Kinetics Tuning of Li-Ion Diffusion in Layered Li(NixMnyCoz)O2

Wei, Yi; Zheng, Jiaxin; Cui, Suihan; Song, Xiaohe; Su, Yantao; Deng, Wenjun; Wu, Zhongzhen; Wang, Xinwei; Wang, Weidong; Rao, Mumin; Lin, Yuan; Wang, Chongmin; Amine, Khalil; Pan, Feng

doi:10.1021/jacs.5b04040

Cited by 324 publications

(187 citation statements)

References 27 publications

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“…41-44 and 45; original research on the material can be found in Ref. [50][51][52][53][54][55][56][57][58][59][60]. In this work, we apply our thermodynamic modeling to Ni 0.6 Mn 0.2 Co 0.2 .…”

Section: Discussion Of Resultsmentioning

confidence: 99%

Thermodynamic Model for Substitutional Materials: Application to Lithiated Graphite, Spinel Manganese Oxide, Iron Phosphate, and Layered Nickel-Manganese-Cobalt Oxide

Baker

Koch²,

Xiao

et al. 2017

J. Electrochem. Soc.

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We derive and implement a method to describe the thermodynamics of electrode materials based on a substitutional lattice model. To assess the utility and generality of the method, we compare model results with experimental data for a variety of electrode materials: lithiated graphite and layered nickel-manganese-cobalt oxide (Chevrolet Bolt Electric Vehicle negative and positive electrode materials, respectively), manganese oxide (in the positive electrodes of the Gen 1 and Gen 2 Chevrolet Volt Extended Range Electric Vehicle and the positive electrode of many high-power-density batteries), and iron phosphate (Gen 1 Chevrolet Spark Electric Vehicle positive electrode material and of immediate interest for 12 and 48 V applications). An early version of the model has been applied to lithiated silicon (Li-Si). As was found in the Li-Si study, the model enables one to quantitatively represent experimental data from these different electrode materials with a small number of parameters, and, in this sense, the approach is both general and efficient. An open question is the utility of controlled-potential vs. controlled-current experiments for the elucidation of the system thermodynamics. We provide commentary on this question, and we highlight other open questions throughout this work. Central to the modeling of electrochemical systems, particularly batteries relying on solid-state diffusion within the active materials, is an accurate description of the system thermodynamics.1-4 We describe and implement a thermodynamic model for substitutional electrode materials. At the heart of the model is a simple expression for the open-circuit potential U in terms of the fraction of filled sites x within a host material. To assess the value of the model, we apply it to four electrode materials of commercial interest today: lithiated graphite, spinel manganese oxide, iron phosphate, and nickel-manganese-cobalt oxide. The model is an expanded version of that described in Ref. 12. A slight alteration is needed to describe the nickel-manganese-cobalt oxide so that inaccessible lithium can be considered (giving rise to x 0 in Table I), and we also describe how reactions between sites within the electrode material can be addressed.This document is organized as follows. First, we provide an overview of the materials and instrumentation for the experimental characterization of the electrode materials. An introduction of the thermodynamic model is then presented, followed by a detailed description of the model. A discussion of results is then presented, followed by a brief Appendix devoted to the convergence properties of the series summation employed in the U(x) model. • C under about 0.01 Torr vacuum. Other materials were dried at 100 Experimental• C under vacuum of about 0.01 Torr. Cell assembly and cycling were performed under an inert argon atmosphere with O 2 and H 2 O concentrations < 1 ppm. Cycling was performed with a Princeton Applied Research PMC 2000 potentiostat/galvanostat. For the voltammetry work on the Ni 0.6 Mn 0.2 Co ...

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Section: Discussion Of Resultsmentioning

confidence: 99%

Thermodynamic Model for Substitutional Materials: Application to Lithiated Graphite, Spinel Manganese Oxide, Iron Phosphate, and Layered Nickel-Manganese-Cobalt Oxide

Baker

Koch²,

Xiao

et al. 2017

J. Electrochem. Soc.

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“…However, it suffers from the disadvantage of high cost and poor safety. Recently, some derivative layered cathodes are explored that are safer and more affordable, such as LiNi x Mn y Co z O 2 (x + y + z = 1) systems [9][10][11][12]. These materials are expanding in their application.…”

Section: Introductionmentioning

confidence: 99%

Capacity Decay Mechanism of the LCO + NMC532/Graphite Cells Combined with Post-Mortem Technique

2017

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Lithium ion batteries are widely used in portable electronics and transportations due to their high energy and high power with low cost. However, they suffer from capacity degradation during long cycling, thus making it urgent to study their decay mechanisms. Commercial 18650-type LiCoO 2 + LiNi 0.5 Mn 0.3 Co 0.2 O 2 /graphite cells are cycled at 1 C rate for 700 cycles, and a continuous post-mortem analysis is performed. Based on these tests, the decay mechanism of the cells is finally proposed. The changes of differential capacity curves of the full cells show that the loss of active materials, loss of lithium ions and cell polarization are the main factors contributing to capacity loss. Non-fully charging of the electrodes is also one of the reasons, but only takes up a minor portion. Impedance results indicate that the charge transfer resistance becomes larger during cycling, especially at low state of charge. Morphology and surface chemistry analysis demonstrates that the electrode particles after cycling exhibit some minor cracks and some additional layers are formed on surfaces of both the cathode and anode electrodes. All of these effects may contribute to the impedance increase, and consequently lead to degradation of the full cells. Thus, a good protection of the surface of the cathode and anode shows great potential to improve the capacity maintenance and prolong the cycle life of the cells.

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“…78 Near the fully lithiated limit, Li diffusion occurs primarily via an ODH pathway. 77 To understand the effect of Al-doping on Li diffusion, we investigate the Li hopping mechanism from one Li octahedral site to another vacant Li octahedral site, via an ODH pathway. To compute the Li diffusion profile we created a single Li vacancy (i.e.…”

mentioning

confidence: 99%

Unraveling the Effects of Al Doping on the Electrochemical Properties of LiNi_0.5Co_0.2Mn_0.3O₂Using First Principles

Dixit

Markovsky

Aurbach

et al. 2017

J. Electrochem. Soc.

130

108

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One of the prevailing approaches to tune properties of materials is lattice doping with metal cations. Aluminum is a common choice, and numerous studies have demonstrated the ability of Al 3+ doping to stabilize different positive electrode materials, such as Li [Ni-Co-Mn] In recent decades, rechargeable batteries have demonstrated tremendous promise as alternate energy storage devices. In particular, Li-ion batteries (LIB) have revolutionized electronic devices, ranging from portable electronics to electric vehicles (EVs), due to their excellent power and energy density.1 The bottleneck of LIB in terms of capacity and performance is often considered to be the nature of the positive electrodes (cathodes).1-6 Among the cathode materials for LIB, layered transition metal (TM) oxides (LiTMO 2, TM = Ni, Co, Mn) are very promising candidates, and in particular LiCoO 2 . However, in spite of the commercialization and wide use of LiCoO 2 in portable LIB, it suffers from several drawbacks. Key disadvantages include high cost and safety concerns associated with cobalt.2-6 Other limitations of LiCoO 2 include low practical capacity (140 mAhg −1 ) and oxygen loss on charge. 7-10 Consequently, in a quest to move beyond LiCoO 2 , a new class of mixed transition metal oxides were designed, wherein Ni and Mn were introduced into the material (i.e. Li[Ni x Co y Mn z ]O 2 or simply NCM).11,12 The Ni-rich variants of these materials have emerged as the most promising low-cost and high capacity alternatives to the already mature LiCoO 2 . 10,13,14,11 These Nirich materials show improved performance; however, the capacities and stabilities are still too low for practical commercialization for EVs. 12Key hurdles in the commercialization of these materials for EV applications are associated with oxygen release at high voltages and cation migration, which leads to structural transformations. 15,16 Recently, it has been demonstrated that oxygen loss and cation migration are concurrent events. 16,17 To address these challenges, lattice doping of cations 18 has been adopted to improve the performance of these materials, and various cations were explored.18-24 A particularly promising dopant for these materials is Al, although its effect is still not fully understood. Early theoretical studies proposed that Al substitution in LiCoO 2 25 and NCMs 26 could increase the intercalation potential, and these predictions were verified experimentally. 27 Various studies reported beneficial effects of Al doping on LiCoO 2 and LiNiO 2 and NCMs. ), and found that Al doping reduces the reversible capacity, but significantly improves the thermal stability of the electrode in the de-intercalated state.36 Al doping in Li-rich-Mn-rich NCMs has also improved the thermal stabilities of these materials. 37 In a detailed theoretical study, Dianat et al. studied the effect of Al doping on Li-Mn-Ni-O based cathode materials.38 They reported that Al doping stabilizes the partially intercalated states, but increases the Li-diffusion barriers. Park et al. studie...

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Kinetics Tuning of Li-Ion Diffusion in Layered Li(Ni_xMn_yCo_z)O₂

Cited by 324 publications

References 27 publications

Thermodynamic Model for Substitutional Materials: Application to Lithiated Graphite, Spinel Manganese Oxide, Iron Phosphate, and Layered Nickel-Manganese-Cobalt Oxide

Thermodynamic Model for Substitutional Materials: Application to Lithiated Graphite, Spinel Manganese Oxide, Iron Phosphate, and Layered Nickel-Manganese-Cobalt Oxide

Capacity Decay Mechanism of the LCO + NMC532/Graphite Cells Combined with Post-Mortem Technique

Unraveling the Effects of Al Doping on the Electrochemical Properties of LiNi_0.5Co_0.2Mn_0.3O₂Using First Principles

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Kinetics Tuning of Li-Ion Diffusion in Layered Li(NixMnyCoz)O2

Cited by 324 publications

References 27 publications

Thermodynamic Model for Substitutional Materials: Application to Lithiated Graphite, Spinel Manganese Oxide, Iron Phosphate, and Layered Nickel-Manganese-Cobalt Oxide

Thermodynamic Model for Substitutional Materials: Application to Lithiated Graphite, Spinel Manganese Oxide, Iron Phosphate, and Layered Nickel-Manganese-Cobalt Oxide

Capacity Decay Mechanism of the LCO + NMC532/Graphite Cells Combined with Post-Mortem Technique

Unraveling the Effects of Al Doping on the Electrochemical Properties of LiNi0.5Co0.2Mn0.3O2Using First Principles

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Product

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Kinetics Tuning of Li-Ion Diffusion in Layered Li(Ni_xMn_yCo_z)O₂

Unraveling the Effects of Al Doping on the Electrochemical Properties of LiNi_0.5Co_0.2Mn_0.3O₂Using First Principles