Electrochemical characteristics of LiNi1−xCoxO2 as positive electrode materials for lithium secondary batteries

Kinoshita, Akira; Yanagida, Katsunori; Yanai, Atsushi; Kida, Yoshinori; Funahashi, Atsuhiro; Nohma, Toshiyuki; Yonezu, I.

doi:10.1016/s0378-7753(01)00806-0

Cited by 37 publications

(18 citation statements)

References 15 publications

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“…1 Towards this end, much previous research focused on the development of LiNi 1-x Co x O 2 (NC) [2][3][4][5][6][7][8][9][10] cathode due to its high capacity (∼275 mAh/g) and favorable operating cell voltage (4.3 V vs. Li/Li + ), which is within the voltage stability window of current liquid electrolytes, and lower cost than LiCoO 2 . Despite extensive optimization, e.g., with respect to the Ni/Co ratio, 2-10 NC suffers from poor structural stability during electrochemical cycling.…”

mentioning

confidence: 99%

Characterization of Electronic and Ionic Transport in Li_1-_xNi_0.33Mn_0.33Co_0.33O₂(NMC₃₃₃) and Li_1-_xNi_0.50Mn_0.20Co_0.30O₂(NMC₅₂₃) as a Function of Li Content

Amin

Chiang

2016

J. Electrochem. Soc.

227

135

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Despite the extensive commercial use of Li 1-x Ni 1-y-z Mn z Co y O 2 (NMC) as the positive electrode in Li-ion batteries, and its long research history, its fundamental transport properties are poorly understood. These properties are crucial for designing high energy density and high power Li-ion batteries. Here, the transport properties of NMC 333 and NMC 523 are investigated using impedance spectroscopy and DC polarization and depolarization techniques. The electronic conductivity is found to increase with decreasing Li-content (increasing state-of-charge) from ∼10 −7 Scm −1 to ∼10 −2 Scm −1 over Li concentrations x = 0.00 to 0.75, corresponding to an upper charge voltage of 4.8 V with respect to Li/Li + . The lithium ion diffusivity is at least one order of magnitude lower, and decreases with increasing x to at x = ∼0.5. The ionic conductivity and diffusivity obtained from the two measurements techniques (EIS and DC) Cathodes having high energy and power density, adequate safety, excellent cycle life, and low cost are a critical need for Li-ion batteries to enable the commercialization of electric transportation and stationary storage.1 Towards this end, much previous research focused on the development of LiNi 1-x Co x O 2 (NC) 2-10 cathode due to its high capacity (∼275 mAh/g) and favorable operating cell voltage (4.3 V vs. Li/Li + ), which is within the voltage stability window of current liquid electrolytes, and lower cost than LiCoO 2 . Despite extensive optimization, e.g., with respect to the Ni/Co ratio, 2-10 NC suffers from poor structural stability during electrochemical cycling. 11Significant efforts were subsequently focused on improving structural stability and electrochemical performance by partial substitution Mn 12-17 (electrochemically inactive in this compound over the operating cell voltage window). Thus our objective in this work is to systematically characterize and interpret the transport properties of NMC 333 and NMC 523 . We use additive-free, single phase sintered samples in which the extrinsic effects due to binders, conductive additives, and particle microstructures that may be present in composite electrodes are avoided. Using electron blocking and ionic blocking cell configurations, respectively, and electrochemical impedance spectroscopy and DC polarization and depolarization techniques (see Table I), we deconvolute the electronic and ionic conductivities of NMC 333 and NMC 523 as a function of temperature and Li content, up to a lithium deficiency of x = 0.75, which corresponds to high charge voltages of 4.7 V and 4.8 V for NMC 333 and NMC 523 respectively. Our sample configuration permits measurement of single-phase properties up to delithiation levels (state-of-charge) where electrochemically-induced microfracture intrudes. Electronic conductivity was not apparently affected by these effects, whereas ionic transport shows an apparent increase beyond x = 0.50 which we attribute to fast transport paths created by microfracture. • C for 12 h in ambient atmosphere, preceded by h...

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confidence: 99%

Characterization of Electronic and Ionic Transport in Li_1-_xNi_0.33Mn_0.33Co_0.33O₂(NMC₃₃₃) and Li_1-_xNi_0.50Mn_0.20Co_0.30O₂(NMC₅₂₃) as a Function of Li Content

Amin

Chiang

2016

J. Electrochem. Soc.

227

135

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“…Conventionally, LiNi 1−y Co y O 2 is prepared by the standard ceramic process, i.e., solid-state route [8][9][10]. In the standard ceramic process, the starting materials are mixed and then calcinated at high temperature.…”

Section: Introductionmentioning

confidence: 99%

Study on the rapid synthesis of LiNi1−xCoxO2 cathode material for lithium secondary battery

Wang

Zhou

et al. 2007

Electrochimica Acta

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“…As a result, the development of LiCoO 2 based electrode materials are inhibited the widespread use as a cathode active electrode for rechargeable lithium batteries. Several researchers have addressed the following obstacles by doping or surface modifying of cathode active electrodes [6][7][8][9]. Although LiCoO 2 has a high theoretical specific capacity (274 mA h g À 1 ), the reversible specific capacity is limited to only 160 mA h g À 1 or less when cycled between 3.0 and 4.3 V (vs. Li/Li þ ) [10,11].…”

Section: Introductionmentioning

confidence: 99%

p-type LiCr0.33V0.33Mn0.33O2 semiconductor as a cathode electrode for high rate Li-ion batteries

Tokur

Erdaş

Nalci

et al. 2015

Materials Science in Semiconductor Processing

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Electrochemical characteristics of LiNi1−xCoxO2 as positive electrode materials for lithium secondary batteries

Cited by 37 publications

References 15 publications

Characterization of Electronic and Ionic Transport in Li_1-_xNi_0.33Mn_0.33Co_0.33O₂(NMC₃₃₃) and Li_1-_xNi_0.50Mn_0.20Co_0.30O₂(NMC₅₂₃) as a Function of Li Content

Characterization of Electronic and Ionic Transport in Li_1-_xNi_0.33Mn_0.33Co_0.33O₂(NMC₃₃₃) and Li_1-_xNi_0.50Mn_0.20Co_0.30O₂(NMC₅₂₃) as a Function of Li Content

Study on the rapid synthesis of LiNi1−xCoxO2 cathode material for lithium secondary battery

p-type LiCr0.33V0.33Mn0.33O2 semiconductor as a cathode electrode for high rate Li-ion batteries

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Electrochemical characteristics of LiNi1−xCoxO2 as positive electrode materials for lithium secondary batteries

Cited by 37 publications

References 15 publications

Characterization of Electronic and Ionic Transport in Li1-xNi0.33Mn0.33Co0.33O2(NMC333) and Li1-xNi0.50Mn0.20Co0.30O2(NMC523) as a Function of Li Content

Characterization of Electronic and Ionic Transport in Li1-xNi0.33Mn0.33Co0.33O2(NMC333) and Li1-xNi0.50Mn0.20Co0.30O2(NMC523) as a Function of Li Content

Study on the rapid synthesis of LiNi1−xCoxO2 cathode material for lithium secondary battery

p-type LiCr0.33V0.33Mn0.33O2 semiconductor as a cathode electrode for high rate Li-ion batteries

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Characterization of Electronic and Ionic Transport in Li_1-_xNi_0.33Mn_0.33Co_0.33O₂(NMC₃₃₃) and Li_1-_xNi_0.50Mn_0.20Co_0.30O₂(NMC₅₂₃) as a Function of Li Content

Characterization of Electronic and Ionic Transport in Li_1-_xNi_0.33Mn_0.33Co_0.33O₂(NMC₃₃₃) and Li_1-_xNi_0.50Mn_0.20Co_0.30O₂(NMC₅₂₃) as a Function of Li Content