Recent progress in cathode materials research for advanced lithium ion batteries

Xu, Bo; Qian, Danna; Wang, Ziying; Meng, Ying Shirley

doi:10.1016/j.mser.2012.05.003

Cited by 657 publications

(458 citation statements)

References 156 publications

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“…Although it is generally accepted that the capacity of Li(Ni 1/3 Mn 1/3 Co 1/3 )O 2 arises from the Ni 2+ /Ni 3+ /Ni 4+ redox centers within the 3-4 V operating window, the contribution of the Mn 3+ /Mn 4+ and Co 3+ /Co 4+ redox couples to this capacity is also reported. [30][31][32][33] In this work, we report a Li-rich Li 1+x MO 2 (xLi 2 MO 3 •(1-x)(Li 5/6 Ni 1/6 )(Li 1/6 Ni 1/6 Mn 1/3 Co 1/3 )O 2 composite material, M = Li, Ni, Mn, Fe) that is Co free. We study its electrochemical performance and function, determining the phase evolution of the active phase (Li 5/6 Ni 1/6 )(Li 1/6 Ni 1/6 Mn 1/3 Co 1/3 )O 2 using operando neutron powder diffraction (NPD).…”

Section: Introductionmentioning

confidence: 89%

Electrochemistry and structure of the cobalt-free Li_1+xMO₂(M = Li, Ni, Mn, Fe) composite cathode

Pang

Kalluri

Peterson

et al. 2014

Phys. Chem. Chem. Phys.

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The development of cathode materials with high capacity and cycle stability is essential to emerging electricvehicle technologies, however, of serious environmental concern is that materials with these properties developed so far contain the toxic and expensive Co. We report here the Li-rich, Co-free Li1+xMO2 (M = Li, Ni, Mn, Fe) composite cathode material, prepared via a template-free, one-step wet-chemical method followed by conventional annealing in an oxygen atmosphere. The cathode has an unprecedented level of cation mixing, where the electrochemically-active component contains four elements at the transition-metal (3a) site and 20% Ni at the active Li site (3b). We find Ni2+/Ni3+/Ni4+ to be the active redox-center of the cathode with lithiation/delithiation occurring via a solid-solution reaction where the lattice responds approximately linearly with cycling, differing to that observed for iso-structural commercial cathodes with a lower level of cation mixing. The composite cathode has ∼75% active material and delivers an initial dischargecapacity of ∼103 mA h g-1 with a reasonable capacity retention of ∼84.4% after 100 cycles. Notably, the electrochemically-active component possesses a capacity of ∼139 mA h g-1, approaching that of the commercialized LiCoO2 and Li(Ni1/3Mn1/3Co1/3)O2 materials. Importantly, our operando neutron powder-diffraction results suggest excellent structural stability of this active component, which exhibits ∼80% less change in its stacking-axis than for LiCoO2 with approximately the same capacity, a characteristic that may be exploited to enhance significantly the capacity retention of this and similar materials. The development of cathode materials with high capacity and cycle stability is essential to emerging electric-vehicle technologies, however, of serious environmental concern is that materials with these properties developed so far contain the toxic and expensive Co. We report here the Li-rich, Co-free Li 1+x MO 2 (M = Li, Ni, Mn, Fe) composite cathode material, prepared via a template-free, one-step wetchemical method followed by conventional annealing in an oxygen atmosphere. The cathode has an unprecedented level of cation mixing, where the electrochemically-active component contains four elements at the transition-metal (3a) site and 20% Ni at the active Li site (3b Importantly, our operando neutron powder-diffraction results suggest excellent structural stability of this active component, which exhibits ~ 80% less change in its stacking-axis than for LiCoO 2 with approximately the same capacity, a characteristic that may be exploited to enhance significantly the capacity retention of this and similar materials.

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Section: Introductionmentioning

confidence: 89%

Electrochemistry and structure of the cobalt-free Li_1+xMO₂(M = Li, Ni, Mn, Fe) composite cathode

Pang

Kalluri

Peterson

et al. 2014

Phys. Chem. Chem. Phys.

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“…Currently, lithium cobalt oxide (LiCoO 2 ), which is known for its high energy density and good cycling stability, is the most commercialized cathode material for LIBs. However, the high cost and toxicity of cobalt have prevented its use in next-generation green LIBs [3,4]. Spinel lithium manganese oxide (LiMn 2 O 4 ) is an inexpensive and eco-friendly alternative cathode material that can substitute LiCoO 2 in high-power lithium ion batteries [5][6][7].…”

Section: Introductionmentioning

confidence: 99%

Solution combustion synthesis of LiMn2O4 fine powders for lithium ion batteries

Chen

Nobuta

Saito

et al. 2014

Advanced Powder Technology

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In this work, fine powders of spinel-type LiMn 2 O 4 as cathode materials for lithium ion batteries (LIBs) were produced by a facile solution combustion synthesis using glycine as fuel and metal nitrates as oxidizers. Single phase of LiMn 2 O 4 products were successfully prepared by SCS with a subsequent calcination treatment at 600 to 1000 ºC. The structure and morphology of the powders were studied in detail by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The electrochemical properties were characterized by galvanostatic charge-discharge cycling and cyclic voltammetry. The crystallinity, morphology, and size of the products were greatly influenced by the calcination temperature. The sample calcined at 900 ºC had good crystallinity and particle sizes between 500 and 1000 nm. It showed the best performance with an initial discharge capacity of 115.6 mAh g -1 and a capacity retention of 93% after 50 cycles at a 1 C rate. In comparison, the LiMn 2 O 4 sample prepared by the solid-state reaction showed a lower capacity of around 80 mAh g -1 .

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“…[1][2][3][4][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).…”

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confidence: 99%

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

Tian

Nordlund

Xin

et al. 2018

J. Electrochem. Soc.

135

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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Recent progress in cathode materials research for advanced lithium ion batteries

Cited by 657 publications

References 156 publications

Electrochemistry and structure of the cobalt-free Li_1+xMO₂(M = Li, Ni, Mn, Fe) composite cathode

Electrochemistry and structure of the cobalt-free Li_1+xMO₂(M = Li, Ni, Mn, Fe) composite cathode

Solution combustion synthesis of LiMn2O4 fine powders for lithium ion batteries

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

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Recent progress in cathode materials research for advanced lithium ion batteries

Cited by 657 publications

References 156 publications

Electrochemistry and structure of the cobalt-free Li1+xMO2(M = Li, Ni, Mn, Fe) composite cathode

Electrochemistry and structure of the cobalt-free Li1+xMO2(M = Li, Ni, Mn, Fe) composite cathode

Solution combustion synthesis of LiMn2O4 fine powders for lithium ion batteries

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

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Product

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Electrochemistry and structure of the cobalt-free Li_1+xMO₂(M = Li, Ni, Mn, Fe) composite cathode

Electrochemistry and structure of the cobalt-free Li_1+xMO₂(M = Li, Ni, Mn, Fe) composite cathode

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