<i>Ab initio</i>study of lithium intercalation in metal oxides and metal dichalcogenides

Aydınol, Mehmet Kadri; Kohan, A. F.; Ceder, Gerbrand; Cho, Kang; Joannopoulos, John D.

doi:10.1103/physrevb.56.1354

Cited by 1,226 publications

(1,087 citation statements)

References 48 publications

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“…The Li 0.5 CoO 2 phase possesses a higher activity than the LiCoO 2 phase, which may originate from the change of the electronic structure. Previous reports [28][29][30][31] have shown that the electron charge transfer resulting from Li þ extraction simultaneously involves cobalt and oxygen, which can both be considered to undergo a partial oxidation process, and that more charge is transferred to the oxygen ions than to the metal ions. Therefore, the enhanced OER activity of De-LiCoO 2 may be attributed to the following possible reasons.…”

Section: Resultsmentioning

confidence: 99%

Electrochemical tuning of layered lithium transition metal oxides for improvement of oxygen evolution reaction

et al. 2014

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Searching for low-cost and efficient catalysts for the oxygen evolution reaction has been actively pursued owing to its importance in clean energy generation and storage. While developing new catalysts is important, tuning the electronic structure of existing catalysts over a wide electrochemical potential range can also offer a new direction. Here we demonstrate a method for electrochemical lithium tuning of catalytic materials in organic electrolyte for subsequent enhancement of the catalytic activity in aqueous solution. By continuously extracting lithium ions out of LiCoO 2 , a popular cathode material in lithium ion batteries, to Li 0.5 CoO 2 in organic electrolyte, the catalytic activity is significantly improved. This enhancement is ascribed to the unique electronic structure after the delithiation process. The general efficacy of this methodology is demonstrated in several mixed metal oxides with similar improvements. The electrochemically delithiated LiCo 0.33 Ni 0.33 Fe 0.33 O 2 exhibits a notable performance, better than the benchmark iridium/carbon catalyst.

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Section: Resultsmentioning

confidence: 99%

Electrochemical tuning of layered lithium transition metal oxides for improvement of oxygen evolution reaction

et al. 2014

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“…38 The layered oxides have been extensively studied both experimentally 5,39 and theoretically. [40][41][42][43] Because the layered dichalcogenide, LiTiS 2 , was once considered as a positive electrode material, 1 we have included this material in our investigations to ascertain if a different anion would modify the differences between the lithium vs sodium intercalation properties.…”

Section: Structure Selectionmentioning

confidence: 99%

Voltage, stability and diffusion barrier differences between sodium-ion and lithium-ion intercalation materials

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et al. 2011

Energy Environ. Sci.

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To evaluate the potential of Na-ion batteries, we contrast in this work the difference between Na-ion and Li-ion based intercalation chemistries in terms of three key battery properties -voltage, phase stability and diffusion barriers. The compounds investigated comprise the layered AMO 2 and AMS 2 structures, the olivine and maricite AMPO 4 structures, and the NA-SICON A 3 V 2 (PO 4 ) 3 structures. The calculated Na voltages for the compounds investigated are 0.18-0.57 V lower than that of the corresponding Li voltages, in agreement with previous experimental data. We believe the observed lower voltages for Na compounds are predominantly a cathodic effect related to the much smaller energy gain from inserting Na into the host structure compared to inserting Li. We also found a relatively strong dependence of battery properties with structural features. In general, the difference between the Na and Li voltage of the same compound, ∆V Na-Li , is less negative for the maricite structures preferred by Na, and * To whom correspondence should be addressed 1 more negative for the olivine structures preferred by Li. The layered compounds have the most negative ∆V Na-Li . In terms of phase stability, we found that open structures, such as the layered and NASICON structures that are better able to accommodate the larger Na + ion generally have both Na and Li versions of the same compound. For the close-packed AMPO 4 structures, our results show that Na generally prefers the maricite structure, while Li prefers the olivine structure, in agreement with previous experimental work. We also found surprising evidence that the barriers for Na + migration can potentially be lower than that for Li + migration in the layered structures. Overall, our findings indicate that Na-ion systems can be competitive with Li-ion systems.

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“…While this has led to considerable success in predicting the trends of Li insertion voltages 4 and even new phases 15 , it has been noted that LDA or GGA can give relatively large errors for the average Li insertion potential 4,21 . For example, Table I compares the experimental voltage for different structures with the one calculated in the GGA approximation and with computational details discussed in section III.…”

Section: Introductionmentioning

confidence: 99%

“…First principles calculations have been used extensively to predict important properties of Li-insertion materials such as the average potential 4,5,6,7,8,9,10,11,12,13,14 and potential profile 15,16 for Li insertion, phase stability 17,18,19 and Li diffusion 20 . While this has led to considerable success in predicting the trends of Li insertion voltages 4 and even new phases 15 , it has been noted that LDA or GGA can give relatively large errors for the average Li insertion potential 4,21 .…”

Section: Introductionmentioning

confidence: 99%

First-principles prediction of redox potentials in transition-metal compounds withLDA+U

et al. 2004

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First-principles calculations within the Local Density Approximation (LDA) or Generalized Gradient Approximation (GGA), though very successful, are known to underestimate redox potentials, such as those at which lithium intercalates in transition metal compounds. We argue that this inaccuracy is related to the lack of cancellation of electron self-interaction errors in LDA/GGA and can be improved by using the DFT+U method with a self-consistent evaluation of the U parameter.We show that, using this approach, the experimental lithium intercalation voltages of a number of transition metal compounds, including the olivine Li x MPO 4 (M=Mn, Fe Co, Ni), layered Li x MO 2 (x =Co, Ni) and spinel-like Li x M 2 O 4 (M=Mn, Co), can be reproduced accurately.

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Ab initiostudy of lithium intercalation in metal oxides and metal dichalcogenides

Cited by 1,226 publications

References 48 publications

Electrochemical tuning of layered lithium transition metal oxides for improvement of oxygen evolution reaction

Electrochemical tuning of layered lithium transition metal oxides for improvement of oxygen evolution reaction

Voltage, stability and diffusion barrier differences between sodium-ion and lithium-ion intercalation materials

First-principles prediction of redox potentials in transition-metal compounds withLDA+U

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