharging of the secondary battery. Since the volume of F is flexibly reduced, the volume of the negative electrode portion of the secondary battery as a whole can be kept constant, thereby minimizing the degradation and destruction of the secondary battery.
  • FIG. 1 conceptually illustrates the structure of an air-zinc secondary battery as an example of a secondary battery according to the present invention.
  • first and second may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another.
  • the present invention relates to a secondary battery, more specifically, a positive electrode portion; And a negative electrode part, wherein the negative electrode active material of the negative electrode part includes expanded graphite powder.
  • the secondary battery means a battery that can be repeatedly charged and discharged, and examples thereof include an air-zinc secondary battery, a lithium ion secondary battery, and a silicon secondary battery.
  • the positive electrode portion is a concept including a positive electrode current collector and a positive electrode active material
  • the negative electrode portion is a concept including a negative electrode current collector and a negative electrode active material.
  • the negative electrode active material is a zinc active material containing zinc (Zn) when the secondary battery is an air-zinc secondary battery, when the secondary battery is a lithium ion secondary battery is a lithium active material containing lithium,
  • the secondary battery may be a silicon active material including silicon.
  • the expanded graphite generally has a gas generated by evaporating the acid when the interlayer compound or residual compound coated with an acid such as sulfuric acid is rapidly heated to a temperature close to 1000 ° C between the layers of graphite. It is formed by expanding the interlayer of graphite by the expansion pressure of the gas, the expanded graphite has a characteristic that the elasticity of the elasticity can be expanded and reduced in accordance with the situation.
  • the negative electrode active material of the negative electrode electrode includes expanded graphite in which volume expansion and contraction are elastic
  • the volume of the expanded graphite expands as much as the volume of expansion of the negative electrode active material as the secondary battery charges and discharges repeatedly. Since the flexible shrinkage can maintain a constant volume of the negative electrode portion of the secondary battery as a whole, there is an advantage that can minimize the performance degradation and breakage (crack) of the secondary battery.
  • the content of the expanded graphite powder included in the negative electrode active material is not particularly limited.
  • the amount of expanded graphite is small, the content of the expanded graphite is too low, so it is difficult to expect the effect of inhibiting the volume expansion of the negative electrode part due to the volume expansion of the negative electrode active material. This is because the negative volume expansion inhibitory effect is excellent, but the specific gravity occupied by the negative electrode active material is too low, causing a problem of significantly lowering the capacity of the secondary battery.
  • an air-zinc secondary battery according to an embodiment of the present invention includes an air anode part 200, which is a cathode electrode part, and a zinc gel cathode part 400, which is a cathode electrode part, in the case 100.
  • the separator 300 is interposed between the 200 and the zinc gel cathode 400.
  • a plurality of air holes 110 are formed at an upper portion of the case 100 to allow external air to flow into the battery, and a terminal exposed portion 120 is formed at the lower portion of the case 100.
  • Air-zinc secondary battery includes the expanded graphite powder 500 in the zinc gel corresponding to the negative electrode active material of the zinc gel anode 400, the charge and discharge of the air-zinc secondary battery As it is repeated, even if volume expansion of the zinc gel as the negative electrode active material occurs, the volume of the expanded graphite is flexibly reduced as much as the volume of expansion, so that the volume of the zinc gel electrode part 400 of the air-zinc secondary battery as a whole can be kept constant. As a result, performance degradation and destruction of the air-zinc secondary battery can be minimized.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Materials Engineering (AREA)

Abstract

The present invention relates to a secondary battery, more specifically to a secondary battery, which comprises a positive electrode and a negative electrode, comprising expanded graphite powder in negative electrode active material of the negative electrode. According to the present invention, the overall volume of the negative electrode of the secondary battery can be maintained at a constant as the negative electrode active material of the negative electrode contains expanded graphite which can volumetrically expand and contract elastically. Thus, when volumetric expansion of the negative electrode active material occurs due to repeated charging and discharging of the secondary battery, the volume of expanded graphite contracts elastically by the amount of expanded volume, thereby providing the benefit of minimizing functional degradation and deterioration of the secondary battery.

Description

이차전지Secondary battery
본 발명은 반복 지속되는 충·방전에도 음극 전극부의 부피 변화를 최소화할 수 있는 이차전지에 관한 것이다.The present invention relates to a secondary battery capable of minimizing the volume change of the negative electrode portion even after repeated charging and discharging.
리튬이온 이차전지는 가역적으로 리튬 이온의 삽입과 탈리가 가능한 물질을 양극 및 음극으로 사용하고, 상기 양극과 음극 사이에 유기 전해액 또는 폴리머 전해질을 충전시켜 제조하는 것으로, 리튬 이온이 양극 및 음극에서 삽입 및 탈리될 때의 환원 및 산화 반응에 의하여 전기 에너지를 생성하게 된다. 상기 리튬 이차 전지는 사용되는 전극 활물질의 재료에 따라 전지의 충방전 전압, 사이클 수명 특성 및 보존 특성 등이 크게 좌우되며, 이러한 전지의 특성을 향상시키기 위해 양 전극의 활물질을 개선하고자 하는 노력이 꾸준히 진행되고 있다.Lithium ion secondary batteries are prepared by reversibly inserting and detaching lithium ions as a positive electrode and a negative electrode, and filling an organic electrolyte or a polymer electrolyte between the positive electrode and the negative electrode, and lithium ions are inserted in the positive electrode and the negative electrode. And electrical energy is generated by the reduction and oxidation reactions upon desorption. The lithium secondary battery greatly depends on the charge and discharge voltage, cycle life characteristics and storage characteristics of the battery according to the material of the electrode active material used, and efforts to improve the active material of both electrodes to improve the characteristics of the battery is steadily It's going on.
현재 리튬 이차 전지의 음극 활물질로서 상용화되는 탄소계 활물질은 고체전해질 막(solid electrolyte interface)에 의한 안정성 및 초기 비가역 용량 감소를 통한 용량 증가를 이루기 위해 표면 개질 등에 대한 연구가 진행되고 있는 실정이다.Currently, carbon-based active materials commercialized as a negative electrode active material of a lithium secondary battery have been studied for surface modification and the like in order to achieve a capacity increase through stability and initial irreversible capacity by a solid electrolyte interface.
고용량의 음극 물질 중, 리튬 합금계인 LiyM (M = Al, Si, Sn, Pb, Ge, In 등)는 0.1 내지 1.0 V의 범위에서 리튬 금속과 다른 반응 전위를 가지며, 충전 용량이 탄소재에 비해서 2 내지 10배 정도 높다. LixSn (x =1 ~ 4.4) 경우는 Li-rich상의 녹는점이 400℃ 이상으로 폭발의 위험이 현저하게 감소되어 전지의 안전성을 도모할 수 있다. Among the high-capacity negative electrode materials, LiyM (M = Al, Si, Sn, Pb, Ge, In, etc.), which is a lithium alloy, has a reaction potential different from that of lithium metal in the range of 0.1 to 1.0 V, and the charging capacity is higher than that of the carbon material. 2 to 10 times higher. In the case of LixSn (x = 1 to 4.4), the melting point of the Li-rich phase is higher than 400 ° C., which greatly reduces the risk of explosion, thereby improving battery safety.
그러나, 합금 형성 및 분해(alloy forming/decomposition) 과정에서 일어나는 큰 부피 변화로 인한 기계적 응력이 입자들 간의 점진적인 균열을 일으키며, 심지어 전류 집전체와의 혹은 금속 입자간의 접촉을 잃게 하는 파쇄를 일으켜 사이클 특성이 저하되는 문제점을 갖고 있다. 따라서, 저장 용량면에서의 잇점에도 불구하고, 리튬 합금계는 상용화되기 어려운 실정이었으며, 합금계의 모양(morphology)이나 구조를 조절하여도 사이클 특성은 여전히 불만족스러웠다. 이런 단점을 극복하기 위한 주된 접근법으로서, 고에너지 밀링 방법을 이용한 나노 입자화로 활물질의 입자 크기를 줄이거나 또는 부피 변화가 적은 재료와의 다상(multi-phase) 혹은 금속간 화합물을 만들어 부피 팽창을 줄이는데 초점이 맞추어졌으나, 여전히 비가역적 용량 손실과 사이클 특성에서 큰 문제점을 가지고 있다.However, mechanical stress due to large volume change during alloy forming / decomposition results in gradual cracking between the particles and even fractures resulting in loss of contact with current collectors or metal particles. This has a problem of deterioration. Therefore, despite the advantages in terms of storage capacity, the lithium alloy system was difficult to commercialize, and even if the morphology or structure of the alloy system was adjusted, the cycle characteristics were still unsatisfactory. As a major approach to overcome this shortcoming, nanoparticle granulation using high-energy milling methods reduces the particle size of the active material or creates multi-phase or intermetallic compounds with materials with small volume changes to reduce volume expansion. Although focused, there are still major problems with irreversible capacity loss and cycle characteristics.
실리콘 이차전지의 경우 역시 전지의 충·방전시 발생하는 실리콘 활물질의 부피 변화 및 이로 인한 전극의 열화에 의해 장수명 사이클 특성이 저하되는 문제점을 가지고 있다.In the case of the silicon secondary battery, there is a problem in that the long life cycle characteristics are deteriorated due to the volume change of the silicon active material generated during the charging and discharging of the battery and the deterioration of the electrode.
즉, 반복되는 충·방전시 음극 활물질의 부피변화로 인해 막이 전류 집전체로부터 박리(exfoliation)되고, 결과적으로 상기의 문제점들로 인해 전기적 접촉 저하에 따른 전지의 사이클 특성 저하가 발생하는 문제는 비단 상기의 리튬이온 이차전지에만 국한되는 것이 아니라, 공기-아연 이차전지, 실리콘 이차전지 등 다른 타입의 이차전지에도 정도의 차이는 있지만 공통적으로 발생하는 문제이다.That is, the film is exfoliated from the current collector due to the volume change of the negative electrode active material during repeated charging and discharging, and as a result, the problem of deterioration of the cycle characteristics of the battery due to the decrease in electrical contact due to the above problems is The lithium ion secondary battery is not limited to the above, but other types of secondary batteries such as an air-zinc secondary battery and a silicon secondary battery have a degree of difference, but they are a common problem.
본 발명은 상기와 같은 문제점을 해결하기 위해 도출된 것으로, 본 발명 목적은 이차전지의 충·방전이 반복됨에 따라 음극 활물질의 부피 팽창이 발생하더라도 이차전지의 음극 전극부 전체의 부피 변화를 최소화할 수 있는 이차전지를 제공하는 것이다. The present invention was derived to solve the above problems, the object of the present invention is to minimize the volume change of the entire negative electrode portion of the secondary battery even if the volume expansion of the negative electrode active material as the charge and discharge of the secondary battery is repeated. It is to provide a secondary battery that can be.
본 발명은 이차전지에 관한 것으로, 보다 구체적으로 양극 전극부; 및 음극 전극부;를 포함하는 이차전지에 있어서, 상기 음극 전극부의 음극 활물질이 팽창 흑연(expanded graphite) 분말을 포함하는 것을 특징으로 한다.The present invention relates to a secondary battery, more specifically, a positive electrode portion; And a negative electrode part, wherein the negative electrode active material of the negative electrode part includes expanded graphite powder.
본 발명에 의하면, 음극 전극부의 음극 활물질이 부피의 팽창 및 축소가 탄력적인 팽창 흑연을 포함함으로써, 이차전지의 충·방전이 반복됨에 따라 음극 활물질의 부피 팽창이 발생하더라도 팽창하는 부피만큼 상기 팽창 흑연의 부피가 유연하게 축소되기 때문에 전체적으로 이차전지의 음극 전극부의 부피를 일정하게 유지할 수 있으며, 이에 따라 이차전지의 성능 저하 및 파괴를 최소화할 수 있는 이점이 있다. According to the present invention, since the negative electrode active material of the negative electrode part includes expanded graphite in which volume expansion and contraction are elastic, the expanded graphite is expanded by the volume that expands even when volume expansion of the negative electrode active material occurs due to repeated charging and discharging of the secondary battery. Since the volume of F is flexibly reduced, the volume of the negative electrode portion of the secondary battery as a whole can be kept constant, thereby minimizing the degradation and destruction of the secondary battery.
도 1은 본 발명에 따른 이차전지의 일예인 공기-아연 이차전지의 구조를 개념적으로 도시한 것이다.1 conceptually illustrates the structure of an air-zinc secondary battery as an example of a secondary battery according to the present invention.
본 발명은 다양한 변환을 가할 수 있고 여러 가지 실시 예를 가질 수 있는 바, 특정 실시 예들을 도면에 예시하고 상세한 설명에서 상세하게 설명하고자 한다. 그러나, 이는 본 발명을 특정한 실시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변환, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. 본 발명을 설명함에 있어서 관련된 공지 기술에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우 그 상세한 설명을 생략한다.As the inventive concept allows for various changes and numerous embodiments, particular embodiments will be illustrated in the drawings and described in detail in the written description. However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all transformations, equivalents, and substitutes included in the spirit and scope of the present invention. In the following description of the present invention, if it is determined that the detailed description of the related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted.
본 출원에서 사용한 용어는 단지 특정한 실시예를 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 출원에서, "포함하다" 또는 "가지다" 등의 용어는 명세서상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "have" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof.
제1, 제2 등의 용어는 다양한 구성요소들을 설명하는데 사용될 수 있지만, 상기 구성요소들은 상기 용어들에 의해 한정되어서는 안 된다. 상기 용어들은 하나의 구성요소를 다른 구성요소로부터 구별하는 목적으로만 사용된다.Terms such as first and second may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another.
본 발명은 이차전지에 관한 것으로, 보다 구체적으로 양극 전극부; 및 음극 전극부;를 포함하는 이차전지에 있어서, 상기 음극 전극부의 음극 활물질이 팽창 흑연(expanded graphite) 분말을 포함하는 것을 특징으로 한다.The present invention relates to a secondary battery, more specifically, a positive electrode portion; And a negative electrode part, wherein the negative electrode active material of the negative electrode part includes expanded graphite powder.
본 발명에서 상기 이차전지는 반복적으로 충·방전이 가능한 전지를 의미하며, 예를 들면 공기-아연 이차전지, 리튬이온 이차전지, 실리콘 이차전지 등이 이에 해당된다.In the present invention, the secondary battery means a battery that can be repeatedly charged and discharged, and examples thereof include an air-zinc secondary battery, a lithium ion secondary battery, and a silicon secondary battery.
본 발명에서 상기 양극 전극부는 양극 집전체 및 양극 활물질을 포함하는 개념이며, 상기 음극 전극부는 음극 집전체 및 음극 활물질을 포함하는 개념이다.In the present invention, the positive electrode portion is a concept including a positive electrode current collector and a positive electrode active material, the negative electrode portion is a concept including a negative electrode current collector and a negative electrode active material.
본 발명에서 상기 음극 활물질은 상기 이차전지가 공기-아연 이차전지일 경우에는 아연(Zn)을 포함하는 아연 활물질이며, 상기 이차전지가 리튬이온 이차전지일 경우에는 리튬을 포함하는 리튬 활물질이고, 상기 이차전지가 실리콘 이차전지인 경우에는 실리콘을 포함하는 실리콘 활물질일 수 있다.In the present invention, the negative electrode active material is a zinc active material containing zinc (Zn) when the secondary battery is an air-zinc secondary battery, when the secondary battery is a lithium ion secondary battery is a lithium active material containing lithium, When the secondary battery is a silicon secondary battery, the secondary battery may be a silicon active material including silicon.
본 발명에서 상기 팽창 흑연(expanded graphite)은 일반적으로 흑연의 층 사이에 황산과 같은 산을 도포한 층간화합물 또는 잔류화합물을 1000℃에 가까운 온도로 급 가열하게 되면 산이 기화되어 가스가 발생되고, 발생한 가스의 팽창압에 의해 흑연의 층간이 팽창하게 되어 형성되는 것으로서, 상기 팽창 흑연은 탄성력이 좋아 상황에 따라 부피의 팽창 및 축소가 가능한 특성을 가지고 있다.In the present invention, the expanded graphite generally has a gas generated by evaporating the acid when the interlayer compound or residual compound coated with an acid such as sulfuric acid is rapidly heated to a temperature close to 1000 ° C between the layers of graphite. It is formed by expanding the interlayer of graphite by the expansion pressure of the gas, the expanded graphite has a characteristic that the elasticity of the elasticity can be expanded and reduced in accordance with the situation.
본 발명은 음극 전극부의 음극 활물질이 부피의 팽창 및 축소가 탄력적인 팽창 흑연을 포함함으로써, 이차전지의 충·방전이 반복됨에 따라 음극 활물질의 부피 팽창이 발생하더라도 팽창하는 부피 만큼 상기 팽창 흑연의 부피가 유연하게 축소되기 때문에 전체적으로 이차전지의 음극 전극부의 부피를 일정하게 유지할 수 있으며, 이에 따라 이차전지의 성능 저하 및 파괴(균열)를 최소화할 수 있는 이점이 있다.According to the present invention, since the negative electrode active material of the negative electrode electrode includes expanded graphite in which volume expansion and contraction are elastic, the volume of the expanded graphite expands as much as the volume of expansion of the negative electrode active material as the secondary battery charges and discharges repeatedly. Since the flexible shrinkage can maintain a constant volume of the negative electrode portion of the secondary battery as a whole, there is an advantage that can minimize the performance degradation and breakage (crack) of the secondary battery.
본 발명에서 상기 음극 활물질에 포함되는 팽창 흑연 분말의 함량은 특별히 제한적인 것은 아니다. 팽창 흑연의 함량이 소량일 경우에는 팽창 흑연의 함량이 지나치게 낮아 음극 활물질의 부피 팽창에 따른 음극 전극부의 부피 팽창 억제 효과를 기대하기 어려운 문제가 있으며, 반대로 팽창 흑연의 함량이 대량일 경우에는 음극 전극부의 부피 팽창 억제 효과는 우수하나, 음극 활물질이 차지하는 비중이 지나치게 낮아져 이차전지의 용량을 현저히 저하시키는 문제가 발생하기 때문이다.In the present invention, the content of the expanded graphite powder included in the negative electrode active material is not particularly limited. When the amount of expanded graphite is small, the content of the expanded graphite is too low, so it is difficult to expect the effect of inhibiting the volume expansion of the negative electrode part due to the volume expansion of the negative electrode active material. This is because the negative volume expansion inhibitory effect is excellent, but the specific gravity occupied by the negative electrode active material is too low, causing a problem of significantly lowering the capacity of the secondary battery.
이하에서는 본 발명에 대한 이해를 돕기 위해 도면에 도시된 일예를 통해 설명하다. 하지만, 하기 도면에 도시된 일예는 본 발명을 설명하기 위한 예시에 지나지 않으며, 이에 의해 본 발명의 범위가 제한되는 것은 아니다.Hereinafter will be described through an example shown in the drawings to help understand the present invention. However, one example illustrated in the following drawings is only an example for describing the present invention, and the scope of the present invention is not limited thereto.
도 1은 본 발명에 따른 이차전지의 일예인 공기-아연 이차전지의 구조를 개념적으로 도시한 것이다. 도 1에 의하면, 본 발명의 일예에 따른 공기-아연 이차전지는 케이스(100) 내에 양극 전극부인 공기 양극부(200) 및 음극 전극부인 아연겔 음극부(400)를 포함하며, 상기 공기 양극부(200) 및 아연겔 음극부(400) 사이에 세퍼레이터(300)가 개재되어 있다. 한편, 상기 케이스(100)의 상부에는 외부의 공기가 전지 내로 유입되도록 하는 복수의 공기구멍(110)이 형성되어 있고, 하부에는 단자 노출부(120)가 형성되어 있다.1 conceptually illustrates the structure of an air-zinc secondary battery as an example of a secondary battery according to the present invention. According to FIG. 1, an air-zinc secondary battery according to an embodiment of the present invention includes an air anode part 200, which is a cathode electrode part, and a zinc gel cathode part 400, which is a cathode electrode part, in the case 100. The separator 300 is interposed between the 200 and the zinc gel cathode 400. Meanwhile, a plurality of air holes 110 are formed at an upper portion of the case 100 to allow external air to flow into the battery, and a terminal exposed portion 120 is formed at the lower portion of the case 100.
본 발명의 일예에 따른 공기-아연 이차전지는 상기 아연겔 음극부(400)의 음극 활물질에 해당하는 아연겔 내에 팽창 흑연 분말(500)을 포함하고 있어, 공기-아연 이차전지의 충·방전이 반복됨에 따라 음극 활물질인 아연겔의 부피 팽창이 발생하더라도 팽창하는 부피만큼 상기 팽창 흑연의 부피가 유연하게 축소되기 때문에 전체적으로 공기-아연 이차전지의 아연겔 전극부(400)의 부피를 일정하게 유지할 수 있으며, 결과적으로 공기-아연 이차전지의 성능 저하 및 파괴를 최소화할 수 있게 된다.Air-zinc secondary battery according to an embodiment of the present invention includes the expanded graphite powder 500 in the zinc gel corresponding to the negative electrode active material of the zinc gel anode 400, the charge and discharge of the air-zinc secondary battery As it is repeated, even if volume expansion of the zinc gel as the negative electrode active material occurs, the volume of the expanded graphite is flexibly reduced as much as the volume of expansion, so that the volume of the zinc gel electrode part 400 of the air-zinc secondary battery as a whole can be kept constant. As a result, performance degradation and destruction of the air-zinc secondary battery can be minimized.
이상에 설명한 바와 같이, 본 발명이 속하는 기술 분야의 당업자는 본 발명이 그 기술적 사상이나 필수적 특징을 변경하지 않고서 다른 구체적인 형태로 실시될 수 있다는 것을 이해할 수 있을 것이다. 본 발명의 범위는 상기의 상세한 설명보다는 후술할 특허청구범위에 의하여 나타내어지며, 특허청구범위의 의미 및 범위 그리고 그 등가개념으로부터 도출되는 모든 변경 또는 변형된 형태가 본 발명의 범위에 포함되는 것으로 해석되어야 한다.As described above, those skilled in the art will understand that the present invention can be implemented in other specific forms without changing the technical spirit or essential features. The scope of the present invention is shown by the claims to be described later rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts are included in the scope of the present invention. Should be.

Claims (2)

  1. 양극 전극부; 및 An anode electrode portion; And
    음극 전극부;를 포함하는 이차전지에 있어서,In the secondary battery comprising a negative electrode portion,
    상기 음극 전극부의 음극 활물질이 팽창 흑연(expanded graphite) 분말을 포함하는 이차전지.The negative electrode active material of the negative electrode portion includes expanded graphite (expanded graphite) powder.
  2. 제 1항에 있어서,The method of claim 1,
    상기 음극 활물질은 아연 활물질, 리튬 활물질 및 실리콘 활물질로 이루어진 군으로부터 선택된 어느 하나인 것을 특징으로 하는 이차전지.The anode active material is any one selected from the group consisting of a zinc active material, a lithium active material and a silicon active material.
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