A stable lithium-rich surface structure for lithium-rich layered cathode materials

Kim, Sangryun; Cho, Woosuk; Zhang, Xiaobin; Oshima, Yoshifumi; Choi, Jang Wook

doi:10.1038/ncomms13598

Cited by 171 publications

(135 citation statements)

References 58 publications

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“…That is why, surface coatings with Al 2 O 3 , AlF 3 , AlPO 4 , MgO, with a novel surface configuration of Mg 3 (PO 4 ) 2 or effective modification by Li 2 MnO 3 which suppress layered-to-spinel transitions can stabilize capacity and voltage decay upon prolonged cycling of Li-, Mn-rich cathodes. [60][61][62][63][64][65] Similar results were obtained by doping of these cathodes with foreign cations (Na, Mg, Al, Zr, etc.) as described below.…”

Section: Efforts To Reduce Capacity Fading and Discharge Voltage Decasupporting

confidence: 68%

Review on Challenges and Recent Advances in the Electrochemical Performance of High Capacity Li‐ and Mn‐Rich Cathode Materials for Li‐Ion Batteries

Nayak

Erickson

Schipper

et al. 2017

Advanced Energy Materials

519

304

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CO 2 emissions. Hence, transportation dependent on electrical propulsion (electric vehicles) instead of internal combustion engines can greatly reduce the pollution caused by our transportation infrastructure. While rechargeable Li-ion batteries are the major power source for portable electronic devices such as smartphones and laptop computers, further improvements in their energy density is required in order to promote electrochemical propulsion devices that can compete with internal combustion engines. [1] The energy density of Li-ion batteries depends on the specific capacities and redox potentials of their electrode materials. Layered lithiated transition metal oxides such as LiCoO 2 , LiNi 1/2 Mn 1/2 O 2 , and LiNi 1/3 Mn 1/3 Co 1/3 O 2 ("NMC 111") were extensively studied as cathodes, which can exhibit specific capacities ≤160 mA h g −1 with an upper potential limit of 4.3 V versus Li. [2] The high cost, low thermal stability, and fast capacity fading at high current rates or during deep cycling of currently used LiCoO 2 necessitated the development of other layered cathodes, such as LiNi 1/2 Mn 1/2 O 2 , NMC 111, etc. The electrochemical performance of these layered metal oxides was recently reviewed by Yushin and coworkers. [3] Higher capacities can be extracted from layered metal oxide cathodes by cycling to upper potentials of about 4.5 V, however, driving these layered cathode materials to such high potentials enhances the structural instability and impedance growth. [4,5] Another important direction is the development of Ni-rich NCM cathode materials. As the content of Ni is higher, the specific capacity that can be extracted is higher as

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Section: Efforts To Reduce Capacity Fading and Discharge Voltage Decasupporting

confidence: 68%

Review on Challenges and Recent Advances in the Electrochemical Performance of High Capacity Li‐ and Mn‐Rich Cathode Materials for Li‐Ion Batteries

Nayak

Erickson

Schipper

et al. 2017

Advanced Energy Materials

519

304

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“…

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%

“…To build the next generation LIBs with higher performances, high energy density materials are urgently pursued worldwide. [9][10][11][12][13] In this regard, multifarious modification approaches, such as doping and surface coating, have been intensively investigated. 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.).…”

mentioning

confidence: 99%

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

et al. 2019

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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...

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“…[34] Obviously, the capacities of slope region are almost the same (about 160 mAh g −1 ), Adv. [45][46][47] In addition, the rate of performance and cycling stabilities are shown in Figure 3e,f. 2019, 6, 1802114 is confirmed by the X-ray photoelectron spectroscopy (XPS) analysis in Figure S7, Supporting Information.…”

Section: Resultsmentioning

confidence: 96%

Uniform Na⁺ Doping‐Induced Defects in Li‐ and Mn‐Rich Cathodes for High‐Performance Lithium‐Ion Batteries

Liu

et al. 2019

Advanced Science

100

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The corrosion of Li‐ and Mn‐rich (LMR) electrode materials occurring at the solid–liquid interface will lead to extra electrolyte consumption and transition metal ions dissolution, causing rapid voltage decay, capacity fading, and detrimental structure transformation. Herein, a novel strategy is introduced to suppress this corrosion by designing an Na + ‐doped LMR (Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 ) with abundant stacking faults, using sodium dodecyl sulfate as surfactant to ensure the uniform distribution of Na + in deep grain lattices—not just surface‐gathering or partially coated. The defective structure and deep distribution of Na + are verified by Raman spectrum and high‐resolution transmission electron microscopy of the as‐prepared electrodes before and after 200 cycles. As a result, the modified LMR material shows a high reversible discharge specific capacity of 221.5 mAh g −1 at 0.5C rate (1C = 200 mA g −1 ) after 200 cycles, and the capacity retention is as high as 93.1% which is better than that of pristine‐LMR (64.8%). This design of Na + is uniformly doped and the resultanting induced defective structure provides an effective strategy to enhance electrochemical performance which should be extended to prepare other advanced cathodes for high performance lithium‐ion batteries.

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A stable lithium-rich surface structure for lithium-rich layered cathode materials

Cited by 171 publications

References 58 publications

Review on Challenges and Recent Advances in the Electrochemical Performance of High Capacity Li‐ and Mn‐Rich Cathode Materials for Li‐Ion Batteries

Review on Challenges and Recent Advances in the Electrochemical Performance of High Capacity Li‐ and Mn‐Rich Cathode Materials for Li‐Ion Batteries

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

Uniform Na⁺ Doping‐Induced Defects in Li‐ and Mn‐Rich Cathodes for High‐Performance Lithium‐Ion Batteries

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A stable lithium-rich surface structure for lithium-rich layered cathode materials

Cited by 171 publications

References 58 publications

Review on Challenges and Recent Advances in the Electrochemical Performance of High Capacity Li‐ and Mn‐Rich Cathode Materials for Li‐Ion Batteries

Review on Challenges and Recent Advances in the Electrochemical Performance of High Capacity Li‐ and Mn‐Rich Cathode Materials for Li‐Ion Batteries

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

Uniform Na+ Doping‐Induced Defects in Li‐ and Mn‐Rich Cathodes for High‐Performance Lithium‐Ion Batteries

Contact Info

Product

Resources

About

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

Uniform Na⁺ Doping‐Induced Defects in Li‐ and Mn‐Rich Cathodes for High‐Performance Lithium‐Ion Batteries