Insight into the atomic structure of Li<sub>2</sub>MnO<sub>3</sub> in Li-rich Mn-based cathode materials and the impact of its atomic arrangement on electrochemical performance

Song, Yuanzhe; Zhao, Xuebing; Wang, Chao; Bi, Han; Zhang, Jie; Li, Sesi; Wang, Min; Che, Renchao

doi:10.1039/c7ta02151h

Cited by 56 publications

(24 citation statements)

References 46 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However, in Li‐aluminate and Na‐aluminate coated samples, the changes in the c ‐lattice parameter are rather noticeable (≈3.7% and ≈2.7%, respectively). This observation may relate to the degree of cubic spinel phase formation [ 73 ] though further studies for revealing this observation were beyond the scope of this work. The results of the post‐cycling TEM analysis of the uncoated and coated HE‐NCM electrodes are presented in Figures and ; Figure S10, Supporting Information.…”

Section: Resultsmentioning

confidence: 99%

Understanding the Role of Alumina (Al₂O₃), Pentalithium Aluminate (Li₅AlO₄), and Pentasodium Aluminate (Na₅AlO₄) Coatings on the Li and Mn‐Rich NCM Cathode Material 0.33Li₂MnO₃·0.67Li(Ni_0.4Co_0.2Mn_0.4)O₂ for Enhanced Electrochemical Performance

Maiti

Sclar

Sharma

et al. 2020

Adv Funct Materials

View full text Add to dashboard Cite

The active role of alumina, pentalithium aluminate (Li5AlO4, Li‐aluminate), and pentasodium aluminate (Na5AlO4, Na‐aluminate) as the surface protection coatings produced via atomic layer deposition on Li and Mn‐rich NCM cathode materials 0.33Li2MnO3·0.67LiNi0.4Co0.2Mn0.4O2 is discussed. A notable improvement in the electrochemical behavior of the coated cathodes has been found while tested in Li‐coin cells at 30 °C. Though all the coated cathodes demonstrate enhanced electrochemical cycling and rate performances, Na‐aluminate coated cathodes exhibit exemplary behavior. Prolonged cycling and rate capability testing demonstrate that after more than 400 cycles at 1 C rate, the uncoated cathode delivers only 63 mAh g−1, while those with alumina, Li‐aluminate, and Na‐aluminate coatings exhibit approximately two times higher specific capacities. The coated cathodes display steady average discharge potential and lower evolution of the voltage hysteresis during prolonged cycling compared to the uncoated cathode. Importantly, Na‐aluminate coated cathode shows a lowering in gases (O2, CO2, H2, etc.) evolution. Post‐cycling analysis of the electrodes demonstrates higher morphological integrity of the coated cathode materials and lower transition metals dissolution from them. The coatings mitigate undesirable side reactions between the electrodes and the electrolyte solution in the cells.

show abstract

Section: Resultsmentioning

confidence: 99%

Understanding the Role of Alumina (Al₂O₃), Pentalithium Aluminate (Li₅AlO₄), and Pentasodium Aluminate (Na₅AlO₄) Coatings on the Li and Mn‐Rich NCM Cathode Material 0.33Li₂MnO₃·0.67Li(Ni_0.4Co_0.2Mn_0.4)O₂ for Enhanced Electrochemical Performance

Maiti

Sclar

Sharma

et al. 2020

Adv Funct Materials

View full text Add to dashboard Cite

show abstract

“…For more detailed information on the pristine structures of both NCM [2,17,18,28,61,115,116] and HE-NCM, [34,41,48,51,112,[117][118][119][120][121][122][123][124][125] we refer to other reports available in the literature. Note that by this evaluation method, the number of subsequently stacked defect-free TM layers is determined.…”

Section: Structure Of Li-rich He-ncmmentioning

confidence: 99%

Chemical, Structural, and Electronic Aspects of Formation and Degradation Behavior on Different Length Scales of Ni‐Rich NCM and Li‐Rich HE‐NCM Cathode Materials in Li‐Ion Batteries

et al. 2019

View full text Add to dashboard Cite

costs are required. Current state-of-theart LIBs using, e.g., well-established LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NCM111) cathode material are yet not able to fulfill all these demands. In order to increase the energy density of LIBs, battery produ cers and researchers pursue various strategies. Substitution of expensive Co by Ni to achieve LiNi 1−x−y Co x Mn y O 2 compounds with x < 0.3 in order to increase the structural stability at high state-of-charge (SOC) is one possible approach. Another promising material class is represented by Li-rich high-energy NCM (HE-NCM) materials (cLi 2 MnO 3 ⋅[1 − c]LiTMO 2 [TM = Ni, Co, Mn, etc.]). All of these subgroups of layered oxides have in common a crystal structure that is prone to irreversible changes and fatigue during continuous Li (de-)intercalation. The relevant changes in electronic and crystal structure strongly depend on the particular cathode composition and micro/nanostructure. The development of a target-oriented roadmap to improved LIBs that meet the above requirements must address the underlying mechanisms on different cell levels, i.e., from the atomic level to the electrode level. A comprehensive summary of the properties and developments in the field of Ni-rich NCM [1][2][3][4][5][6][7][8][9] and Li-rich HE-NCM [10][11][12][13][14][15][16] has been presented recently In order to satisfy the energy demands of the electromobility market, both Ni-rich and Li-rich layered oxides of NCM type are receiving much attention as high-energy-density cathode materials for application in Li-ion batteries. However, due to different stability issues, their longevity is limited. During formation and continuous cycling, especially the electronic and crystal structure suffers from various changes, eventually leading to fatigue and mechanical degradation. In recent years, comprehensive battery research has been conducted at Karlsruhe Institute of Technology, mainly aiming at better understanding the primary degradation processes occurring in these layered transition metal oxides. The characteristic process of formation and mechanisms of fatigue are fundamentally characterized and the effect of chemical composition on cell chemistry, electrochemistry, and cycling stability is addressed on different length scales by use of state-of-the-art analytical techniques, ranging from "standard" characterization tools to combinations of advanced in situ and operando methods. Here, the results are presented and discussed within a broader scientific context. by several authors. Here, we focus on the detailed characterization of these materials on different length scales, including the processes during formation and fatigue.After a brief introduction of the different materials addressed here, their characteristic process of formation and mechanisms of fatigue are discussed with respect to cell chemistry, electrochemistry, and cycling stability. Based on the fundamental results of our experimental studies on the material level, the effect of formation and fatigue on different cell levels is evalu...

show abstract

“…It is reported that Li‐rich materials are composed of two phases of Li 2 MnO 3 ( C 2/m ) and LiMO 2 (

R \bar{3} m

) (M = Ni, Co, Mn, etc.) . Despite the above advantages, several concerns including structural instability and the resulted voltage degradation, as well as the poor diffusion kinetics at the interface have become the bottlenecks of Li‐rich materials …”

Section: Introductionmentioning

confidence: 99%

“…

HEVs (PHEVs), besides the traditional applications in portable devices. [5][6][7][8][9] Despite the above advantages, several concerns including structural instability and the resulted voltage degradation, as well as the poor diffusion kinetics at the interface have become the bottlenecks of Li-rich materials. [1][2][3] Lithium-rich (Li-rich) materials, with the specific capacity over 260 mAh g −1 and energy density up to ≈1000 Wh kg −1 , [4] have attracted great interest in the past decades.

…”

mentioning

confidence: 99%

Local Electric‐Field‐Driven Fast Li Diffusion Kinetics at the Piezoelectric LiTaO₃ Modified Li‐Rich Cathode–Electrolyte Interphase

et al. 2019

View full text Add to dashboard Cite

HEVs (PHEVs), besides the traditional applications in portable devices. To build the next generation LIBs with higher performances, high energy density materials are urgently pursued worldwide. [1][2][3] Lithium-rich (Li-rich) materials, with the specific capacity over 260 mAh g −1 and energy density up to ≈1000 Wh kg −1 , [4] have attracted great interest in the past decades. It is reported that Li-rich materials are composed of two phases of Li 2 MnO 3 (C 2/m ) and LiMO 2 (R m 3 ) (M = Ni, Co, Mn, etc.). [5][6][7][8][9] Despite the above advantages, several concerns including structural instability and the resulted voltage degradation, as well as the poor diffusion kinetics at the interface have become the bottlenecks of Li-rich materials. [9][10][11][12][13] In this regard, multifarious modification approaches, such as doping and surface coating, have been intensively investigated. [14][15][16] Particularly, Li + diffusion at the cathode-electrolyte interphase (CEI) is widely regarded as the rate determining step in LIBs. [17][18][19] From this viewpoint, metal fluorides (FeF 3 , [20] MOF, [21,22] AlF 3 , [23,24] etc.), metal oxides (MgO, [25] Al 2 O 3 , [26,27] etc.), metal phosphates (AlPO 4 , [28] LaPO 4 , [29] Li 3 PO 4 , [30] FePO 4 /Li 3 PO 4 , [31] Li-Mn-PO 4 , [32] etc.), and those with similar structure of Li-rich Li 2 MnO 3 (Li 2 SiO 3 [33,34] and Li 2 SnO 3 , [35] ) have been widely applied to modify the surface of bulk Li-rich materials. Recently, fast lithium-ion conductors (LiVO 3 , [36] Li 2 ZrO 3 , [37] Li-La-Ti-O, [38,39] LiPON, [40] etc.) have also been proposed to decorate the surface of Li-rich cathodes to enhance the apparent diffusion coefficients. All the aforesaid surface modification materials, unexceptionally, have been proved to be effective in both stabilizing the structure and facilitating the Li + kinetics. Nevertheless, in general, the decoration layers themselves seem rather "passive" in promoting Li + diffusion. Assuming they are Li + conductive (e.g., solid electrolyte materials), fast Li + diffusion channels will be provided besides the general separation effect (in suppressing side reactions and inevitable TM dissolution). As for Li + insulators (e.g., metal fluorides), only the benefit of physical barriers could be exploited. Therefore, a more "initiative" function interface is imperative to be built to more effectively promote the Li + transport at the electrode-electrolyte interphase.It is noteworthy that piezoelectric material, as an important category in the energy-conversion community, works on the As one of the most promising cathodes for next-generation lithium ion batteries (LIBs), Li-rich materials have been extensively investigated for their high energy densities. However, the practical application of Li-rich cathodes is extremely retarded by the sluggish electrode-electrolyte interface kinetics and structure instability. In this context, piezoelectric LiTaO 3 is employed to functionalize the surface of Li 1.2 Ni 0.17 Mn 0.56 Co 0.07 O 2 (LNMCO), aiming to boost t...

show abstract

Insight into the atomic structure of Li₂MnO₃ in Li-rich Mn-based cathode materials and the impact of its atomic arrangement on electrochemical performance

Cited by 56 publications

References 46 publications

Understanding the Role of Alumina (Al₂O₃), Pentalithium Aluminate (Li₅AlO₄), and Pentasodium Aluminate (Na₅AlO₄) Coatings on the Li and Mn‐Rich NCM Cathode Material 0.33Li₂MnO₃·0.67Li(Ni_0.4Co_0.2Mn_0.4)O₂ for Enhanced Electrochemical Performance

Understanding the Role of Alumina (Al₂O₃), Pentalithium Aluminate (Li₅AlO₄), and Pentasodium Aluminate (Na₅AlO₄) Coatings on the Li and Mn‐Rich NCM Cathode Material 0.33Li₂MnO₃·0.67Li(Ni_0.4Co_0.2Mn_0.4)O₂ for Enhanced Electrochemical Performance

Chemical, Structural, and Electronic Aspects of Formation and Degradation Behavior on Different Length Scales of Ni‐Rich NCM and Li‐Rich HE‐NCM Cathode Materials in Li‐Ion Batteries

Local Electric‐Field‐Driven Fast Li Diffusion Kinetics at the Piezoelectric LiTaO₃ Modified Li‐Rich Cathode–Electrolyte Interphase

Contact Info

Product

Resources

About

Insight into the atomic structure of Li2MnO3 in Li-rich Mn-based cathode materials and the impact of its atomic arrangement on electrochemical performance

Cited by 56 publications

References 46 publications

Understanding the Role of Alumina (Al2O3), Pentalithium Aluminate (Li5AlO4), and Pentasodium Aluminate (Na5AlO4) Coatings on the Li and Mn‐Rich NCM Cathode Material 0.33Li2MnO3·0.67Li(Ni0.4Co0.2Mn0.4)O2 for Enhanced Electrochemical Performance

Understanding the Role of Alumina (Al2O3), Pentalithium Aluminate (Li5AlO4), and Pentasodium Aluminate (Na5AlO4) Coatings on the Li and Mn‐Rich NCM Cathode Material 0.33Li2MnO3·0.67Li(Ni0.4Co0.2Mn0.4)O2 for Enhanced Electrochemical Performance

Chemical, Structural, and Electronic Aspects of Formation and Degradation Behavior on Different Length Scales of Ni‐Rich NCM and Li‐Rich HE‐NCM Cathode Materials in Li‐Ion Batteries

Local Electric‐Field‐Driven Fast Li Diffusion Kinetics at the Piezoelectric LiTaO3 Modified Li‐Rich Cathode–Electrolyte Interphase

Contact Info

Product

Resources

About

Insight into the atomic structure of Li₂MnO₃ in Li-rich Mn-based cathode materials and the impact of its atomic arrangement on electrochemical performance

Understanding the Role of Alumina (Al₂O₃), Pentalithium Aluminate (Li₅AlO₄), and Pentasodium Aluminate (Na₅AlO₄) Coatings on the Li and Mn‐Rich NCM Cathode Material 0.33Li₂MnO₃·0.67Li(Ni_0.4Co_0.2Mn_0.4)O₂ for Enhanced Electrochemical Performance

Understanding the Role of Alumina (Al₂O₃), Pentalithium Aluminate (Li₅AlO₄), and Pentasodium Aluminate (Na₅AlO₄) Coatings on the Li and Mn‐Rich NCM Cathode Material 0.33Li₂MnO₃·0.67Li(Ni_0.4Co_0.2Mn_0.4)O₂ for Enhanced Electrochemical Performance

Local Electric‐Field‐Driven Fast Li Diffusion Kinetics at the Piezoelectric LiTaO₃ Modified Li‐Rich Cathode–Electrolyte Interphase