KR20140058928A - The non-aqueous and high-capacity lithium secondary battery - Google Patents
The non-aqueous and high-capacity lithium secondary battery Download PDFInfo
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Abstract
Description
본 발명은 비수계 리튬 이차전지 음극의 리튬 덴드라이트를 방지하는 방법 및 이를 이용한 비수계 리튬 이차전지에 관한 것이다.
The present invention relates to a method for preventing lithium dendrite in an anode of a non-aqueous lithium secondary battery and a non-aqueous lithium secondary battery using the same.
최근, 휴대 전화, 노트북, PDA 등의 모바일 기기는 물론 자동차의 소형화ㆍ경량화가 현저하게 진행되고 있고, 또한 다기능화에 수반하여 소비 전력도 증가하고 있어, 이들 전원으로서 사용되는 비수계 전해질 이차 전지에 있어서도, 고용량, 고에너지 밀도 및 고안정성에 대한 요구가 높아지고 있다.2. Description of the Related Art In recent years, automobiles such as mobile phones, laptops, and PDAs have been remarkably advanced in size and weight as well as in automobiles. In addition, power consumption has been increasing along with multifunctionality. In the non-aqueous electrolyte secondary battery There is a growing demand for high capacity, high energy density and high stability.
비수계 전해질 이차 전지에 있어서, 정극 활물질로서는, 코발트산리튬(LiCoO2), 스피넬형 망간산리튬(LiMn2O4), 코발트ㆍ니켈ㆍ망간의 리튬 복합 산화물, 알루미늄ㆍ니켈ㆍ망간의 리튬 복합 산화물, 알루미늄ㆍ니켈ㆍ코발트의 리튬 복합 산화물 등이 알려져 있다. 또한, 부극 활물질로서는, 금속 리튬, 흑연 등의 탄소, 또는 실리콘이나 주석 등[Journal of Electrochemical Society 150 (2003) A679]의 리튬과 합금화하는 재료가 알려져 있다. 부극 활물질로 금속 리튬을 사용하는 경우, 취급이 용이하지 않고 충방전에 의해 바늘 형상의 금속리튬을 포함하는 덴드라이트가 발생하여 정극과의 사이에 내부 단락이 유발되고, 전지의 수명 또는 안전성에서 문제가 있었다.In the non-aqueous liquid electrolyte secondary battery, examples of the positive electrode active material include lithium cobalt oxide (LiCoO 2 ), spinel type lithium manganese oxide (LiMn 2 O 4 ), lithium composite oxide of cobalt nickel manganese, Oxides, and lithium composite oxides of aluminum, nickel, and cobalt. As the negative electrode active material, a material such as metal lithium, graphite or other carbon, or a material which alloys with lithium of silicon, tin or the like (Journal of Electrochemical Society 150 (2003) A679) is known. In the case of using metallic lithium as the negative electrode active material, it is not easy to handle, and a dendrite containing needle-shaped metallic lithium is generated by charging and discharging, causing an internal short circuit with the positive electrode, .
한편, 부극 활물질로 탄소를 사용하는 경우, 덴드라이트 발생으로 인한 단락 또는 안전성의 문제는 없으나, 층간 화합물 LiC6의 이론 용량은 372mAh/g이어서, 상기 설시한 고용량, 고에너지 밀도에 대한 요구를 충족하기 어렵다.On the other hand, when carbon is used as the negative electrode active material, there is no short-circuit or safety problem due to dendrite generation, but the theoretical capacity of the intercalation compound LiC 6 is 372 mAh / g to meet the demand for the high capacity and high energy density It is difficult to do.
또한, 전지의 고출력을 위하여 정극에 활성탄, 부극에 흑연 등의 탄소질 재료를 이용(일본 특허공개 2001-68094호, 일본 특허공개 2001-256968호, 일본 특허공개 2003-157833호)하는 검토도 되고 있으나 부극의 흑연의 입출력 특성이 좋지 않기 때문에 여전히 리튬 덴드라이트 발생의 문제가 해결되지 못하고 있다. Further, for the high power of the battery, there is also considered the use of a carbonaceous material such as activated carbon for the positive electrode and graphite for the negative electrode (JP 2001-68094 A, JP 2001-256968 A, and JP 2003-157833 A) However, since the input / output characteristics of the graphite of the negative electrode are not good, the problem of lithium dendrite generation still can not be solved.
상기의 문제점을 해결하기 위한 종래의 기술로 출원10-2011-0070151호에서, 서로 상이한 충방전 전압을 발휘하고 서로 상이한 경도를 가지는 두 종류의 음극 활물질의 조합을 포함하고 있으며, 상기 음극 활물질에서 상대적으로 경도가 낮은 음극 활물질(A) 표면은 카본 또는 그것의 복합체로 피복되어 있고, 상대적으로 경도가 높은 음극 활물질(B) 입자 크기는 음극 활물질(A)입자 크기 대비 2-1배 이하인 것을 특징으로 하는 이차전지용 음극을 개시하고 있다. 한편, 국제출원 PCT/JP2009/066776호는, 부극 집전체 및 상기 집전체의 표면에 형성된 부극 활물질을 포함하는 부극층을 갖는 부극을 구비하는 리튬 2차 전지이며, 상기 부극층은, 부극 활물질을 주성분으로 하는 부극 활물질층과, 상기 부극 활물질층 상에 형성된 절연성 필러를 주성분으로 하는 절연층에 의해 구성되어 있고, 상기 절연층의 세공 비표면적(Sb:㎡/g)과 상기 부극 활물질층의 세공 비표면적(Sa:㎡/g)의 비율(Sb/Sa)이, 1.2≤(Sb/Sa)≤2.5를 만족하는 것을 특징으로 하는 리튬 2차 전지를 개시하고 있다. 또한, 국제출원PCT/JP2010/000600호는, 높은 전류 밀도에서의 충방전이 가능한 리튬 도핑된 전이금속 산화물을 메인 활물질로 하는 리튬 2차 전지용 섬유 정극을 염가로 양산하는 방법을 개시하고 있다.
As a conventional technique for solving the above problems, Japanese Patent Application No. 10-2011-0070151 discloses a lithium secondary battery comprising a combination of two kinds of negative electrode active materials exhibiting different charging / discharging voltages and having mutually different hardness, Characterized in that the surface of the negative electrode active material (A) having a low hardness is coated with carbon or a composite thereof and the particle size of the negative electrode active material (B) having a relatively high hardness is 2-1 times or less the particle size of the negative electrode active material (A) A negative electrode for a secondary battery. On the other hand, International Application No. PCT / JP2009 / 066776 discloses a lithium secondary battery having a negative electrode having a negative electrode layer including a negative electrode collector and a negative electrode active material formed on the surface of the collector, wherein the negative electrode layer comprises a negative electrode active material (Sb: m < 2 > / g) of the insulating layer and a pore-specific surface area of the negative electrode active material layer And a ratio (Sb / Sa) of a specific surface area (Sa: m 2 / g) satisfies 1.2? (Sb / Sa)? 2.5. International application PCT / JP2010 / 000600 discloses a method for inexpensively mass producing a fiber cathode for a lithium secondary battery using a lithium-doped transition metal oxide capable of charge / discharge at a high current density as a main active material.
현재 음극 활물질로 주로 사용되고 있는 흑연의 경우 g당 372 mAh의 이론 용량을 가지고 있는 반면, 리튬 금속의 경우 3862 mAh/g 의 이론 용량으로 흑연에 비해 10배 이상의 이론 용량을 가지고 있다. 따라서 리튬 금속을 음극에 적용할 경우 전지 시스템의 상당한 용량증가가 예상된다. 하지만 이러한 리튬 금속을 음극으로 적용하는 경우 충방전 반복시 덴드라이트(dendrite)라고 하는 수지상 구조 형성에 의해 안정적인 충방전 반복성을 기대하기 어렵고, 또한 이러한 덴드라이트의 형성이 심하게 진행되는 경우 양음극을 절연하고 있는 세퍼레이터를 파손하여 내부 쇼트를 발생시켜 전지 안전성에도 위험 요소로 작용할 수 있다.Graphite, which is mainly used as an anode active material, has a theoretical capacity of 372 mAh per gram, while lithium metal has a theoretical capacity of 3862 mAh / g and has a theoretical capacity more than 10 times that of graphite. Therefore, a significant increase in the capacity of the battery system is expected when lithium metal is applied to the cathode. However, when such a lithium metal is applied to a cathode, it is difficult to expect stable repetition of charging / discharging due to the formation of a dendritic structure called dendrite by repetition of charging and discharging. When the formation of such a dendrite is severe, The separator is damaged and internal short-circuiting is generated, which may be a risk factor for battery safety.
이에 본 발명은 리튬 음극의 특성을 향상하여 고용량 리튬 이차전지를 구현하기 위하여 리튬 덴드라이트를 억제할 수 있는 방법 및 그 방법을 이용하여 제조된 고용량 리튬 이차전지를 제공하고자 한다.
Accordingly, it is an object of the present invention to provide a method capable of suppressing lithium dendrite in order to realize a high capacity lithium secondary battery by improving the characteristics of the lithium negative electrode, and a high capacity lithium secondary battery manufactured using the method.
본 발명은, 고용량인 리튬 고함유 양극활물질과 리튬 금속 음극활물질로 전지를 구성함에에 있어서; Disclosure of the Invention The present invention provides a battery comprising a high-capacity lithium-containing positive electrode active material and a lithium metal negative electrode active material;
상기 음극 활물질은 폼(foam)형 리튬 구조물을 포함하며;The negative electrode active material comprises a foam type lithium structure;
상기 폼형 리튬 구조물은 폼형 금속 구조물에 리튬을 도포하는 방법으로 제조되는 것인 비수계 고용량 리튬 이차전지의 제조 방법을 제공한다.Wherein the foamed lithium structure is manufactured by a method of applying lithium to a foamed metal structure.
또한, 본 발명은, 상기 폼형 금속 구조물에 리튬을 도포하는 방법으로서 전기화학적 도금하는 방법을 제공한다.
The present invention also provides a method of electrochemical plating as a method of applying lithium to the foamed metal structure.
본 발명의 음극을 포함하는 리튬 이차전지는 고용량을 유지하면서 반복된 충방전 사이클을 통하여서도 덴드라이트가 발생하지 않아 안정적으로 이용할 수 있다.The lithium secondary battery including the negative electrode of the present invention can be stably used without generating dendrite through repeated charge / discharge cycles while maintaining a high capacity.
또한 본 발명은 공기, 유황, 바나듐산화물 등의 고용량 양극과 함께 적용할 경우, 초기 리튬 도포량을 늘려 사용하면 충분히 큰 에너지밀도 구현이 가능하다.
Further, when the present invention is applied together with a high capacity anode such as air, sulfur or vanadium oxide, it is possible to realize a sufficiently large energy density by increasing the initial amount of lithium applied.
도1은 폼(foam)형 리튬 음극의 모식도이다.
도2는 일반적인 리튬 금속을 음극으로 사용한 경우 표면에 형성되는 덴드라이트 성장을 나타내는 모식도이다.
도3은 폼(foam)형 리튬 음극을 사용한 경우 표면에 덴드라이트 형성이 억제되는 것을 나타내는 모식도이다.1 is a schematic view of a foam-type lithium negative electrode.
2 is a schematic diagram showing dendrite growth formed on a surface when a general lithium metal is used as a cathode.
3 is a schematic view showing that dendrite formation is suppressed on the surface when a foam-type lithium negative electrode is used.
최근 들어 리튬 금속을 음극으로 사용하여 전지의 고용량화를 시도하는 노력이 많이 진행되고 있다. 리튬 유황, 리튬 공기 전지 등이 가장 많이 연구 진행되고 있으며, 바나듐 산화물 양극을 포함한 연구도 많이 진행되고 있다. 이러한 전지들의 공통점은 양극에 전지에너지 저장을 위한 주요 원소인 리튬을 포함하고 있지 않고, 리튬 금속이 리튬 공급원으로 작용한다는 것이다. 아래 그림과 같이 초기 상태에서 리튬을 리튬 금속 쪽으로 전달하게 되면 덴드라이트가 형성될 가능성이 더 커지게 되는데, 이러한 이유에 의해서도 초기 상태의 양극은 리튬을 포함하지 않은 물질로 구성하지 않는 것이 유리하다.In recent years, attempts have been made to increase the capacity of a battery using lithium metal as a cathode. Lithium sulphide and lithium air battery are the most studied, and many studies including vanadium oxide anode have been carried out. The common point of these cells is that they do not contain lithium, which is a key element for storing energy in the anode, and that lithium metal acts as a lithium source. As shown in the figure below, when lithium is transferred to the lithium metal in the initial state, the possibility of formation of dendrites becomes greater. For this reason, it is advantageous not to configure the anode in the initial state as lithium-free material.
유황, 공기, 바나듐 산화물 등을 양극으로 사용하게 되면, 기존의 리튬 산화물 양극 대비 더 큰 에너지밀도를 기대할 수 있지만, 이러한 양극들은 각기 많은 문제점을 가지고 있으며 아직까지 실제 적용하기에 적합하지 못한 수준임을 감안하면, 본 발명의 경우 기존 상용화된 양극을 모두 적용할 수 있으며 최근 고용량 양극 소재로 거의 상용화 단계에 도달해 있는 Over Lithiated Oxide (OLO) 등을 양극으로 적용할 경우 특히 큰 효과를 기대할 수 있다. 이에 본 발명을 하기에 더욱 구체적으로 설명하며, 이는 본 발명의 일구체예일 뿐 본 발명의 범위가 여기에 한정되는 것은 아님을 주지한다. The use of sulfur, air, vanadium oxide, etc. as an anode can provide a greater energy density compared to conventional lithium oxide anodes, but considering that these anodes have many problems and are not yet suitable for actual applications In the case of the present invention, it is possible to apply all of the existing commercialized electrodes and it is expected to have a great effect particularly when an over-lithium oxide (OLO) or the like, which has recently reached a commercialization stage with a high capacity anode material, is applied as an anode. The present invention will be described in more detail with reference to the following examples, but it should be understood that the present invention is not limited thereto.
본 발명은;SUMMARY OF THE INVENTION
고용량인 리튬 고함유 양극활물질과 리튬 금속 음극활물질로 전지를 구성함에에 있어서; In constructing the battery with a high capacity lithium-containing positive electrode active material and a lithium metal negative electrode active material,
상기 음극 활물질은 폼(foam)형 리튬 구조물을 포함하며;The negative electrode active material comprises a foam type lithium structure;
상기 폼형 리튬 구조물은 폼형 금속 구조물에 리튬을 도포하는 방법으로 제조되는 것인 비수계 고용량 리튬 이차전지의 제조 방법을 제공한다.Wherein the foamed lithium structure is manufactured by a method of applying lithium to a foamed metal structure.
여기에서 폼형이란 일반금속과 같이 기공이 하나도 없는 형태가 아닌 거품형, 즉 기공을 많이 포함한 것(형태에 제한 없이 기공율 75 ~ 95% 를 가진 것), 바람직하게는 80~90% 기공율을 갖는 형태를 말한다. 기공율이 적은 경우 공간 확보가 잘 되지 않아 리튬 함량이 제한적이므로 용량 증가가 어렵고, 기공율이 너무 큰 경우 전극을 지지하는 것이 어렵기 때문이다. Here, the foam-type is not a form having no pores such as a common metal, that is, a foam type having a large porosity (having porosity of 75 to 95% without limitation of form), preferably a porosity having a porosity of 80 to 90% . When the porosity is low, it is difficult to increase the capacity because the space is not secured and the lithium content is limited, and it is difficult to support the electrode when the porosity is too large.
여기에서, 금속이란 니켈, 구리, 혹은 그것들을 포함하는 합금일 수 있으며, 바람직하게는 니켈 혹은 구리 일 수 있다. 니켈이나 구리는 일반적으로 음극 집전체 혹은 음극 리드탭에 사용되는 재질로서 리튬 금속이 가지는 전위(0 V) 부근에서 가장 안정한 금속이기 때문이다. Here, the metal may be nickel, copper, or an alloy containing them, preferably nickel or copper. Nickel or copper is generally the most stable metal near the potential (0 V) of the lithium metal used for the negative electrode collector or the negative lead tab.
또한, 본 발명은, 상기 폼형 금속 구조물에 리튬을 도포하는 방법으로서 전해질 내에서 전기분해 하는 방법을 제공한다.Further, the present invention provides a method of applying electrolysis to an electrolyte in the foamed metal structure.
리튬 금속을 도포하는 방법으로는 진공상태에서 리튬을 기화시켜 금속표면에 증착하는 방법과 전해액 내에서 리튬 금속을 도금하는 전해 도금 방법이 가능한데 바람직하게는 전해도금 방법을 이용할 수 있다. 기화에 의한 증착의 경우 거품형 지지체 내부까지 골고루 증착시키기 어렵고, 또한 양을 조절하는 것이 매우 어렵기 때문이다. 본 발명에서는 전해액 내에서 리튬 금속을 전해 도금하는 방법을 이용하였고, 이러한 방법은 도금 시간과 전류 속도로 리튬의 양을 조절할 수 있다.Examples of the method of applying lithium metal include a method of vaporizing lithium in a vacuum state to deposit on a metal surface, and an electrolytic plating method of plating lithium metal in an electrolytic solution, and an electrolytic plating method can be used. In vapor deposition, it is difficult to deposit evenly into the bubble-like support and it is very difficult to control the amount. In the present invention, a method of electrolytically plating lithium metal in an electrolytic solution is used. In this method, the amount of lithium can be controlled by the plating time and the current rate.
이하, 본 발명의 실시예를 하기에 설명한다.Hereinafter, embodiments of the present invention will be described.
(실시예 1) : 실험에 사용한 양극은 일반적으로 잘 알려진 방법에 의해 합성한 Li2MnO3를 양극활물질로, 탄소재로 TIMCAL사의 SuperC, 바인더로 SOLVEY사의 PVdF를 90/5/5 중량비로 혼합하여 NMP 용매에서 슬러리를 만들고 알루미늄 호일에 도포하여 110도 건조하여 제조하였다. 음극은 니켈폼과 리튬 금속을 양쪽 극에 연결한 후 1.5M LiPF6 가 염으로 녹아 있는 EC/DEC 전해액에서 리튬을 전기 분해하여 니켈폼쪽에 도금하여 사용하였다. 이때 도금된 리튬의 양은 도금 전후의 전극 무게로 계산하였으며 양극에 포함된 리튬의 양을 기준으로 단위 면적당 두 배 정도의 양을 도금하여 사용하였다.(Example 1) The anode used in the experiment was prepared by mixing Li 2 MnO 3 synthesized by a well-known method as a cathode active material, SuperC of TIMCAL as a carbon material and PVDF of SOLVEY as a binder at a weight ratio of 90/5/5 The slurry was prepared in NMP solvent, applied to aluminum foil, and dried at 110 ° C. The negative electrode was prepared by connecting a nickel foam and a lithium metal to both electrodes and then electrolyzing lithium in an EC / DEC electrolytic solution in which 1.5M LiPF 6 was dissolved in a salt, and plating the same on the nickel foam side. At this time, the amount of plated lithium was calculated by the weight of the electrode before and after plating, and the plating amount was used twice as much as the unit area based on the amount of lithium contained in the positive electrode.
이렇게 만들어진 양극은 지름 14 mm, 음극은 15 mm 의 원형으로 펀칭하여 전극으로 사용하였으며, PE 분리막을 이용하여 2032 코인셀을 제작하였다. 전해액으로는 1M LiPF6 리튬염을 3/7 EC/DEC에 녹인 용액을 사용하였다.2032 coin cells were fabricated using PE membrane by punching the formed anode with a circular shape with a diameter of 14 mm and a cathode of 15 mm. As the electrolytic solution, 1M LiPF 6 A solution of the lithium salt dissolved in 3/7 EC / DEC was used.
상기와 같이 제작된 코인셀은 상온에서 6시간 이상 안정화시킨 후 초기 4.5 V 까지 정전류 충전하고, 3 V 까지 방전하여 용량을 측정하였다. 이때 전류의 세기는 0.2 C rate로 하였다. 이후 충방전 반복을 전압 범위는 4.5 V ~ 3.0 V, 전류 세기는 0.5C rate로 진행하였다. 표 1의 방전용량은 양극 활물질 기준으로 나타내었고, 용량유지율은 1회 방전량 대비 150회 방전 후 용량의 비율로 나타내었다.The thus prepared coin cell was stabilized at room temperature for 6 hours or more, then charged at an initial current of 4.5 V, and discharged to 3 V to measure its capacity. At this time, the current intensity was set at 0.2 C rate. The charge / discharge repetition was performed at a voltage range of 4.5 V to 3.0 V and a current intensity of 0.5 C rate. The discharge capacity shown in Table 1 is expressed on the basis of the cathode active material, and the capacity retention rate is expressed as a ratio of capacity after 150 discharges to one discharge amount.
(실시예 2) : 양극활물질로 LiCoO2를 사용하고 충전전압을 4.3 V로 한 것 외에는 실시예 1과 같이 실험을 수행하였고 그 결과를 표 1에 나타내었다.(Example 2): An experiment was carried out in the same manner as in Example 1 except that LiCoO 2 was used as the cathode active material and the charging voltage was 4.3 V, and the results are shown in Table 1.
(실시예 3) : 양극활물질로 LiCo0 .33Ni0 .33Mn0 .33 을 사용하고 충전전압을 4.3 V로 한 것 외에는 실시예 1과 같이 실험을 수행하였고 그 결과를 표 1에 나타내었다.(Example 3) was used LiCo 0 .33 Ni 0 .33 Mn 0 .33 as a cathode active material, and carrying out experiments in the same manner as in Example 1 except that the charging voltage to 4.3 V The results are shown in Table 1 .
(비교예 1) : 음극으로 200 um 두께의 호일을 사용한 것 외에는 실시예 1과 같이 실험하였다. (Comparative Example 1): An experiment was conducted in the same manner as in Example 1 except that a foil having a thickness of 200 mu m was used as a cathode.
(비교예2) : 음극으로 200 um 두께의 호일을 사용한 것 외에는 실시예 2와 같이 실험 하였다.(Comparative Example 2) An experiment was conducted as in Example 2 except that a foil having a thickness of 200 mu m was used as a cathode.
(비교예3) : 음극으로 200 um 두께의 호일을 사용한 것 외에는 실시예 3과 같이 실험 하였다.(Comparative Example 3): An experiment was conducted as in Example 3 except that a foil having a thickness of 200 mu m was used as a cathode.
(비교예4) : 음극은 흑연과 PVdF를 9:1 중량비로 혼합하여 NMP 용매에 슬러리를 만들고 구리 기재 위에 도포 후 건조하여 사용하였고, 나머지는 실시예 2와 같이 실험하였다.(Comparative Example 4): The negative electrode was prepared by mixing graphite and PVdF in a weight ratio of 9: 1, forming a slurry in an NMP solvent, coating on a copper substrate, and drying.
상기 실시예와 비교예를 통하여 만들어진 코인형 전지는 6시간 이상의 안정화 시간 후에 ARBIN사의 배터리 충방전기를 사용하여 정전류 충방전 하였고, 충방전 전위는 물질에 따라 4.3~4.5V 까지 충전, 3V 까지 방전하였다. 150회의 충방전 실험을 통하여 방전 용량을 측정하고 산출한 용량 유지율을 하기 표1에 나타내었다.
The coin-type battery produced through the above Examples and Comparative Examples was charged and discharged at a constant current using ARBIN's battery charge / discharge device after a stabilization time of 6 hours or more. The charge / discharge potential was charged to 4.3 to 4.5 V depending on the material, . The discharge capacity was measured through 150 charge-discharge experiments and the calculated capacity retention ratios are shown in Table 1 below.
(mAh/g)1 st discharge capacity
(mAh / g)
(mAh/g)150 th discharge capacity
(mAh / g)
(%)Capacity retention rate
(%)
리튬 foam 음극/OLOExample 1
Lithium foam anode / OLO
리튬 foam 음극/LCOExample 2
Lithium foam cathode / LCO
리튬 foam 음극/NCMExample 3
Lithium foam cathode / NCM
리튬 foil 음극/OLOComparative Example 1
Lithium foil cathode / OLO
리튬 foil 음극/LCOComparative Example 2
Lithium foil cathode / LCO
리튬 foil 음극/NCMComparative Example 3
Lithium foil cathode / NCM
흑연/LCOComparative Example 4
Graphite / LCO
Claims (9)
상기 음극 활물질은 폼(foam)형 리튬 구조물을 포함하며;
상기 폼형 리튬 구조물은 폼형 금속 구조물에 리튬을 도포하는 방법으로 제조되는 것인 비수계 고용량 리튬 이차전지의 제조 방법.
In constructing the battery with a high capacity lithium-containing positive electrode active material and a lithium metal negative electrode active material;
The negative electrode active material comprises a foam type lithium structure;
Wherein the foamed lithium structure is manufactured by applying lithium to a foamed metal structure.
The method according to claim 1, wherein the foam is in the form of a metal foam having a porosity of 75 to 95%.
The method of claim 1, further comprising a vapor deposition method of depositing lithium on the metal surface by vaporizing lithium in a vacuum state or an electrolytic plating method of plating lithium metal in an electrolytic solution as a method of applying lithium to the foamed metal structure, A method of manufacturing a secondary battery.
4. The method for manufacturing a nonaqueous-based high-capacity lithium secondary battery according to claim 3, wherein the method comprises applying an electrolytic plating method to the foamed metal structure.
The method of claim 1, wherein the metal of the foamed metal structure is selected from the group consisting of nickel, copper, and nickel-copper alloy.
상기 음극 활물질은 폼(foam)형 리튬 구조물을 포함하며;
상기 폼형 리튬 구조물은 폼형 금속 구조물에 리튬이 도포된 것인 비수계 고용량 리튬 이차전지.
In constructing the battery with a high capacity lithium-containing positive electrode active material and a lithium metal negative electrode active material;
The negative electrode active material comprises a foam type lithium structure;
Wherein the foamed lithium structure is formed by applying lithium to the foamed metal structure.
The non-aqueous high-capacity lithium secondary battery according to claim 6, wherein the metal is selected from the group consisting of nickel, copper, and nickel-copper alloy.
The nonaqueous-based high-capacity lithium secondary battery according to claim 6, wherein the foam is in the form of a metal foam having a porosity of 75 to 95%.
The nonaqueous-based high-capacity lithium secondary battery according to claim 6, wherein the applied lithium is applied by a vapor deposition method or an electrolytic plating method.
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| WO2018070728A1 (en) * | 2016-10-11 | 2018-04-19 | 주식회사 엘지화학 | Anode for lithium metal secondary battery and lithium metal secondary battery comprising same |
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