Taminato, So*; Hirayama, Masaaki*; Suzuki, Kota*; Kim, K.-S.*; Tamura, Kazuhisa; Kanno, Ryoji*
Journal of Physical Chemistry C, 122(29), p.16607 - 16612, 2018/07
Lithium-rich layered rocksalt oxides are promising cathode materials for lithium-ion batteries. We investigate the effects of surface modification by amorphous LiPO on the structures and electrochemical reactions in the surface region of an epitaxial LiRuO(010) film electrode. Structural characterization using SXRD, HAXPES, and NR shows that surface modification by LiPO resulted in the partial substitution of P for Li in the surface region of LiRuO. The modified (010) surface exhibits better rate capability at 20 C compared to the unmodified surface. surface XRD confirmed that highly reversible structural changes occurred at the modified surface during lithium (de)intercalation. These results demonstrate that this surface modification stabilizes the crystal structure in the surface region, and it can improve the rate capability of lithium-rich layered rocksalt oxide cathodes.
Abe, Machiko*; Iba, Hideki*; Suzuki, Kota*; Minamishima, Hiroaki*; Hirayama, Masaaki*; Tamura, Kazuhisa; Mizuki, Junichiro*; Saito, Tomohiro*; Ikuhara, Yuichi*; Kanno, Ryoji*
Journal of Power Sources, 345, p.108 - 119, 2017/03
The surface structure of the Li(Ni, Co, Mn)O electrode was studied during charge/discharge process using electrochemical methods and X-ray/Neutron scattering techniques. It was found that during charge/discharge process the coverage of spinel structure increased. The spinel structure has low electrochemical activity and is not involved in Li insertion/extraction. After the surface modification, it was found that the coverage of the spinel structure did not increase. Further, it was also found out that the Li concentration at the electrode/electrolyte interface increased.
Taminato, So*; Hirayama, Masaaki*; Suzuki, Kota*; Tamura, Kazuhisa; Minato, Taketoshi*; Arai, Hajime*; Uchimoto, Yoshiharu*; Ogumi, Zempachi*; Kanno, Ryoji*
Journal of Power Sources, 307, p.599 - 603, 2016/03
An epitaxial-film model electrode of LiCoO(104) was fabricated on SrRuO(100)/Nb:SrTiO(100) using pulsed laser deposition. The 50 nm thick LiCoO(104) film exhibited lithium (de-)intercalation activity with a first discharge capacity of 119 mAh g between 3.0 and 4.4 V, followed by a gradual capacity fading with subsequent charge-discharge cycles. In contrast, a 3.2 nm thick LiPO-coated film exhibited a higher intercalation capacity of 148 mAh g with superior cycle retention than the uncoated film. In situ surface X-ray diffraction measurements revealed a small lattice change at the coated surface during the (de-)intercalation processes compared to the uncoated surface. The surface modification of LiCoO by the LiPO coating could lead to improvement of the structural stability at the surface region during lithium (de-)intercalation at high voltage.
Kanno, Ryoji*; Hirayama, Masaaki*; Suzuki, Kota*; Tamura, Kazuhisa
Hyomen Kagaku, 37(2), p.52 - 59, 2016/02
Batteries are a key technology in today's society. Since the lithium-ion configuration has been widely accepted, significant efforts have been devoted to attain high energy and power densities to produce an excellent energy storage system without any safety issue. To improve the reliability and power characteristics of batteries, deep insights into the reactions at the electrode/electrolyte interface are necessary. The model systems with epitaxial thin-film electrodes might be suitable for understanding these reactions. The in situ techniques for directly observing surface structural changes of the electrodes have been developed for surface X-ray scattering and neutron reflectivity techniques. These techniques are reviewed and future studies on the interfacial reaction in batteries will be discussed.
Suzuki, Kota*; Hirayama, Masaaki*; Kim, K.-S.*; Taminato, So*; Tamura, Kazuhisa; Son, J.-Y.*; Mizuki, Junichiro; Kanno, Ryoji*
Journal of the Electrochemical Society, 162(13), p.A7083 - A7090, 2015/08
The effects of surface coatings on LiMnO were investigated using LiMnO epitaxial thin films with a thickness of 30 nm. Bare and surface-coated LiMnO epitaxial thin films were synthesized on SrTiO(111) substrates using a pulsed laser deposition method. The surface coating, which was formed using the solid electrolyte LiPO and had a thickness of 3 nm, improved the reversibility of the electrochemical reactions undergone by the LiMnO epitaxial thin films. The changes induced in the surface structure were maintained during battery operation; in contrast, the bare LiMnO thin film exhibited structural degradation and Mn dissolution. The structural changes induced in the coated electrode and the increase in its surface stability were intrinsic effects of the LiPO coating and improved the electrochemical performance of the LiMnO thin-film electrode.
Taminato, So*; Hirayama, Masaaki*; Suzuki, Kota*; Kim, K.-S.*; Zheng, Y.*; Tamura, Kazuhisa; Mizuki, Junichiro; Kanno, Ryoji*
Journal of Materials Chemistry A, 2(34), p.17875 - 17882, 2014/11
The surface structure of a lithium-rich layered material and its relation to intercalation properties were investigated by synchrotron X-ray surface structural analyses using LiRuO epitaxial-film model electrodes with different lattice planes of (010) and (001). Electrochemical charge-discharge measurements confirmed reversible lithium intercalation activity through both planes, corresponding to three-dimensional lithium diffusion within the LiRuO. The (001) plane exhibited higher discharge capacities compared to the (010) plane under high rate operation (over 5 C). Direct observations of surface structural changes by surface X-ray diffraction (XRD) and surface X-ray absorption near edge structure (XANES) established that an irreversible phase change occurs at the (010) surface during the first (de)intercalation process, whereas reversible structural changes take place at the (001) surface.
Kim, K.-S.*; Tojigamori, Takeshi*; Suzuki, Kota*; Taminato, So*; Tamura, Kazuhisa; Mizuki, Junichiro; Hirayama, Masaaki*; Kanno, Ryoji*
Denki Kagaku Oyobi Kogyo Butsuri Kagaku, 80(10), p.800 - 803, 2012/10
Electrochemical properties and structure changes of nano-sized LiTiO during lithium (de)intercalation wereinvestigated using a two-dimensional thin film electrode. LiTiO thin films were deposited on a Nb:SrTiO(110)substrate by a pulsed laser deposition technique. In situ X-ray diffraction measurements clarified the drastic structural changes of the LiTiOfilm upon soaking in the electrolyte and during the first intercalation and deintercalation processes. The surfaceregion of LiTiO had a different structure from the bulk during electrochemical cycling and could cause the nanosizedLiTiO electrodes to have high capacities and poor stabilities.
Hirayama, Masaaki*; Ido, Hidekazu*; Kim, K.-S.*; Cho, W.*; Tamura, Kazuhisa; Mizuki, Junichiro; Kanno, Ryoji*
Journal of the American Chemical Society, 132(43), p.15268 - 15276, 2010/11
Epitaxial LiMnO thin films with restricted lattice planes (111) and (110) are grown on SrTiO substrates by pulsed laser deposition. In situ SXRD studies have revealed dynamic structural changes that reduce the atomic symmetry at the electrode surface during the initial electrochemical reaction. The surface structural changes commence with the formation of an electric double layer, which is followed by surface reconstruction when a voltage is applied in the first charge process. Transmission electron microscopy images after 10 cycles confirm the formation of a solid electrolyte interface (SEI) layer on both the (111) and (110) surfaces and Mn dissolution from the (110) surface. The (111) surface is more stable than the (110) surface. The electrode stability of LiMnO depends on the reaction rate of SEI formation and the stability of the reconstructed surface structure.
Sakamoto, Kazuyuki*; Hirayama, Masaaki*; Konishi, Hiroaki*; Sonoyama, Noriyuki*; Dupr, N.*; Guyomard, D.*; Tamura, Kazuhisa; Mizuki, Junichiro; Kanno, Ryoji*
Physical Chemistry Chemical Physics, 12(15), p.3815 - 3823, 2010/04
Surface and bulk structural changes of LiNiMnO were investigated during electrochemical reaction using synchrotron X-ray scattering and a restricted reaction plane consisting of two dimensional epitaxial-film electrodes. The changes in bulk structure confirmed lithium diffusion through the (110) surface, which was perpendicular to the two-dimensional (2D) edges of the layered structure. No (de)intercalation reaction was observed through the (003) surface at voltages of 3.0-5.0 V. However, intercalation did proceed through the (003) plane below 3.0 V, indicating unusual three-dimensional (3D) lithium diffusion in the over-lithiated 2D structure. During the electrochemical process, the surface of the electrode showed different structure changes from those of the bulk structure. The reaction echanism of the intercalation electrodes for lithium batteries is discussed on the basis of surface and bulk structural changes.
Sakamoto, Kazuyuki*; Hirayama, Masaaki*; Sonoyama, Noriyuki*; Mori, Daisuke*; Yamada, Atsuo*; Tamura, Kazuhisa; Mizuki, Junichiro; Kanno, Ryoji*
Chemistry of Materials, 21(13), p.2632 - 2640, 2009/05
Surface and bulk structural changes in LiNiCoO were observed during electrochemical reactions using synchrotron X-ray scattering and a restricted reaction plane of two-dimensional (2D) epitaxial-film electrodes. The bulk structural changes confirmed lithium diffusion through the (110) surface, which is perpendicular to the 2D edges of the layered structure. No (de)intercalation reaction was observed through the (003) surface in the voltage range of 3.0-5.0 V. However, intercalation proceeded below 3.0 V, which indicates unusual three-dimensional lithium diffusion in the 2D structure in the overlithiated state. Structural changes at the electrode surface were different from those in the bulk.
Hirayama, Masaaki*; Sakamoto, Kazuyuki*; Hiraide, Tetsuya*; Mori, Daisuke*; Yamada, Atsuo*; Kanno, Ryoji*; Sonoyama, Noriyuki*; Tamura, Kazuhisa; Mizuki, Junichiro
Electrochimica Acta, 53(2), p.871 - 881, 2007/12
An experimental technique was developed for detecting structure changes at the electrode/electrolyte interface of lithium cell using synchrotron X-ray reflectometry and two-dimensional model electrodes with a restricted lattice plane. The electrode was constructed with an epitaxial film of LiNiCoO synthesized by the pulsed laser deposition method. These films provided an ideal reaction field suitable for detecting structure changes at the electrode/electrolyte interface during the electrochemical reaction. The X-ray reflectometry indicated a formation of a thin-film layer at the LiNiCoO (1 1 0)/electrolyte interface during the first charge-discharge cycle, while the LiNiCoO (0 0 3) surface showed an increase in the surface roughness without forming the surface thin-film layer.
Sakamoto, Kazuyuki*; Konishi, Hiroaki*; Sonoyama, Noriyuki*; Yamada, Atsuo*; Tamura, Kazuhisa; Mizuki, Junichiro; Kanno, Ryoji*
Journal of Power Sources, 174(2), p.678 - 682, 2007/12
Structure changes of LiNiMnO were detected at the electrode/electrolyte interface of lithium cell using synchrotron X-ray scattering and two-dimensional model electrodes. The electrodes were constructed by an epitaxial film of LiNiMnO synthesized by pulsed laser deposition (PLD) method. The orientation of the film depends on the substrate plane; the 2D layer of LiNiMnO is parallel to the SrTiO(1 1 0) substrate ((1 1 0) LiNiMnO//(1 1 0) SrTiO), while the 2D layer is perpendicular to the SrTiO(1 1 1) substrate ((0 0 3) LiNiMnO//(1 1 1) SrTiO). The X-ray diffraction of LiNiMnO(0 0 3) confirmed three-dimensional lithium diffusion through the two-dimensional transition meal layers. The intercalation reaction of LiNiMnO will be discussed.
Hirayama, Masaaki*; Sonoyama, Noriyuki*; Abe, Takashi*; Minoura, Machiko*; Ito, Masumi*; Mori, Daisuke*; Yamada, Atsuo*; Kanno, Ryoji*; Terashima, Takahito*; Takano, Mikio*; et al.
Journal of Power Sources, 168(2), p.493 - 500, 2007/06
A new experimental technique was developed for detecting structure changes at electrode/electrolyte interface of lithium cell using X-ray reflectometry and two-dimensional model electrodes with a restricted lattice-plane. The electrodes were constructed with an epitaxial film of LiCoO synthesized by pulsed laser deposition method. The anisotropic properties were confirmed by electrochemical measurements. X-ray reflectivity measurements indicated that the impurity layer existed on the as-grown LiCoO was dissolved and a new SEI layer with lower density was formed after soaking into the electrolyte. X-ray reflectivity measurements indicated that the surface roughness of the intercalation (1 1 0) plane increased with applying voltages, while no significant changes in surface morphology were observed for the intercalation non-active (0 0 3) plane during the pristine stage of the charge-discharge process.
Hirayama, Masaaki*; Sonoyama, Noriyuki*; Ito, Masumi*; Minoura, Machiko*; Mori, Daisuke*; Yamada, Atsuo*; Tamura, Kazuhisa; Mizuki, Junichiro; Kanno, Ryoji*
Journal of the Electrochemical Society, 154(11), p.A1065 - A1072, 2007/00
Structural changes at electrode/electrolyte interface of a lithium cell were studied by X-ray reflectometry and two-dimensional model electrodes with a restricted lattice plane of LiMnO. The ex situ reflectometry indicated that a thin impurity layer covered the lattice plane of the as-grown film. The impurity layer was dissolved and a solid-electrolyte-interface-like phase appeared after the electrode was soaked into the electrolyte. The in situ observation clarified that the surface reactivity depended on the lattice planes of the spinel; the defect layer at the (111) plane was stable during the electrochemical reaction, whereas a slight decrease in the film thickness was observed for the (110) plane. Our surface characterization of the intercalation electrode indicated that the surface structure changes during the pristine stage of the change-discharge processes and these changes are dependent on the lattice orientation of LiMnO.
Lee, S.*; Park, J.-G.*; Adroja, D. T.*; Khomskii, D.*; Streltsov, S.*; McEwen, K. A.*; Sakai, Hironori; Yoshimura, Kazuyoshi*; Anisimov, V. I.*; Mori, Daisuke*; et al.
Nature Materials, 5(6), p.471 - 476, 2006/06
Here we show that the three-dimensional cubic system of TlRuO most probably evolves into a one-dimensional spin-one Haldane system with a spin gap below 120 K, accompanied by anomalies in the structure, resistivity, and susceptibility. We argue that these anomalies are due to an orbital ordering of Ru electrons, with a strong coupling among three degrees of freedom: orbital, spin, and lattice. Our work provides a unique example of the spontaneous formation of Haldane system with an insight into the intriguing interplay of different degrees of freedom.