KR20170006663A - A method for analyzing pore distribution in secondary battery cathode and polymer therefor - Google Patents
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- 239000011148 porous material Substances 0.000 title claims abstract description 48
- 238000009826 distribution Methods 0.000 title claims abstract description 24
- 229920000642 polymer Polymers 0.000 title claims abstract description 18
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- 238000000992 sputter etching Methods 0.000 claims abstract description 8
- 238000010884 ion-beam technique Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 2
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- 239000003822 epoxy resin Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
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Abstract
Description
본 발명은 이차 전지 양극 내부 기공 분포 분석 방법 및 이를 위한 고분자에 대한 것이다. The present invention relates to a method for analyzing the pore distribution in the anode of a secondary battery and a polymer for the same.
전지는 크게 양극, 음극, 분리막, 전해액으로 구성되어 있다. 이들 구성 재료가 3차원적으로 분포하고 있어서, 이들의 틈새에 무수한 기공이 존재하고 있다. 전극의 기공은 실제로 이차 전지 내에서 전해액으로 채워져 리튬 이온 등의 통로가 된다. 따라서 기공의 크기, 개수, 분포 등이 상기 리튬 이온의 확산성에 영향을 주며, 이것이 전극 성능에 큰 영향을 미치기 때문에 양극 내부 기공의 분포를 정확하게 분석하는 것이 중요하다.The battery is largely composed of an anode, a cathode, a separator, and an electrolytic solution. These constituent materials are distributed three-dimensionally, so that there are innumerable pores in these gaps. The pores of the electrode are actually filled with an electrolyte in the secondary battery, thereby becoming a passage for lithium ions and the like. Therefore, it is important to accurately analyze the distribution of the pores in the anode, since the size, number, and distribution of the pores influence the diffusibility of the lithium ions, which greatly affects the electrode performance.
하지만 종래에는 양극 단면 상에서는 기공 분포의 관찰이 어려웠으며, 주사 전자 현미경에서는 깊은 초점 심도 때문에 기공 뒤에 존재하는 활물질이 단면 이미지 상에서 함께 나타나 기공 및 활물질의 구분이 어려운 문제가 있었다.Conventionally, however, it has been difficult to observe the pore distribution on the anode section. In the scanning electron microscope, there is a problem in that the active material existing behind the pore is difficult to distinguish between the pore and the active material due to the deep focal depth.
이와 관련하여, 일본 특허공개공보 제2015-041434호에서 전극의 기공에 금속을 압입 충전하여 기공 구조를 평가하는 방법에 대해 개시하고 있으나, 상기와 같은 단점은 여전히 해결하지 못한 실정이다. In this regard, Japanese Laid-Open Patent Application No. 2015-041434 discloses a method of pressurizing and charging a metal into pores of an electrode to evaluate a pore structure. However, such disadvantages as described above have not yet been solved.
본 발명은 상기와 같은 종래 기술의 문제점을 해결하기 위한 것으로서, 다른 양극 구성 물질과 기공을 명확하게 구분하여 관찰하고, 이를 통해 전극의 상층, 중층 및 하층에 따른 기공의 분포를 계산하여 전극 성능을 예상하기 위하여, 신규한 이차 전지 양극 내부 기공 분포 분석 방법 및 이차 전지 양극 내부 기공 분포 분석용 고분자를 제공하는 것을 목적으로 한다.DISCLOSURE OF THE INVENTION The present invention has been made to solve the problems of the prior art as described above, and it is an object of the present invention to observe clearly the pores of other cathode materials and to analyze the distribution of pores according to the upper layer, middle layer and lower layer, It is an object of the present invention to provide a novel method for analyzing the pore distribution in the anode of a secondary battery and a polymer for analyzing the pore distribution in the cathode of the secondary battery.
상기 목적을 달성하기 위해서, 본 발명은 1) 이차 전지 양극 내부에 하기 화학식 1로 표시되는 반복 단위를 갖는 고분자를 매립하여 양극 내부의 기공을 채우는 제 1단계; 및In order to achieve the above object, the present invention provides a method for manufacturing a secondary battery, comprising the steps of: 1) filling a polymer having a repeating unit represented by the following formula (1) And
2) 이온 밀링(ion milling) 장치를 이용하여 이차 전지 양극에 이온 빔을 조사하여 현미경 관찰용 시료를 제작하는 제 2단계2) a second step of preparing a sample for observing the microscope by irradiating the ion beam to the anode of the secondary battery using an ion milling apparatus
를 포함하는 이차 전지 양극 내부 기공 분포 분석 방법을 제공한다:The method comprising the steps of:
<화학식 1>≪ Formula 1 >
식 중, n은 20 내지 400임.Wherein n is from 20 to 400;
또 본 발명은 상기 화학식 1로 표시되는 반복 단위를 갖는, 이차 전지 양극 내부 기공 분포 분석용 고분자를 제공한다. The present invention also provides a polymer for analyzing the internal pore distribution of a cathode of a secondary battery having the repeating unit represented by the above formula (1).
본 발명에서 제공하는 이차 전지 양극 내부 기공 분포 분석 방법에 따르면 다른 양극 구성 물질과 기공을 명확하게 구분하여 관찰할 수 있으며, 관찰한 사진을 이용하여 전극의 상층, 중층 및 하층에 따른 기공의 분포를 계산하여 전극 성능을 예상할 수 있는 효과가 있다. According to the method for analyzing the internal pore distribution of a cathode of a secondary battery provided in the present invention, it is possible to clearly distinguish between other cathode materials and pores, and the distribution of pores according to the upper, middle, There is an effect that the electrode performance can be estimated by calculation.
도 1은 비교예 1에 의해 얻은 SEM 사진을 확대한 사진이다.
도 2는 비교예 2에 의해 얻은 SEM 사진을 확대한 사진이다.
도 3은 실시예 1에 의해 얻은 SEM 사진을 확대한 사진이다.
도 4는 이차 전지 양극 상층 및 하층의 기공률(porosity)이 상이한 시료의 SEM 사진이다.
도 5는 이차 전지 양극 상층 및 하층의 기공률이 유사한 시료의 SEM 사진이다.
도 6은 이차 전지 양극 상층 및 하층의 기공률 분포에 따른 방전 특성을 나타낸 그래프이다.
도 7은 실시예 1에 의해 얻은 SEM 사진이다.
도 8은 실시예 1에 의해 얻은 SEM 사진을 이미지 프로세싱에 적용하여 얻은 공극률(porosity) 정량 결과 값을 나타낸 그래프이다.
도 9는 이온 밀링(ion milling) 장치의 모식도이다. Fig. 1 is an enlarged photograph of a SEM photograph obtained in Comparative Example 1. Fig.
Fig. 2 is an enlarged photograph of the SEM photograph obtained in Comparative Example 2. Fig.
3 is an enlarged photograph of the SEM photograph obtained in Example 1. Fig.
4 is an SEM photograph of a sample having different porosities in the upper and lower layers of the secondary battery anode.
5 is a SEM photograph of a sample having a similar porosity in the upper and lower layers of the secondary battery anode.
6 is a graph showing discharge characteristics according to the porosity distribution in the upper and lower layers of the secondary battery anode.
7 is a SEM photograph taken in Example 1. Fig.
8 is a graph showing porosity quantification result values obtained by applying the SEM photograph obtained in Example 1 to image processing.
9 is a schematic diagram of an ion milling apparatus.
본 발명은 하기 단계를 포함하는 이차 전지 양극 내부 기공 분포 분석 방법에 대한 것이다.The present invention relates to a method for analyzing the internal pore distribution of a cathode of a secondary battery including the following steps.
이차 전지 양극 내부 기공 분포 분석은, 동일한 기공률을 갖더라도 표면의 기공이 넓은 경우 리튬의 이동 통로에 저항이 적게 걸려서 방전 특성이 좋아지기 때문에 중요하다. 수치상으로 평균 기공률이 동일하더라도 본 발명에 따라 기공 분포 분석을 하였을 때 상층은 높은 기공률을 갖고 하층은 낮은 기공률을 갖는 경우(도 4)에, 상층과 하층이 유사한 기공률을 갖는 경우(도 5)보다 방전 특성이 좋기 때문이다(도 6). Analysis of the internal pore distribution of the secondary battery anode is important because it has less resistance to the lithium passage when the pores on the surface are wide even though they have the same porosity. The pore distribution analysis according to the present invention shows that when the upper layer has a high porosity and the lower layer has a low porosity (FIG. 4), the upper and lower layers have similar porosity (FIG. 5) This is because the discharge characteristics are good (Fig. 6).
이하에서 본 발명의 분석 방법에 대해 상세하게 설명한다. Hereinafter, the analysis method of the present invention will be described in detail.
먼저, 1) 이차 전지 양극 내부에 하기 화학식 1로 표시되는 반복 단위를 갖는 고분자를 매립하여 양극 내부의 기공을 채우는 제 1단계를 수행한다:First, 1) a first step of filling the pores inside the anode with a polymer having a repeating unit represented by the following formula (1) in the interior of the anode of the secondary battery is performed:
<화학식 1> ≪ Formula 1 >
식 중, n은 20 내지 400이다.Wherein n is from 20 to 400.
종래에는 이차 전지 양극 내부 기공 관찰을 위해 에폭시 수지를 매립하였으나, 이 경우 기공이 전부 에폭시 수지로 채워져 기공 뒤에 존재하는 활물질의 형상이 보이지는 않았지만, 양극 구성 물질인 바인더, 도전재 등과 구분이 명확하게 되지 않아 단면 상에서 기공 분포를 보기가 어려웠다. Conventionally, an epoxy resin is embedded for observing the pores in the anode of the secondary battery. In this case, the pores are completely filled with the epoxy resin and the shape of the active material existing behind the pores is not visible. However, And it was difficult to see the pore distribution on the cross section.
에폭시 수지 대신 상기 화학식 1의 반복 단위를 갖는 고분자를 이차 전지 양극 내부에 매립할 경우 기공 뒤에 존재하는 활물질의 형상도 보이지 않으며, 이차 전지 양극 구성 물질과 기공을 명확하게 구분하여 관찰할 수 있다. When the polymer having the repeating unit represented by the above formula (1) is embedded in the anode of the secondary battery instead of the epoxy resin, the shape of the active material existing behind the pores is not seen, and the constituent material of the anode and the pores of the secondary battery can be clearly distinguished.
이후, 2) 이온 밀링(ion milling) 장치를 이용하여 이차 전지 양극에 이온 빔을 조사하여 현미경 관찰용 시료를 제작하는 제 2단계를 수행한다. 이후 상기 현미경 관찰용 시료를 현미경으로 관찰한다.Thereafter, a second step of irradiating the ion beam to the anode of the secondary battery using an ion milling apparatus to produce a sample for observing the microscope is performed. Thereafter, the sample for observing the microscope is observed with a microscope.
이온 밀링(ion milling) 장치에 대해 보다 상세하게 설명한다. The ion milling device will be described in more detail.
이온 건(ion gun)에서 생성된 집속 이온 빔(ion beam)이 마스크(mask)를 거쳐 양극 시료의 표면 끝단에 조사된다. 시료의 끝단에서 약 100 ㎛ 안쪽으로 조사된 이온 빔에 의해 양극 물질들이 스퍼터링(sputtering)되어 물리적 손상이 없는 깨끗한 단면 시료를 얻을 수 있게 되는 것이다. 도 9에 이온 밀링 장치의 모식도를 나타내었다. The focused ion beam generated from the ion gun is irradiated to the surface of the cathode sample through a mask. The anode materials are sputtered by the ion beam irradiated to the inside of about 100 탆 at the end of the sample to obtain a clean section sample free from physical damage. 9 is a schematic view of the ion milling apparatus.
이렇게 얻은 단면 시료를 똑바로 세워 주사 전자 현미경(SEM)으로 단면의 표면을 관찰할 수 있다. The section sample thus obtained can be stood upright and the surface of the cross section can be observed with a scanning electron microscope (SEM).
본 발명의 일 실시예에 있어서, 상기 이온 빔은 아르곤(Ar) 이온 빔인 것이 바람직하나 이에 한정되지 않는다.In one embodiment of the present invention, the ion beam is preferably an argon (Ar) ion beam, but is not limited thereto.
본 발명의 다른 일 실시예에 있어서, 상기 현미경 관찰용 시료는 주사 전자 현미경(SEM)으로 관찰하는 것이 바람직하나 이에 한정되지 않는다.In another embodiment of the present invention, the sample for microscopic observation is preferably observed with a scanning electron microscope (SEM), but is not limited thereto.
이하 본 발명을 비한정적인 실시예에 의해 더욱 상세하게 설명한다. 하기에 개시되는 본 발명의 실시 형태는 어디까지 예시로써, 본 발명의 범위는 이들의 실시 형태에 한정되지 않는다. 본 발명의 범위는 특허청구범위에 표시되었고, 더욱이 특허 청구범위 기록과 균등한 의미 및 범위 내에서의 모든 변경을 함유하고 있다. 또한, 이하의 실시예, 비교예에서 함유량을 나타내는 "%" 및 "부"는 특별히 언급하지 않는 한 질량 기준이다.Hereinafter, the present invention will be described in more detail by way of non-limiting examples. The embodiments of the present invention described below are by way of example only and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and moreover, includes all changes within the meaning and range of equivalency of the claims. In the following Examples and Comparative Examples, "%" and "part" representing the content are on a mass basis unless otherwise specified.
실시예Example
실시예Example 1. 이차 전지 양극 내부 기공 분포 분석 방법 1. Analysis of pore distribution in anode of secondary battery
1) 이차 전지 양극 내부에 하기 화학식 1의 반복단위를 갖는 고분자를 매립하였다:1) A polymer having a repeating unit represented by the following formula (1) was embedded in an anode of a secondary battery:
<화학식 1>≪ Formula 1 >
식 중, n은 20 내지 400임.Wherein n is from 20 to 400;
2) 아르곤 이온 밀링(Ar ion milling) 장치(IM 4000, Hitachi 사 제조)를 이용하여 고분자가 매립된 이차 전지 양극에 집속 아르곤(Ar) 이온 빔을 조사하여 표면을 깎아 내어 평활한 현미경 관찰용 시료를 제작하였다. 2) Using a Ar ion milling apparatus (IM 4000, manufactured by Hitachi), a focused ion beam of an argon (Ar) ion beam was applied to a secondary battery cell filled with a polymer, and the surface was shaved to obtain a smooth microscope observation sample Respectively.
3) 상기 현미경 관찰용 시료를 주사 전자 현미경(SEM)으로 관찰하고, SEM 사진을 촬영하였다. 촬영한 SEM 사진을 확대하여 도 3에 나타내었다.3) The sample for microscopic observation was observed with a scanning electron microscope (SEM), and a SEM photograph was taken. The photographed SEM photograph is enlarged and shown in Fig.
상기 화학식 1의 반복 단위를 갖는 고분자를 매립하는 경우, 상기 고분자 내 Si 성분을 이용하여 주사 전자 현미경 내에서 원자 번호 차이에 의한 대비(contrast)를 극대화시켜서 기공(pore) 지역을 바인더 지역 및 도전재 지역과 명확하게 구분할 수 있었다. When the polymer having the repeating unit represented by
비교예Comparative Example 1. 이차 전지 양극 내부 기공 분포 분석 방법 1. Analysis of pore distribution in anode of secondary battery
상기 실시예 1의 1)에서 이차 전지 양극 내부에 고분자를 매립하지 않은 것을 제외하고는 실시예 1과 동일한 방법으로 이차 전지 양극 내부 기공 분포를 분석하기 위해 SEM 사진을 촬영하였다. SEM photographs were taken to analyze the pore distribution in the anode of the secondary battery in the same manner as in Example 1, except that the polymer was not embedded in the anode of the secondary battery in 1) of Example 1 above.
그 결과를 도 1에 나타내었다. 고분자를 매립하지 않은 양극 단면에서는 주사 전자 현미경(SEM)의 높은 초점 심도 때문에 기공(pore) 뒤에 존재하는 양극 활물질이 함께 관찰되어 순수한 기공만을 구분하여 관찰하기에는 어려움이 있었다. The results are shown in Fig. In the anode section where the polymer is not buried, the cathode active material existing behind the pore is observed together due to the high depth of focus of the scanning electron microscope (SEM), and it is difficult to observe only the pure pores.
비교예Comparative Example 2. 이차 전지 양극 내부 기공 분포 분석 방법 2. Analysis of pore distribution in anode of secondary battery
상기 실시예 1의 1)에서 이차 전지 양극 내부에 하기 화학식 1의 반복단위를 갖는 고분자 대신 에폭시 수지를 매립한 것을 제외하고는 실시예 1과 동일한 방법으로 이차 전지 양극 내부 기공 분포를 분석하기 위해 SEM 사진을 촬영하였다. In the same manner as in Example 1 except that an epoxy resin was embedded in the interior of the secondary battery anode in place of the polymer having a repeating unit represented by the following
<화학식 1>≪
그 결과를 도 2에 나타내었다. 에폭시 수지를 매립한 경우 도 2에 나타난 것처럼 바인더 및 도전재 지역과 기공(pore) 지역의 이미지 대비 차이가 크지 않아 구분하는 데 어려움이 있었다. The results are shown in Fig. As shown in FIG. 2, when the epoxy resin was embedded, it was difficult to distinguish between the binder and the conductive material region and the pore region.
응용예Application example 1. 이미지 프로세싱(image processing)을 적용한 양극 내부 기공률 정량 분석 1. Quantitative analysis of porosity inside the anode with image processing
본 발명이 제공하는 이차 전지 양극 내부 기공 분포 분석에 의해 전극의 성능을 미리 예측해 볼 수 있다. 도 7에 나타낸 실시예 1에 의해 얻은 SEM 사진을 이미지 프로세싱(image processing)에 적용하면 전극의 상층, 중층 및 하층에 따른 정량 결과값(하기 표 1, 도 8)을 도출할 수 있으며, 이를 이용하여 전극의 성능을 미리 예측할 수 있다.The performance of the electrode can be estimated in advance by analyzing the distribution of the pores in the anode of the secondary battery provided by the present invention. When the SEM photograph obtained in Example 1 shown in FIG. 7 is applied to image processing, quantitative result values according to the upper layer, middle layer and lower layer of the electrode can be derived (Table 1, FIG. 8) So that the performance of the electrode can be predicted in advance.
(녹색)Cathode active material
(green)
(흰색)Binder + Conductive material
(White)
(적색)pore
(Red)
Claims (4)
2) 이온 밀링(ion milling) 장치를 이용하여 이차 전지 양극에 이온 빔을 조사하여 현미경 관찰용 시료를 제작하는 제 2단계
를 포함하는 이차 전지 양극 내부 기공 분포 분석 방법:
<화학식 1>
식 중, n은 20 내지 400임.1) a first step of filling a polymer having a repeating unit represented by the following formula (1) into a positive electrode of a secondary battery to fill pores inside the positive electrode; And
2) a second step of preparing a sample for observing the microscope by irradiating the ion beam to the anode of the secondary battery using an ion milling apparatus
Lt; RTI ID = 0.0 > of: < / RTI >
≪ Formula 1 >
Wherein n is from 20 to 400;
상기 현미경 관찰용 시료를 주사 전자 현미경(SEM)으로 관찰하는 것을 특징으로 하는 이차 전지 양극 내부 기공 분포 분석 방법. The method according to claim 1,
Wherein the sample for observing the microscope is observed with a scanning electron microscope (SEM).
상기 이온 빔은 아르곤(Ar) 이온 빔인 것을 특징으로 하는 이차 전지 양극 내부 기공 분포 분석 방법. The method according to claim 1,
Wherein the ion beam is an argon (Ar) ion beam.
<화학식 1>
식 중, n은 20 내지 400임.A polymer for analyzing the internal pore distribution of a cathode of a secondary battery having a repeating unit represented by the following formula (1)
≪ Formula 1 >
Wherein n is from 20 to 400;
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