Stabilizing nickel-rich layered cathode materials by a high-charge cation doping strategy: zirconium-doped LiNi0.6Co0.2Mn0.2O2

Schipper, Florian; Dixit, Mudit; Kovacheva, Daniela; Talianker, M.; Haik, Ortal; Grinblat, Judith; Erickson, Evan M.; Ghanty, Chandan; Major, Dan Thomas; Markovsky, Boris; Aurbach, Doron

doi:10.1039/c6ta06740a

Cited by 314 publications

(320 citation statements)

References 53 publications

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“…We have recently reported the beneficial impact of zirconium doping in NCM622 [96] self-combustion reaction and annealed at 800 °C under oxygen flow. Based on computational considerations, the Ni 2+ /Ni 3+ ratio was calculated for zirconium doping in place of cobalt, nickel or manganese ( Figure 13).…”

Section: Zirconium and Aluminum Doping Of Li[nixcoymnz]o2 Materialsmentioning

confidence: 99%

“…On the one hand, they can act as pillars in the lithium layers and lead to the suppression of c-lattice contraction at the end of the charge, resulting in improved rate capability of the electrode [96]. Furthermore, with dopants occupying lithium sites, the Li + /Ni 2+ mixing can be reduced and, hence, the formation of inactive rock salt on the surface is suppressed, resulting in lower charge-transfer-resistance growth with cycling [96,97,102]. Since most of the synthetic strategies of NCM make use of the lithium excess to achieve the correct stoichiometry and minimize the cation mixing during annealing, the material has some excess lithium on the surface.…”

Section: Zirconium and Aluminum Doping Of Li[nixcoymnz]o2 Materialsmentioning

confidence: 99%

“…The materials under examination were LiNi0.6Co0.2Mn0.2O2 and LiNi0.54Zr0.04Co0.2Mn0.2O2, synthesized by a [68,[96][97][98][99][100][101]. Dopants play various roles in the material.…”

Section: Zirconium and Aluminum Doping Of Li[nixcoymnz]o2 Materialsmentioning

confidence: 99%

“…While small pores act as transport channels for ions to the bulk of the electrode, larger pores allow for easy mass transport of solvated ions [94,95]. [68,[96][97][98][99][100][101]. Dopants play various roles in the material.…”

Section: Porous Li-and Mn-rich High-energy-density Cathode Materialsmentioning

confidence: 99%

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Study of Cathode Materials for Lithium-Ion Batteries: Recent Progress and New Challenges

et al. 2017

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Amongst a number of different cathode materials, the layered nickel-rich LiNi y Co x Mn 1−y−x O 2 and the integrated lithium-rich xLi 2 MnO 3 ·(1 − x)Li[Ni a Co b Mn c ]O 2 (a + b + c = 1) have received considerable attention over the last decade due to their high capacities of~195 and~250 mAh·g −1 , respectively. Both materials are believed to play a vital role in the development of future electric vehicles, which makes them highly attractive for researchers from academia and industry alike. The review at hand deals with both cathode materials and highlights recent achievements to enhance capacity stability, voltage stability, and rate capability, etc. The focus of this paper is on novel strategies and established methods such as coatings and dopings.

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Section: Zirconium and Aluminum Doping Of Li[nixcoymnz]o2 Materialsmentioning

confidence: 99%

Section: Zirconium and Aluminum Doping Of Li[nixcoymnz]o2 Materialsmentioning

confidence: 99%

“…The materials under examination were LiNi0.6Co0.2Mn0.2O2 and LiNi0.54Zr0.04Co0.2Mn0.2O2, synthesized by a [68,[96][97][98][99][100][101]. Dopants play various roles in the material.…”

Section: Zirconium and Aluminum Doping Of Li[nixcoymnz]o2 Materialsmentioning

confidence: 99%

Section: Porous Li-and Mn-rich High-energy-density Cathode Materialsmentioning

confidence: 99%

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Study of Cathode Materials for Lithium-Ion Batteries: Recent Progress and New Challenges

et al. 2017

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“…6 To circumvent these problems, several different strategies have been utilized to improve cycling, particularly to higher potentials. These include partial substitution with Ti [7][8][9] or Zr, 10 engineering the micro-or nano-structure to reduce surface Ni content using metal segregation, 11 surface pillared structures, 12 and concentration gradients, 13 coating particle surfaces, 14 and development of electrolyte additives. 15,16 While all of these approaches have resulted in improvements, further understanding of the factors that lead to capacity fading is clearly needed in order to meet the stringent performance requirements of traction applications.…”

mentioning

confidence: 99%

Depth-Dependent Redox Behavior of LiNi_0.6Mn_0.2Co_0.2O₂

Tian

Nordlund

Xin

et al. 2018

J. Electrochem. Soc.

136

125

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Nickel-rich layered materials are emerging as cathodes of choice for next-generation high energy density lithium ion batteries intended for electric vehicles. This is because of their higher practical capacities compared to compositions with lower Ni content, as well as the potential for lower raw materials cost. The higher practical capacity of these materials comes at the expense of shorter cycle life, however, due to undesirable structure and chemical transformations, especially at particle surfaces. To understand these changes more fully, the charge compensation mechanism and bulk and surface structural changes of LiNi 0.6 Mn 0.2 Co 0.2 O 2 were probed using synchrotron techniques and electron energy loss spectroscopy in this study. In the bulk, both the crystal and electronic structure changes are reversible upon cycling to high voltages, whereas particle surfaces undergo significant reduction and structural reconstruction. While Ni is the major contributor to charge compensation, Co and O (through transition metal-oxygen hybridization) are also redox active. An important finding from depth-dependent transition metal L-edge and O K-edge X-ray spectroscopy is that oxygen redox activity exhibits depth-dependent characteristics. This likely drives the structural and chemical transformations observed at particle surfaces in Ni-rich materials. The need for lithium-ion batteries with higher energy density and lower cost than currently available, particularly for transport applications, has led to intensified interest in Ni-rich NMC (LiNi x Mn y Co z O 2 ; x+y+z≈1, where x>y) cathode materials.1-5 These materials deliver higher practical capacities in a typically used voltage range than NMCs with lower Ni content (e.g., LiNi 1/3 Mn 1/3 Co 1/3 O 2 or NMC-333), and most formulations contain less of the expensive Co component, reducing raw material costs. The increase in practical capacity roughly scales with the Ni content, but comes at the expense of cycle life and thermal stability at high states-of-charge (SOC). 6 To circumvent these problems, several different strategies have been utilized to improve cycling, particularly to higher potentials. These include partial substitution with Ti 7-9 or Zr, 10 engineering the micro-or nano-structure to reduce surface Ni content using metal segregation, 11 surface pillared structures, 12 and concentration gradients, 13 coating particle surfaces, 14 and development of electrolyte additives. 15,16 While all of these approaches have resulted in improvements, further understanding of the factors that lead to capacity fading is clearly needed in order to meet the stringent performance requirements of traction applications.The formation of a resistive cathode/electrolyte interphase (CEI), such as an electrolyte decomposition layer, has been observed during cycling of LiNi 0. 20 In the study of NMC-532, it was found that surface reconstruction to a rock salt phase dominates when high voltage (4.8 V) cutoffs are used due to oxygen loss under the highly oxidizing conditions, while ...

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Simultaneously Dual Modification of Ni‐Rich Layered Oxide Cathode for High‐Energy Lithium‐Ion Batteries

Yang

et al. 2019

Adv Funct Materials

472

274

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A critical challenge in the commercialization of layer-structured Ni-rich materials is the fast capacity drop and voltage fading due to the interfacial instability and bulk structural degradation of the cathodes during battery operation. Herein, with the guidance of theoretical calculations of migration energy difference between La and Ti from the surface to the inside of LiNi 0.8 Co 0.1 Mn 0.1 O 2 , for the first time, Ti-doped and La 4 NiLiO 8 -coated LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathodes are rationally designed and prepared, via a simple and convenient dual-modification strategy of synchronous synthesis and in situ modification. Impressively, the dual modified materials show remarkably improved electrochemical performance and largely suppressed voltage fading, even under exertive operational conditions at elevated temperature and under extended cutoff voltage. Further studies reveal that the nanoscale structural degradation on material surfaces and the appearance of intergranular cracks associated with the inconsistent evolution of structural degradation at the particle level can be effectively suppressed by the synergetic effect of the conductive La 4 NiLiO 8 coating layer and the strong TiO bond. The present work demonstrates that our strategy can simultaneously address the two issues with respect to interfacial instability and bulk structural degradation, and it represents a significant progress in the development of advanced cathode materials for high-performance lithium-ion batteries.

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Stabilizing nickel-rich layered cathode materials by a high-charge cation doping strategy: zirconium-doped LiNi_0.6Co_0.2Mn_0.2O₂

Abstract: The high charge-state dopant Zr4+ improves the structural stability and electrochemical behavior of the lithiated transition metal oxide LiNi0.6Co0.2Mn0.2O2.

Cited by 314 publications

References 53 publications

Study of Cathode Materials for Lithium-Ion Batteries: Recent Progress and New Challenges

Study of Cathode Materials for Lithium-Ion Batteries: Recent Progress and New Challenges

Depth-Dependent Redox Behavior of LiNi_0.6Mn_0.2Co_0.2O₂

Simultaneously Dual Modification of Ni‐Rich Layered Oxide Cathode for High‐Energy Lithium‐Ion Batteries

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Stabilizing nickel-rich layered cathode materials by a high-charge cation doping strategy: zirconium-doped LiNi0.6Co0.2Mn0.2O2

Abstract: The high charge-state dopant Zr4+ improves the structural stability and electrochemical behavior of the lithiated transition metal oxide LiNi0.6Co0.2Mn0.2O2.

Cited by 314 publications

References 53 publications

Study of Cathode Materials for Lithium-Ion Batteries: Recent Progress and New Challenges

Study of Cathode Materials for Lithium-Ion Batteries: Recent Progress and New Challenges

Depth-Dependent Redox Behavior of LiNi0.6Mn0.2Co0.2O2

Simultaneously Dual Modification of Ni‐Rich Layered Oxide Cathode for High‐Energy Lithium‐Ion Batteries

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Stabilizing nickel-rich layered cathode materials by a high-charge cation doping strategy: zirconium-doped LiNi_0.6Co_0.2Mn_0.2O₂

Depth-Dependent Redox Behavior of LiNi_0.6Mn_0.2Co_0.2O₂