KR20020007881A - Fabrication Method of Lithium Phosphate Target for High Performance Electrolyte of Thin Film Micro-Battery - Google Patents
Fabrication Method of Lithium Phosphate Target for High Performance Electrolyte of Thin Film Micro-Battery Download PDFInfo
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Abstract
본 발명은 리튬 이온 전지의 전해질로 이용되는 LiPON 박막의 원료인 박막 전지를 위한 전해질용 리튬인산염 스퍼터링 타겟 제조 방법에 관한 것으로, 리튬인산염 분말을 600∼950℃의 온도 범위에서 하소 처리하는 단계와; 상기 단계에서 하소 처리된 분말을 분쇄하는 단계와; 상기 단계에서 분쇄된 분말을 압축 성형하는 단계와; 상기 단계에서 압축 성형된 성형체를 500∼1500℃의 온도 범위에서 소결 처리하는 단계를 포함하여 이루어진다.The present invention relates to a method for preparing a lithium phosphate sputtering target for an electrolyte for a thin film battery which is a raw material of a LiPON thin film used as an electrolyte of a lithium ion battery, comprising: calcining a lithium phosphate powder in a temperature range of 600 to 950 ° C .; Pulverizing the calcined powder in the step; Compression molding the powder pulverized in the step; It comprises the step of sintering the compression-molded molded body in the temperature range of 500 ~ 1500 ℃.
Description
본 발명은 박막 전지를 위한 전해질용 리튬인산염 스퍼터링 타겟 제조 방법에 관한 것으로, 보다 상세하게는 리튬 이온 전지의 전해질로 이용되는 LiPON 박막을 제조하기 위한 리튬인산염 스퍼터링 타겟 제조 방법에 관한 것이다.The present invention relates to a method for producing a lithium phosphate sputtering target for an electrolyte for a thin film battery, and more particularly to a method for producing a lithium phosphate sputtering target for manufacturing a LiPON thin film used as an electrolyte of a lithium ion battery.
일반적으로, 박막 전지란 음극(cathode), 양극(anode)과 전해질 등 전지의구성 요소들이 고상의 박막으로 제조되는 이차전지로, 최근 전자기기들이 소형화, 경량화 되고 마이크로 기술을 응용한 초미세 소자들이 개발되면서 이들의 에너지원으로 주목받고 있다.In general, a thin film battery is a secondary battery in which components of a battery, such as a cathode, an anode, and an electrolyte, are manufactured as a solid thin film. Recently, electronic devices have been miniaturized, lightened, and ultra-fine devices using micro technology have been developed. It is attracting attention as their energy source as it is developed.
박막 전지의 음극(cathode) 재료로는 LiCoO2, LiNiO2, LiMn2O4, V2O5등의 물질이 박막화되어 응용되고 있으며, 양극(anode) 재료로는 높은 에너지 밀도를 가지고 있는 Li 금속이 사용되고 있다.Materials such as LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , V 2 O 5, etc., are being used as a cathode material for thin film batteries, and Li metal having high energy density as an anode material. Is being used.
박막 전지에 응용될 수 있는 고체 전해질은 크게 무기질계와 폴리머계 전해질로 구분되며, 전해 박막으로 사용되기 위해서는 높은 리튬 이온(Li+) 전도성을 가지고 있으면서, 0∼5V의 작동 구간에서 Li 금속과 반응하지 않는 전기 화학적 안정성을 가지고 있어야 한다.Solid electrolytes that can be applied to thin film batteries are largely classified into inorganic and polymer electrolytes. To be used as an electrolytic thin film, the solid electrolyte has high lithium ion (Li + ) conductivity and reacts with Li metal in an operating region of 0 to 5V. It must have electrochemical stability that does not.
최근 벌크형 이차전지용 고체 전해질로는 유기용매 전해질과 유사한 이온 전도도를 가지는 폴리머계 전해질이 개발되고 있으나, Li 금속과의 반응 때문에 박막 전지에의 응용에는 많은 제한을 받고 있다.Recently, a polymer electrolyte having a ionic conductivity similar to that of an organic solvent electrolyte has been developed as a solid electrolyte for a bulk secondary battery. However, due to the reaction with Li metal, application to a thin film battery has been limited.
따라서, 무기물계 물질 중에서 특히, 비정질인 유리질계 전해질이 박막 전지용 전해질로 주목받고 있으며, 이에 관한 연구가 활발히 진행되고 있다.Therefore, in particular, an amorphous glass-based electrolyte has been attracting attention as an electrolyte for a thin film battery among inorganic materials, and research on this has been actively conducted.
현재까지 보고된 결과에 의하면, LixPOyNz(LiPON) 전해질이 실제 박막 전지에 응용 가능한 것으로 평가되고 있다. 이 물질은 미국 ORNL(Oak Ridge National Lab)의 닥터 J. 베이트(Dr. J. Bates) 그룹에 의하여 특허가 출원되어 있다. 예를 들어, RF 스퍼터링에 의하여 Li3PO4타겟을 질소 분위기에서 스퍼터링함으로써Li2.9PO3.3N0.46의 조성으로 제작되는데, 이는 상온에서 3.3×10-6S/cm의 비교적 높은 이온 전도도를 가지며, 0∼5V의 넓은 전기화학적 안정 구간을 가질 뿐만 아니라 음극(cathode) 및 양극(anode)과 매우 안정적인 기계/화학적 계면을 형성한다고 보고되고 있다.According to the results reported so far, Li x PO y N z (LiPON) electrolyte is evaluated to be applicable to the actual thin film battery. The material has been patented by Dr. J. Bates Group of Oak Ridge National Lab (ORNL). For example, by sputtering the Li 3 PO 4 target in a nitrogen atmosphere by RF sputtering, Li 2.9 PO 3.3 N 0.46 is produced, which has a relatively high ion conductivity of 3.3 × 10 −6 S / cm at room temperature, In addition to having a wide electrochemical stability section of 0-5V, it has been reported to form a very stable mechanical / chemical interface with cathodes and anodes.
박막 전지에 대한 수요의 필요성이 증가되고, 이를 위한 연구 개발이 활성화되고 있기 때문에 LiPON 박막을 제작하기 위한 리튬인산염 스퍼터링 타겟에 대한 요구도 증가되고 있다.The demand for thin film batteries is increasing, and the research and development for this is being activated. Therefore, the demand for lithium phosphate sputtering targets for manufacturing LiPON thin films is increasing.
그러나, 현재 미국의 세락(cerac)사와 일본의 고순도화학사 등에서 제조되어 시판되고 있는 종래의 리튬인산염의 스퍼터링 타겟은 실제 스퍼터링 공정중에 온도구배에 의한 열응력(thermal stress)으로 타겟이 파손되는 현상이 발생하는 등 많은 문제점을 안고 있어 실제 이들 회사에서는 제품의 생산이나 개발을 거의 포기한 상태인 것으로 알려지고 있다.However, conventional sputtering targets of lithium phosphate, which are manufactured and marketed by US cerac and Japanese high purity chemicals, etc., may cause the target to break due to thermal stress due to temperature gradient during the actual sputtering process. It is known that these companies have almost given up on producing or developing products.
특히, 종래의 리튬인산염타겟은 그 제조공정상 하소 처리(Calcination)를 1000℃ 이상에서 수행하기 때문에 유리상이 생성되어 소결 처리를 하는 도중에 치밀화되지 않아서 타겟의 저밀도화를 유발한다. 이러한 저밀도 타겟은 낮은 파워에서는 문제가 없으나, 높은 RF 파워에서는 타겟 표면에 균열이 발생될 수 있으며, 증착 중에 질소 가스가 유입되어 타겟 표면의 조성이 변화하는 문제점이 있었다.In particular, since the conventional lithium phosphate target is calcined (Calcination) in the manufacturing process at 1000 ℃ or more, the glass phase is generated and is not densified during the sintering process, causing the target to be lowered. The low density target has no problem at low power, but may have cracks on the target surface at high RF power, and nitrogen gas is introduced during deposition to change the composition of the target surface.
본 발명자들은, 리튬인산염 스퍼터링 타겟이 저밀도 상태로 제작되면 낮은 파워에서는 문제가 없으나, 높은 RF 파워에서는 타겟 표면에 균열이 발생될 수 있으며, 증착 중에 질소 가스가 유입되어 타겟 표면의 조성이 변화하는 사실에 착안하여, 이에 관하여 예의 연구를 거듭한 결과, 종래의 리튬인산염 타겟의 출발원료로 사용되는 물질은 수화되어 있는 상태이기 때문에 OH와 수분을 완전히 제거해야만 가압 성형 후에 소결 공정을 거치면서 액상 형성 또는 뒤틀림 현상이 발생될 수 있다는 사실을 발견하여 본 발명을 완성하였다.The inventors have found that if the lithium phosphate sputtering target is manufactured in a low density state, there is no problem at low power, but at high RF power, cracks may occur on the target surface, and nitrogen gas is introduced during deposition to change the composition of the target surface. As a result of intensive research on this, as a starting material of a conventional lithium phosphate target, since the material used is a hydrated state, it is necessary to completely remove OH and moisture to form a liquid phase through a sintering process after pressure molding. The present invention has been completed by discovering that distortion can occur.
따라서, 본 발명은 이러한 종래 기술의 문제점을 감안하여 안출된 것으로, 그 목적은 박막 전지의 전해질로써 우수한 특성을 나타내는 LiPON을 제조하기 위한 리튬인산염타겟의 품질을 향상시켜 주는 박막 전지를 위한 전해질용 리튬인산염 스퍼터링 타겟 제조 방법을 제공하는데 그 목적이 있다.Accordingly, the present invention has been made in view of the problems of the prior art, and an object thereof is a lithium for electrolyte for a thin film battery which improves the quality of a lithium phosphate target for producing LiPON exhibiting excellent properties as an electrolyte of a thin film battery. It is an object to provide a method for preparing a phosphate sputtering target.
도 1은 본 발명의 제조 방법을 설명하기 위한 공정도.1 is a process chart for explaining the manufacturing method of the present invention.
도 2는 교류 임피던스 분석을 해석하기 위한 등가회로.2 is an equivalent circuit for analyzing AC impedance analysis.
도 3은 본 발명에 따라 제작된 Li3PO4타겟을 이용한 LiPON 박막에 대한 임피던스 측정 결과를 나타낸 그래프.Figure 3 is a graph showing the impedance measurement results for the LiPON thin film using a Li 3 PO 4 target prepared according to the present invention.
도 4는 본 발명에 따라 제작된 Li3PO4타겟을 이용한 LiPON 박막의 전기 화학적 안정 전위 구간을 나타낸 그래프.4 is a graph showing an electrochemical stable potential region of a LiPON thin film using a Li 3 PO 4 target prepared according to the present invention.
상기한 목적을 달성하기 위하여, 본 발명은 리튬인산염분말을 600∼950℃의 온도 범위에서 하소하는 단계와; 상기 단계에서 하소 처리된 분말을 분쇄하는 단계와; 상기 단계에서 분쇄된 분말을 압축 성형하는 단계와; 상기 단계에서 압축 성형된 성형체를 500∼1500℃의 온도 범위에서 소결 처리하는 단계를 포함하여 이루어지는 것을 특징으로 하는 박막 전지를 위한 전해질용 리튬인산염 스퍼터링 타겟 제조 방법을 제공한다.In order to achieve the above object, the present invention comprises the steps of calcining the lithium phosphate powder in the temperature range of 600 ~ 950 ℃; Pulverizing the calcined powder in the step; Compression molding the powder pulverized in the step; It provides a method for producing a lithium phosphate sputtering target for an electrolyte for a thin film battery comprising the step of sintering the compression molded molded body in the temperature range of 500 ~ 1500 ℃ in the step.
그리고, 리튬인산염분말을 압축 성형하기 전에 성형성을 높이기 위하여 바인더를 첨가하는 단계를 더 포함할 수 있다. 상기 압축 성형 단계에서의 압축 하중은 50∼200kgf/cm2가 적당하다.Further, the method may further include adding a binder to increase moldability before compression molding the lithium phosphate powder. The compression load in the compression molding step is 50 ~ 200kgf / cm 2 is suitable.
본 발명에서는 하소 처리 온도가 매우 중요한데, 그 이유는 하소 온도가 너무 높으면(950℃ 이상) 리튬인산염분말이 용융되며, 반대로 너무 낮을 경우(600℃ 미만)에는 리튬인산염분말에 포함된 OH 또는 H2O의 완전한 제거가 이루어지지 않는다. 또한, OH 또는 H2O가 제거되지 않은 상태에서 소결 처리할 경우에 소결 온도에서 국부적 용융이 발생하기 때문이다.In the present invention, the calcination treatment temperature is very important because the lithium phosphate powder melts if the calcination temperature is too high (over 950 ° C.), and conversely, if it is too low (under 600 ° C.), OH or H 2 contained in the lithium phosphate powder There is no complete removal of O. This is also because local melting occurs at the sintering temperature when the sintering treatment is performed without OH or H 2 O removed.
본 발명의 리튬인산염 타겟은 LixPyO4로 이루어지는 조성이다. 여기서 x, y는 각각 2.5≤x≤3.5, 0.7≤y≤1.3의 범위의 값을 가지는 것이 바람직한데, 그 이유는 얻고자 하는 LiPON 전해질 박막의 화학조성에 따라 이에 대응하여 리튬과량의 타겟이나 리튬 부족 또는 과량의 P를 갖는 타겟을 제조할 필요가 있기 때문이다.The lithium phosphate target of this invention is a composition which consists of Li x P y O 4 . Here, x and y preferably have values in the range of 2.5 ≦ x ≦ 3.5 and 0.7 ≦ y ≦ 1.3, respectively. The reason for this is according to the chemical composition of the LiPON electrolyte thin film to be obtained. This is because it is necessary to produce a target having an insufficient or excess P.
본 발명에서 사용될 수 있는 대표적인 리튬인산염 분말은 Li3PO4분말이다.Representative lithium phosphate powders that can be used in the present invention are Li 3 PO 4 powders.
한편, 압축성형체의 소결은 500∼1,500℃의 범위에서 수행한다.On the other hand, the sintering of the compact is carried out in the range of 500 ~ 1500 ℃.
상기한 바와 같이 Li 과량의 타겟을 제조하고자 하는 경우에, 상기 Li3PO4분말에 Li2O 과 Li2CO3분말 중에서 어느 한 분말을 더 첨가하며, Li 부족 또는 과량의 P를 갖는 타겟을 제조하고자 하는 경우에, 상기 Li3PO4분말에 P2O5분말을 더 첨가한다.As described above, when one intends to produce an excess Li target, one of Li 2 O and Li 2 CO 3 powder is further added to the Li 3 PO 4 powder, and a target having Li deficiency or excess P is added. In the case of preparation, P 2 O 5 powder is further added to the Li 3 PO 4 powder.
상기 Li3PO4분말은 Li20-P2O3과 Li2CO3-P2O5중에서 어느 한 조성을 선택하여혼합하여 하소 처리하여 제조할 수 있다. 이때 상기 하소 처리는 600∼1100℃ 온도 범위에서 수행한다.The Li 3 PO 4 powder may be prepared by calcination are mixed by selecting any of the composition from the Li 2 0-P 2 O 3 and Li 2 CO 3 -P 2 O 5 . At this time, the calcination treatment is carried out in the temperature range of 600 ~ 1100 ℃.
상기한 바와 같이 본 발명에서는 박막 전지의 전해질로 이용되는 LiPON 전해질을 제조하기 위한 리튬인산염스퍼터링 타겟의 품질을 향상시킴으로써, 고품질의 전해질을 안정적으로 제조할 수 있게 한다.As described above, in the present invention, by improving the quality of the lithium phosphate sputtering target for producing the LiPON electrolyte used as the electrolyte of the thin film battery, it is possible to stably manufacture a high quality electrolyte.
(실시예)(Example)
이하에 상기한 본 발명을 바람직한 실시예가 도시된 첨부 도면을 참고하여 더욱 상세하게 설명한다.Hereinafter, with reference to the accompanying drawings showing a preferred embodiment of the present invention described above in more detail.
첨부한 도면, 도 1은 본 발명의 제조 방법을 설명하기 위한 공정도, 도 2는 교류 임피던스 분석을 해석하기 위한 등가회로, 도 3은 본 발명에 따라 제작된 Li3PO4타겟을 이용한 LiPON 박막에 대한 임피던스 측정 결과를 나타낸 그래프, 도 4는 본 발명에 따라 제작된 Li3PO4타겟을 이용한 LiPON 박막의 전기 화학적 안정 전위 구간을 나타낸 그래프이다.1 is a process chart for explaining the manufacturing method of the present invention, FIG. 2 is an equivalent circuit for analyzing AC impedance analysis, and FIG. 3 is a LiPON thin film using a Li 3 PO 4 target manufactured according to the present invention. 4 is a graph showing impedance measurement results, FIG. 4 is a graph showing an electrochemical stable potential region of a LiPON thin film using a Li 3 PO 4 target manufactured according to the present invention.
본 발명은 LiPON 박막의 증착을 위한 출발 물질인 4인치 크기의 Li3PO4스퍼터링 타겟을 제조하여 RF(Radio Frequency) 반응성 스퍼터링에 의하여 LiPON 전해질 박막을 제작하여 그 특성을 분석하였다.In the present invention, a 4 inch size Li 3 PO 4 sputtering target, which is a starting material for depositing a LiPON thin film, was prepared, and a LiPON electrolyte thin film was manufactured by RF (Radio Frequency) reactive sputtering and analyzed for its characteristics.
본 발명에 따라 4인치 크기의 Li3PO4타겟을 제조하기 위한 방법에 대하여 도 1을 참조하여 설명한다.A method for producing a 4 inch size Li 3 PO 4 target according to the present invention will be described with reference to FIG.
먼저, Li3PO4분말을 850℃ 온도에서 하소 처리(Calcination)한 후(S 10), 24시간 동안 볼밀(ball mill)하여 분쇄한 다음(S 20), 상기와 같이 하소 처리한 후에 볼밀 방법으로 분쇄된 분말을 건조시킨다(S 30).First, the Li 3 PO 4 powder is calcined at 850 ° C. (Calcination) (S 10), and then pulverized by ball milling for 24 hours (S 20), and then calcined as described above. Dry the powder pulverized (S 30).
4인치(inch) 크기의 디스크 타입으로 성형하기 위하여 볼밀하여 분쇄한 후에 건조된 Li3PO4분말에 바인더(binder)를 첨가하는데, 첨가되는 바인더는 5중량%의 폴리비닐 알콜(PVA, Polyvinyl Alcohol)을 사용하였다.Binder is added to the dried Li 3 PO 4 powder after being ball milled to form a 4 inch sized disc type. The added binder is 5% by weight of polyvinyl alcohol (PVA). ) Was used.
상기 Li3PO4분말과 5중량%의 PVA를 100 : 25의 중량비로 하여 혼합하여 균일하게 혼합하기 위하여 그라인딩시킨다(S 49).The Li 3 PO 4 powder and 5% by weight of PVA were mixed at a weight ratio of 100: 25 and ground to uniformly mix (S 49).
혼합되어 분쇄된 Li3PO4와 PVA를 균일한 크기의 입자로 유지하기 위하여 50메쉬 씨브(sieve)를 이용하여 분급(sieving)한다(S 50).In order to maintain the mixed and ground Li 3 PO 4 and PVA as particles of uniform size, the sieves are classified using 50 mesh sieves (S 50).
그리고, 50∼200(보다 적절한 하중은 100)kgf/cm2의 하중으로 상온에서 단축(Uni-axial) 방향으로 압축 성형하였다(S 60). 이 때, 압축 성형된 성형체의 외경은 12.5cm이다.Then, compression molding was performed in a uni-axial direction at room temperature with a load of 50 to 200 (more suitable load was 100) kgf / cm 2 (S 60). At this time, the outer diameter of the compression molded molded body is 12.5 cm.
성형된 시편 즉, 성형체로부터 상기 단계(S 40)에서 혼합된 바인더(PVA)를 제거하기 위하여 번-아웃(burn-out) 방법을 이용하는데, 1단계로 공기 분위기에서 600℃에서 3시간 동안 유지한 후, 2단계로 900℃까지 온도를 올려서 3시간 동안 소결하였으며(S 70), 소결 처리가 끝난 타겟을 기계적으로 연마하여 정확한 4인치 크기로 완성하였다.A burn-out method is used to remove the binder (PVA) mixed in the step (S 40) from the molded specimen, that is, the molded body, which is maintained at 600 ° C. for 3 hours in an air atmosphere in one step. After that, the temperature was raised to 900 ° C in two steps and sintered for 3 hours (S 70). The sintered target was mechanically polished to complete an accurate 4 inch size.
이렇게 제작된 타겟을 이용한 전해 박막의 특성을 알기 위하여 LiPON 박막을 제작하였다. LiPON 박막은 Li3PO4타겟을 상온에서 RF 마그네트론 스퍼터링함으로써 증착하였으며, 기판으로는 백금/티타늄(Pt/Ti)이 콜렉터로 증착된 규소(Si) 기판을 사용하였다.In order to know the characteristics of the electrolytic thin film using the target thus produced, a LiPON thin film was manufactured. The LiPON thin film was deposited by RF magnetron sputtering of a Li 3 PO 4 target at room temperature, and a silicon (Si) substrate on which a platinum / titanium (Pt / Ti) was deposited as a collector was used.
질소/산소(N2/O2)의 혼합가스 분위기에서 전체 가스 압력은 5mtorr로 유지하고 RF 파워(RF power)는 300W로 하여 스퍼터링 하였다.In a mixed gas atmosphere of nitrogen / oxygen (N 2 / O 2 ), the total gas pressure was maintained at 5 mtorr and the RF power was set at 300 W, and sputtered.
타겟 표면에 묻은 오염물들을 제거하기 위하여 증착하기 전에 20분 동안 프리-스퍼터링(pre-sputtering)을 실시한 후 박막을 증착하였다.A thin film was deposited after pre-sputtering for 20 minutes prior to deposition to remove contaminants on the target surface.
상기한 바와 같이 제조된 LiPON 박막의 이온 전도도를 측정하기 위하여 전기화학적 임피던스 측정기(Electrochemical Impedance Spectroscopy)를 사용하여, 1Hz에서 1MHz의 범위에서 임피던스(Impedance) 측정을 실시하였다.In order to measure the ion conductivity of the LiPON thin film prepared as described above, an impedance measurement was performed in the range of 1 Hz to 1 MHz using an electrochemical impedance spectroscopy.
측정용 시편은 백금(Pt) 콜렉터 위에 LiPON 박막을 증착한 후 리튬(Li) 금속을 증착하여 이루어진 Pt/LiPON/Li 구조로 제조하였다.The test specimen was manufactured in a Pt / LiPON / Li structure formed by depositing a LiPON thin film on a platinum (Pt) collector and then depositing a lithium (Li) metal.
LiPON 박막의 두께는 1.4㎛이었으며, 실제 제작된 박막의 면적은 1.2×1.2㎝였다.The thickness of the LiPON thin film was 1.4 μm, and the area of the actual thin film was 1.2 × 1.2 cm.
LiPON 박막의 전기화학적 안정성을 확인하기 위하여 전기화학적 분석 장비(Potentiostat/Galvanostat EG&G M263A)를 사용하여 전압과 전류의 변화(cyclic voltamogram)에 대한 측정을 실시하였다.In order to confirm the electrochemical stability of the LiPON thin film, electrochemical analysis equipment (Potentiostat / Galvanostat EG & G M263A) was used to measure the change in voltage and current (cyclic voltamogram).
그리고, LiPON 박막의 이온 전도도를 측정하기 위하여 교류 임피던스(ACimpedance) 분석을 실시하였으며, 이 결과를 해석하기 위한 등가회로를 도 2에 나타내었다.In addition, an AC impedance analysis was performed to measure the ion conductivity of the LiPON thin film, and an equivalent circuit for analyzing the result is shown in FIG. 2.
두 전극에 의해 전하의 흐름이 완전히 차단된 이온 전도체는 저항 Cc- 저항 Rion- 캐패시터 Cc에 해당하는 회로로 표시할 수 있다.An ion conductor whose charge flow is completely blocked by two electrodes can be represented by a circuit corresponding to the resistance C c -resistance R ion -capacitor C c .
저항 Rion은 전해질에서 나타나는 직렬 저항 성분이며, 캐패시터 Cc는 전극-전해질 계면에서 형성되는 캐패시턴스(capacitance)이다.The resistance R ion is a series resistance component that appears in the electrolyte, and the capacitor C c is a capacitance formed at the electrode-electrolyte interface.
그러나, 실제 시편에서는 두 전극과 전해질의 계면에서 전하의 이동이 발생하므로, 이에 따른 저항 Rt, 캐패시터 Cg의 값이 고려되어 도 2와 같은 복합 회로로 구성될 수 있다.However, in the actual specimen, since the movement of charge occurs at the interface between the two electrodes and the electrolyte, the resistance R t and the capacitor C g may be considered, and thus may be configured as a composite circuit as shown in FIG. 2.
저항 Rt는 전하 이동(charge transfer)에 따른 저항값이며, 캐패시터 Cg는 박막 전극에서의 리미팅 캐패시턴스(limiting capacitance)이다.The resistor R t is a resistance value according to charge transfer, and the capacitor C g is a limiting capacitance at the thin film electrode.
도 3에 증착된 LiPON 박막에 대한 임피던스(Impedance) 측정 결과를 나타내었다.The impedance measurement results for the LiPON thin film deposited in FIG. 3 are shown.
도 2의 등가회로를 적용하면, 첫 번째 반원의 끝점이 전해질 박막의 저항값이 되며, 전도도(k) = 길이(L) / {면적(A) ×저항(R)} 식을 이용하여 이온 전도도(k[S/cm])를 계산하였다.When the equivalent circuit of FIG. 2 is applied, the end point of the first semicircle becomes the resistance value of the electrolyte thin film, and the conductivity (k) = length (L) / {area (A) × resistance (R)} is obtained using the equation (k [S / cm]) was calculated.
그 결과, 산소/질소(O2/N2)의 비가 1/5인 혼합 가스 분위기에서 증착한 LiPON 박막의 이온 전도도(k)는 1.9×10-6S/cm이었다.As a result, the ion conductivity k of the LiPON thin film deposited in the mixed gas atmosphere having an oxygen / nitrogen (O 2 / N 2 ) ratio of 1/5 was 1.9 × 10 −6 S / cm.
도 4는 LiPON 박막의 전기화학적 안정성을 확인하기 위하여 1.2∼4V 구간에서 실시한 전압과 전류간의 관계에 대한 측정 결과이며, 1.2∼4V의 전 구간에서 전류 밀도(current density)가 매우 안정적인 상태를 유지함을 알 수 있었다.4 is a measurement result of the relationship between the voltage and the current carried out in the 1.2 ~ 4V section in order to confirm the electrochemical stability of the LiPON thin film, it is maintained that the current density (current density) is very stable in the entire range of 1.2 ~ 4V Could know.
상기한 바와 같이 이루어진 본 발명은 박막 전지의 전해질로 이용되는 LiPON 전해질을 제조하기 위한 Li3PO4스퍼터링 타겟의 품질을 향상시킴으로써, 고품질의 전해질을 안정적으로 제조할 수 있게 해 주는 효과를 제공한다.The present invention made as described above improves the quality of the Li 3 PO 4 sputtering target for producing a LiPON electrolyte used as the electrolyte of the thin film battery, thereby providing an effect that makes it possible to stably manufacture a high quality electrolyte.
이상에서는 본 발명을 특정의 바람직한 실시예를 예로 들어 도시하고 설명하였으나, 본 발명은 상기한 실시예에 한정되지 아니하며 본 발명의 정신을 벗어나지 않는 범위 내에서 당해 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에 의해 다양한 변경과 수정이 가능할 것이다.In the above, the present invention has been illustrated and described with reference to specific preferred embodiments, but the present invention is not limited to the above-described embodiments and the general knowledge in the technical field to which the present invention pertains without departing from the spirit of the present invention. Various changes and modifications will be made by those who possess.
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| US10680277B2 (en) | 2010-06-07 | 2020-06-09 | Sapurast Research Llc | Rechargeable, high-density electrochemical device |
| WO2013154118A1 (en) * | 2012-04-11 | 2013-10-17 | 株式会社コベルコ科研 | Li-CONTAINING PHOSPHORIC-ACID COMPOUND SINTERED BODY AND SPUTTERING TARGET, AND METHOD FOR MANUFACTURING SAID LI-CONTAINING PHOSPHORIC-ACID COMPOUND SINTERED BODY |
| US9892891B2 (en) | 2012-04-11 | 2018-02-13 | Kobelco Research Institute, Inc. | Li-containing phosphoric-acid compound sintered body and sputtering target, and method for manufacturing said Li-containing phosphoric-acid compound sintered body |
| CN116253570A (en) * | 2023-03-20 | 2023-06-13 | 超威电源集团有限公司 | LiPON target material and preparation method and application of film |
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