Microvoltammetric studies on single particles of battery active materials

Uchida, Isamu; Fujiyoshi, Hironobu; Waki, Shinichi

doi:10.1016/s0378-7753(96)02623-7

Cited by 81 publications

(48 citation statements)

References 23 publications

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“…5b, these second peaks do not depend in a linear manner on the square root of the scan rate as do the first peaks above a certain scan rate. The predicted dimensionless peak current density dependence on scan rate presented here agrees well with that reported by Uchida et al 10 They determined experimentally that the second peak current density was proportional to v 0.7-0. 8 To show the effect of the upper plateau of the open-circuit potential on the third dimensionless peak current density, we ran the model by starting the scans in the cathodic direction at 4.3102 V with an initial dimensionless concentration (y) of 0.17 instead of using a starting potential of 3.5102 V (with y ϭ 1.00) and then scanning anodically, as done above.…”

Section: Cyclic Voltammograms For Various Scan Rates V-supporting

confidence: 91%

“…1 as the reaction mechanism 4,16 [8] Combination of Eq. 7 and 8 yields [9] or [10] and i 0 ϭ Fk(c 1 ) 1Ϫ␤ (c ) 1Ϫ␤ (c s ) ␤ [11] where r 0 is the radius of the particle, k is a reaction rate constant, c l is the Li ϩ concentration in the liquid phase (treated here as a constant, known value), c (ϭ c t Ϫ c s ) is the surface concentration of vacant sites ready for lithium intercalation, c s is the concentration of lithium ions on the surface of the electrode, and c t is the concentration of total sites for seating lithium ions. The overpotential is defined as…”

Section: Initial Conditionmentioning

confidence: 99%

“…The open-circuit potential expression (see the Appendix) for Reaction 1 was given by Doyle et al 16 In this simulation the applied potential range, U app , is from 3.5102 to 4.3102 V vs. Li/Li ϩ . 10 The predicted dimensionless current density j is obtained by solving the governing equations with the parameter values given in Table I. The predictions for j were made by beginning the potential sweep at t ϭ 0 with U app ϭ 3.5102 V so that j ϭ 0 since U app ϭ U| yϭ1 ϭ 3.5102 V. Then by incrementing time U app is increased by 1 mV per second and j is obtained by solving the equations.…”

Section: Initial Conditionmentioning

confidence: 99%

See 2 more Smart Citations

Modeling Lithium Intercalation of a Single Spinel Particle under Potentiodynamic Control

Zhang

Popov

White

2000

J. Electrochem. Soc.

179

118

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A mathematical model is presented for the lithium intercalation of a single spinel particle as a microelectrode under the stimulus of a cyclic linear potential sweep. The model includes both lithium diffusion within the particle and kinetics at the particle/electrolyte interface. The model is used to predict that peak current densities depend linearly on the scan rate to a certain power with a constant term, which is different from the predicted peak current density for a conventional redox system.

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Section: Cyclic Voltammograms For Various Scan Rates V-supporting

confidence: 91%

Section: Initial Conditionmentioning

confidence: 99%

Section: Initial Conditionmentioning

confidence: 99%

See 1 more Smart Citation

Modeling Lithium Intercalation of a Single Spinel Particle under Potentiodynamic Control

Zhang

Popov

White

2000

J. Electrochem. Soc.

179

118

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“…4,5 Particle-level characterization of electrochemical kinetics or microstructural changes during cycling have been separately conducted, but not directly correlated with each other. [6][7][8][9][10] Moreover, the experimental designs in prior work have involved either ''open'' electrochemical cells or use of low-vapor pressure ionic liquid electrolytes, which do not represent a realistic Li ion battery environment.…”

Section: Introductionmentioning

confidence: 99%

Single-particle measurements of electrochemical kinetics in NMC and NCA cathodes for Li-ion batteries

Tsai

Wen

Wolfman

et al. 2018

Energy Environ. Sci.

267

229

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aThe electrochemical kinetics of battery electrodes at the single-particle scale are measured as a function of state-of-charge, and interpreted with the aid of concurrent transmission X-ray microscopy (TXM) of the evolving particle microstructure. An electrochemical cell operating with near-picoampere current resolution is used to characterize single secondary particles of two widely-used cathode compounds, NMC333 and NCA. Interfacial charge transfer kinetics are found to vary by two orders of magnitude with state-of-charge (SOC) in both materials, but the origin of the SOC dependence differs greatly. NCA behavior is dominated by electrochemically-induced microfracture, although thin binder coatings significantly ameliorate mechanical degradation, while NMC333 demonstrates strongly increasing interfacial reaction rates with SOC for chemical reasons. Micro-PITT is used to separate interfacial and bulk transport rates, and show that for commercially relevant particle sizes, interfacial transport is rate-limiting at low SOC, while mixed-control dominates at higher SOC. These results provide mechanistic insight into the mesoscale kinetics of ion intercalation compounds, which can guide the development of high performance rechargeable batteries. Broader contextThe performance of high performance Li-ion batteries, central to both electric transportation and grid scale storage, is ultimately reliant on the performance of critical components such as their cathode and anode compounds. For ease of manufacturing, the prevailing technological forms of these materials are secondary particles of nearly spherical morphology containing many nanocrystallites. The electrochemical kinetics at this critical length scale have been difficult to assess; particle-level behavior has primarily been deduced from macroscale cell measurements. Thus the microelectrode technique developed in this work, combined with state-of-the-art TXM imaging, allows for the first time the direct measurement of electrochemical kinetics of particles as they are charged and discharged. Surprising behavior is revealed -interfacial charge transfer kinetics are found to vary greatly with state-of-charge and cycling history, both for intrinsic chemical reasons (in NMC333) and because of massively damaging ''electrochemical shock'' (in NCA). Moreover, a thin coating of polymer binder is found to ameliorate fracture damage. These results, and the techniques demonstrated, provide a bridge between macroscopic battery function and microscale electrode kinetics as influenced by electrochemomechanical stress and charging history.

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“…In fact, it has been reported by a few authors 59,[101][102][103] that the linear sweep/cyclic voltammograms from the intercalation compounds were difficult to analyze under the diffusion control concept. In addition, the voltammetric results in a number of references 9,35,[104][105][106] seem to show abnormal trends without any explanation offered.…”

Section: Discussionmentioning

confidence: 99%

Mechanisms of Lithium Transport through Transition Metal Oxides and Carbonaceous Materials

Shin

Pyun

Modern Aspects of Electrochemistry

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Microvoltammetric studies on single particles of battery active materials

Cited by 81 publications

References 23 publications

Modeling Lithium Intercalation of a Single Spinel Particle under Potentiodynamic Control

Modeling Lithium Intercalation of a Single Spinel Particle under Potentiodynamic Control

Single-particle measurements of electrochemical kinetics in NMC and NCA cathodes for Li-ion batteries

Mechanisms of Lithium Transport through Transition Metal Oxides and Carbonaceous Materials

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