Atomistic Conversion Reaction Mechanism of WO<sub>3</sub> in Secondary Ion Batteries of Li, Na, and Ca

He, Yang; Gu, Meng; Xiao, Haiyan; Luo, Langli; Shao, Yuyan; Gao, Fei; Du, Yingge; Mao, Scott X.; Wang, Chongmin

doi:10.1002/anie.201601542

Cited by 90 publications

(52 citation statements)

References 31 publications

(33 reference statements)

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“…1c and 1d). This structure mimics the underlying [22,23]. We evaluate the presence of defects in WO 3 by measuring rocking curves around the film (001) peak.…”

Section: Film Growthmentioning

confidence: 99%

Charge doping and large lattice expansion in oxygen-deficient heteroepitaxial WO3

Mattoni

Filippetti

Manca

et al. 2018

Phys. Rev. Materials

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Tungsten trioxide is a versatile material with widespread applications ranging from electrochromic and optoelectronic devices to water splitting and catalysis of chemical reactions. For technological applications, thin films of WO 3 are particularly appealing, taking advantage from high surface-tovolume ratio and tunable physical properties. However, the growth of stoichiometric, crystalline thin films is challenging because the deposition conditions are very sensitive to the formation of oxygen vacancies. In this work, we show how background oxygen pressure during pulsed laser deposition can be used to tune the structural and electronic properties of WO 3 thin films. By performing X-ray diffraction and low-temperature transport measurements, we find changes in WO 3 lattice volume up to 10 %, concomitantly with an insulator-to-metal transition as a function of increased level of electron doping. We use advanced ab initio calculations to describe in detail the properties of the oxygen vacancy defect states, and their evolution in terms of excess charge concentration. Our results depict an intriguing scenario where structural, electronic, optical, and transport properties of WO 3 single-crystal thin films can all be purposely tuned by a suited control of oxygen vacancies formation during growth. arXiv:1711.05106v1 [cond-mat.mtrl-sci]

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“…1c and 1d). This structure mimics the underlying [22,23]. We evaluate the presence of defects in WO 3 by measuring rocking curves around the film (001) peak.…”

Section: Film Growthmentioning

confidence: 99%

Charge doping and large lattice expansion in oxygen-deficient heteroepitaxial WO3

Mattoni

Filippetti

Manca

et al. 2018

Phys. Rev. Materials

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“…For this reason this material is often utilized in electrochemical applications and electrochromic devices [20][21][22]. Also, both crystalline and amorphous WO 3 can host vacancies and interstitial atoms, thus allowing cation accommodation and diffusion, with a tendency to form compounds such as tungsten bronzes [23,24]. Recent progress demonstrated the high-quality growth of WO 3 thin films on perovskite materials [25][26][27].…”

mentioning

confidence: 99%

Insulator-to-Metal Transition at Oxide Interfaces Induced by WO₃ Overlayers

Mattoni

Baek²,

Manca

et al. 2017

ACS Appl. Mater. Interfaces

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Interfaces between complex oxides constitute a unique playground for 2D electron systems (2DES), where superconductivity and magnetism can arise from combinations of bulk insulators. The 2DES at the LaAlO 3 /SrTiO 3 interface is one of the most studied in this regard, and its origin is determined by both the presence of a polar field in LaAlO 3 and the insurgence of point defects, such as oxygen vacancies and intermixed cations. These defects usually reside in the conduction channel and are responsible for a decreased electronic mobility. In this work, we use an amorphous WO 3 overlayer to control the defect formation and obtain an increased electron mobility in WO 3 /LaAlO 3 /SrTiO 3 heterostructures. The studied system shows a sharp insulator-to-metal transition as a function of both LaAlO 3 and WO 3 layer thickness. Low-temperature magnetotransport reveals a strong magnetoresistance reaching 900% at 10 T and 1.5 K, the presence of multiple conduction channels with carrier mobility up to 80 000 cm 2 V −1 s −1 and an unusually high effective mass of 5.6 me. The amorphous character of the WO 3 overlayer makes this a versatile approach for defect control at oxide interfaces, which could be applied to other heterestrostures disregarding the constraints imposed by crystal symmetry.The formation of a two-dimensional electron system (2DES) at the interface between band insulators SrTiO 3 (STO) and LaAlO 3 (LAO) is among the most intriguing effects studied in oxide electronics [1]. Gate tunable superconductivity [2,3], strong spin-orbit coupling [4,5] and magnetism [6,7] are some of the many phenomena observed. The origin of this 2DES is a long standing question in the solid state community and recent results indicate that a consistent picture should take into account both the built-in polar field and the presence of point defects [8][9][10]. Among these, oxygen vacancies and cation off-stoichiometry in STO are capable of inducing a 2DES [11,12]. However, defects residing in the conductive channel are usually responsible for a decreased electronic mobility [13]. In order to promote high electron mobility, it is crucial to confine donor sites away from the conducting plane, without preventing the 2DES formation in the STO top layers. Previous attempts to control the defect concentration profile and thus enhance the mobility involved the use of crystalline insulating overlayers [14,15] [18,19]. A promising material to control defect formation is tungsten oxide WO 3 . The several possible oxidations states of tungsten make WO 3 particularly active in undergoing redox reactions. For this reason this material is often utilized in electrochemical applications and electrochromic devices [20][21][22]. Also, both crystalline and amorphous WO 3 can host vacancies and interstitial atoms, thus allowing cation accommodation and diffusion, with a tendency to form compounds such as tungsten bronzes [23,24]. Recent progress demonstrated the high-quality growth of WO 3 thin films on perovskite materials [25][26][27].In this work we co...

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“…[86] These materials generally have a character that they have empty site for Li ion insertion compared with direct conversion materials. Among these, spinel transition metal oxides are widely used as electrode materials for LIBs because they are inexpensive and nontoxic and have high electronic conductivities and energy densities.…”

Section: Two-step Conversion Processmentioning

confidence: 99%

Atomic‐Scale Monitoring of Electrode Materials in Lithium‐Ion Batteries using In Situ Transmission Electron Microscopy

Shang

Wen

Xiao

et al. 2017

Advanced Energy Materials

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Lithium‐ion batteries (LIBs) are energy storage devices that have received much attention because of their high energy density, high power capacity, and long lifetime. However, even though they are used widely in daily life, their cycling life and safety need further improvement. Understanding the reaction mechanisms and the structural degradation during the lithiation/delithiation process is a prerequisite to further improve the performance of LIBs. In situ transmission electron microscopy (TEM) allows one to monitor structural evolution at the atomic scale in real time, thus providing an unprecedented opportunity to characterize the lithiation reaction pathway in a nonequilibrium state during battery cycling. In this article, the recent advances with respect to elucidating the relationships of dynamic structural evolution, reaction kinetics, and performance of different nanostructured electrode materials at the atomic scale using in situ TEM, based on three representative reaction mechanisms, are described. Specifically, the three systems are intercalation reaction, conversion reaction, and alloying reaction. Based on the advances that have been made, it is expected that in situ TEM will play an indispensable role on future design of LIBs electrode materials.

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Atomistic Conversion Reaction Mechanism of WO₃ in Secondary Ion Batteries of Li, Na, and Ca

Cited by 90 publications

References 31 publications

Charge doping and large lattice expansion in oxygen-deficient heteroepitaxial WO3

Charge doping and large lattice expansion in oxygen-deficient heteroepitaxial WO3

Insulator-to-Metal Transition at Oxide Interfaces Induced by WO₃ Overlayers

Atomic‐Scale Monitoring of Electrode Materials in Lithium‐Ion Batteries using In Situ Transmission Electron Microscopy

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Atomistic Conversion Reaction Mechanism of WO3 in Secondary Ion Batteries of Li, Na, and Ca

Cited by 90 publications

References 31 publications

Charge doping and large lattice expansion in oxygen-deficient heteroepitaxial WO3

Charge doping and large lattice expansion in oxygen-deficient heteroepitaxial WO3

Insulator-to-Metal Transition at Oxide Interfaces Induced by WO3 Overlayers

Atomic‐Scale Monitoring of Electrode Materials in Lithium‐Ion Batteries using In Situ Transmission Electron Microscopy

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Atomistic Conversion Reaction Mechanism of WO₃ in Secondary Ion Batteries of Li, Na, and Ca

Insulator-to-Metal Transition at Oxide Interfaces Induced by WO₃ Overlayers