Temperature and potential dependence electrochemical impedance studies of LiMn2O4

Kumar, Surender; Nayak, Prasant Kumar; Hariharan, Krishnan S.; Munichandraiah, N.

doi:10.1007/s10800-013-0601-y

Cited by 5 publications

(10 citation statements)

References 54 publications

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“…From these data, we calculated the activation energy for the electrolyte resistance as 0.15 eV, similar to previous reports. 43,47 As discussed below, we attributed the intermediate frequency response (characterized by convoluted depressed semicircles) to the interfacial components of the electrode resistance; this group of features exhibited an increase in resistance following each C-rate spike. The lowest frequency "tail" is commonly assigned to bulk diffusive processes within the electrode or electrolyte and is not discussed further herein.…”

Section: Correlation Of Fracture With Acoustic Emissionsmentioning

confidence: 98%

“…Generally, the ohmic resistance at the high frequency offset is consistent with ionic transport resistance through the electrolyte and separator (∼10 ). 43,46 Thus, we assigned the high frequency offset to the electrolyte, as assumed commonly by others. From these data, we calculated the activation energy for the electrolyte resistance as 0.15 eV, similar to previous reports.…”

Section: Correlation Of Fracture With Acoustic Emissionsmentioning

confidence: 99%

“…Finally, the detailed studies of impedance spectra for LMO and related spinels available in the literature aid our analysis of the complex impedance responses to fracture shown herein. [42][43][44][45] In this study, we combined the advantages of both mechanical and electrochemical characterization techniques, so that we could induce fracture events and concurrently monitor any detectable changes in electrochemical performance. We monitored fracture during cycling with an acoustic emissions sensor, and confirmed the occurrence of widespread fracture in the electrodes via post mortem scanning electron microscopy.…”

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confidence: 99%

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Connecting Particle Fracture with Electrochemical Impedance in Li_XMn₂O₄

McGrogan

Bishop

Chiang

et al. 2017

J. Electrochem. Soc.

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Li-ion battery (LIB) electrodes subjected to repeated electrochemical cycling exhibit limited lifetime and gradual performance loss. Fracture of the active electrode particles, though one of the most widely discussed degradation mechanisms, is still not understood fully in even the most studied positive electrode systems. Here, we develop the connection between fracture and impedance in Li X Mn 2 O 4 composite electrodes via cycling schedules designed to produce discrete fracture events. We establish a correlation between these fracture events and acoustic emissions, as well as a parallel correlation between acoustic emissions and impedance growth. Through extensive impedance analysis, including conversion of impedance data to distributions of relaxation times, we identify the sources of impedance growth as electronic contact impedance and ionic surface layer impedance. Through measurements at multiple temperatures, we also estimate activation energies of ∼0.1 eV for electrolyte resistance, bulk contact resistance, and current collector resistance, ∼0.4 eV for charge-transfer resistance, and ∼0.3 eV for cathode surface layer resistance. We thus demonstrate a direct and correlative relationship between electrochemomechanical fatigue and performance loss, which can inform LIB design and characterization for improved longevity and late-life performance.

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Section: Correlation Of Fracture With Acoustic Emissionsmentioning

confidence: 98%

Section: Correlation Of Fracture With Acoustic Emissionsmentioning

confidence: 99%

mentioning

confidence: 99%

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Connecting Particle Fracture with Electrochemical Impedance in Li_XMn₂O₄

McGrogan

Bishop

Chiang

et al. 2017

J. Electrochem. Soc.

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“…Large polyhedral spinel particles without multilayer shells structure increase electrochemical impedance [44][45][46], large polyhedral spinel particles is against for lithium ion diffusion by decreasing the contact area of the electrode/electrolyte [47]. Multilayer shell structure has a low electrochemical impedance resulting from good diffusion coefficient of lithium ion [48,49]. The electric charge transfer resistance (Rct) of LNMO-900 is the lowest in table 1.…”

Section: Xpsmentioning

confidence: 99%

Preparation of spherical LiNi_0.5Mn_1.5O₄with core-multilayer shells structure by co-precipitation method and long cycle performance

Guo-jiang

Zhou³

et al. 2020

E3S Web Conf.

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As a promising cathode material for lithium ion battemensionalry of high voltage, spinel LiNi0.5Mn1.5O4 has attracted interest due to its high discharging voltage at 4.7 V and high energy density of 610 Wh kg-1. In this work, LiNi0.5Mn1.5O4 with a new core-multilayer shells structure (LNMO-900) is synthesized successfully by co-precipitation method and shows a better electrochemical performance. The formation of the core-multilayer shells structure is related to the kirkendall effect, the shell maintains structural stability, and improves long cycle performance. Core-multilayer shells structure is also beneficial for transmission of lithium ion, increasing rate performance. The effects of sintering temperature on the performance of LNMO were further investigated. Core-multilayer shells LiNi0.5Mn1.5O4 is synthesized successfully at 900 °C for 12 h uniquely. From the integral calculation of XPS spectra, a higher content of Mn4+ is observed in the outer shell of LNMO-900 compared with other homogeneous solid particles. The discharge specific capacity of LNMO-900 is 129.3 mAh g-1 at 1 C which is superior to others, and after 1000 cycles, LNMO-900 shows capacity retention of 87.9%. The initial capacity of LNMO-900 is 104.9 mAh g-1 at 5 C.

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“…Multiple researchers have reported these impedance contributions in LMO under a variety of conditions. [52][53][54] A full impedance characterization of identically prepared LMO cells, including identification of DRT peaks, is provided in our previous work. 41 We consider the impedance spectra herein to belong chiefly to the LMO cathodes, as determined via three-electrode impedance measurements discussed in the Supplementary Material of Ref.…”

Section: Sudden Growth Of Interfacial Electrode Impedance-figurementioning

confidence: 99%

Electrochemomechanical Fatigue: Decoupling Mechanisms of Fracture-Induced Performance Degradation in Li_XMn₂O₄

McGrogan

Raja

Chiang

et al. 2018

J. Electrochem. Soc.

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Decades of Li-ion battery (LIB) research have identified mechanical and chemical culprits that limit operational lifetime of LIB electrodes. For example, severe capacity fade of unmodified Li X Mn 2 O 4 electrodes has been linked historically with Mn dissolution and, more recently, fracture of the electrochemically active particles. Mitigation approaches targeting both effects have prolonged cycle and calendar life, but the fundamental mechanistic sequences linking fracture to capacity fade in Li X Mn 2 O 4 and many other cathode materials remain ambiguous. Here, we investigate specifically the temporal correlations of fracture, capacity fade, and impedance growth to gain understanding of the interplay between these phenomena and the time scales over which they occur. By conducting controlled excursions into the cubic-tetragonal phase transformation regime of Li X Mn 2 O 4 , we find that fracture contributes to impedance growth and capacity fade by two distinct mechanisms occurring over different time scales: (1) poorly conducting crack surfaces immediately hinder electronic conduction through the bulk of the electrode, and (2) capacity fades at a faster rate over multiple cycles, due plausibly to dissolution reactions occurring at newly formed electrode-electrolyte interfaces. The deconvolution of these effects in a well-studied cathode material such as Li X Mn 2 O 4 facilitates understanding of the complex relationship between mechanics and electrochemistry in LIB electrodes.) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 18.82.0.142 Downloaded on 2018-09-13 to IP ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 18.82.0.142 Downloaded on 2018-09-13 to IP ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 18.82.0.142 Downloaded on 2018-09-13 to IP

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Temperature and potential dependence electrochemical impedance studies of LiMn2O4

Cited by 5 publications

References 54 publications

Connecting Particle Fracture with Electrochemical Impedance in Li_XMn₂O₄

Connecting Particle Fracture with Electrochemical Impedance in Li_XMn₂O₄

Preparation of spherical LiNi_0.5Mn_1.5O₄with core-multilayer shells structure by co-precipitation method and long cycle performance

Electrochemomechanical Fatigue: Decoupling Mechanisms of Fracture-Induced Performance Degradation in Li_XMn₂O₄

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Temperature and potential dependence electrochemical impedance studies of LiMn2O4

Cited by 5 publications

References 54 publications

Connecting Particle Fracture with Electrochemical Impedance in LiXMn2O4

Connecting Particle Fracture with Electrochemical Impedance in LiXMn2O4

Preparation of spherical LiNi0.5Mn1.5O4with core-multilayer shells structure by co-precipitation method and long cycle performance

Electrochemomechanical Fatigue: Decoupling Mechanisms of Fracture-Induced Performance Degradation in LiXMn2O4

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Connecting Particle Fracture with Electrochemical Impedance in Li_XMn₂O₄

Connecting Particle Fracture with Electrochemical Impedance in Li_XMn₂O₄

Preparation of spherical LiNi_0.5Mn_1.5O₄with core-multilayer shells structure by co-precipitation method and long cycle performance

Electrochemomechanical Fatigue: Decoupling Mechanisms of Fracture-Induced Performance Degradation in Li_XMn₂O₄