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Role of Cathode-Electrolyte-Ferroelectric Interface for High Performance Lithium Ion Battery

材料科学 阴极 电解质 铁电性 锂(药物) 薄膜 脉冲激光沉积 纳米技术 电极 化学工程 分析化学(期刊) 光电子学 电介质 化学 物理化学 色谱法 医学 工程类 内分泌学
作者
Sou Yasuhara,Keisuke Chajima,Takashi Teranishi,Shintaro Yasui,Tomoyasu Taniyama,Mitsuru Itoh
出处
期刊:Meeting abstracts 卷期号:MA2016-02 (3): 504-504
标识
DOI:10.1149/ma2016-02/3/504
摘要

Next generation lithium ion battery(LIB) should be endowed with a performance of high-speed chargeability and dischargeability. LiCoO 2 is commercially used as a cathode material of LIB but long period of time is generally needed to charge, which is originated from diffusion-rate-limitation of lithium ions. Usually, charge-discharge reaction is impeded by the side reaction at the electrode/electrolyte interface, where the cathode is coated by a solid electrolyte interface (SEI). The formation of SEI is well recognized in LIB and it mainly blocks intercalation/deintercaration of lithium ion into/from the cathode. In 2014, Teranishi et al. reported that LiCoO 2 supported with ferroelectric BaTiO 3 showed a good performance at high charge-discharge rate measurement. 1,2 However, at the present time, the role of BaTiO 3 in the improvement of charge-discharge speed is unknown. To make this point clear, we have fabricated epitaxial thin films and dots of BaTiO 3 on single crystalline LiCoO 2 films, evaluated the rate property of the charge and discharge of prepared samples, and examined the role of BaTiO 3 . Firstly, we prepared ‘Bare-LiCoO 2 ’ which was LiCoO 2 epitaxial thin films deposited on conductive SrRuO 3 /(100)SrTiO 3 substrates by pulsed laser deposition method.Then we fabricated two types of BaTiO 3 /LiCoO 2 epitaxial thin films. One is ‘Planer BaTiO 3 ’, the other ‘Dot BaTiO 3 ’. ‘Planer BaTiO 3 ’ were coated by a sub-nm thickness of BaTiO 3 on LiCoO 2 surface. ‘Dot BaTiO 3 ’ were partially coated by BaTiO 3 nano-dots on LiCoO 2 surface. We succeeded to obtain different shaped BaTiO 3 by adjusting the P (O 2 ) during deposition. Crystal structure of thin films were evaluated by high resolution X-ray diffraction (HRXRD) and cross sectional high angle annular dark field scanning transmission electron microscopy (HAADF-STEM). We also prepared coin cell(half-cell); Li│1mol/L LiPF 6 EC:DEC (3:7 v/v) │LiCoO 2 and measured cathode properties by successive charge-discharge measurements. Cut off potential was set 3.3 V - 4.2 V vs. Li + /Li and charge-discharge rate was investigated in the range of 1 C to 100 C. Out of plane XRD measurement showed that LiCoO 2 104 was grown along (100) c SrRuO 3 //(100)SrTiO 3 001 without any secondary phases and other orientations. HRXRD-RSM measurement clearly showed that all the prepared films were found to be epitaxially grown on (100)SrTiO 3 substrates. From HAADF-STEM-EDS images, BaTiO 3 layer was also found to be epitaxially grown on LiCoO 2 . All epitaxial relationships of each layers are expressed as follows; [001]BaTiO 3 //[104]LiCoO 2 //[001]SrRuO 3 //[001]SrTiO 3 , [100]BaTiO 3 //[0-14]LiCoO 2 //[100]SrRuO 3 //[100]SrTiO 3 and [010]BaTiO 3 //[-114]LiCoO 2 //[010]SrRuO 3 //[010]SrTiO 3 . We performed to measure charge-discharge cycle for ‘Bare LiCoO 2 ’ films. The charge-discharge curve was confirmed to be almost similar to the bulk one. 2 nm-‘Planer BaTiO 3 ’ films showed lower discharge capacity at high C rate than ‘Bare LiCoO 2 ’ one. Then, 1 nm-‘Planer BaTiO 3 ’ films showed better performance at high C rate than that of ‘Bare LiCoO 2 ’ and 2 nm-‘Planer BaTiO 3 ’ films. On the other hand, ‘Dot BaTiO 3 ’ films showed the best performance at high C rate, discharge capacity at 100 C only reduced by 40% of that at 1 C. Only ‘Dot BaTiO 3 ’ films were still working at 100 C even though the other type films were not working under same measurement condition. Here, we will discuss about effect of film thickness of BaTiO 3 . 1 nm-‘Planer BaTiO 3 ’ films (NOT fully covered on LiCoO 2 ) worked as cathode however 2 nm-‘Planer BaTiO 3 ’ one (fully covered on LiCoO 2 ) did not work. It is considered that Li + cannot penetrate into the inside of BaTiO 3 grains however it could pass through grain boundaries. From the result of ‘Dot BaTiO 3 ’ films, we expect that an enhancement of discharge capacity at high C rate was caused by BaTiO 3 /LiCoO 2 /electrolyte three-phase interfaces. It is informed that ‘electric field concentration’ may be occurred around the three-phase interfaces, then Li + are expected preferentially to pass around the three-phase interfaces. In summary, the origin of this enhancement by BaTiO 3 was attributed to the three-phase interface due to an electric field concentration. The necessity of BaTiO 3 for the enhancement of the charge-discharge performance is still unclear because similar reports using non ferroelectric ZrO 2 3 and Al 2 O 3 4 showed enhancement of Li + intercalation. However, dischargecapacity ratio of 10 C/1 C in this study is better than these previous reports. 1. T. Teranishi et al. , Appl. Phys. Lett. , 105 , 143904 (2014) 2. T. Teranishi et al. , ECS Electrochem. Lett. , 4 (12) , A137 (2015) 3. D. Takamatsu et al. , J. Electrochem. Soc. , 160 (5) , A3054 (2013) 4. I. D. Scott, et al. , Nano Lett ., 11 , 414 (2011)

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