KR101822991B1 - The Method for Preparing Lithium Secondary Battery and the Lithium Secondary Battery Prepared by Using the Same - Google Patents
The Method for Preparing Lithium Secondary Battery and the Lithium Secondary Battery Prepared by Using the Same Download PDFInfo
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- KR101822991B1 KR101822991B1 KR1020140126630A KR20140126630A KR101822991B1 KR 101822991 B1 KR101822991 B1 KR 101822991B1 KR 1020140126630 A KR1020140126630 A KR 1020140126630A KR 20140126630 A KR20140126630 A KR 20140126630A KR 101822991 B1 KR101822991 B1 KR 101822991B1
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- South Korea
- Prior art keywords
- secondary battery
- lithium secondary
- lithium
- battery
- voltage
- Prior art date
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 56
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000001994 activation Methods 0.000 claims abstract description 45
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- -1 CO 3 Inorganic materials 0.000 claims abstract description 22
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- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 claims abstract description 9
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- 150000001450 anions Chemical class 0.000 claims abstract description 5
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- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 4
- 150000003624 transition metals Chemical class 0.000 claims abstract description 4
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- 238000007599 discharging Methods 0.000 claims description 21
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- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VROAXDSNYPAOBJ-UHFFFAOYSA-N lithium;oxido(oxo)nickel Chemical compound [Li+].[O-][Ni]=O VROAXDSNYPAOBJ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- 230000005012 migration Effects 0.000 description 1
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- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
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- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 235000015041 whisky Nutrition 0.000 description 1
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Abstract
본 발명은 양극 활물질을 포함하는 리튬 이차전지를 제조하는 방법으로서, 상기 양극 활물질은 하기 화학식 1로 표현되는 화합물 중에서 선택된 하나 이상의 리튬 전이금속 산화물을 포함하며; 상기 리튬 이차전지는 4.0V 내지 4.8V 범위에서 5회 내지 20회의 충전 및 방전을 반복하여 수행하는 활성화 과정을 거치는 것을 특징으로 하는 리튬 이차전지의 제조방법을 제공한다.
(1-x)LiM’O2-yAy -xLi2MnO3-y’Ay’ (1)
상기 식에서,
M’은 MnaMb이고;
M은 Ni, Ti, Co, Al, Cu, Fe, Mg, B, Cr, Zr, Zn 및 2주기 전이금속들로 이루어진 군에서 선택되는 하나 이상이며;
A는 PO4, BO3, CO3, F 및 NO3의 음이온으로 이루어진 군에서 선택되는 하나 이상이고;
0<x<1; 0≤y≤0.02; 0≤y’≤0.02; 0≤a≤0.5; 0.5≤b≤1.0; a + b = 1 이다.The present invention relates to a process for producing a lithium secondary battery comprising a cathode active material, wherein the cathode active material comprises at least one lithium transition metal oxide selected from the group consisting of compounds represented by the following general formula (1); Wherein the lithium secondary battery is subjected to an activation process in which charge and discharge are repeatedly performed for 5 to 20 times in the range of 4.0V to 4.8V.
(1-x) LiM'O 2-y A y -xLi 2 MnO 3 -y ' A y' (1)
In this formula,
M 'is Mn a M b ;
M is one or more selected from the group consisting of Ni, Ti, Co, Al, Cu, Fe, Mg, B, Cr, Zr, Zn and two period transition metals;
A is at least one selected from the group consisting of anions of PO 4 , BO 3 , CO 3 , F and NO 3 ;
0 < x <1; 0? Y? 0.02; 0? Y? 0.02; 0? A? 0.5; 0.5? B? 1.0; a + b = 1.
Description
본 발명은 리튬 이차전지의 제조방법 및 이를 사용하여 제조되는 리튬 이차전지에 관한 것이다.The present invention relates to a method for producing a lithium secondary battery and a lithium secondary battery manufactured using the same.
모바일 기기에 대한 기술 개발과 수요가 증가함에 따라 에너지원으로서의 이차전지의 수요가 급격히 증가하고 있고, 그러한 이차전지 중 높은 에너지 밀도와 전압을 가지고, 사이클 수명이 길며, 자기방전율이 낮은 리튬 이차전지가 상용화되어 널리 사용되고 있다.As technology development and demand for mobile devices are increasing, the demand for secondary batteries as energy sources is rapidly increasing. Among such secondary batteries, lithium secondary batteries having high energy density and voltage, long cycle life and low self- It has been commercialized and widely used.
이러한 리튬 이차전지의 활물질로는 주로 리튬 함유 코발트 산화물(LiCoO2)이 사용되고 있고, 그 외에 층상 결정구조의 LiMnO2, 스피넬 결정구조의 LiMn2O4 등의 리튬 함유 망간 산화물과, 리튬 함유 니켈 산화물(LiNiO2)의 사용도 고려되고 있다.Lithium-containing cobalt oxide (LiCoO 2 ) is mainly used as an active material of such a lithium secondary battery, and a lithium-containing manganese oxide such as LiMnO 2 having a layered crystal structure and LiMn 2 O 4 having a spinel crystal structure, (LiNiO 2 ) is also being considered.
LiCoO2은 우수한 사이클 특성 등 제반 물성이 우수하여 현재 많이 사용되고 있지만, 안전성이 낮으며, 원료로서 코발트의 자원적 한계로 인해 고가이고 전기자동차 등과 같은 분야의 동력원으로 대량 사용하는 함에는 한계가 있다. LiNiO2은 그것의 제조방법에 따른 특성상, 합리적인 비용으로 실제 양산공정에 적용하기에 어려움이 있다.LiCoO 2 has excellent properties such as excellent cycle characteristics and is widely used at present, but its safety is low and it is expensive due to the resource limit of cobalt as a raw material, and there is a limit to mass use as a power source for fields such as electric vehicles. LiNiO 2 is difficult to apply to actual mass production process at a reasonable cost due to its characteristics depending on its manufacturing method.
반면에, LiMnO2, LiMn2O4 등의 리튬 망간 산화물은 원료로서 자원이 풍부하고 환경친화적인 망간을 사용한다는 장점을 가지고 있으므로, LiCoO2를 대체할 수 있는 양극 활물질로서 많은 관심을 모으고 있다. 그러나, 이들 리튬 망간 산화물 역시 사이클 특성 등이 나쁘다는 단점을 가지고 있다.On the other hand, lithium manganese oxides such as LiMnO 2 and LiMn 2 O 4 have the advantage of using manganese which is rich in resources and environment-friendly as a raw material, and thus attracts much attention as a cathode active material capable of replacing LiCoO 2 . However, these lithium manganese oxides also have a disadvantage of poor cycle characteristics and the like.
우선, LiMnO2은 초기 용량이 작고, 특히 일정한 용량에 이를 때까지 수십 회의 충방전 사이클이 필요하다는 단점을 가지고 있다. 또한, LiMn2O4 은 사이클이 계속됨에 따라 용량 저하가 심각하고, 특히 50도 이상의 고온에서 전해액의 분해, 망간의 용출 등으로 인해 사이클 특성이 급격히 저하되는 단점을 가지고 있다.First, LiMnO 2 has a disadvantage in that the initial capacity is small, and in particular, several tens of charge / discharge cycles are required until a certain capacity is reached. In addition, LiMn 2 O 4 has a disadvantage in that the capacity deteriorates as the cycle continues, and in particular, at a high temperature of 50 ° C or higher, the cycle characteristics are drastically lowered due to decomposition of the electrolytic solution and elution of manganese.
한편, 리튬 함유 망간 산화물 중에는 LiMnO2, LiMn2O4 이외에 Li2MnO3이 있다. Li2MnO3은 구조적 안정성이 매우 우수하지만 전기화학적으로 불성이므로, 그 자체로는 이차전지의 양극 활물질로서 사용되지 못한다. 따라서, 일부 선행기술 중에는 Li2MnO3를 LiMO2 (M = Co, Ni, Ni0.5Mn0.5, Mn)와 고용체를 형성하여 양극 활물질로 사용하는 기술을 제시하고 있다. On the other hand, among the lithium-containing manganese oxides, there are Li 2 MnO 3 in addition to LiMnO 2 and LiMn 2 O 4 . Li 2 MnO 3 has excellent structural stability but is not electrochemically inert and thus can not be used as a cathode active material of a secondary battery. Therefore, among some prior arts, there is proposed a technique of using Li 2 MnO 3 as a cathode active material by forming a solid solution with LiMO 2 (M = Co, Ni, Ni 0.5 Mn 0.5 , Mn).
그러나, 이러한 망간 과량의 양극 활물질은 4.3V 내지 4.5V 이상의 고전압에서 리튬과 산소가 결정구조로부터 이탈되어 전기화학적 활성을 나타내게 되므로, 고용량을 발현하기 위해 고전압으로 작동시키는데, 초기 활성화 과정에서 활성화가 되지 못한 영역이 고전압에서 사이클이 진행되면서 지속적으로 활성화되어 양극 활물질로부터 기인한 산소가 전해액과 부반응을 초래하여 다량의 가스를 발생시키는 문제가 있다.However, since lithium and oxygen are separated from the crystal structure at a high voltage of 4.3V to 4.5V or higher, the manganese excess amount of the cathode active material exhibits electrochemical activity, so that it operates at a high voltage in order to exhibit a high capacity. The oxygen is continuously activated as the cycle progresses at a high voltage and the oxygen resulting from the cathode active material causes a side reaction with the electrolyte and generates a large amount of gas.
특히 각형 및 원형 전지와는 달리 파우치 전지의 경우에는 전지의 외형을 일정한 힘으로 유지시켜주기 어렵기 때문에, 상기 발생된 가스로 인해 파우치가 부풀어서 벤팅(venting) 되거나 전극 사이에 가스가 트랩(trap)되어 존재하면서 가스가 Li 이온의 이동을 방해함에 따라 전극의 균일하고 원활한 반응을 방해한다.In particular, unlike a rectangular or circular cell, it is difficult to maintain the external shape of the battery at a constant force in the case of a pouch battery. Therefore, the pouch is swollen due to the generated gas and is vented, ), The gas interferes with the uniform and smooth reaction of the electrode as it interferes with the migration of Li ions.
한편, 이와 같이 충전과정에서 가스로 인해 원활한 이동을 방해 받은 Li 이온은 음극 표면에서 석출되어 Li plating 현상을 발생시키고 이는 전지의 저항 증가 및 퇴화에 영향을 미칠 뿐만 아니라, 가역 Li 이온들이 Li plating 으로 인해 손실되기 때문에 방전과정에서 비가역 용량이 증가하게 되어 효율을 감소시킨다. 또한, 상기 트랩된 가스는 사이클이 진행되면서 지속적으로 Li 이온의 이동을 방해하므로 Li plating 현상이 누적되어 전지의 수명 감소에 큰 영향을 미치는 문제가 있다.On the other hand, Li ions, which are prevented from smooth movement due to gas during the charging process, precipitate from the surface of the negative electrode to cause Li plating phenomenon, which not only affects the resistance increase and degradation of the battery, The irreversible capacity increases during the discharge process, thereby decreasing the efficiency. In addition, since the trapped gas interferes with the movement of Li ions continuously as the cycle progresses, there is a problem that accumulation of lithium plating accumulates and greatly affects the life of the battery.
따라서, 상기와 같은 문제를 해결할 수 있는 기술에 대한 필요성이 매우 높은 실정이다.Therefore, there is a great need for a technique capable of solving the above problems.
본 발명은 상기와 같은 종래기술의 문제점과 과거로부터 요청되어온 기술적 과제를 해결하는 것을 목적으로 한다.SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems of the prior art and the technical problems required from the past.
본 출원의 발명자들은 심도 있는 연구와 다양한 실험을 거듭한 끝에, 이후 설명하는 바와 같이, 고전압에서 수차례 충전 및 방전을 반복하여 수행하는 활성화 과정을 행하여 리튬 이차전지를 제조하는 경우, 기존의 활성화 과정을 행한 경우와 비교하여 활성화 직후의 방전 용량 및 효율 등의 전지특성은 동등 수준으로 유지되면서도 사이클 과정에서 발생하는 가스량은 감소시킬 수 있음을 확인하고, 본 발명을 완성하기에 이르렀다.The inventors of the present application have conducted intensive research and various experiments and have found that when a lithium secondary battery is manufactured by performing an activation process of repeatedly performing charge and discharge several times at a high voltage as described later, , It was confirmed that the battery characteristics such as the discharge capacity and efficiency immediately after the activation are maintained at the same level and the amount of gas generated in the course of the cycle can be reduced, thereby completing the present invention.
따라서, 본 발명에 따른 리튬 이차전지 제조방법은, 양극 활물질을 포함하는 리튬 이차전지를 제조하는 방법으로서, 상기 양극 활물질은 하기 화학식 1로 표현되는 화합물 중에서 선택된 하나 이상의 리튬 전이금속 산화물을 포함하며; 상기 리튬 이차전지는 4.0V 내지 4.8V 범위에서 5회 내지 20회의 충전 및 방전을 반복하여 수행하는 활성화 과정을 거치는 것을 특징으로 한다.Accordingly, a method for manufacturing a lithium secondary battery according to the present invention is a method for manufacturing a lithium secondary battery including a cathode active material, wherein the cathode active material comprises at least one lithium transition metal oxide selected from the group consisting of compounds represented by Chemical Formula 1; The lithium secondary battery is characterized in that it undergoes an activation process in which charging and discharging are repeatedly performed for 5 to 20 times in the range of 4.0V to 4.8V.
(1-x)LiM’O2-yAy -xLi2MnO3-y’Ay’ (1)(1-x) LiM'O 2-y A y -xLi 2 MnO 3 -y ' A y' (1)
상기 식에서, In this formula,
M’은 MnaMb이고;M 'is Mn a M b ;
M은 Ni, Ti, Co, Al, Cu, Fe, Mg, B, Cr, Zr, Zn 및 2주기 전이금속들로 이루어진 군에서 선택되는 하나 이상이며;M is one or more selected from the group consisting of Ni, Ti, Co, Al, Cu, Fe, Mg, B, Cr, Zr, Zn and two period transition metals;
A는 PO4, BO3, CO3, F 및 NO3의 음이온으로 이루어진 군에서 선택되는 하나 이상이고;A is at least one selected from the group consisting of anions of PO 4 , BO 3 , CO 3 , F and NO 3 ;
0<x<1; 0≤y≤0.02; 0≤y’≤0.02; 0≤a≤0.5; 0.5≤b≤1.0; a + b = 1 이다.0 < x <1; 0? Y? 0.02; 0? Y? 0.02; 0? A? 0.5; 0.5? B? 1.0; a + b = 1.
상기 화학식 1로 표현되는 화합물은, 화학식 1에서 보여지는 바와 같이, 층상형의 LiM’O2-yAy와 Li2MnO3-y’Ay’의 고용체 형태로서, 층상형의 LiM’O2-yAy은 하나의 결정 구조에 2개의 M’O2-yAy층이 존재하며 각 M’O2-yAy층 사이에 Li 이온이 존재하는 형태이고, Li2MnO3-y’Ay’에서 망간은 안정적인 4가의 양이온으로 존재하며 확산을 위한 활성화 장벽이 높기 때문에 층상 구조를 안정화시키는데 기여한다. 또한, LiM’O2-yAy은 가역적인 충방전을 진행하는 활성 영역이고, Li2MnO3-y’Ay’는 4.3V 내지 4.5 V 미만에서 Mn4+를 가지는 비활성 영역이다. As shown in Formula 1, the compound represented by Formula 1 is a solid solution form of layered LiM'O 2-y A y and Li 2 MnO 3 -y ' A y' , and the layered LiM'O 2-y A y has two M'O 2 -y A y layers in one crystal structure, Li ion exists between each M'O 2 -y A y layer, and Li 2 MnO 3- At y ' A y' , manganese exists as a stable tetravalent cation and contributes to stabilizing the layered structure because of the high activation barrier for diffusion. LiM'O 2-y A y is an active region that undergoes reversible charge and discharge, and Li 2 MnO 3-y ' A y' is an inactive region having Mn 4+ at less than 4.3 V to 4.5 V.
이러한 상기 Li2MnO3-y’Ay’는 상기 설명한 바와 같이, 4.3V 내지 4.5V이상의 전압을 가하면 리튬과 산소가 결정구조로부터 이탈되어 전기화학 반응이 일어나는데, 이 경우 MnO2가 생성되면서 활성물질로 변하게 된다. Such a Li 2 MnO 3-y 'A y' is ileonaneunde this, is separated from 4.3V to lithium and oxygen are determined Applying a voltage above 4.5V structure electrochemical reaction as described above, in this case as the active MnO 2 is generated Material.
따라서, 본 발명의 상기 화학식 1로 표현되는 화합물 중에서 선택된 하나 이상의 리튬 전이금속 산화물을 양극 활물질로 포함하는 리튬 이차전지는 고전압에서의 활성화 과정이 필수적이다.Therefore, a lithium secondary battery comprising at least one lithium transition metal oxide selected from the compounds represented by the formula 1 of the present invention as a cathode active material is required to be activated at a high voltage.
그러나, 기존의 활성화 과정은 2.5V 내지 4.8V의 전압대에서 충방전을 1회 수행하는 것이 전부였다. 즉, 4.5V 이상의 고전압으로 충전한 뒤 2.5V까지 방전하는 과정을 1회 수행함으로써 활성화 과정을 진행하였다.However, in the conventional activation process, charging and discharging were performed only once at a voltage band of 2.5 V to 4.8 V. That is, the activation process was performed by performing a process of charging to a high voltage of 4.5V or more and discharging to 2.5V once.
그러나, 본 출원의 발명자들이 확인한 바에 따르면, 상기와 같이 2.5V까지 방전하는 과정을 거치는 경우에는, Mn3+ 형태를 갖는 물질의 발생으로 Mn3+가 불균일 반응에 의해 Mn2+ 와 Mn4+ 형태로 분해되고 그 중에서 Mn2+가 전해질로 용출(dissolution)됨에 따라 전지가 퇴화되는 문제가 있었을 뿐만 아니라, 1회의 활성화 과정으로는 상기에서 설명한 바와 같이, 활성화되지 못한 영역이 존재함에 따라, 이후 고전압에서 사이클이 진행되는 경우에 활성화 과정에서 활성화되지 못한 영역이 지속적으로 활성화되는 바, 양극 활물질로부터 이탈되는 리튬과 산소가, 음극 표면에서의 리튬 석출 및 산소와 전해액의 부반응에 따른 다량의 가스를 발생시키는 문제가 있었다.However, as confirmed according to the inventors of the present invention, when undergoing a process of discharging to 2.5V as described above, with a Mn 3+ Mn 2+ and Mn 4+ generated by the non-uniform reaction of the material with a Mn 3+ forms There is a problem that the cell is degraded due to dissolution of Mn 2+ into an electrolyte, and in addition, as described above, in the single activation process, as there is an activated region, In the case where the cycle proceeds at high voltage, the region that is not activated in the activation process is continuously activated, so that lithium and oxygen released from the cathode active material are liable to form a large amount of gas due to lithium precipitation on the surface of the cathode, There was a problem to generate.
따라서, 본 출원의 발명자들은, 심도있는 연구를 거듭한 끝에, 리튬 이차전지를 4.0V 내지 4.8V 범위에서 5회 내지 20회 충전 및 방전시켜 활성화 과정을 행하는 경우, 망간 용출이나 활성화 단계에서 양극 활물질의 활성화되지 못한 영역이 존재하는 문제를 해결하여 전지 퇴화의 문제점을 해결할 수 있음을 확인하였다. Therefore, the inventors of the present application have conducted intensive research and have found that when the activation process is performed by charging and discharging the lithium
구체적으로, 상기 활성화 과정의 충전 전압은 리튬 전이금속 산화물의 Li2MnO3-y’Ay’이 전기화학 반응을 일으키기 시작하는 전압(활성 전압) 이상 내지 4.8V 이하이고, 활성화 과정의 방전 전압은 4.0V 이상 내지 상기 활성 전압 미만일 수 있으며, 상기 활성 전압은 대응 음극 활물질의 구성과, 전지셀구조 등에 따라 조금씩 차이를 갖는 바, 이때, 활성 전압은 4.3V 내지 4.5V일 수 있다.Specifically, the charging voltage of the activation process is higher than the voltage (active voltage) at which Li 2 MnO 3 -y ' A y' of the lithium transition metal oxide starts to cause an electrochemical reaction to 4.8 V or less, May be 4.0 V or more to less than the activation voltage, and the activation voltage may be slightly different depending on the configuration of the corresponding anode active material, the cell structure, etc., and the activation voltage may be 4.3V to 4.5V.
따라서, 본 발명에 따른 활성화 과정은, 활성 전압이 4.3V인 경우에는, 4.3V 이상 내지 4.8V 이하의 전압범위로 충전하고, 4.0V 내지 4.3V 미만의 전압범위로 방전하여 수행될 수 있고, 활성 전압이 4.4V인 경우에는, 4.4V 이상 내지 4.8V 이하의 전압범위로 충전하고, 4.0V 내지 4.4V 미만의 전압범위로 방전하여 수행될 수 있으며, 활성 전압이 4.5V인 경우에는, 4.5V 이상 내지 4.8V 이하의 전압범위로 충전하고, 4.0V 내지 4.5V 미만의 전압범위로 방전하여 수행될 수 있다. Therefore, the activation process according to the present invention can be performed by charging in a voltage range of 4.3 V or more to 4.8 V or less and discharging in a voltage range of 4.0 V to 4.3 V when the active voltage is 4.3 V, When the active voltage is 4.4 V, it can be performed by charging in a voltage range of 4.4 V to 4.8 V and discharging in a voltage range of 4.0 V to 4.4 V. When the active voltage is 4.5 V, 4.5 V to a voltage range of 4.8 V or less and discharging to a voltage range of 4.0 V to less than 4.5 V. [
상기 범위를 벗어나, 4.0V 미만의 범위로 방전하거나, 활성 전압 미만의 범위로 충전하여 활성화 과정을 수행하는 경우에는, 양극 활물질이 활성화되지 않는 영역이 여전히 많이 존재하여 본 발명이 소망하는 효과를 얻기 어렵고, 활성 전압 이상의 범위로 방전하거나, 4.8V를 초과하는 범위로 충전하여 활성화 과정을 수행하는 경우에는, 양극 활물질의 손상이 매우 커져 오히려 전지가 퇴화되는 문제가 있어 바람직하지 않다.When the battery is discharged in a range of less than 4.0 V or charged in a range of less than the active voltage to carry out the activation process, the region where the cathode active material is not activated still exists, In the case of performing the activation process by discharging in the range of the active voltage or higher or charging in the range exceeding 4.8 V, the damage of the cathode active material becomes very large and the battery is rather degraded, which is not preferable.
이러한 활성화 과정의 전압 범위는, 더욱 상세하게는, 4.2V 내지 4.6V 범위일 수 있다.The voltage range of this activation process may more particularly be in the range of 4.2V to 4.6V.
또한, 상기 고전압 활성화 과정은 상기 전압 범위뿐 아니라, 충전 및 방전의 횟수가 매우 중요한데, 상기에서와 같이 5회 내지 20회 반복하는 것이 바람직하다.In addition, the high voltage activation process is important not only in the voltage range but also in the number of times of charging and discharging. It is preferable that the high voltage activation process is repeated 5 to 20 times as described above.
상기 범위를 벗어나, 5회 미만으로 수행하는 경우에는, 상기에서 설명한 바와 같이 여전히 양극 활물질이 활성화되지 않는 영역이 많이 존재하여 본 발명이 소망하는 효과를 얻기 어렵고, 20회를 초과하여 수행하는 경우에는, 양극 활물질의 손상이 매우 커져 오히려 전지가 퇴화되는 문제가 있는 바, 바람직하지 않다.If the operation is carried out less than 5 times out of the above range, there are still many regions where the cathode active material is not activated as described above, so that it is difficult to obtain the desired effect of the present invention. , There is a problem that the damage of the positive electrode active material becomes so large that the battery deteriorates, which is not preferable.
이러한 활성화 과정에서의 충전 및 방전 횟수는, 더욱 상세하게는, 충전에서방전까지를 하나로 할 때, 10회 내지 20회일 수 있다.More specifically, the number of times of charging and discharging in the activation process may be 10 times to 20 times, from charging to discharging.
한편, 상기에서 설명한 바와 같이, 고전압 활성화 과정에서는 상기 화학식 1로 표현되는 화합물, 즉 리튬 전이금속 산화물을 포함하는 양극 활물질로부터 기인한 산소가 전해액과 부반응을 초래하여 다량의 가스를 발생시키는 것이 일반적이다. 따라서, 이 경우 발생된 가스를 제거하는 과정이 필요하므로, 상기 활성화 과정은 충전 및 방전을 반복함에 따라 발생한 가스를 제거하는 과정을 더 포함할 수 있다. As described above, in the high-voltage activation process, oxygen generated from the cathode active material including the compound represented by the formula (1), that is, the lithium transition metal oxide, causes a side reaction with the electrolyte solution to generate a large amount of gas . Therefore, in this case, since the process of removing the generated gas is necessary, the activation process may further include a process of removing gas generated as the charge and discharge are repeated.
상기 가스를 제거하는 과정은 복수회의 충방전이 모두 끝난 활성화 과정의 맨 마지막 단계에 수행될 수 있으며, 활성화 과정의 맨 마지막 단계에 수행하는 것을 포함하면, 그 중간 단계에서도 수행될 수 있고, 그 횟수는 한정되지 아니한다. 즉, 상기 가스를 제거하는 과정은 활성화 과정의 맨 마지막 단계에만 수행될 수도 있고, 상기 활성화 과정의 중간 단계 및 맨 마지막 단계에 2회 이상에 걸쳐 수행될 수 있다. The process of removing the gas may be performed at the final stage of the activation process in which a plurality of charge and discharge processes have been completed. If the process includes performing the process at the last stage of the activation process, Is not limited. That is, the process of removing the gas may be performed only at the final stage of the activation process, or may be performed at least twice at the intermediate stage and the final stage of the activation process.
이러한 가스의 제거 방법은 특별히 한정되지 아니하며, 당해 기술분야에서 공지된 방법을 이용할 수 있다.The method of removing such a gas is not particularly limited, and a method known in the art can be used.
하나의 구체적인 예에서, 본 발명에 따른 양극 활물질은, 상기 화학식 1로 표현되는 화합물 중에서 선택된 하나 이상의 리튬 전이금속 산화물 이외에 리튬 코발트 산화물(LiCoO2), 리튬 니켈 산화물(LiNiO2) 등의 층상 화합물이나 1 또는 그 이상의 전이금속으로 치환된 화합물; 화학식 Li1+xMn2-xO4 (여기서, x 는 0 ~ 0.33 임), LiMnO3, LiMn2O3, LiMnO2 등의 리튬 망간 산화물; 리튬 동 산화물(Li2CuO2); LiV3O8, LiFe3O4, V2O5, Cu2V2O7 등의 바나듐 산화물; 화학식 LiNi1-xMxO2 (여기서, M = Co, Mn, Al, Cu, Fe, Mg, B 또는 Ga 이고, x = 0.01 ~ 0.3 임)으로 표현되는 Ni 사이트형 리튬 니켈 산화물; 화학식 LiMn2-xMxO2 (여기서, M = Co, Ni, Fe, Cr, Zn 또는 Ta 이고, x = 0.01 ~ 0.1 임) 또는 Li2Mn3MO8 (여기서, M = Fe, Co, Ni, Cu 또는 Zn 임)으로 표현되는 리튬 망간 복합 산화물; LiNixMn2-xO4로 표현되는 스피넬 구조의 리튬 망간 복합 산화물; 화학식의 Li 일부가 알칼리토금속 이온으로 치환된 LiMn2O4; 디설파이드 화합물; Fe2(MoO4)3 등을 포함할 수 있고, 이 경우, 상기 화학식 1로 표현되는 화합물 중에서 선택된 하나 이상의 리튬 전이금속 산화물은 양극 활물질 전체 중량을 기준으로 60 중량% 이상, 더욱 상세하게는, 80 중량% 이상 포함될 수 있다.In one specific example, the cathode active material according to the present invention is a layered compound such as lithium cobalt oxide (LiCoO 2 ) or lithium nickel oxide (LiNiO 2 ) in addition to at least one lithium transition metal oxide selected from the compounds represented by the above formula Compounds substituted with one or more transition metals; Lithium manganese oxides such as Li 1 + x Mn 2 -x O 4 (where x is 0 to 0.33), LiMnO 3 , LiMn 2 O 3 , LiMnO 2 and the like; Lithium copper oxide (Li 2 CuO 2 ); Vanadium oxides such as LiV 3 O 8 , LiFe 3 O 4 , V 2 O 5 and Cu 2 V 2 O 7 ; A Ni-site type lithium nickel oxide expressed by the formula LiNi 1-x M x O 2 (where M = Co, Mn, Al, Cu, Fe, Mg, B or Ga and x = 0.01 to 0.3); Formula LiMn 2-x M x O 2 ( where, M = Co, Ni, Fe , Cr, and Zn, or Ta, x = 0.01 ~ 0.1 Im) or Li 2 Mn 3 MO 8 (where, M = Fe, Co, Ni, Cu, or Zn); A lithium manganese composite oxide having a spinel structure represented by LiNi x Mn 2-x O 4 ; LiMn 2 O 4 in which a part of Li in the formula is substituted with an alkaline earth metal ion; Disulfide compounds; Fe 2 (MoO 4 ) 3 , and the like. In this case, the at least one lithium transition metal oxide selected from the compounds represented by Formula 1 may be used in an amount of 60 wt% or more based on the total weight of the cathode active material, 80% by weight or more.
한편, 상기 화학식 1로 표현되는 화합물은 하기 화학식 2로 표현되는 화합물 중에서 선택된 하나 이상의 리튬 니켈망간코발트 산화물일 수 있다.Meanwhile, the compound represented by Formula 1 may be at least one lithium nickel manganese cobalt oxide selected from compounds represented by Formula 2 below.
LipNiqCorMn1-q-rO2-wBw (2)Li p Ni q Co r Mn 1-qr O 2-w B w (2)
상기 식에서,In this formula,
B는 PO4, BO3, CO3, F 및 NO3의 음이온으로 이루어진 군에서 선택되는 하나 이상이고;B is at least one selected from the group consisting of anions of PO 4 , BO 3 , CO 3 , F and NO 3 ;
1.0<p≤1.5, 0<q≤0.35, 0<r≤0.35, 0≤w≤0.04이다.1.0 <p? 1.5, 0 <q? 0.35, 0 <r? 0.35, and 0? W?
본 발명은 또한 상기 제조방법으로 제조한 리튬 이차전지를 제공한다.The present invention also provides a lithium secondary battery manufactured by the above method.
상기 리튬 이차전지는 리튬 이온 전지, 리튬 폴리머 전지, 리튬 이온 폴리머 전지로 이루어진 군에서 선택된 하나일 수 있다.The lithium secondary battery may be one selected from the group consisting of a lithium ion battery, a lithium polymer battery, and a lithium ion polymer battery.
이러한 리튬 이차전지는, 일반적으로, 상기 양극, 음극, 및 상기 양극과 음극 사이에 개재되는 분리막으로 구성된 전극조립체가 전지케이스에 내장되어 있는 상태로 리튬염 함유 비수 전해질로 함침되어 있는 구조로 이루어져 있다. Such a lithium secondary battery generally has a structure in which an electrode assembly composed of the positive electrode, the negative electrode, and a separator interposed between the positive electrode and the negative electrode is impregnated with a lithium salt-containing nonaqueous electrolyte in a state where the electrode assembly is embedded in the battery case .
상기 양극은 양극 집전체 상에 상기 양극 활물질, 도전재 및 바인더의 혼합물인 전극 합제를 도포한 후 건조하여 제조되며, 필요에 따라서는, 상기 혼합물에 충진제를 더 첨가하기도 한다.The positive electrode is prepared by applying an electrode mixture, which is a mixture of the positive electrode active material, a conductive material and a binder, on a positive electrode collector, followed by drying. If necessary, a filler may be further added to the mixture.
상기 양극 집전체는 일반적으로 3 ~ 500 ㎛의 두께로 만든다. 이러한 양극 집전체는, 당해 전지에 화학적 변화를 유발하지 않으면서 높은 도전성을 가지는 것이라면 특별히 제한되는 것은 아니며, 예를 들어, 스테인레스 스틸, 알루미늄, 니켈, 티탄, 소성 탄소, 또는 알루미늄이나 스테리인레스 스틸의 표면에 카본, 니켈, 티탄, 은 등으로 표면처리한 것 등이 사용될 수 있다. 집전체는 그것의 표면에 미세한 요철을 형성하여 양극 활물질의 접착력을 높일 수도 있으며, 필름, 시트, 호일, 네트, 다공질체, 발포체, 부직포체 등 다양한 형태가 가능하다.The cathode current collector generally has a thickness of 3 to 500 mu m. Such a positive electrode current collector is not particularly limited as long as it has high conductivity without causing chemical changes in the battery. Examples of the positive electrode current collector include stainless steel, aluminum, nickel, titanium, sintered carbon, aluminum or stainless steel A surface treated with carbon, nickel, titanium, silver or the like may be used. The current collector may have fine irregularities on the surface thereof to increase the adhesive force of the cathode active material, and various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric are possible.
상기 도전재는 통상적으로 양극 활물질을 포함한 혼합물 전체 중량을 기준으로 1 내지 50 중량%로 첨가된다. 이러한 도전재는 당해 전지에 화학적 변화를 유발하지 않으면서 도전성을 가진 것이라면 특별히 제한되는 것은 아니며, 예를 들어, 천연 흑연이나 인조 흑연 등의 흑연; 카본블랙, 아세틸렌 블랙, 케첸 블랙, 채널 블랙, 퍼네이스 블랙, 램프 블랙, 서머 블랙 등의 카본블랙; 탄소 섬유나 금속 섬유 등의 도전성 섬유; 불화 카본, 알루미늄, 니켈 분말 등의 금속 분말; 산화아연, 티탄산 칼륨 등의 도전성 위스키; 산화 티탄 등의 도전성 금속 산화물; 폴리페닐렌 유도체 등의 도전성 소재 등이 사용될 수 있다.The conductive material is usually added in an amount of 1 to 50% by weight based on the total weight of the mixture including the cathode active material. Such a conductive material is not particularly limited as long as it has electrical conductivity without causing chemical changes in the battery, for example, graphite such as natural graphite or artificial graphite; Carbon black such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and summer black; Conductive fibers such as carbon fiber and metal fiber; Metal powders such as carbon fluoride, aluminum, and nickel powder; Conductive whiskey such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
상기 바인더는 활물질과 도전재 등의 결합과 집전체에 대한 결합에 조력하는 성분으로서, 통상적으로 양극 활물질을 포함하는 혼합물 전체 중량을 기준으로 1 내지 50 중량%로 첨가된다. 이러한 바인더의 예로는, 폴리불화비닐리덴, 폴리비닐알코올, 카르복시메틸셀룰로우즈(CMC), 전분, 히드록시프로필셀룰로우즈, 재생 셀룰로우즈, 폴리비닐피롤리돈, 테트라플루오로에틸렌, 폴리에틸렌, 폴리프로필렌, 에틸렌-프로필렌-디엔 테르 폴리머(EPDM), 술폰화 EPDM, 스티렌 브티렌 고무, 불소 고무, 다양한 공중합체 등을 들 수 있다.The binder is a component that assists in bonding of the active material and the conductive material and bonding to the current collector, and is usually added in an amount of 1 to 50 wt% based on the total weight of the mixture containing the cathode active material. Examples of such binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene , Polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butylene rubber, fluorine rubber, various copolymers and the like.
상기 충진제는 양극의 팽창을 억제하는 성분으로서 선택적으로 사용되며, 당해 전지에 화학적 변화를 유발하지 않으면서 섬유상 재료라면 특별히 제한되는 것은 아니며, 예를 들어, 폴리에틸렌, 폴리프로필렌 등의 올리핀계 중합체; 유리섬유, 탄소섬유 등의 섬유상 물질이 사용된다.The filler is optionally used as a component for suppressing the expansion of the anode, and is not particularly limited as long as it is a fibrous material without causing a chemical change in the battery. Examples of the filler include olefin polymers such as polyethylene and polypropylene; Fibrous materials such as glass fibers and carbon fibers are used.
상기 음극은 음극 집전체 상에 음극 활물질을 도포, 건조 및 프레싱하여 제조되며, 필요에 따라 상기에서와 같은 도전재, 바인더, 충진제 등이 선택적으로 더 포함될 수 있다.The negative electrode is prepared by applying, drying and pressing an anode active material on an anode current collector, and may optionally further include a conductive material, a binder, a filler, and the like as described above.
상기 음극 활물질은, 예를 들어, 난흑연화 탄소, 흑연계 탄소 등의 탄소; LixFe2O3(0≤x≤1), LixWO2(0≤x≤1), SnxMe1-xMe’yOz (Me: Mn, Fe, Pb, Ge; Me’: Al, B, P, Si, 주기율표의 1족, 2족, 3족 원소, 할로겐; 0<x≤1; 1≤y≤3; 1≤z≤8) 등의 금속 복합 산화물; 리튬 금속; 리튬 합금; 규소계 합금; 주석계 합금; SnO, SnO2, PbO, PbO2, Pb2O3, Pb3O4, Sb2O3, Sb2O4, Sb2O5, GeO, GeO2, Bi2O3, Bi2O4, and Bi2O5 등의 금속 산화물; 폴리아세틸렌 등의 도전성 고분자; Li-Co-Ni 계 재료; 티타늄 산화물; 리튬 티타늄 산화물 등을 사용할 수 있다.The negative electrode active material may include, for example, carbon such as non-graphitized carbon or graphite carbon; Li x Fe 2 O 3 (0≤x≤1 ), Li x WO 2 (0≤x≤1), Sn x Me 1-x Me 'y O z (Me: Mn, Fe, Pb, Ge; Me' : Metal complex oxides such as Al, B, P, Si, Group 1,
상기 음극 집전체는 일반적으로 3 ~ 500 ㎛의 두께로 만들어진다. 이러한 음극 집전체는, 당해 전지에 화학적 변화를 유발하지 않으면서 도전성을 가진 것이라면 특별히 제한되는 것은 아니며, 예를 들어, 구리, 스테인레스 스틸, 알루미늄, 니켈, 티탄, 소성 탄소, 구리나 스테인레스 스틸의 표면에 카본, 니켈, 티탄, 은 등으로 표면처리한 것, 알루미늄-카드뮴 합금 등이 사용될 수 있다. 또한, 양극 집전체와 마찬가지로, 표면에 미세한 요철을 형성하여 음극 활물질의 결합력을 강화시킬 수도 있으며, 필름, 시트, 호일, 네트, 다공질체, 발포체, 부직포체 등 다양한 형태로 사용될 수 있다.The negative electrode current collector is generally made to have a thickness of 3 to 500 mu m. Such an anode current collector is not particularly limited as long as it has electrical conductivity without causing chemical changes in the battery, and examples of the anode current collector include copper, stainless steel, aluminum, nickel, titanium, sintered carbon, a surface of copper or stainless steel A surface treated with carbon, nickel, titanium, silver or the like, an aluminum-cadmium alloy, or the like can be used. In addition, like the positive electrode collector, fine unevenness can be formed on the surface to enhance the bonding force of the negative electrode active material, and it can be used in various forms such as films, sheets, foils, nets, porous bodies, foams and nonwoven fabrics.
상기 분리막은 양극과 음극 사이에 개재되며, 높은 이온 투과도와 기계적 강도를 가지는 절연성의 얇은 박막이 사용된다. 분리막의 기공 직경은 일반적으로 0.01 ~ 10 ㎛이고, 두께는 일반적으로 5 ~ 300 ㎛이다. 이러한 분리막으로는, 예를 들어, 내화학성 및 소수성의 폴리프로필렌 등의 올레핀계 폴리머; 유리섬유 또는 폴리에틸렌 등으로 만들어진 시트나 부직포 등이 사용된다. 전해질로서 폴리머 등의 고체 전해질이 사용되는 경우에는 고체 전해질이 분리막을 겸할 수도 있다.The separation membrane is interposed between the anode and the cathode, and an insulating thin film having high ion permeability and mechanical strength is used. The pore diameter of the separator is generally 0.01 to 10 mu m and the thickness is generally 5 to 300 mu m. Such separation membranes include, for example, olefinic polymers such as polypropylene, which are chemically resistant and hydrophobic; A sheet or nonwoven fabric made of glass fiber, polyethylene or the like is used. When a solid electrolyte such as a polymer is used as an electrolyte, the solid electrolyte may also serve as a separation membrane.
상기 전지케이스는 금속 캔, 또는 수지층과 금속층을 포함하는 라미네이트 시트의 파우치형 전지케이스일 수 있고, 상세하게는 파우치형 전지케이스일 수 있다. 상기에서 설명한 바와 같이, 파우치형 전지케이스는 전지의 외형을 일정한 힘으로 유지시켜주기 어렵기 때문에, 활성화 과정에서 활성화가 되지 못한 영역이 고전압에서 사이클이 진행되면서 지속적으로 활성화됨에 따라 발생된 가스로 인해, 파우치가 부풀어서 벤팅(venting) 되거나 전극 사이에 가스가 트랩(trap)되어 존재하면서 가스가 Li 이온의 이동을 방해함에 따라 전극의 균일하고 원활한 반응을 방해하는 문제가 크므로, 본 발명에 따른 이차전지의 제조방법을 적용하는 경우 더 큰 효과를 나타낼 수 있다.The battery case may be a metal can, or a pouch type battery case of a laminate sheet including a resin layer and a metal layer, and more specifically, a pouch type battery case. As described above, since the pouch-shaped battery case is difficult to keep the external shape of the battery at a constant force, the region that is not activated during the activation process is continuously activated at the high voltage, , The pouch is swollen and vented, or gas is trapped between the electrodes, and the gas interferes with the movement of Li ions, which hinders uniform and smooth reaction of the electrode. Therefore, A greater effect can be obtained when the manufacturing method of the secondary battery is applied.
상기 리튬염 함유 비수 전해질은, 비수 전해액과 리튬으로 이루어져 있고, 상기 비수 전해액로는 비수계 유기용매, 유기 고체 전해질, 무기 고체 전해질 등이 사용되지만 이들만으로 한정되는 것은 아니다.The lithium salt-containing nonaqueous electrolyte is composed of a nonaqueous electrolyte and lithium, and examples of the nonaqueous electrolyte include nonaqueous organic solvents, organic solid electrolytes, inorganic solid electrolytes, and the like.
상기 비수계 유기용매로는, 예를 들어, N-메틸-2-피롤리디논, 프로필렌 카르보네이트, 에틸렌 카르보네이트, 부틸렌 카르보네이트, 디메틸 카르보네이트, 디에틸 카르보네이트, 감마-부틸로 락톤, 1,2-디메톡시 에탄, 테트라히드록시 프랑(franc), 2-메틸 테트라하이드로푸란, 디메틸술폭시드, 1,3-디옥소런, 포름아미드, 디메틸포름아미드, 디옥소런, 아세토니트릴, 니트로메탄, 포름산 메틸, 초산메틸, 인산 트리에스테르, 트리메톡시 메탄, 디옥소런 유도체, 설포란, 메틸 설포란, 1,3-디메틸-2-이미다졸리디논, 프로필렌 카르보네이트 유도체, 테트라하이드로푸란 유도체, 에테르, 피로피온산 메틸, 프로피온산 에틸 등의 비양자성 유기용매가 사용될 수 있다.Examples of the non-aqueous organic solvent include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma -Butyrolactone, 1,2-dimethoxyethane, tetrahydroxyfuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane , Acetonitrile, nitromethane, methyl formate, methyl acetate, triester phosphate, trimethoxymethane, dioxolane derivatives, sulfolane, methylsulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate Nonionic organic solvents such as tetrahydrofuran derivatives, ethers, methyl pyrophosphate, ethyl propionate and the like can be used.
상기 유기 고체 전해질로는, 예를 들어, 폴리에틸렌 유도체, 폴리에틸렌 옥사이드 유도체, 폴리프로필렌 옥사이드 유도체, 인산 에스테르 폴리머, 폴리 에지테이션 리신(agitation lysine), 폴리에스테르 술파이드, 폴리비닐 알코올, 폴리 불화 비닐리덴, 이온성 해리기를 포함하는 중합제 등이 사용될 수 있다.Examples of the organic solid electrolyte include a polymer electrolyte such as a polyethylene derivative, a polyethylene oxide derivative, a polypropylene oxide derivative, a phosphate ester polymer, an agitation lysine, a polyester sulfide, a polyvinyl alcohol, a polyvinylidene fluoride, A polymer containing an ionic dissociation group and the like may be used.
상기 무기 고체 전해질로는, 예를 들어, Li3N, LiI, Li5NI2, Li3N-LiI-LiOH, LiSiO4, LiSiO4-LiI-LiOH, Li2SiS3, Li4SiO4, Li4SiO4-LiI-LiOH, Li3PO4-Li2S-SiS2 등의 Li의 질화물, 할로겐화물, 황산염 등이 사용될 수 있다.Examples of the inorganic solid electrolyte include Li 3 N, LiI, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , Nitrides, halides and sulfates of Li such as Li 4 SiO 4 -LiI-LiOH and Li 3 PO 4 -Li 2 S-SiS 2 can be used.
상기 리튬염은 상기 비수계 전해질에 용해되기 좋은 물질로서, 예를 들어, LiCl, LiBr, LiI, LiClO4, LiBF4, LiB10Cl10, LiPF6, LiCF3SO3, LiCF3CO2, LiAsF6, LiSbF6, LiAlCl4, CH3SO3Li, (CF3SO2)2NLi, 클로로 보란 리튬, 저급 지방족 카르본산 리튬, 4 페닐 붕산 리튬, 이미드 등이 사용될 수 있다.The lithium salt is a material that is readily soluble in the non-aqueous electrolyte, for example, LiCl, LiBr, LiI,
또한, 상기 리튬염 함유 비수 전해질에는 충방전 특성, 난연성 등의 개선을 목적으로, 예를 들어, 피리딘, 트리에틸포스파이트, 트리에탄올아민, 환상 에테르, 에틸렌 디아민, n-글라임(glyme), 헥사 인산 트리 아미드, 니트로벤젠 유도체, 유황, 퀴논 이민 염료, N-치환 옥사졸리디논, N,N-치환 이미다졸리딘, 에틸렌 글리콜 디알킬 에테르, 암모늄염, 피롤, 2-메톡시 에탄올, 삼염화 알루미늄 등이 첨가될 수도 있다. 경우에 따라서는, 불연성을 부여하기 위하여, 사염화탄소, 삼불화에틸렌 등의 할로겐 함유 용매를 더 포함시킬 수도 있고, 고온 보존 특성을 향상시키기 위하여 이산화탄산 가스를 더 포함시킬 수도 있으며, FEC(Fluoro-Ethylene Carbonate), PRS(Propene sultone) 등을 더 포함시킬 수 있다.The lithium salt-containing non-aqueous electrolyte may further contain, for the purpose of improving charge / discharge characteristics, flame retardancy, etc., for example, pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylenediamine, glyme, N, N-substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxyethanol, aluminum trichloride, etc. May be added. In some cases, halogen-containing solvents such as carbon tetrachloride and ethylene trifluoride may be further added to impart nonflammability. In order to improve the high-temperature storage characteristics, carbon dioxide gas may be further added. FEC (Fluoro-Ethylene Carbonate, PRS (Propene sultone), and the like.
하나의 구체적인 예에서, LiPF6, LiClO4, LiBF4, LiN(SO2CF3)2 등의 리튬염을, 고유전성 용매인 EC 또는 PC의 환형 카보네이트와 저점도 용매인 DEC, DMC 또는 EMC의 선형 카보네이트의 혼합 용매에 첨가하여 리튬염 함유 비수계 전해질을 제조할 수 있다.In one specific example, LiPF 6, LiClO 4, LiBF 4, LiN (SO 2 CF 3) 2 , such as a lithium salt, a highly dielectric solvent of DEC, DMC or EMC Fig solvent cyclic carbonate and a low viscosity of the EC or PC of And then adding it to a mixed solvent of linear carbonate to prepare a lithium salt-containing non-aqueous electrolyte.
본 발명은, 상기 이차전지를 단위전지로 포함하는 전지모듈, 상기 전지모듈을 포함하는 전지팩, 및 상기 전지팩을 전원으로 포함하는 디바이스를 제공한다.The present invention provides a battery module including the secondary battery as a unit cell, a battery pack including the battery module, and a device including the battery pack as a power source.
이 때, 상기 디바이스의 구체적인 예로는, 전지적 모터에 의해 동력을 받아 움직이는 파워 툴(power tool); 전기자동차(Electric Vehicle, EV), 하이브리드 전기자동차(Hybrid Electric Vehicle, HEV), 플러그-인 하이브리드 전기자동차(Plug-in Hybrid Electric Vehicle, PHEV) 등을 포함하는 전기차; 전기 자전거(E-bike), 전기 스쿠터(E-scooter)를 포함하는 전기 이륜차; 전기 골프 카트(electric golf cart); 전력저장용 시스템 등을 들 수 있으나, 이에 한정되는 것은 아니다.At this time, specific examples of the device include a power tool that is powered by an electric motor and moves; An electric vehicle including an electric vehicle (EV), a hybrid electric vehicle (HEV), a plug-in hybrid electric vehicle (PHEV), and the like; An electric motorcycle including an electric bike (E-bike) and an electric scooter (E-scooter); An electric golf cart; And a power storage system, but the present invention is not limited thereto.
상기에서 설명한 바와 같이, 본 발명에 따른 리튬 이차전지 제조방법은, 4.0V 내지 4.8V 범위의 고전압으로 5회 내지 20회의 충전 및 방전을 반복하여 수행하는 이차전지 활성화 과정을 포함함으로써, 기존의 활성화 과정을 행하여 제조된 리튬 이차전지와 비교하여 활성화 직후의 방전 용량 및 효율 등의 전지특성은 동등 수준으로 유지하면서도, 사이클 과정에서 발생하는 산소에 따른 전해액의 추가적인 부반응을 억제함에 따라, 사이클 과정에서 발생하는 가스량을 감소시키는 효과가 있다.As described above, the method for manufacturing a lithium secondary battery according to the present invention includes the step of activating the secondary battery by repeatedly performing charging and discharging five times to 20 times at a high voltage ranging from 4.0 V to 4.8 V, The battery characteristics such as discharge capacity and efficiency immediately after the activation are maintained at the same level as compared with the lithium secondary battery manufactured through the process, and the additional side reaction of the electrolyte due to oxygen generated in the cyclic process is suppressed, There is an effect of reducing the amount of gas to be supplied.
도 1은 실험예 1에 따른 초기 방전 용량 및 효율 측정 그래프이다;
도 2는 실험예 1에 따른 레이트 특성을 나타내는 그래프이다;
도 3은 실험예 1에 따른 사이클에 따라 방전 저항을 측정한 그래프이다.1 is an initial discharge capacity and efficiency measurement graph according to Experimental Example 1;
2 is a graph showing the rate characteristic according to Experimental Example 1;
3 is a graph showing discharge resistance measured according to the cycle according to Experimental Example 1. FIG.
이하, 본 발명의 실시예를 참조하여 설명하지만, 하기 실시예는 본 발명을 예시하기 위한 것이며, 본 발명의 범주가 이들만으로 한정되는 것은 아니다.
Hereinafter, the present invention will be described with reference to Examples. However, the following Examples are intended to illustrate the present invention and the scope of the present invention is not limited thereto.
<실시예 1>≪ Example 1 >
리튬 이차전지의 제조Manufacture of lithium secondary battery
양극 활물질로서 Li1.05Ni0.3Mn0.5Co0.2O2 90 중량%, 도전재로서 천연흑연 5.0 중량%, 바인더로서 PVdF 5.0 중량%를 용제인 NMP에 넣고 믹싱(mixing)하여 양극 합제를 제조하고, 20 ㎛ 두께의 알루미늄 호일에 상기 양극 합제를 200 ㎛ 두께로 코팅한 후 압연 및 건조하여 양극을 제조하였다. 90% by weight of Li 1.05 Ni 0.3 Mn 0.5 Co 0.2 O 2 as a cathode active material, 5.0% by weight of natural graphite as a conductive material and 5.0% by weight of PVdF as a binder were mixed in NMP as a solvent and mixed to prepare a cathode mixture. The positive electrode mixture was coated on an aluminum foil having a thickness of 200 mu m to a thickness of 200 mu m, rolled and dried to prepare a positive electrode.
음극 활물질로서 인조흑연 95 중량%, 도전재(Super-P) 1.5 중량% 및 바인더(PVdF) 3.5 중량%를 용제인 NMP에 넣고 믹싱(mixing)하여 음극 합제를 제조하고, 20 ㎛ 두께의 구리 호일에 상기 음극 합제를 200 ㎛ 두께로 코팅한 후 압연 및 건조하여 음극을 제조하였다.A negative electrode material mixture was prepared by adding 95% by weight of artificial graphite, 1.5% by weight of a conductive material (Super-P) and 3.5% by weight of a binder (PVdF) as a negative electrode active material to NMP as a solvent and mixing, , The negative electrode mixture was coated to a thickness of 200 탆, rolled and dried to prepare a negative electrode.
상기 양극과 음극 사이에 다공성 폴리에틸렌 분리막을 개재한 후 EC : EMC = 1 : 2의 carbonate solvent에 LiPF6가 1M 녹아있는 전해액을 주입하여 리튬 이차전지를 제조하였다. A porous polyethylene separator was sandwiched between the anode and the cathode, and an electrolyte solution containing 1 M of LiPF 6 dissolved in a carbonate solvent of EC: EMC = 1: 2 was injected to prepare a lithium secondary battery.
활성화 과정Activation process
상기와 같이 제조된 리튬 이차전지를 0.1C 조건으로 4.6 V에서 충전한 뒤, 4.2 V로 방전하는 과정을 20회 진행하였다.
The lithium secondary battery thus prepared was charged at 4.6 V under 0.1 C, and then discharged at 4.2 V for 20 times.
<비교예 1>≪ Comparative Example 1 &
상기 실시예 1과 동일하게 제조된 리튬 이차전지를 0.1C 조건으로 4.6 V에서 충전한 뒤, 4.2 V로 방전하는 과정을 50회 진행하였다.
The lithium secondary battery prepared in the same manner as in Example 1 was charged at 4.6 V under 0.1 C, and discharged at 4.2 V for 50 cycles.
<비교예 2>≪ Comparative Example 2 &
상기 실시예 1과 동일하게 제조된 리튬 이차전지를 0.1C 조건으로 4.6 V에서 충전한 뒤, 2.5 V로 방전하는 과정을 1회 진행하였다.
The lithium secondary battery prepared in the same manner as in Example 1 was charged at 4.6 V under a condition of 0.1 C, and discharged at 2.5 V once.
<실험예 1 ><Experimental Example 1>
초기 방전 용량 및 효율 측정Initial discharge capacity and efficiency measurement
상기 실시예 1 및 비교예 1, 2에서 제조된 리튬 이차전지들의 활성화 과정 이후, 0.1C 조건으로 4.6 V 내지 2.5 V 전압 영역에서 충전 및 방전을 진행하고, 첫번째 방전 용량 및 효율을 확인하여, 그 결과를 하기 도 1에 나타내었다. 상기 효율은 충전 용량 대비 방전 용량을 계산한 값이다.After the activation process of the lithium secondary batteries prepared in Example 1 and Comparative Examples 1 and 2, charging and discharging were performed in the voltage range of 4.6 V to 2.5 V at 0.1 C, and the first discharging capacity and efficiency were checked. The results are shown in FIG. The efficiency is a value obtained by calculating the discharge capacity in relation to the charging capacity.
레이트 특성 측정Rate characterization
상기 실시예 1 및 비교예 1, 2에서 제조된 리튬 이차전지들의 활성화 과정 이후, 2.5 V 내지 4.4 V 전압 영역에서 0.1C 및 0.5C 레이트로 충전 및 방전을 진행하고, 각각 첫번째 방전 용량을 확인하여, 그 결과를 하기 도 2에 나타내었다.After the activation of the lithium secondary batteries prepared in Example 1 and Comparative Examples 1 and 2, charging and discharging were performed at 0.1 C and 0.5 C rates in the voltage range of 2.5 V to 4.4 V, and the first discharging capacity was checked , And the results are shown in Fig.
사이클에 따른 방전 저항 측정Measurement of discharging resistance according to cycle
상기 실시예 1 및 비교예 1, 2에서 제조된 리튬 이차전지들의 활성화 과정 이후, 4.6 V 내지 2.5 V 전압 영역에서 100회 동안 충방전을 진행하였다. 사이클 전과 100 사이클에서의 이차전지의 저항을 측정하여, 그 결과를 하기 도 3에 나타내었다.After the activation process of the lithium secondary batteries prepared in Example 1 and Comparative Examples 1 and 2, charge and discharge were performed 100 times in the 4.6 V to 2.5 V voltage region. The resistance of the secondary battery before and after the cycle was measured, and the results are shown in Fig.
사이클에 따른 가스 발생량 측정Measurement of gas generation by cycle
상기 실시예 1 및 비교예 1, 2에서 제조된 리튬 이차전지들의 활성화 과정 이후, 4.6 V 내지 2.5 V 전압 영역에서 100회 동안 충방전을 진행하였다. 사이클 동안 발생한 가스량을 측정하여, 그 결과를 하기 표 1에 나타내었다.After the activation process of the lithium secondary batteries prepared in Example 1 and Comparative Examples 1 and 2, charge and discharge were performed 100 times in the 4.6 V to 2.5 V voltage region. The amount of gas generated during the cycle was measured, and the results are shown in Table 1 below.
도 1 내지 도 3, 및 표 1을 참조하면, 본 발명에 따른 활성화 과정을 거친 실시예 1의 리튬 이차전지는 기존의 활성화 과정을 거친 비교예 2의 리튬 이차전지와 비교하여, 활성화 직후의 방전 용량 및 효율 등의 전지특성은 동등 수준으로 유지하면서도, 사이클 과정에서 발생하는 가스량을 감소시키는 것을 확인할 수 있다. 이는, 사이클 과정에서 발생하는 산소에 따른 전해액의 추가적인 부반응이 억제되었음을 의미한다. 이로부터 비교예 2 역시 100 사이클까지는 가스 발생량이 이차전지의 수명 열화를 가져올 정도는 아니었지만, 사이클이 진행됨에 따라 급격한 수명 열화가 나타날 것임을 예상할 수 있다.Referring to FIGS. 1 to 3 and Table 1, the lithium secondary battery of Example 1 which has undergone the activation process according to the present invention, as compared with the lithium secondary battery of Comparative Example 2 which has undergone the conventional activation process, It can be seen that the battery characteristics such as capacity and efficiency are maintained at the same level, while the amount of gas generated during the cycle process is reduced. This means that an additional side reaction of the electrolyte due to oxygen generated in the cyclic process is suppressed. From this, it can be expected that the gas generation amount of the battery of Comparative Example 2 is not enough to deteriorate the service life of the secondary battery up to 100 cycles, but the life of the secondary battery will deteriorate rapidly as the cycle progresses.
한편, 고전압 활성화 과정을 본 발명에 따른 적절한 횟수 범위를 초과하여 진행한 비교예 1의 리튬 이차전지는, 적절한 횟수로 고전압 활성화 과정을 거친 실시예 1의 리튬 이차전지와 비교하여, 용량 및 효율, 사이클에 따른 저항이 현저히 증가할 뿐만 아니라, 가스 발생량 역시 기존의 활성화 과정을 행한 경우와 동등한 수준으로 매우 높은 것을 확인할 수 있다. On the other hand, the lithium secondary battery of Comparative Example 1 in which the high-voltage activation process exceeded the appropriate number of times according to the present invention is superior to the lithium secondary battery of Example 1 that has undergone the high-voltage activation process an appropriate number of times, Not only the resistance according to the cycle is remarkably increased, but also the amount of gas generation is very high, which is equivalent to that of the conventional activation process.
이는, 고전압의 활성화 과정을 적절한 횟수를 초과하여 매우 많이 진행하는 경우, 전지 내 활물질의 손상이 매우 커져 오히려 전지가 퇴화되기 때문이다.
This is because, if the activation process of the high voltage exceeds a proper number of times, the damage of the active material in the battery becomes very large and the battery degrades.
본 발명이 속한 분야에서 통상의 지식을 가진 자라면, 상기 내용을 바탕을 본 발명의 범주 내에서 다양한 응용 및 변형을 행하는 것이 가능할 것이다. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (15)
상기 양극 활물질은 하기 화학식 1로 표현되는 화합물 중에서 선택된 하나 이상의 리튬 전이금속 산화물을 포함하며;
상기 리튬 이차전지는 충전 전압은 리튬 전이금속 산화물의 Li2MnO3-y’Ay’이 전기화학 반응을 일으키기 시작하는 전압(활성 전압) 이상 내지 4.8V 이하, 방전 전압은 4.0V 이상 내지 상기 활성 전압 미만의 범위에서 5회 내지 20회의 충전 및 방전을 반복하여 수행하는 활성화 과정을 거치는 것을 특징으로 하는 리튬 이차전지의 제조방법:
(1-x)LiM’O2-yAy -xLi2MnO3-y’Ay’ (1)
상기 식에서,
M’은 MnaMb이고;
M은 Ni, Ti, Co, Al, Cu, Fe, Mg, B, Cr, Zr, Zn 및 2주기 전이금속들로 이루어진 군에서 선택되는 하나 이상이며;
A는 PO4, BO3, CO3, F 및 NO3의 음이온으로 이루어진 군에서 선택되는 하나 이상이고;
0<x<1; 0≤y≤0.02; 0≤y’≤0.02; 0≤a≤0.5; 0.5≤b≤1.0; a + b = 1 이다.A method of manufacturing a lithium secondary battery comprising a cathode active material,
Wherein the cathode active material comprises at least one lithium transition metal oxide selected from the group consisting of compounds represented by the following formula (1);
The charging voltage of the lithium secondary battery is such that Li 2 MnO 3 -y ' A y' of the lithium transition metal oxide starts to cause an electrochemical reaction to be higher than the voltage (active voltage) to 4.8 V and the discharge voltage is higher than 4.0 V Wherein the lithium secondary battery is subjected to an activation process in which charging and discharging are repeatedly performed for 5 to 20 times in a range of less than the active voltage.
(1-x) LiM'O 2-y A y -xLi 2 MnO 3 -y ' A y' (1)
In this formula,
M 'is Mn a M b ;
M is one or more selected from the group consisting of Ni, Ti, Co, Al, Cu, Fe, Mg, B, Cr, Zr, Zn and two period transition metals;
A is at least one selected from the group consisting of anions of PO 4 , BO 3 , CO 3 , F and NO 3 ;
0 < x <1; 0? Y? 0.02; 0? Y? 0.02; 0? A? 0.5; 0.5? B? 1.0; a + b = 1.
LipNiqCorMn1-q-rO2-wBw (2)
상기 식에서,
B는 PO4, BO3, CO3, F 및 NO3의 음이온으로 이루어진 군에서 선택되는 하나 이상이고;
1.0<p≤1.5, 0<q≤0.35, 0<r≤0.35, 0≤w≤0.04이다.The method for producing a lithium secondary battery according to claim 1, wherein the compound represented by Formula 1 is at least one lithium nickel manganese cobalt oxide selected from compounds represented by Formula 2:
Li p Ni q Co r Mn 1-qr O 2-w B w (2)
In this formula,
B is at least one selected from the group consisting of anions of PO 4 , BO 3 , CO 3 , F and NO 3 ;
1.0 <p? 1.5, 0 <q? 0.35, 0 <r? 0.35, and 0? W?
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