Evidence for Interfacial-Storage Anomaly in Nanocomposites for Lithium Batteries from First-Principles Simulations

Zhukovskii, Yuri F.; Balaya, Palani; Kotomin, E. A.; Maier, Joachim

doi:10.1103/physrevlett.96.058302

Cited by 215 publications

(173 citation statements)

References 15 publications

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“…At 50 mA g − 1 , the discharge capacities for LVO and Ni-LVO electrodes were higher than the theoretical value (591 mAh g − 1 ). The extra capacity at low potential may be related to the decomposition of the electrolyte upon reduction with the formation of a gel-like polymeric film 31 and interfacial storage, 32,33 which has also been observed in other anode materials such as SnO 2 , 34 CoO 35 and CoS x . 36 The capacity of the LVO electrode decreased rapidly at 50 mA g − 1 .…”

Section: Resultsmentioning

confidence: 99%

Effects of high surface energy on lithium-ion intercalation properties of Ni-doped Li3VO4

et al. 2016

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Nickel was doped into Li 3 VO 4 (Ni-LVO) successfully via a facile room temperature reaction, and the resulting Ni-LVO nanocrystallites showed excellent lithium-ion storage properties with a capacity of 650 mAh g − 1 at 50 mAh g − 1 and excellent capacity stability as an anode in lithium-ion batteries, maintaining nearly 100% of the initial reversible capacity after 800 cycles at 1 A g − 1 . The superior electrochemical properties arose largely from the nickel doping in the Ni-LVO. The surface energy of the electrode material was analyzed by an inverse gas chromatography method, and the Ni-LVO surface energy, 43.91 mJ m − 2 , was much higher than the 30.74 mJ m − 2 of Li 3 VO 4 . X-ray photoelectron spectra results demonstrated that nickel doping promoted the formation of tetravalent vanadium ions, V 4+ , as well as a more amorphous surface of Li 3 VO 4 , thus probably resulting in more nucleation sites for the phase transformation and reduced activation energy of the redox reactions and phase transition during the lithium-ion intercalation/extraction processes. NPG Asia Materials (2016) 8, e287; doi:10.1038/am.2016.95; published online 22 July 2016 INTRODUCTION Li 3 VO 4 (LVO), whose structure consists of corner-sharing VO 4 and LiO 4 tetrahedra, has been studied as a promising anode material for lithium-ion batteries. 1,2 It possesses several advantages over other anode materials. First, LVO has a small structural and volume change during lithiation/delithiation processes, thus resulting in good cyclic durability. 3 Second, it has high ionic conductivity (~10 − 4 S cm − 1 ), which facilitates the effective diffusion of lithium ions in bulk. 4 Third, compared with Li 4 Ti 5 O 12 , LVO can intercalate lithium ions in a low-voltage region (between 0.5 and 1.0 V vs Li/Li + ), thus eventually offering a high full cell energy density and maintaining good safety. 3,5 Finally, the hollow, lantern-like, three-dimensional structure of LVO crystal provides many empty sites to accommodate lithium ions and serves as lithium ion insertion channels. Theoretical calculations indicate that the inserted lithium ions have two different Wyckoff sites, which are stably occupied by three external lithium ions corresponding to a theoretical capacity of 591 mAh g − 1 when discharged to 0.01 V vs Li/Li + . 6 Despite these advantages, LVO suffers from low electrical conductivity, which may cause large polarization and poor rate capability. Hybridization with carbon materials such as graphite, 7,8 carbon nanotubes 9 and graphene 10,11 and reduction of the LVO particle size have been proven to be effective ways to enhance electrical conductivity and abate polarization. For example, carbon-encapsulated LVO nanoparticles synthesized by a simple solid-state method exhibit excellent rate capability and long cycling performance. 1 In addition, defects introduced by doping, thermal treatment at an inert or

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Section: Resultsmentioning

confidence: 99%

Effects of high surface energy on lithium-ion intercalation properties of Ni-doped Li3VO4

et al. 2016

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“…3b). The higher capacity relative to the theoretical capacity (718 mAh g À 1 ) suggests that interfacial charge storage and/or reversible side reactions play roles in the extra capacity 22,36 . The reversible side reactions probably include but are not limited to lithium storage in carbon black 37 and CuO 38 at the surface of the Cu current collector, and reversible conversion of LiOH to Li 2 O and LiH 39 .…”

Section: Morphology and Electronic Structure Of Nio Nanosheetsmentioning

confidence: 99%

Phase evolution for conversion reaction electrodes in lithium-ion batteries

et al. 2014

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The performance of battery materials is largely governed by structural and chemical evolutions during electrochemical reactions. Therefore, resolving spatially dependent reaction pathways could enlighten mechanistic understanding, and enable rational design for rechargeable battery materials. Here, we present a phase evolution panorama via spectroscopic and three-dimensional imaging at multiple states of charge for an anode material (that is, nickel oxide nanosheets) in lithium-ion batteries. We reconstruct the threedimensional lithiation/delithiation fronts and find that, in a fully electrolyte immersion environment, phase conversion can nucleate from spatially distant locations on the same slab of material. In addition, the architecture of a lithiated nickel oxide is a bent porous metallic framework. Furthermore, anode-electrolyte interphase is found to be dynamically evolving upon charging and discharging. The present study has implications for resolving the inhomogeneity of the general electrochemically driven phase transition (for example, intercalation reactions) and for the origin of inhomogeneous charge distribution in large-format battery electrodes.

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“…35,36 In theory, the first principle calculation proved the reasonability of interface storage from the view point of thermodynamics. 5 Such mechanism is beneficial not only to increase the storage capacity at low potential but also to improve the rate performance.…”

Section: Space Charge Layer Effects On Conductivities At Various Bounmentioning

confidence: 99%

“…Variation of not only the magnitude but also the type of conductivity were verified in composites, grain boundaries in polycrystalline materials and epitaxial heterostructures. [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] Conductivities of various functional materials might be manipulated for fundamental research as well as application. Introduction of interfaces not only led to strong variations in conductivity, but also induced qualitatively change of the type of conductivity.…”

Section: Introductionmentioning

confidence: 99%

Space Charge Layer Effect in Solid State Ion Conductors and Lithium Batteries: Principle and Perspective

Chen

Guo

2016

ACSi

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This paper is dedicated to Prof. Dr. Janko Jamnik, who was my enthusiastic and helpful MPI colleague as well as with high academic level and reputation in science community. AbstractThe space charge layer (SCL) effects were initially developed to explain the anomalous conductivity enhancement in composite ionic conductors. They were further extended to qualitatively as well as quantitatively understand the interfacial phenomena in many other ionic-conducting systems. Especially in nanometre-scale systems, the SCL effects could be used to manipulate the conductivity and construct artificial conductors. Recently, existence of such effects either at the electrolyte/cathode interface or at the interfaces inside the composite electrode in all solid state lithium batteries (ASSLB) has attracted attention. Therefore, in this article, the principle of SCL on basis of defect chemistry is first presented. The SCL effects on the carrier transport and storage in typical conducting systems are reviewed. For ASSLB, the relevant effects reported so far are also reviewed. Finally, the perspective of interface engineer related to SCL in ASSLB is addressed.

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Evidence for Interfacial-Storage Anomaly in Nanocomposites for Lithium Batteries from First-Principles Simulations

Cited by 215 publications

References 15 publications

Effects of high surface energy on lithium-ion intercalation properties of Ni-doped Li3VO4

Effects of high surface energy on lithium-ion intercalation properties of Ni-doped Li3VO4

Phase evolution for conversion reaction electrodes in lithium-ion batteries

Space Charge Layer Effect in Solid State Ion Conductors and Lithium Batteries: Principle and Perspective

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