Fluoride-Ion Shuttle Battery with High Volumetric Energy Density

Nakano, Hiroyuki; Matsunaga, Toshiyuki; Mori, Toshiyuki; Nakanishi, Koji; Morita, Yukari; Ide, Kazuto; Okazaki, Kenichi; Orikasa, Yuki; Minato, Taketoshi; Yamamoto, Kentaro; Ogumi, Zempachi; Uchimoto, Yoshiharu

doi:10.1021/acs.chemmater.0c04570

Cited by 38 publications

(42 citation statements)

References 32 publications

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“…The impedances of Cu and Cu−Pb were evaluated by EIS, as shown in Figure 5. In the equivalent circuit, R, CPE, and W s represented resistances, constant phase elements, and finite-diffusion Warburg resistance, respectively, where the high-frequency and medium-frequency semicircles could be assigned to grain-boundary (which can be observed in Cu-bulk TEM images in our previous work 38 ) and chargetransfer effects in the working electrode. 39 Although the suppressed impedance in Cu−Pb verified the promotion effect of the nanocomposite strategy, such suppressions on impedances were not so significant as the optimizations on electrochemical performance.…”

Section: Resultsmentioning

confidence: 99%

Cu–Pb Nanocomposite Cathode Material toward Room-Temperature Cycling for All-Solid-State Fluoride-Ion Batteries

Zhang

Yoshinari

Yamamoto

et al. 2021

ACS Appl. Energy Mater.

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All-solid-state fluoride-ion batteries (FIBs) are regarded as attractive alternatives to traditional energy storage systems because of their high energy density; however, they are not applicable at room temperature owing to sluggish ion transport in both the electrolyte and electrode. In this study, a rational design of a Cu–Pb nanocomposite is reported, which was tested as a room-temperature cathode material for all-solid-state FIBs. Following electrochemical pretreatment, self-generated PbF2 could act as a fast fluoride-ion conductor and consequently enhance the kinetics of the Cu/CuF2 phase transition process upon cycling. The detailed reaction mechanism and phase transition process were verified using the X-ray absorption near edge structure. The Cu–Pb nanocomposite could realize reversible (de)fluorination at room temperature with high performance and good cyclability.

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Section: Resultsmentioning

confidence: 99%

Cu–Pb Nanocomposite Cathode Material toward Room-Temperature Cycling for All-Solid-State Fluoride-Ion Batteries

Zhang

Yoshinari

Yamamoto

et al. 2021

ACS Appl. Energy Mater.

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“…In our previous study, 14,27,28 we demonstrated that the 3dtransition-metal cathode (Cu, Co, and Ni) and the selfgenerated La/LaF 3 anode in thin-film all-solid-state FIBs show clear charge−discharge behavior. The combinations of Cu, Co, and Ni cathodes and representative anodes (La/LaF 3 , Ce/ CeF 2 , Pb/PbF 2 , etc.)…”

Section: Introductionmentioning

confidence: 89%

Rate-Determining Process at Electrode/Electrolyte Interfaces for All-Solid-State Fluoride-Ion Batteries

Zhang

Nakano

Yamamoto

et al. 2021

ACS Appl. Mater. Interfaces

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Developing high-performance solid electrolytes that are operable at room temperature is one of the toughest challenges related to all-solid-state fluoride-ion batteries (FIBs). In this study, tetragonal β-Pb 0.78 Sn 1.22 F 4 , a promising solid electrolyte material for mild-temperature applications, was modified through annealing under various atmospheres using thin-film models. The annealed samples exhibited preferential growth and enhanced ionic conductivities. The ratedetermining factor for electrode/electrolyte interface reactions in all-solid-state FIBs was also investigated by comparing β-Pb 0.78 Sn 1.22 F 4 with representative fluoride-ionand lithium-ion-conductive materials, namely, LaF 3 , CeF 3 , and Li 7 La 3 Zr 2 O 12 . The overall rate constant of the interfacial reaction, k 0 , which included both mass and charge transfers, was determined using chronoamperometric measurements and Allen-Hickling simulations. Arrhenius-type correlations between k 0 and temperature indicated that activation energies calculated from k 0 and ionic conductivities (σ ion ) were highly consistent. The results indicated that the mass transfer (electrolyte-side fluoride-ion conduction) should be the rate-determining process at the electrode/electrolyte interface. β-Pb 0.78 Sn 1.22 F 4 , with a large σ ion value, had a larger k 0 value than Li 7 La 3 Zr 2 O 12 . Therefore, it is hoped that the development of high-conductivity solid electrolytes can lead to all-solid-state FIBs with superior rate capabilities similar to those of all-solid-state Li-ion batteries.

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“…S2, ESI†). It is reasonable that the formed LaF 3 is stable under our measurement conditions because the reduction potential of LaF 3 to La is −2.4 V vs. Pb/PbF 2 , 12 which is a much lower potential than that in our charge and discharge measurements. On the basis of ADF STEM images in Fig.…”

Section: Resultsmentioning

confidence: 63%

“…11 To solve this fluorination issue on cathode metals, several morphological control strategies of metals have been proposed such as forming nanoparticles and thin films. 1,9,11,12 However, the proposed methodologies significantly restrict the design of electrodes, and moreover they would cause other technical difficulties, i.e. , oxidation of electrodes or poor electric contact between electrodes and electrolytes.…”

Section: Introductionmentioning

confidence: 99%