Atomic Structure of a Lithium-Rich Layered Oxide Material for Lithium-Ion Batteries: Evidence of a Solid Solution

Jarvis, Karalee; Deng, Ziwei; Allard, Lawrence F.; Manthiram, Arumugam; Ferreira, Paulo J.

doi:10.1021/cm200831c

Cited by 448 publications

(398 citation statements)

References 28 publications

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“…However, they can be easily differentiated via atomicresolution HAADF-STEM imaging, and the three-time periodicity of the atomic configuration along the 110 Â Ã zone axis of the C2/m structure which is absent in the R3m phase. On the basis of this fact, Jarvis et al 23 reported that their Li-excess layered material is a solid solution. By contrast, Bareno et al 24 found a locally Li 2 MnO 3 -like region within the parent rhombohedral Li-excess layered material structure, and Boulineau et al 25 observed the coexistence of the two phases, R3m and C2/m, with the same nominal composition.…”

Section: Electrode Materialsmentioning

confidence: 97%

Advanced analytical electron microscopy for lithium-ion batteries

Qian

et al. 2015

NPG Asia Mater

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Lithium-ion batteries are a leading candidate for electric vehicle and smart grid applications. However, further optimizations of the energy/power density, coulombic efficiency and cycle life are still needed, and this requires a thorough understanding of the dynamic evolution of each component and their synergistic behaviors during battery operation. With the capability of resolving the structure and chemistry at an atomic resolution, advanced analytical transmission electron microscopy (AEM) is an ideal technique for this task. The present review paper focuses on recent contributions of this important technique to the fundamental understanding of the electrochemical processes of battery materials. A detailed review of both static (ex situ) and real-time (in situ) studies will be given, and issues that still need to be addressed will be discussed. NPG Asia Materials (2015) 7, e193; doi:10.1038/am.2015.50; published online 26 June 2015 INTRODUCTIONTo implement the commercialization of lithium-ion batteries in electric vehicles and smart grid systems, further improvements are required, especially with respect to the energy/power density, coulombic efficiency and cycle life. These parameters primarily depend on the diffusion of lithium-metal ions, electron transport, structure and chemical dynamics of the electrode/electrolyte materials, among others. During electrochemical cycling, significant changes in the material structure and elemental distributions occur, including ion relocation, lattice expansion/contraction, phase transition and structure/surface reconstruction. These changes could substantially influence ion and electron transport and affect the performance of the entire battery system. Understanding the structure-property relationships for each component and their synergistic behaviors during electrochemical processes is, therefore, essential for the design of new battery materials and the optimization of existing systems.Although many analysis techniques (for example, X-ray diffraction, X-ray absorption spectroscopy, neutron diffraction, nuclear magnetic resonance and so on) have been employed for such studies, most of them can acquire only spatially averaged information. Nevertheless, the structural and chemical evolution of battery materials upon electrochemical cycling can often be linked to specific nanofeatures, such as defects, interfaces and surfaces. As a result, techniques based on analytical transmission electron microscopy (AEM) are ideal tools to study these issues. The capability of AEM to precisely probe the structural/chemical evolutions at an ultrahigh spatial resolution frequently provides insight that cannot be obtained directly using macroscopic characterization methods.

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Section: Electrode Materialsmentioning

confidence: 97%

Advanced analytical electron microscopy for lithium-ion batteries

Qian

et al. 2015

NPG Asia Mater

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“…111,118 Lirich NMCs are considered either a solid solution or a composite of Li 2 MnO 3 (monoclinic structure, C2/m space group) and LiMO 2 (trigonal structure, R 3m space group). [119][120][121] Despite their promise, these cathodes suffer from first cycle irreversible capacity loss, impedance rise during high-voltage cycling, and most importantly, a significant drop in the voltage profile (voltage fade) with cycling. 122 The voltage fade has been attributed to chemical and structural changes including oxygen evolution, Ni and Co migration from the surface into the bulk, reduction of Mn 4+ to Mn 3+ , and formation of a spinel-like phase.…”

Section: High-voltage Cathode Materialsmentioning

confidence: 99%

Toward Low-Cost, High-Energy Density, and High-Power Density Lithium-Ion Batteries

Ruther

et al. 2017

JOM

204

129

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Reducing cost and increasing energy density are two barriers for widespread application of lithium-ion batteries in electric vehicles. Although the cost of electric vehicle batteries has been reduced by $70% from 2008 to 2015, the current battery pack cost ($268/kWh in 2015) is still >2 times what the USABC targets ($125/kWh). Even though many advancements in cell chemistry have been realized since the lithium-ion battery was first commercialized in 1991, few major breakthroughs have occurred in the past decade. Therefore, future cost reduction will rely on cell manufacturing and broader market acceptance. This article discusses three major aspects for cost reduction: (1) quality control to minimize scrap rate in cell manufacturing; (2) novel electrode processing and engineering to reduce processing cost and increase energy density and throughputs; and (3) material development and optimization for lithium-ion batteries with high-energy density. Insights on increasing energy and power densities of lithium-ion batteries are also addressed.

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“…The layered lithium Ni-Mn-Co oxides Li 1+x (Ni y Mn z Co (1-y-z) ) 1-x O 2 (NMC) are considered to be promising positive electrode materials. [15][16][17][18][19][20][21][22][23] In our previous report 24 and in numerous literature reports, 6,14,16,17,19,[25][26][27][28][29][30][31][32] it has been shown that the electrochemical performance of these lithium-rich layered materials is dependent on their structure and composition. The lithium-rich manganese-rich NMC materials with excess lithium in the transition metal layer can have extraordinary high specific capacity of more than 250 mAh/g with an average potential of ∼3.6 V (vs. Li + /Li) after an irreversible oxygen release activation process at ∼4.5 V (vs. Li + /Li).…”

mentioning

confidence: 99%

Study of the Failure Mechanisms of LiNi_0.8Mn_0.1Co_0.1O₂Cathode Material for Lithium Ion Batteries

Downie

et al. 2015

J. Electrochem. Soc.

420

365

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LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) can deliver a high capacity of ∼200 mAh/g with an average discharge potential of ∼3.8 V (vs. Li + /Li), making it a promising positive electrode material for high energy density lithium ion batteries. However, electrochemical tests from half cells and full cells show poor cycling performance when charged to potentials above 4.2 V. The calendar and cycle lifetimes of cells are affected by the structural stability of the active electrode materials as well as the parasitic reactions that occur in lithium ion batteries. In order to explore the major failure mechanisms of the material, half cells (coin cells) with control electrolyte and full cells (pouch cells) with control electrolyte and with selected electrolyte additives were tested over four different potential ranges. Isothermal microcalorimetry was used to explore the parasitic reactions and their potential dependence. In-situ and ex-situ X-ray diffraction and scanning electron microscopy were used to investigate the structural and morphological degradation of the materials over cycling. It was found that the dramatic c-axis change of the active material during charge and discharge may not be the major problem for cells that are cycled to higher potentials. The parasitic reactions that arise from the interactions between the electrolyte and the highly reactive delithiated cathode surface at high potentials are suggested as the main reason for the failure of cells cycled above 4.2 V. It should be possible to further improve the performance of NMC811 at high potentials by modifying the cathode surface and/or identifying and using electrolyte blends which reduce parasitic reactions. High energy density lithium ion batteries (LIBs) that are cheaper, safer, and with longer lifetimes need to be developed in order to meet the increasing demand for applications such as electric vehicles and large scale stationary energy storage. The energy density of LIBs can be increased by increasing the specific capacity and average potential of the cells. The calendar and cycle lifetimes of cells are affected by the structural stability of the active electrode materials as well as the parasitic reactions that occur in lithium ion batteries. The degree of lithium utilization of LiCoO 2 is limited to ∼70% in order avoid the O3 -H1-3 -O1 phase transformation when charged above 4.45 V.1 Parasitic reactions such as electrolyte oxidation at the cathode-electrolyte interface can ultimately cause cell failure.2-5 The rate of the parasitic reactions is related to both the catalytic role of the cathode surface which depends on its composition and surface area, 3,6 as well as on the stability of the electrolyte.2-5 Methods such as the use of electrolyte additives 7-11 and core-shell positive electrode materials [12][13][14] have been developed and studied to reduce the rate and extent of parasitic reactions, and hence increase capacity retention and lifetime of high-voltage Li-ion cells. The layered lithium Ni-Mn-Co oxides Li 1+x (Ni y Mn z Co (1-y-z) ) 1...

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Atomic Structure of a Lithium-Rich Layered Oxide Material for Lithium-Ion Batteries: Evidence of a Solid Solution

Cited by 448 publications

References 28 publications

Advanced analytical electron microscopy for lithium-ion batteries

Advanced analytical electron microscopy for lithium-ion batteries

Toward Low-Cost, High-Energy Density, and High-Power Density Lithium-Ion Batteries

Study of the Failure Mechanisms of LiNi_0.8Mn_0.1Co_0.1O₂Cathode Material for Lithium Ion Batteries

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Atomic Structure of a Lithium-Rich Layered Oxide Material for Lithium-Ion Batteries: Evidence of a Solid Solution

Cited by 448 publications

References 28 publications

Advanced analytical electron microscopy for lithium-ion batteries

Advanced analytical electron microscopy for lithium-ion batteries

Toward Low-Cost, High-Energy Density, and High-Power Density Lithium-Ion Batteries

Study of the Failure Mechanisms of LiNi0.8Mn0.1Co0.1O2Cathode Material for Lithium Ion Batteries

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Study of the Failure Mechanisms of LiNi_0.8Mn_0.1Co_0.1O₂Cathode Material for Lithium Ion Batteries