Dynamic Structural Changes at LiMn<sub>2</sub>O<sub>4</sub>/Electrolyte Interface during Lithium Battery Reaction

Hirayama, Masaaki; Ido, Hedekazu; Kim, KyungSu; Cho, Woosuk; Tamura, Kazuhisa; Мizuki, J.; Kanno, Ryoji

doi:10.1021/ja105389t

Cited by 344 publications

(381 citation statements)

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“…6), suggesting gradual SEI growth during cycling. The SEI thickness obtained in this study by indentation was thicker than the reported values measured by other techniques, such as ellipsometry and TEM, 9,11,22 which reported that the SEI thickness was in the range of 2-5 nm, much smaller than the result in this study. The relatively thin SEI from TEM measurements probably appears because of SEI decomposition by the focused electron beam under high vacuum condition, 10 while the ellipsometry technique seems to underestimate the thickness due to an assumption of an optically homogeneous and isotropic SEI.…”

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confidence: 85%

“…It has been known that thin surface layer can be formed on electrode surface by contact with electrolyte. 11,12,22 The growth of the SEI during the initial cycle is rapid (1.526 nm/cycle), suggesting that the low Coulombic efficiency during the initial cycling test can be attributed to rapid SEI growth on the LiMn 2 O 4 surface. This is consistent with the studies that correlated SEI formation with Coulombic efficiency.…”

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confidence: 99%

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Evolution of Solid Electrolyte Interphase during Cycling and Its Effect on Electrochemical Properties of LiMn₂O₄

Hwang

Jang

2014

J. Electrochem. Soc.

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Thickness variation of the solid electrolyte interphase (SEI) produced during charge-discharge cycling is investigated to analyze the effect of SEI on the electrochemical properties of LiMn 2 O 4 . Atomic force microscopy (AFM) is used to measure the SEI thickness and elastic modulus on the LiMn 2 O 4 surface. The SEI shows a broad thickness distribution due to the random nature of the LiMn 2 O 4 electrode surfaces, while the average SEI thickness increases with cycling and stabilizes after the 20 th cycle. Formation of a relatively thin SEI on the LiMn 2 O 4 surface accompanies low Coulombic efficiency at early cycling stages. The SEI produced in the early stages of cycling is vulnerable to capacity fading due to inefficient surface protection against possible side reactions. A fully-grown stable SEI after 20 cycles shields the cathode surface from the electrolyte, minimizing capacity fading. © The Author Solid electrolyte interphase (SEI) is the layer produced on the surface of active materials during charge-discharge cycling of a battery. SEI affects electrochemical properties of active materials, such as capacity retention and rate performance, and a stable SEI is known to protect the active materials from electrolyte side reactions. A wellknown example is the excellent cycling performance of graphite due to the thin SEI produced on the surface. SEI control for cathode materials is, therefore, important to improve the electrochemical performance of Li-secondary batteries. In particular, much interest has been given to the study of SEI formation on LiMn 2 O 4 particles, as its SEI is relatively unstable and ineffective in protecting the electrode surface from side reactions with a protic electrolyte, causing capacity fading due to Mn 2+ ion dissolution. 3-5Although LiMn 2 O 4 has been considered as a promising cathode material for lithium ion secondary batteries due to its stability and high discharge voltage, as well as its non-toxicity and low cost, its capacity fading is known to be a part of the reason for its limited commercial application. Many researchers have studied the effect of SEI on electrochemical properties; however, the transient nature of SEI formed during cycling, and their nanoscale dimension made detailed analyses difficult. 6,7 Transmission electron microscopy (TEM) has been used for the observation of SEI,8,9 however, this has inherent shortcomings since SEI, which is composed of organic and inorganic materials (LiF, Li 2 CO 3 , R-CO 3 Li), can be decomposed at ultra-high vacuum conditions and by the high energy focused electron beam. 10 Other techniques, such as spectroscopic ellipsometry 11 and X-ray reflectivity analysis, 12 were also used to analyze SEI. They found that the thickness of the SEI layer was less than 5 nm in the early stages of cycling.10-12 Atomic force microscopy (AFM) has been used to examine electrode surfaces, while most AFM research has been focused on the change in topography, particle morphology, and electrical conductivity of the electrode surface.13-15 Recentl...

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confidence: 99%

Evolution of Solid Electrolyte Interphase during Cycling and Its Effect on Electrochemical Properties of LiMn₂O₄

Hwang

Jang

2014

J. Electrochem. Soc.

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“…Hirayama et al and Liu et al found, that the {110} facets are vulnerable to manganese dissolution. 28,33,34 Since the cycling of 2 Li eq. involves Mn 4+ /Mn 3+ as the active redox couple below 3.5 V vs. Li + /Li, there is a higher risk of manganese disproportionation and dissolution during cycling.…”

Section: Resultsmentioning

confidence: 99%

Influence of Synthesis, Dopants and Cycling Conditions on the Cycling Stability of Doped LiNi_0.5Mn_1.5O₄Spinels

Höweling

Stoll

Schmidt

et al. 2017

J. Electrochem. Soc.

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The high voltage LiNi 0.5 Mn 1.5 O 4 spinel suffers from severe capacity fade when cycled against a graphitic anode as well as a relatively low theoretical capacity. Using metallic lithium as counter electrode, the stability is improved and the ability of the spinel structure to host 2 Li eq. can be used to improve the capacity. This leads to a theoretical specific energy of ∼1000 Wh kg −1 . Unfortunately, the cycling of 2 Li eq. involves a phase transition from cubic to tetragonal associated with material degradation. In this work doping is used to improve capacity retention when cycling between 2.0 and 5.0 V. Initial capacities and stabilities are directly dependent on synthesis conditions and doping elements. Therefore, Fe-and Ti-doped spinels are compared with Ru-and Ti-doped spinels and tested at different cycling conditions. The cycling stability can be improved significantly by using reannealed material and by changing the discharge cutoff criteria. Thus a capacity of 190 mAh g −1 is achieved at a rate of C/2 with a capacity retention of ∼92% after 100 cycles. Furthermore, differences in the discharge behavior between the differently treated Ru-and Ti-doped materials are discussed based on the electrochemical behavior, the particle morphology and in-situ XRD analysis. The LiNi 0.5 Mn 1.5 O 4 spinel (LNMO) is a potential candidate for a high-energy cathode material in Li ion batteries. This is due to the high operating voltage of ∼ 4.7 V vs. Li + /Li. 1,2 Regardless of the high voltage the spinel offers a lower specific energy compared with other cathode materials (e.g. Li-rich layered oxides with capacities of ca. 220 -250 mAh g −1 ). 3-5However, the ability to host an additional lithium on the 16c octahedral sites 6,7 when a lithium metal anode is used, leads to an increased specific energy. The theoretical capacity increases up to 294 mAh g −1 and a theoretical energy of around 1000 Wh kg 9,10 Furthermore the trivalent manganese is Jahn-Teller active and cycling is accompanied by a strong Jahn-Teller-distortion.7,9 The c-axis parameter is increased by ∼6% while the a-and b-axis parameters shrink by ca. 0.6% leading to a phase transition from cubic to tetragonal symmetry. 11,12 The loss of manganese and the mechanical strain due to the phase transition lead to a severe capacity fade. Therefore, stable cycling of 2 Li eq. in the LNMO\\Li metal system is not possible.In order to enhance the electrochemical stability of spinel cathode materials several studies use various elements as dopants (e.g. Cr, Fe, Ga;13 Fe, Cu, Al, Mg; 14C r, Fe, Co, Ga; 15 Ti 16 ). In many publications the positive influence of Fe-and/or Ti-doping on the electrochemical stability of LNMO has been shown. 13,14,[16][17][18][19][20] Another promising doping element is Ruthenium. It has also been investigated as dopant in previous studies for the manganese spinel 21 and the LNMO spinel. 22-25It leads to an increased rate capability due to a higher electronic conductivity as well as faster lithium diffusion. However, except from z E-mai...

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“…The wavelength of X-ray used was 0.82552 ¡ (15 keV), and the detailed measurement conditions were described elsewhere. 14,18 In the XRD measurements, a reciprocal coordinate system (H,K,L) tetra was used when L describes the projection along the surface normal direction while H and K indicate the projection parallel to the surface. The reciprocal coordinate system was a tetrahedral system, and the relation between (H,K,L) tetra and (h,k,l) cubic is as follows: for two diffraction peaks; the out-of-plane (0,0,8) tetra and in-plane (4,0) tetra diffraction peaks, which correspond respectively to the (440) cubic and (004) cubic reflections for the original cubic cell.…”

Section: ¹3mentioning

confidence: 99%

Characterization of Nano-Sized Epitaxial Li4Ti5O12(110) Film Electrode for Lithium Batteries

et al. 2012

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Electrochemical properties and structure changes of nano-sized Li 4 Ti 5 O 12 during lithium (de)intercalation were investigated using a two-dimensional thin film electrode. Li 4 Ti 5 O 12 thin films were deposited on a Nb:SrTiO 3 (110) substrate by a pulsed laser deposition technique. X-ray diffraction and reflectometry measurements confirmed the epitaxial growth of 27.6-nm-thick Li 4 Ti 5 O 12 (110) films. Galvanostatic charge-discharge curves showed a large discharge capacity of 217 mAh g −1 at the initial discharge cycle, although the reversible capacity decreased in subsequent cycles. In situ X-ray diffraction measurements clarified the drastic structural changes of the Li 4 Ti 5 O 12 film upon soaking in the electrolyte and during the first intercalation and deintercalation processes. The surface region of Li 4 Ti 5 O 12 had a different structure from the bulk during electrochemical cycling and could cause the nanosized Li 4 Ti 5 O 12 electrodes to have high capacities and poor stabilities.

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Dynamic Structural Changes at LiMn₂O₄/Electrolyte Interface during Lithium Battery Reaction

Cited by 344 publications

References 44 publications

Evolution of Solid Electrolyte Interphase during Cycling and Its Effect on Electrochemical Properties of LiMn₂O₄

Evolution of Solid Electrolyte Interphase during Cycling and Its Effect on Electrochemical Properties of LiMn₂O₄

Influence of Synthesis, Dopants and Cycling Conditions on the Cycling Stability of Doped LiNi_0.5Mn_1.5O₄Spinels

Characterization of Nano-Sized Epitaxial Li4Ti5O12(110) Film Electrode for Lithium Batteries

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Dynamic Structural Changes at LiMn2O4/Electrolyte Interface during Lithium Battery Reaction

Cited by 344 publications

References 44 publications

Evolution of Solid Electrolyte Interphase during Cycling and Its Effect on Electrochemical Properties of LiMn2O4

Evolution of Solid Electrolyte Interphase during Cycling and Its Effect on Electrochemical Properties of LiMn2O4

Influence of Synthesis, Dopants and Cycling Conditions on the Cycling Stability of Doped LiNi0.5Mn1.5O4Spinels

Characterization of Nano-Sized Epitaxial Li4Ti5O12(110) Film Electrode for Lithium Batteries

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Dynamic Structural Changes at LiMn₂O₄/Electrolyte Interface during Lithium Battery Reaction

Evolution of Solid Electrolyte Interphase during Cycling and Its Effect on Electrochemical Properties of LiMn₂O₄

Evolution of Solid Electrolyte Interphase during Cycling and Its Effect on Electrochemical Properties of LiMn₂O₄

Influence of Synthesis, Dopants and Cycling Conditions on the Cycling Stability of Doped LiNi_0.5Mn_1.5O₄Spinels