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Yoshimoto, Masataka*; Tamura, Kazuhisa; Watanabe, Kenta*; Shimizu, Keisuke*; Horisawa, Yuhei*; Kobayashi, Takeshi*; Tsurita, Hanae*; Suzuki, Kota*; Kanno, Ryoji*; Hirayama, Masaaki*
Sustainable Energy & Fuels (Internet), 8(6), p.1236 - 1244, 2024/03
Times Cited Count:0 Percentile:0.01(Chemistry, Physical)Photo-rechargeable systems, which can efficiently convert and store solar energy into chemical energy within single devices, are essential to harness sunlight effectively. Photo-(de)intercalation plays a pivotal role in the functionality of photorechargeable systems. Nevertheless, the photo-(de)intercalation process has not been conclusively confirmed owing to potential interference from side reactions, such as the decomposition of liquid electrolytes and the elution of electrode materials. In this study, we successfully demonstrated photo-responsive Li-deintercalation using an all-solid-state thin-film battery comprised of epitaxially-grown anatase TiO
doped with Nb (a-TiO
:Nb) as the cathode. Under light irradiation, Li
-deintercalation occurred and was subsequently reversibly intercalated into a-TiO
:Nb during discharge.
Watanabe, Kenta*; Horisawa, Yuhei*; Yoshimoto, Masataka*; Tamura, Kazuhisa; Suzuki, Kota*; Kanno, Ryoji*; Hirayama, Masaaki*
Nano Letters, 24(6), p.1916 - 1922, 2024/02
Times Cited Count:2 Percentile:98.52(Chemistry, Multidisciplinary)Electrochemistry has extended from reactions at solid/liquid interfaces to those at solid/solid interfaces. In this study, we achieve the stable photoelectrochemical reaction at the semiconductor-electrode/solid-electrolyte interface in Nb-doped anatase-TiO (a-TiO
:Nb)/Li
PO
(LPO)/Li all-solid-state cell. The oxidative currents of a-TiO
:Nb/LPO/Li increase upon light irradiation when a-TiO
:Nb is located at a potential that is more positive than its flat-band potential. The photoelectrochemical reaction at the semiconductor/solid-electrolyte interface is driven by the same principle as that at semiconductor/liquid-electrolyte interfaces. Thus, we extend photoelectrochemistry to all-solid-state systems composed of solid/solid interfaces.
Matsuzaki, Akira*; Hirayama, Masaaki*; Oguchi, Shoya*; Komo, Mamoru*; Ikezawa, Atsunori*; Suzuki, Kota*; Tamura, Kazuhisa; Arai, Hajime*; Kanno, Ryoji*
Electrochemistry (Internet), 90(10), p.107001_1 - 107001_8, 2022/10
Times Cited Count:0 Percentile:0.01(Electrochemistry)Oxygen reduction and evolution reactions (ORR and OER) of perovskite-type LaSr
CoO
were characterized using two-dimensional model electrodes with different reaction planes. Synthesized by pulsed laser deposition, these thin and flat electrodes can reveal the reaction plane dependence of the ORR activity. From steady-state polarization measurements in KOH (aq.), the ORR activity was the highest on the (001) film during the first ORR/OER cycle, and it decreased significantly during the second cycle. In-situ synchrotron X-ray diffraction clarified crystal structure changes in the bulk and surface regions of La
Sr
CoO
, and these changes are associated with forming oxygen defects during the initial electrochemical process. Furthermore, the La
Sr
CoO
surface partially decomposed upon reacting. Therefore, the interfacial structures formed in the electrochemical reaction field is important for enhancing ORR and OER activities.
Hikima, Kazuhiro*; Hinuma, Yoyo*; Shimizu, Keisuke*; Suzuki, Kota*; Taminato, So*; Hirayama, Masaaki*; Masuda, Takuya*; Tamura, Kazuhisa; Kanno, Ryoji*
ACS Applied Materials & Interfaces, 13(6), p.7650 - 7663, 2021/02
Times Cited Count:12 Percentile:65.55(Nanoscience & Nanotechnology)We evaluated the structural change of the cathode material LiMnO
that was deposited as an epitaxial film with an (001) orientation in an all-solid-state battery. In case of the electrode with LiPO
coating. Experiments revealed a structural change to a high-capacity (activated) phase that proceeded gradually and continuously with cycling. The activated phase barely showed any capacity fading. We propose a mechanism of structural change with cycling: charging to a high voltage at a sufficiently low Li concentration typically induces irreversible transition to a phase detrimental to cycling that could, but not necessarily, be accompanied by the dissolution of Mn and/or the release of O into the electrolyte, while a gradual irreversible transition to an activated phase happens at a similar Li concentration under a lower voltage.
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
Times Cited Count:8 Percentile:30.46(Chemistry, Physical)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 Li
RuO
(010) film electrode. Structural characterization using SXRD, HAXPES, and NR shows that surface modification by Li
PO
resulted in the partial substitution of P for Li in the surface region of Li
RuO
. 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
Times Cited Count:11 Percentile:38.14(Chemistry, Physical)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
Times Cited Count:34 Percentile:72.18(Chemistry, Physical)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 Li
PO
-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 Li
PO
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
Times Cited Count:12 Percentile:38.94(Electrochemistry)The effects of surface coatings on LiMnO
were investigated using LiMn
O
epitaxial thin films with a thickness of 30 nm. Bare and surface-coated LiMn
O
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 Li
PO
and had a thickness of 3 nm, improved the reversibility of the electrochemical reactions undergone by the LiMn
O
epitaxial thin films. The changes induced in the surface structure were maintained during battery operation; in contrast, the bare LiMn
O
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 Li
PO
coating and improved the electrochemical performance of the LiMn
O
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
Times Cited Count:21 Percentile:55.13(Chemistry, Physical)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 Li
RuO
. 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
Times Cited Count:13 Percentile:31.87(Electrochemistry)Electrochemical properties and structure changes of nano-sized LiTi
O
during lithium (de)intercalation wereinvestigated using a two-dimensional thin film electrode. Li
Ti
O
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 Li
Ti
O
film upon soaking in the electrolyte and during the first intercalation and deintercalation processes. The surfaceregion of Li
Ti
O
had a different structure from the bulk during electrochemical cycling and could cause the nanosizedLi
Ti
O
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
Times Cited Count:318 Percentile:98.00(Chemistry, Multidisciplinary)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 LiMn
O
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
Times Cited Count:33 Percentile:74.13(Chemistry, Physical)Surface and bulk structural changes of LiNiMn
O
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
Times Cited Count:41 Percentile:73.79(Chemistry, Physical)Surface and bulk structural changes in LiNiCo
O
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
Times Cited Count:44 Percentile:66.74(Electrochemistry)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 LiNi
Co
O
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 LiNi
Co
O
(1 1 0)/electrolyte interface during the first charge-discharge cycle, while the LiNi
Co
O
(0 0 3) surface showed an increase in the surface roughness without forming the surface thin-film layer.
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
Times Cited Count:89 Percentile:90.10(Chemistry, Physical)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
Times Cited Count:97 Percentile:95.35(Electrochemistry)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 LiMn
O
.
Hirayama, Masaaki*; Matsuzaki, Akira*; Ikezawa, Atsunori*; Suzuki, Kota*; Arai, Hajime*; Kanno, Ryoji*; Tamura, Kazuhisa
no journal, ,
Oxygen reduction and evolution reactions (ORR and OER) of perovskite-type LaSr
CoO
were characterized using two-dimensional model electrodes with different reaction planes. Synthesized by pulsed laser deposition, these thin and flat electrodes can reveal the reaction plane dependence of the ORR activity. From steady-state polarization measurements in KOH (aq.), the ORR activity was the highest on the (001) film during the first ORR/OER cycle, and it decreased significantly during the second cycle. In-situ synchrotron X-ray diffraction clarified crystal structure changes in the bulk and surface regions of La
Sr
CoO
, and these changes are associated with forming oxygen defects during the initial electrochemical process. Furthermore, the La
Sr
CoO
surface partially decomposed upon reacting. Therefore, the interfacial structures formed in the electrochemical reaction field is important for enhancing ORR and OER activities.