Synthesis, structural, magnetic and electrochemical properties of LiNi1/3Mn1/3Co1/3O2 prepared by a sol–gel method using table sugar as chelating agent

Kiziltas-Yavuz, Nilüfer; Herklotz, Markus; Hashem, Ahmed M.; Abuzeid, Hanaa M.; Schwarz, Björn; Ehrenberg, Helmut; Mauger, A.; Julien, C.

doi:10.1016/j.electacta.2013.09.065

Cited by 55 publications

(28 citation statements)

References 53 publications

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“…Bulk crystal structure changes leading to microstrain, 33 cracking, 34 and disconnection 35 have been implicated in cycling losses of layered oxide materials. Synchrotron based in operando XRD offers the opportunity to capture subtle structure changes while performing electrochemistry simultaneously.…”

Section: Resultsmentioning

confidence: 99%

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

Tian

Nordlund

Xin

et al. 2018

J. Electrochem. Soc.

144

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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Section: Resultsmentioning

confidence: 99%

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

Tian

Nordlund

Xin

et al. 2018

J. Electrochem. Soc.

144

125

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“…Reprinted from [67] with permission from Elsevier. Several degradation mechanisms described in the introduction can be attributed to the intrinsic thermodynamic stability of the anode or cathode material.…”

Section: Q10mentioning

confidence: 97%

Fundamental degradation mechanisms of layered oxide Li-ion battery cathode materials: Methodology, insights and novel approaches

Hausbrand

Cherkashinin

Ehrenberg

et al. 2015

Materials Science and Engineering: B

410

280

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Available online xxx a b s t r a c tThis overview addresses the atomistic aspects of degradation of layered LiMO 2 oxide Li-ion cell cathode materials, aiming to shed light on the fundamental degradation mechanisms especially inside active cathode materials and at their interfaces. It includes recent results obtained by novel in situ/in operando diffraction methods, modelling, and quasi in situ surface science analysis. Degradation of the active cathode material occurs upon overcharge, resulting from a positive potential shift of the anode. Oxygen loss and eventual phase transformation resulting in dead regions are ascribed to changes in electronic structure and defect formation. The anode potential shift results from loss of free lithium due to side reactions occurring at electrode/electrolyte interfaces. Such side reactions are caused by electron transfer, and depend on the electron energy level alignment at the interface. Side reactions at electrode/electrolyte interfaces and capacity fade may be overcome by the use of suitable solid-state electrolytes and Licontaining anodes.

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“…There are several well-known failure modes or degradation processes in NMC electrodes, including "cross-over" of metal ions (Mn, Ni, Co) from the cathode to the anode, 6,7 micro-cracks in the particles during cycling, 8 loss of contact between particles, gas evolution, 9,10 phase transformations 11 and surface film formation. 12 We here shed light on yet another failure mechanism of NMC cathodes, triggered by the "cross-talk" between the electrodes, where species from the negative electrode dissolve into the electrolyte and deposit on the positive electrode.…”

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confidence: 99%

How the Negative Electrode Influences Interfacial and Electrochemical Properties of LiNi_1/3Co_1/3Mn_1/3O₂Cathodes in Li-Ion Batteries

Björklund

Brandell

Hahlin

et al. 2017

J. Electrochem. Soc.

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The cycle life of LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NMC) based cells are significantly influenced by the choice of the negative electrode. Electrochemical testing and post mortem surface analysis are here used to investigate NMC electrodes cycled vs. either Li-metal, graphite or Li 4 Ti 5 O 12 (LTO) as negative electrodes. While NMC-LTO and NMC-graphite cells show small capacity fading over 200 cycles, NMC-Li-metal cell suffers from rapid capacity fading accompanied with an increased voltage hysteresis despite the almost unlimited access of lithium. X-ray absorption near edge structure (XANES) results show that no structural degradation occurs on the positive electrode even after >200 cycles, however, X-ray photoelectron spectroscopy (XPS) results shows that the composition of the surface layer formed on the NMC cathode in the NMC-Li-metal cell is largely different from that of the other NMC cathodes (cycled in the NMC-graphite or NMC-LTO cells). Furthermore, it is shown that the surface layer thickness on NMC increases with the number of cycles, caused by continuous electrolyte degradation products formed at the Li-metal negative electrode and then transferred to NMC positive electrode. Li-ion batteries (LiBs) are widely used in applications where rechargeability of high energy density storage units is required, such as portable devices including consumer electronics, vehicles and space applications. It is beneficial that the components are as light-weight as possible for portable devices, thereby decreasing the energy required to transport the device. One widely used positive electrode material contributing to high energy density is LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NMC), either operating at a higher potential or having a larger practical specific capacity than the classical LiMn 2 O 4 and LiFePO 4 materials.1,2 NMC is also less costly than the LiCoO 2 alternative due to the decreased cobalt content.In commercial cells, NMC electrodes are most often cycled vs. graphite negative electrodes which has a low working potential, enabling a large potential difference between the electrodes. However, the low working potential is outside of the electrochemical stability window of most common electrolytes, leading to formation of a solid electrolyte interphase (SEI) layer on the anode surface. A corresponding but thinner layer could also form on the side of the positive electrode depending on the working potential of the cathode. 3,4 Lithium is consumed during SEI formation, which results in a decrease in the cell capacity and an increase in the cell resistance. The problems caused by SEI layer formation can be resolved by changing the negative electrode to an electrode working at a higher potential -within the electrochemical stability window of the electrolytesuch as lithium titanate (Li 4 Ti 5 O 12 ; LTO). Although the increased working potential decreases the energy density of the cell, cycle life is generally increased. The Li-metal anode is another negative electrode that is commonly used as counter/reference electrode, at le...

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Synthesis, structural, magnetic and electrochemical properties of LiNi1/3Mn1/3Co1/3O2 prepared by a sol–gel method using table sugar as chelating agent

Cited by 55 publications

References 53 publications

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

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

Fundamental degradation mechanisms of layered oxide Li-ion battery cathode materials: Methodology, insights and novel approaches

How the Negative Electrode Influences Interfacial and Electrochemical Properties of LiNi_1/3Co_1/3Mn_1/3O₂Cathodes in Li-Ion Batteries

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Synthesis, structural, magnetic and electrochemical properties of LiNi1/3Mn1/3Co1/3O2 prepared by a sol–gel method using table sugar as chelating agent

Cited by 55 publications

References 53 publications

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

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

Fundamental degradation mechanisms of layered oxide Li-ion battery cathode materials: Methodology, insights and novel approaches

How the Negative Electrode Influences Interfacial and Electrochemical Properties of LiNi1/3Co1/3Mn1/3O2Cathodes in Li-Ion Batteries

Contact Info

Product

Resources

About

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

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

How the Negative Electrode Influences Interfacial and Electrochemical Properties of LiNi_1/3Co_1/3Mn_1/3O₂Cathodes in Li-Ion Batteries