In situ Seamless Magnetic Measurements for Solid‐State Electrochemical Processes in Prussian Blue Analogues

Yamada, Tetsuya; Morita, Kantaro; Wang, Heng; Kume, K.; Yoshikawa, Hideki; Awaga, Kunio

doi:10.1002/ange.201301084

Cited by 6 publications

(2 citation statements)

References 38 publications

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“…1a). 32,33 Considering this effect and the sensitivity of operando magnetometry to this process, [54][55][56] cyclic voltammetry (CV) along with operando magnetometry in real time was carried out for Co(OH) 2 , CoOOH and CoO (Fig. S13a-f †).…”

Section: Resultsmentioning

confidence: 99%

Revealing the effect of LiOH on forming a SEI using a Co magnetic “probe”

Zhao,

Ye,

Zhang

et al. 2023

Chem. Sci.

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Section: Resultsmentioning

confidence: 99%

Revealing the effect of LiOH on forming a SEI using a Co magnetic “probe”

Zhao,

Ye,

Zhang

et al. 2023

Chem. Sci.

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“…16 Much effort has been made to improve LIBs in terms of both syntheses of battery materials and microscopic material analyses so far. In particular, real-time pictures obtained by various measurements, 24 such as in situ NMR, 25−28 magnetic resonance imaging (MRI), 29−31 Raman, 32 X-ray diffraction, 33,34 and magnetic measurements, 35 have become important to deduce dynamic properties inside the batteries and understand electrochemical reactions in detail. Currently, the in situ NMR approach with the imaging technique can provide important microscopic information inside the batteries.…”

Section: Introductionmentioning

confidence: 99%

Microscopic Behavior of Active Materials Inside a TCNQ-Based Lithium-Ion Rechargeable Battery by in Situ 2D ESR Measurements

Kanzaki

Mitani

Shiomi

et al. 2018

ACS Appl. Mater. Interfaces

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Real-time spectroscopic measurements in rechargeable batteries are important to understand the electrochemistry of the batteries at the molecular level and improve relevant functionalities. We have applied in situ two-dimensional (2D) electron spin resonance (ESR) spectroscopy to a well-known organic lithium-ion battery, which is composed of 7,7,8,8tetracyanoquinodimethane (TCNQ) as the cathode-active material and a lithium metal anode electrode. The TCNQ rechargeable battery is suitable for investigating electrochemistry in the battery in terms of behavior of electron spin at microscopic levels on both the cathode and anode electrodes. We have discussed two-stage oxidation/reduction reactions of TCNQ, Li deposited/stripped process and their resulting dendritic and/or mossy microstructures, clearly elucidating the cause of the cell capacity degradation upon the charge−discharge cycles. The observed in situ ESR spectra showed that the degradation of the cell capacity was due to the elution of the active molecules, which caused the increase of ion conductivity by the substitution of the electrolyte solution for the adsorbed active materials on the conductive carbon surface. To discriminate paramagnetic species during the charge−discharge process, the generalized 2D correlation spectroscopy has been applied to characterize time-dependent in situ ESR spectra. The correlation analysis with in situ ESR helps us identify the paramagnetic species occurring in the battery cell in a straightforward manner.

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Construction of an Artificial Ferrimagnetic Lattice by Lithium Ion Insertion into a Neutral Donor/Acceptor Metal–Organic Framework

et al. 2016

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Construction of am olecular system in which the magnetic lattice exhibits long-range order is one of the fundamental goals in materials science.I nt his study,w e demonstrate the artificial construction of aferrimagnetic lattice by doping electrons into acceptor sites of an eutral donor/ acceptor metal-organic framework (D/A-MOF). This doping was achieved by the insertion of Li-ions into the D/A-MOF, which was used as the cathode of aL i-ion battery cell. The neutral D/A-MOF is al ayered system composed of ac arboxylate-bridged paddlewheel-type diruthenium(II,II) complex as the donor and aTCNQ derivative as the acceptor.The ground state of the neutral form was am agnetically disordered paramagnetic state.U pon dischargeo ft he cell, spontaneous magnetization was induced;t he transition temperature was variable.T he stability of the magnetically ordered lattice depended on the equilibrium electric potential of the D/A-MOF cathode,which reflected the electron-filling level.Over the past few decades,t he design of molecule-based magnets with long-range magnetic order has attracted much interest in the field of molecular functional materials.[1] One route to achieve such long-range magnetic order is to construct lattices using only paramagnetic metal ions and/or molecules with the help of superexchange coupling between paramagnetic centers via ab ridging ligand. Charge-transfer (CT) framework systems comprising electron donor (D) and electron acceptor (A) + located between layers.[4]Focusing on the generation of the radical AC À in the D 0 2 A 0 system, electron-filling control of the system should be an effective approach for the construction of an artificial magnetically ordered lattice without intra-lattice ET.T aking into account that the present "MOFs" are also characterized as atype of porous frameworks,the electrochemical insertion of ionic guests such as Li + and Na + into host frameworks is potentially applicable for electron-filling control of D/AMOFs.[5] In the process of electrochemical cation insertion, acation and electron pair is introduced into the host material and the valence of the redox-active species (that is,t he acceptor A 0 )i nt he material is directly modulated from A À -filled forms are expected to be paramagnetic, ferrimagnetic, and paramagnetic, respectively.

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In situ Seamless Magnetic Measurements for Solid‐State Electrochemical Processes in Prussian Blue Analogues

Cited by 6 publications

References 38 publications

Revealing the effect of LiOH on forming a SEI using a Co magnetic “probe”

Revealing the effect of LiOH on forming a SEI using a Co magnetic “probe”

Microscopic Behavior of Active Materials Inside a TCNQ-Based Lithium-Ion Rechargeable Battery by in Situ 2D ESR Measurements

Construction of an Artificial Ferrimagnetic Lattice by Lithium Ion Insertion into a Neutral Donor/Acceptor Metal–Organic Framework

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