Dynamic evolution of cathode electrolyte interphase (CEI) on high voltage LiCoO2 cathode and its interaction with Li anode

Zhang, Jie-Nan; Li, Qinghao; Wang, Yi; Zheng, Jieyun; Yu, Xiqian; Li, Hong

doi:10.1016/j.ensm.2018.02.016

Cited by 326 publications

(245 citation statements)

References 57 publications

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“…From the in situ EIS results (Figure ), it shows that the R sei almost maintains stability, even though SEI film gets thicker due to the oxidative decomposition of electrolyte at high voltage (≈4.8 V). The impedance in SEI mainly comes from inorganic salts (Li 2 CO 3 , LiF on cathode), and content of Li 2 CO 3 is more than LiF (Figure S2 and Table S1, Supporting Information, ratio of Li 2 CO 3 to LiF in this study is ≈2.8). The relative stable R sei may be attributed to the almost unchanged content of Li 2 CO 3 in the initial overcharge process.…”

Section: Resultsmentioning

confidence: 63%

“…[8b] So the detected intensity of LiF in 4 nm depth may be affected by the increased SEI films. Another possible reason is LiF physical migration from cathode to anode in charging process, it could also lead to the decrease on the detected LiF intensity. From the in situ EIS results (Figure ), it shows that the R sei almost maintains stability, even though SEI film gets thicker due to the oxidative decomposition of electrolyte at high voltage (≈4.8 V).…”

Section: Resultsmentioning

confidence: 99%

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Investigation of Interfacial Changes on Grain Boundaries of Li(Ni_0.5Co_0.2Mn_0.3)O₂ in the Initial Overcharge Process

Qin

Wang

Qian

et al. 2019

Adv Materials Inter

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for EVs due to the drawback of high cost and safety concern. LiFePO 4 is particularly remarkable due to its low cost, good cyclic performance. But the low discharge potential plateau (around 3.5 V for LiFePO 4 ) leads to the low energy density, [4] limiting its further application in EVs. The Ni-based layered oxides involve the high capacity from nickel, good rate capability from cobalt, and structural stability from inert electrochemical manganese. Herein, content ratios of Ni, Co, and Mn in Li(Ni x Co y Mn 1−x−y )O 2 are investigated to get the optimal performance in commercial batteries.In order to improve the performance of Li-ion batteries, the operating window for charge and discharge is moderated to deliver the optimal compromise between capacity and cycle life. Ni-based layered oxides charging to high voltage yield the higher initial capacity, but the capacity fades faster due to the physical and chemical changes degrading the battery performances. [5] Moreover, the higher energy density mainly depends on the content of nickel in cathode. While, it in turn results in the capacity degradation due to Ni migration into Li-ion layers to form the NiOlike salt rock structure. [6] Additionally, rock-salt phase (NiO) is more dominate under higher potentials. And this high oxidative environment could trigger the oxygen loss from NCM materials. [6,7] The transition of Ni layered NCM materials could be related to the electron removal from metal-O bonding states and the oxidation of lattice oxygen. [8] Microcracks or eventual disintegration are induced by the mechanical stress variation due to the anisotropic volume changes during repeated delithiation/lithiation. [9] Novak [10] investigated the structural changes of Ni-based layered oxides with charging to different upper cutoff voltages, and revealed that vacancies in metal oxide layers and Li/Ni mixing layers lead to the increased microstrain, thus strongly impacting on the cycling performance in the following cycles. Sun's group [7a] studied the Ni-based layered oxides (Li[Ni x Co y Mn 1−x−y ]O 2 ) with various Ni content ratios and found that the phase transition destabilized the internal microcracks and then propagated to the surface.Presently, many researchers focus on fading mechanisms and the impact of microcrack and structure changes on the battery performances after cycling [11] ; while the interfacial changes and Li-ions kinetics on grain boundaries of cathode are still not very clear, especially in the initial overcharge process. Aim to gain the further understanding of interfacial changes in Ni-based layered oxides after overcharge, in this study, electrochemical The interfacial changes and Li ions kinetics on grain boundaries of cathode are still not very clear, especially in the initial overcharge process. Herein, interfacial changes and electrochemical kinetics of Li ions on grain bounda ries of Li(Ni 0.5 Co 0.2 Mn 0.3 )O 2 (NCM523) are investigated in the initial over charge to 4.9 V. The mechanism of electrochemical process and interfacial cha...

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Section: Resultsmentioning

confidence: 63%

Section: Resultsmentioning

confidence: 99%

Investigation of Interfacial Changes on Grain Boundaries of Li(Ni_0.5Co_0.2Mn_0.3)O₂ in the Initial Overcharge Process

Qin

Wang

Qian

et al. 2019

Adv Materials Inter

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“…Electrochemical impedance spectroscopy (EIS) measurements were further performed to study the interfacial property of K 0.44 Ni 0.22 Mn 0.78 O 2 electrodes at various charge stages. As shown in Figure a, for every individual EIS curve, three regions can be clearly identified, including two semicircles at high and mediate frequencies and a slope line at low frequency, which can be ascribed to the contribution from CEI formation, the charge transfer and diffusion processes, respectively . With the increase of the cycle numbers, the semicircles at high frequency increase dramatically and presents slight change after the fifth cycle (inset in Figure a).…”

Section: Resultsmentioning

confidence: 89%

Layered P2‐Type K_0.44Ni_0.22Mn_0.78O₂ as a High‐Performance Cathode for Potassium‐Ion Batteries

Zhang

Yang

et al. 2019

Adv Funct Materials

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Potassium-ion batteries (KIBs) are emerging as one of the most promising candidates for large-scale energy storage owing to the natural abundance of the materials required for their fabrication and the fact that their intercalation mechanism is identical to that of lithium-ion batteries. However, the larger ionic radius of K + is likely to induce larger volume expansion and sluggish kinetics, resulting in low specific capacity and unsatisfactory cycle stability. A new Ni/ Mn-based layered oxide, P2-type K 0.44 Ni 0.22 Mn 0.78 O 2 , is designed and synthesized. A cathode designed using this material delivers a high specific capacity of 125.5 mAh g −1 at 10 mA g −1 , good cycle stability with capacity retention of 67% over 500 cycles and fast kinetic properties. In situ X-ray diffraction recorded for the initial two cycles reveals single solid-solution processes under P2-type framework with small volume change of 1.5%. Moreover, a cathode electrolyte interphase layer is observed on the surface of the electrode after cycling with possible components of K 2 CO 3 , RCO 2 K, KOR, KF, etc. A full cell using K 0.44 Ni 0.22 Mn 0.78 O 2 as the cathode and soft carbon as the anode also exhibits exceptional performance, with capacity retention of 90% over 500 cycles as well as superior rate performance. These findings suggest P2-K 0.44 Ni 0.22 Mn 0.78 O 2 is a promising candidate as a high-performance cathode for KIBs.

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“…Zuschriften decomposition and "cross-talk" behavior between cathode and anode. [49,50] However,c ompared to the stable cycling performance of ac ommercial LiFePO 4 j graphite battery,t he accelerated capacity decrease can be unambiguously attributed to the side reactions of the lithium metal. Therefore,we can trace this capacity decrease related to anode side reactions by monitoring the accumulation of byproducts on the Li metal surface.A si llustrated in Figures 4b,S 23, and S24, the Li anodes of the cells with a5 %c apacity loss displayed nearly the same value of fluorescence intensity after the DMA probing treatment, although the cycling number and current density for each sample was different.…”

Section: Angewandte Chemiementioning

confidence: 98%

Fluorescence Probing of Active Lithium Distribution in Lithium Metal Anodes

Cheng

Xian

et al. 2019

Angew Chem Int Ed

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The uncontrollable growth of Li dendrites and the accumulation of byproducts are two severe concerns for lithium metal batteries,w hich leads to safety hazardsa nd alow Coulombic efficiency.T oinvestigate the deterioration of the cell, it is important to figure out the distribution of active Li species on the anode surface and distinguish Li dendrites from byproducts.H owever,i ti ss till challenging to identify these issues by conventional visual observation methods.I nt his work, we introduce anovel fluorescent probing strategy using 9,10-dimethylanthracene (DMA). By marking the cycled Lianode surface,t he active Li distribution can be visualized by the fluorescence quenching of DMA reacting with active Li. The method demonstrates validity for electrolyte selection and predictive detection of uneven Li deposition on Li metal anodes.F urthermore,t he location of dendrites can be clearly identified after destructive utilization of the anode,w hich will contribute to the development of failure-analysis technology for Li metal batteries.

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Dynamic evolution of cathode electrolyte interphase (CEI) on high voltage LiCoO2 cathode and its interaction with Li anode

Cited by 326 publications

References 57 publications

Investigation of Interfacial Changes on Grain Boundaries of Li(Ni_0.5Co_0.2Mn_0.3)O₂ in the Initial Overcharge Process

Investigation of Interfacial Changes on Grain Boundaries of Li(Ni_0.5Co_0.2Mn_0.3)O₂ in the Initial Overcharge Process

Layered P2‐Type K_0.44Ni_0.22Mn_0.78O₂ as a High‐Performance Cathode for Potassium‐Ion Batteries

Fluorescence Probing of Active Lithium Distribution in Lithium Metal Anodes

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Dynamic evolution of cathode electrolyte interphase (CEI) on high voltage LiCoO2 cathode and its interaction with Li anode

Cited by 326 publications

References 57 publications

Investigation of Interfacial Changes on Grain Boundaries of Li(Ni0.5Co0.2Mn0.3)O2 in the Initial Overcharge Process

Investigation of Interfacial Changes on Grain Boundaries of Li(Ni0.5Co0.2Mn0.3)O2 in the Initial Overcharge Process

Layered P2‐Type K0.44Ni0.22Mn0.78O2 as a High‐Performance Cathode for Potassium‐Ion Batteries

Fluorescence Probing of Active Lithium Distribution in Lithium Metal Anodes

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About

Investigation of Interfacial Changes on Grain Boundaries of Li(Ni_0.5Co_0.2Mn_0.3)O₂ in the Initial Overcharge Process

Investigation of Interfacial Changes on Grain Boundaries of Li(Ni_0.5Co_0.2Mn_0.3)O₂ in the Initial Overcharge Process

Layered P2‐Type K_0.44Ni_0.22Mn_0.78O₂ as a High‐Performance Cathode for Potassium‐Ion Batteries