Localization of vacancies and mobility of lithium ions in Li2ZrO3 as obtained by 6,7Li NMR

Baklanova, Yana V.; Arapova, I. Yu.; Buzlukov, A. L.; Gerashenko, A.; Verkhovskiǐ, S. V.; Михалев, К. Н.; Денисова, Т. А.; Shein, I. R.; Maksimova, L. G.

doi:10.1016/j.jssc.2013.09.030

Cited by 32 publications

(55 citation statements)

References 38 publications

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“…In addition, we do not observe an obvious jump‐like transition from ionic to superionic conduction at around 467°C, which is suggested to be caused by redistribution of lithium ions over Li1 and Li2 lattice sites at elevated temperatures . The jump‐like behavior is closely related to the Li deficiency in Li 2 ZrO 3 ‐type compounds, which can largely be affected by synthesis method and the heat‐treatment protocol . There is a clear discontinuity in the Arrhenius plot of our sample at ~300°C, below which a higher activation energy (1.36 eV) was extracted.…”

Section: Resultssupporting

confidence: 91%

Nonstoichiometry and Li‐ion transport in lithium zirconate: The role of oxygen vacancies

2018

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Understanding Li‐ion migration mechanisms and enhancing Li‐ion transport in Li2ZrO3 (LZO) is important to its role as solid absorbent for reversible CO2 capture at elevated temperatures, as ceramic breeder in nuclear reactors, and as electrode coating in high‐voltage lithium‐ion batteries (LIBs). Although defect engineering is an effective way to tune the properties of ceramics, the defect structure of LZO is largely unknown. This study reports the defect structure and electrical properties of undoped LZO and a series of cation‐doped LZOs: (i) depending on their charge states, cation dopants can control the oxygen vacancy concentration in doped LZOs; (ii) the doped LZOs with higher oxygen vacancy concentrations exhibit better Li+ conductivity, and consequently faster high‐temperature CO2 absorption. In fact, the Fe (II)‐doped LZO shows the highest Li‐ion conductivity reported for LZOs, reaching 3.3 mS/cm at ~300°C that is more than 1 order of magnitude higher than that of the undoped LZO.

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Section: Resultssupporting

confidence: 91%

Nonstoichiometry and Li‐ion transport in lithium zirconate: The role of oxygen vacancies

2018

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“…19 Both the Nb and Ta doped materials behave quite similarly, while the Y doped material shows a similar broadening and then narrowing behaviour, but at a higher temperature. This is indicative of different rates of Li ionic mobility, and the following measurements aim to quantify this difference.…”

Section: Nmrmentioning

confidence: 93%

“…Doping Zr with 5+ atoms such as Nb and Ta is expected to lead to the formation of Li ion vacancies, whereas doping with 3+ atoms such as Y is expected to lead to the formation of Li interstitials, allowing the comparison of the influence of these two different modifications. Through the analysis of the NMR data we were able to determine the activation energy of Li ion diffusion in these doped materials and compare it to the undoped material as reported in Baklanova et al, 19 before considering these results in the context of the observed CO 2 absorption behaviour of these doped materials. This work explores the influence of doping on both ionic conduction and CO 2 absorption, allowing deeper insights to be gained into the underlying mechanism of CO 2 absorption by mixed lithium oxides.…”

Section: Introductionmentioning

confidence: 97%

“…13 for Li ionic conduction, finding that above 500 K there is an abrupt thermally activated diffusion of Li ions through the structure with an activation energy of ∼0.64 eV. 19 Given the importance of ionic conductivity on the behaviour of these materials, new chemical modifications that seek to modify a materials' rate of diffusion could lead to associated changes in its CO 2 absorption properties. A common modification involves the mixing of Li 2 ZrO 3 with other materials such as K 2 CO 3 or Na 2 CO 3 in the hope of improving reaction rates.…”

Section: Introductionmentioning

confidence: 99%

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Ion Dynamics and CO₂ Absorption Properties of Nb-, Ta-, and Y-Doped Li₂ZrO₃ Studied by Solid-State NMR, Thermogravimetry, and First-Principles Calculations

et al. 2017

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Amongst the many different processes proposed for large scale carbon capture and storage (CCS), high temperature CO 2 looping has emerged as a favourable candidate due to the low theoretical energy penalties that can be achieved. Many different materials have been proposed for use in such a process, the process requiring fast CO 2 absorption reaction kinetics, as * To whom correspondence should be addressed † Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, United Kingdom ‡ Department of Chemistry, Lancaster University, Lancaster LA1 4YB, United Kingdom ¶ Department of Chemistry, University of Liverpool, Crown Street, Liverpool L69 7ZD, United Kingdom § Department of Engineering, University of Cambridge, Trumpington Street, Cambridge, CB2 1PZ, United Kingdom 1 well as being able to cycle the material for multiple cycles without loss of capacity. Lithium ternary oxide materials, and in particular Li 2 ZrO 3 , have displayed promising performance but further modifications are needed to improve their rate of reaction with CO 2 . Previous studies have linked rates of lithium ionic conduction with CO 2 absorption in similar materials, and in this work we present work aimed at exploring the effect of aliovalent doping on the efficacy of Li 2 ZrO 3 as a CO 2 sorbent. Using a combination of x-ray powder diffraction, theoretical calculations and solid-state nuclear magnetic resonance, we studied the impact of Nb, Ta and Y doping on the structure, Li ionic motion and CO 2 absorption properties of Li 2 ZrO 3 . These methods allowed us to characterise the theoretical and experimental doping limit into the pure material, suggesting that vacancies formed upon doping are not fully disordered, but instead are correlated to the dopant atom positions, limiting the solubility range. Characterisation of the lithium motion using variable temperature solid-state nuclear magnetic resonance confirms that interstitial doping with Y retards the movement of Li ions in the structure, whereas vacancy doping with Nb or Ta results in a similar activation as Li 2 ZrO 3 . However, a marked reduction in the CO 2 absorption of the Nb and Ta doped samples suggests that doping also leads to a change in the carbonation equilibrium of Li 2 ZrO 3 disfavouring the CO 2 absorption at the reaction temperature. This study shows that a complex mixture of structural, kinetic and dynamic factors can influence the performance of Li-based materials for CCS, and underscores the importance of balancing these different factors in order to optimise the process.

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“…Li 1 sites are in the mixed (Li, Zr) layer while Li 2 is located in the middle of 6-fold octahedral oxygen coordinations. 26 The unique structure makes Li 2 ZrO 3 possess a three-dimensional path for Li-ion diffusion. Owing to the advantages Li 2 ZrO 3 has attracted great interest as a coating layer.…”

Section: Introductionmentioning

confidence: 99%

High Rate Capability and Excellent Thermal Stability of Li⁺-Conductive Li₂ZrO₃-Coated LiNi_1/3Co_1/3Mn_1/3O₂ via a Synchronous Lithiation Strategy

Zhang

Gao

et al. 2015

J. Phys. Chem. C

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A novel synchronous lithiation route has been successfully used to coat Li + -conductive Li 2 ZrO 3 on the surface of LiNi 1/3 Co 1/3 Mn 1/3 O 2 (Li 2 ZrO 3 @LNCMO). In this strategy, Li 2 ZrO 3 layer and LiNi 1/3 Co 1/3 Mn 1/3 O 2 host simultaneously form from ZrO 2 @Ni 1/3 Co 1/3 Mn 1/3 C 2 O 4 ·xH 2 O precursor. In compared to bare LNCMO, the reversible capacity, cycling performance, thermal stability, rate capability, and polarization of Li 2 ZrO 3 @LNCMO have all been greatly improved. At 0.1 and 10 C, the specific capacity of Li 2 ZrO 3 @LNCMO is 192 and 106 mAh g −1 , respectively, while they are 178 and 46 mAh g −1 for bare LNCMO. At a current density of 5 C, the capacity retention of Li 2 ZrO 3 @LNCMO at 25 and 55°C after 400 cycles is enhanced to 93.8% and 85.1%, respectively, compared to 69.2% and 37.4% of bare LNCMO. The largely enhanced electrochemical performances of Li 2 ZrO 3 @LNCMO cathode can be attributed to the high Li-ion conductivity as well as the proctection of Li 2 ZrO 3 coating. Li + conductivity of Li 2 ZrO 3 @LNCMO is about 20 times higher than that of bare LNCMO. Moreover, the migration of partial Zr 4+ to the host LNCMO phase not only benefits Liion or electron conductivity but also alleviates the Li−Ni cation mixing and improves the structure stability. The cations migration, doping effect, and the reduced cation mixing further contribute to the electrochemical performance enhancement.

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Localization of vacancies and mobility of lithium ions in Li2ZrO3 as obtained by 6,7Li NMR

Cited by 32 publications

References 38 publications

Nonstoichiometry and Li‐ion transport in lithium zirconate: The role of oxygen vacancies

Nonstoichiometry and Li‐ion transport in lithium zirconate: The role of oxygen vacancies

Ion Dynamics and CO₂ Absorption Properties of Nb-, Ta-, and Y-Doped Li₂ZrO₃ Studied by Solid-State NMR, Thermogravimetry, and First-Principles Calculations

High Rate Capability and Excellent Thermal Stability of Li⁺-Conductive Li₂ZrO₃-Coated LiNi_1/3Co_1/3Mn_1/3O₂ via a Synchronous Lithiation Strategy

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Localization of vacancies and mobility of lithium ions in Li2ZrO3 as obtained by 6,7Li NMR

Cited by 32 publications

References 38 publications

Nonstoichiometry and Li‐ion transport in lithium zirconate: The role of oxygen vacancies

Nonstoichiometry and Li‐ion transport in lithium zirconate: The role of oxygen vacancies

Ion Dynamics and CO2 Absorption Properties of Nb-, Ta-, and Y-Doped Li2ZrO3 Studied by Solid-State NMR, Thermogravimetry, and First-Principles Calculations

High Rate Capability and Excellent Thermal Stability of Li+-Conductive Li2ZrO3-Coated LiNi1/3Co1/3Mn1/3O2 via a Synchronous Lithiation Strategy

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Product

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Ion Dynamics and CO₂ Absorption Properties of Nb-, Ta-, and Y-Doped Li₂ZrO₃ Studied by Solid-State NMR, Thermogravimetry, and First-Principles Calculations

High Rate Capability and Excellent Thermal Stability of Li⁺-Conductive Li₂ZrO₃-Coated LiNi_1/3Co_1/3Mn_1/3O₂ via a Synchronous Lithiation Strategy