Tracer diffusion coefficients of lithium ion in LiMn2O4 measured by neutron radiography

Takai, Shigeomi; Yoshioka, K.; Iikura, Hitoshi; Matsubayashi, Masahito; Yao, Takeshi; Esaka, Takao

doi:10.1016/j.ssi.2014.01.013

Cited by 41 publications

(52 citation statements)

References 18 publications

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“…A further validation of our MD simulation tool is presented in Figure 3. As seen in this figure, for the fully lithiated LMO spinel, there is a good agreement between the diffusion coefficient values calculated from MD simulations and the experimental data of Takai et al [34] . and Kuwata et al.…”

Section: Resultssupporting

confidence: 82%

“…The findings emanating from this computational work will be useful to the battery research community since performing experiments at the molecular scale are not only very expensive but also continue to pose a great challenge in obtaining precise results, especially for the variety of relevant doping scenarios that we investigate in this work. In fact, the challenge in performing precise experiments is also evident from the wide range of diffusion coefficients values at room temperature (10 −8 –10 −15 cm 2 s −1 ) reported in the literature, all of which are obtained from a variety measuring techniques [32–34] . This is not surprising because in addition to the limitation of the equipment used in these experiments, the transport and other properties strongly depend on the preparatory procedures that can influence the micro structure, defects, and atomic structure of the crystal.…”

Section: Introductionmentioning

confidence: 99%

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Co‐Doping Strategies to Improve the Electrochemical Properties of Li_xMn₂O₄ Cathodes for Li‐Ion Batteries

2022

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Four novel cathode electrode materials with improved material properties have been derived from the Lithium Manganese Oxide spinel using co‐doping strategies. Specifically, Aluminum, Nickel, Magnesium, and Yttrium were selected as the primary dopant to replace a fraction of Mn3+ (5 %), and S2− was selected as the secondary dopant to replace 1 % of O2−. A combination of quantum mechanics and molecular dynamics was used to study the fracture mechanics of the new materials for various State of Charge values, and improved performance is validated with experimental data. The results show that lattice constant values for all the doped structures decrease by 1.87 %–2.07 %. Overall, with co‐doping, the diffusion properties improved, and activation energy required for Li+ vacancy migration reduced (0.21–0.25 eV). We conclude that with reduced inter‐atomic distance, the overall life of the LMO spinel can be improved. The Computational Fluid Dynamics simulations to study the macro‐scale behaviour of these new materials shows a reduction in intercalation induced stress and heat generation.

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Section: Resultssupporting

confidence: 82%

Section: Introductionmentioning

confidence: 99%

Co‐Doping Strategies to Improve the Electrochemical Properties of Li_xMn₂O₄ Cathodes for Li‐Ion Batteries

2022

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“…[ 16,17 ] The calculated Zn‐ion migration barrier is the highest at the transition state—in between the T d and the O h sites—at 0.59 eV, which is notable that it is only slightly higher than the Li‐ion migration barrier of 0.52 eV in spinel LiMn 2 O 4 material that has demonstrated Li‐ion insertion at practical rates. [ 36 ] Hence, it can be concluded that Zn‐ion diffusion in 2H‐NbSe 2 is in fact facile as observed and the relatively low migration barrier for a divalent cation like Zn ion is feasible due to the reduced host‐guest interaction provided by the weakly interacting and widely separated layers of the 2H‐NbSe 2 structure as well as the polarizable Se anions that form the lattice. Also, the metallic nature of 2H‐NbSe 2 would aid in electronic charge distribution during Zn‐ion diffusion.…”

Section: Resultsmentioning

confidence: 88%

Understanding Zn‐Ion Insertion Chemistry through Nonaqueous Electrochemical Investigation of 2H‐NbSe₂

Park

Asl

Manthiram

2021

Adv Materials Inter

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Electrochemical Zn‐ion insertion into 2H‐NbSe2, which can be considered as a platform host, is investigated with bulk and microflower particles formed of nanosheets to bolster the understanding of Zn‐ion insertion chemistry. While electrochemical Zn‐ion insertion into bulk particles of 2H‐NbSe2 is observed to be hindered, it is found to be reversible and facile with microflower particles formed of nanosheets, emphasizing the importance of minimizing the kinetic limitations to Zn‐ion insertion. Also, the facile diffusion characteristics of Zn ions in the microflower particles of 2H‐NbSe2 is determined to be due to both its morphology that provides shortened diffusion length and the relatively low Zn‐ion migration barrier of 0.59 eV in the 2H‐NbSe2 structure, which is comparable to Li‐ion migration barrier in the well‐known spinel LiMn2O4. Such relatively low migration barrier of a multivalent ion like Zn2+ ion in 2H‐NbSe2 highlights the criticality of achieving weaker host–guest interaction for a multivalent‐ion host material as well as the reduced particle size to attain appreciable diffusion and reversible electrochemical behavior.

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“…For nanoarray-based electrodes, it is expected that the open pore geometry enables very direct and unhindered Li + -ion diffusion pathways within the electrode. Furthermore, the Li + -ion diffusion coefficient is several orders of magnitude higher in the electrolyte (~10 −6 cm 2 s −1 for LP30) [47,48] than in LTO (~10 −12 -10 −14 cm 2 s −1 ) [49][50][51] or LMO (~10 −12 -10 −14 cm 2 s −1 ) [52,53]. However, Li + -ion diffusion lengths are several orders of magnitude longer in the electrolyte (up to 175 µm) than in the particles (10-50 nm), which eventually leads to similar time scales for both diffusion processes.…”

Section: Structure Property Relationship In Lto-vacnt Nanoarraysmentioning

confidence: 96%

Nanostructured Networks for Energy Storage: Vertically Aligned Carbon Nanotubes (VACNT) as Current Collectors for High-Power Li4Ti5O12(LTO)//LiMn2O4(LMO) Lithium-Ion Batteries

et al. 2017

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Abstract:As a concept for electrode architecture in high power lithium ion batteries, self-supported nanoarrays enable ultra-high power densities as a result of their open pore geometry, which results in short and direct Li + -ion and electron pathways. Vertically aligned carbon nanotubes (VACNT) on metallic current collectors with low interface resistance are used as current collectors for the chemical solution infiltration of electroactive oxides to produce vertically aligned carbon nanotubes decorated with in situ grown LiMn 2 O 4 (LMO) and Li 4 Ti 5 O 12 (LTO) nanoparticles. The production processes steps (catalyst coating, VACNT chemical vapor deposition (CVD), infiltration, and thermal transformation) are all scalable, continuous, and suitable for niche market production to achieve high oxide loadings up to 70 wt %. Due to their unique transport structure, as-prepared nanoarrays achieve remarkably high power densities up to 2.58 kW kg −1 , which is based on the total electrode mass at 80 C for LiMn 2 O 4 //Li 4 Ti 5 O 12 full cells. The tailoring of LTO and LMO nanoparticle size (~20-100 nm) and VACNT length (array height: 60-200 µm) gives insights into the rate-limiting steps at high current for these kinds of nanoarray electrodes at very high C-rates of up to 200 C. The results reveal the critical structural parameters for achieving high power densities in VACNT nanoarray full cells.

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Tracer diffusion coefficients of lithium ion in LiMn2O4 measured by neutron radiography

Cited by 41 publications

References 18 publications

Co‐Doping Strategies to Improve the Electrochemical Properties of Li_xMn₂O₄ Cathodes for Li‐Ion Batteries

Co‐Doping Strategies to Improve the Electrochemical Properties of Li_xMn₂O₄ Cathodes for Li‐Ion Batteries

Understanding Zn‐Ion Insertion Chemistry through Nonaqueous Electrochemical Investigation of 2H‐NbSe₂

Nanostructured Networks for Energy Storage: Vertically Aligned Carbon Nanotubes (VACNT) as Current Collectors for High-Power Li4Ti5O12(LTO)//LiMn2O4(LMO) Lithium-Ion Batteries

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Tracer diffusion coefficients of lithium ion in LiMn2O4 measured by neutron radiography

Cited by 41 publications

References 18 publications

Co‐Doping Strategies to Improve the Electrochemical Properties of LixMn2O4 Cathodes for Li‐Ion Batteries

Co‐Doping Strategies to Improve the Electrochemical Properties of LixMn2O4 Cathodes for Li‐Ion Batteries

Understanding Zn‐Ion Insertion Chemistry through Nonaqueous Electrochemical Investigation of 2H‐NbSe2

Nanostructured Networks for Energy Storage: Vertically Aligned Carbon Nanotubes (VACNT) as Current Collectors for High-Power Li4Ti5O12(LTO)//LiMn2O4(LMO) Lithium-Ion Batteries

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Product

Resources

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Co‐Doping Strategies to Improve the Electrochemical Properties of Li_xMn₂O₄ Cathodes for Li‐Ion Batteries

Co‐Doping Strategies to Improve the Electrochemical Properties of Li_xMn₂O₄ Cathodes for Li‐Ion Batteries

Understanding Zn‐Ion Insertion Chemistry through Nonaqueous Electrochemical Investigation of 2H‐NbSe₂