Layered Cathode Materials Li[Ni[sub x]Li[sub (1/3−2x/3)]Mn[sub (2/3−x/3)]]O[sub 2] for Lithium-Ion Batteries

Lu, Zhonghua; MacNeil, D. D.; Dahn, J. R.

doi:10.1149/1.1407994

Cited by 931 publications

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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).…”

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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.

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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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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.

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372

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“…Dahn et al reported that x = 1/3, 5/12, 1/2 shows a capacity of 200, 180, 160 mA g ¹1 , respectively. 6 We have reported the charging mechanism of Li 1¹x Ni 0.5 Mn 0.5 O 2 that a charging reaction proceeds with an oxidation of Ni 2+ to Ni 3+ , but not to Ni 4+ while maintaining oxidation state of Mn 4+ up to x = 0.5. 8,9 However, this material showed a rechargeable capacity corresponding to x = 0.7 in the voltage range of 2.5 to 4.3 V. O K-edge absorption spectra for Li 1¹x Ni 0.5 Mn 0.5 O 2 showed a slight shift towards lower energy for beyond the composition of x = 0.5.…”

Section: Introductionmentioning

confidence: 95%

Ion Distributions and the Electrochemical Properties of LiNi0.5Mn0.5O2 Prepared by Ion-Exchange for Positive Electrode

Arachi

Nakamura²,

Maeda

et al. 2012

Electrochemistry

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An order-disorder behavior of Li and Ni in LiNi 0.5 Mn 0.5 O 2 was investigated by means of the ion-exchange preparation and the high-temperature X-ray diffraction measurement using synchrotron radiation. Rietveld refinements at room temperature showed that the occupancy of Ni at the Li site prepared by ion-exchange is less than those by co-precipitation and it increases with an increase in temperature and time for the ion-exchange reaction. In addition, it was found that by high-temperature XRD measurements an order-disorder transition occurs at around 700 K for the sample prepared by the ion-exchange. Further, we have confirmed that an optimum ion distribution in LiNi 0.5 Mn 0.5 O 2 exists to show superior electrochemical performance as a positive electrode for Li-ion batteries. These results demonstrate a close relation between crystal structure and electrochemical properties for LiNi 0.5 Mn 0.5 O 2 which is a member of Li 2 MnO 3 -based materials. It is the first report that presents an order-disorder transition of LiNi 0.5 Mn 0.5 O 2 at elevated temperatures, on the basis of the experimental results.

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“…[32] Recently, substituted or mixed transition metal oxide compounds such as a layered LiNi 0.5 Mn 0.5 O 2 , layered Li-Co-Ni-Mn-O compounds (NCM) and Li-NiCo-Al-O compounds (NCA) cathode materials have been studied to achieve a better material stability, good rate capability and a larger reversible capacity. [39,40] Among them, Li and Mn-rich layered cathode materials, xLi 2 MnO 3 •(1-x)LiMO 2 (M = Mn, Ni, Co) show much higher specific capacity of ~ 250 mAh g -1 than that of conventional transition metal oxide cathodes. [41][42][43] Basically, Li 2 MnO 3 by itself cannot deliver high capacity, but a composite with LiMO 2 on a nanometric scale induces a reversible reaction of the excess Li.…”

Section: Layered Lithium Metal Oxidesmentioning

confidence: 99%

Li‐Ion Batteries and Beyond: Future Design Challenges

Hwa

Cairns

2015

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Light metals have been widely used as electrode materials for batteries owing to their low standard redox potential, their low equivalent weight, large specific capacity, and great abundance. Both primary and secondary cells including light metals as electrode material have influenced all aspects of our lives, e.g., electrically operated toys, power tools, and portable electronics such as cell phones, smart pads, and laptop computers. Among all battery systems, rechargeable lithium (Li) ion cells have been used most widely in recent years owing to their high specific power, high energy density, and ambient temperature operation. However, Li‐ion cells are facing difficult challenges in satisfying the emerging market for advanced applications demanding high‐performance rechargeable batteries for applications such as electric vehicles, high‐performance portable electronics, and large‐scale electrical energy storage systems. Unfortunately, current Li‐ion cells cannot satisfy demands such as low cost, much improved safety, larger energy density, faster charge/discharge rates, and longer service life, so intensive effort is necessary to develop the next generation of cells. In this article, the limitations of current Li‐ion cells and various advanced materials for each component of the Li‐ion cell, in addition to other promising candidates for cells beyond Li ion, such as the Li/S cell and Na‐ and Mg‐based rechargeable cells, and metal/air cells are discussed.

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Layered Cathode Materials Li[Ni[sub x]Li[sub (1/3−2x/3)]Mn[sub (2/3−x/3)]]O[sub 2] for Lithium-Ion Batteries

Cited by 931 publications

References 16 publications

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

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

Ion Distributions and the Electrochemical Properties of LiNi<sub>0.5</sub>Mn<sub>0.5</sub>O<sub>2</sub> Prepared by Ion-Exchange for Positive Electrode

Li‐Ion Batteries and Beyond: Future Design Challenges

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Layered Cathode Materials Li[Ni[sub x]Li[sub (1/3−2x/3)]Mn[sub (2/3−x/3)]]O[sub 2] for Lithium-Ion Batteries

Cited by 931 publications

References 16 publications

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

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

Ion Distributions and the Electrochemical Properties of LiNi<sub>0.5</sub>Mn<sub>0.5</sub>O<sub>2</sub> Prepared by Ion-Exchange for Positive Electrode

Li‐Ion Batteries and Beyond: Future Design Challenges

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

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