Lithium Tracer Diffusion in Sub-Stoichiometric Layered Lithium-Metal-Oxide Compounds

2021 ◽  
Vol 413 ◽  
pp. 125-135
Author(s):  
Daniel Uxa ◽  
Helen J. Holmes ◽  
Kevin Meyer ◽  
Lars Dörrer ◽  
Harald Schmidt

Cathode materials based on lithium-metal-oxide compounds are an essential technical component for lithium-ion batteries, which are still being researched and continuously improved. For a fundamental understanding of kinetic processes at and in electrodes the Li diffusion is of high relevance. Most cathode materials are based on the layered LiCoO2 (LCO) and LiNi0.33Mn0.33Co0.33O2 (NMC333). In the present study Li tracer self-diffusion is investigated in polycrystalline sintered bulk samples of sub-stoichiometric Li0.9CoO2 at 145 °C ≤ T ≤ 350 °C and compared to Li0.9Ni0.33Mn0.33Co0.33O2 in the temperature range between 110 and 350 °C. For analysis, stable 6Li tracers are used in combination with secondary ion mass spectrometry (SIMS). The Li tracer diffusivities D* of both compounds with a sub-stoichiometric Li concentration are identical within error limits and can be described by the Arrhenius law with an activation enthalpy of (0.76 ± 0.13) eV for LCO and (0.85 ± 0.03) eV for NMC333, which is interpreted as the migration energy of a single Li vacancy. This means that a modification of the transition metal (M) layer composition within the LiMO2 structure does not significantly influence lithium diffusion in the temperature range investigated.

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Daniel Uxa ◽  
Harald Schmidt

Abstract The compound LiNi0.5Mn1.5O4 is used as novel cathode material for Li-ion batteries and represents a variant to replace conventional LiMn2O4. For a further improvement of battery materials it is necessary to understand kinetic processes at and in electrodes and the underlying diffusion of lithium that directly influences charging/discharging times, maximum capacities, and possible side reactions. In the present study Li tracer self-diffusion is investigated in polycrystalline sintered bulk samples of near stoichiometric LiNi0.5Mn1.5O4 with an average grain size of about 50–70 nm in the temperature range between 250 and 600 °C. For analysis, stable 6Li tracers are used in combination with secondary ion mass spectrometry (SIMS). The tracer diffusivities can be described by the Arrhenius law with an activation enthalpy of (0.97 ± 0.05) eV, which is interpreted as the sum of the formation and migration energy of a thermally activated Li vacancy.


2021 ◽  
Vol 23 (3) ◽  
pp. 2438-2448
Author(s):  
Gen Hasegawa ◽  
Naoaki Kuwata ◽  
Yoshinori Tanaka ◽  
Takamichi Miyazaki ◽  
Norikazu Ishigaki ◽  
...  

Lithium diffusion is a key factor in determining the charge/discharge rate of Li-ion batteries. Herein, we study the tracer diffusion coefficient of lithium ions in the c-axis oriented LiCoO2 thin film using secondary ion mass spectrometry (SIMS).


RSC Advances ◽  
2013 ◽  
Vol 3 (48) ◽  
pp. 25576 ◽  
Author(s):  
Sujith Kalluri ◽  
Kuok Hau Seng ◽  
Zaiping Guo ◽  
Hua Kun Liu ◽  
Shi Xue Dou

MRS Advances ◽  
2019 ◽  
Vol 4 (09) ◽  
pp. 515-521
Author(s):  
Yuriy Suhak ◽  
Ward L. Johnson ◽  
Andrei Sotnikov ◽  
Hagen Schmidt ◽  
Holger Fritze

ABSTRACTTransport mechanisms in structurally ordered piezoelectric Ca3TaGa3Si2O14 (CTGS) single crystals are studied in the temperature range of 1000-1300 °C by application of the isotope 18O as a tracer and subsequent analysis of diffusion profiles of this isotope using secondary ion mass spectrometry (SIMS). Determined oxygen self-diffusion coefficients enable calculation of oxygen ion contribution to the total conductivity, which is shown to be small. Since very low contributions of the cations have to be expected, the total conductivity must be dominated by electron transport. Ion and electron conductivities are governed by different mechanisms with activation energies (1.9±0.1) eV and (1.2±0.07) eV, respectively. Further, the electromechanical losses are studied as a function of temperature by means of impedance spectroscopy on samples with electrodes and a contactless tone-burst excitation technique. At temperatures above 650 °C the conductivity-related losses are dominant. Finally, the operation of CTGS resonators is demonstrated at cryogenic temperatures and materials piezoelectric strain constants are determined from 4.2 K to room temperature.


2006 ◽  
Vol 972 ◽  
Author(s):  
Haiming Xie ◽  
Haiying Yu ◽  
Abraham F. Jalbout ◽  
Guiling Yang ◽  
Xiumei Pan ◽  
...  

AbstractWe design a way that the anode hosts provide lithium ion in lithium ion battery operation. If the limiting factors of the cathode materials are less, there will be more alternatives for it. It was proven to be successful by two kinds of test cells based on LixCn as anode material, and β-FeOOH or Cr8O21 as cathode materials. Their theoretical capacities are much higher than those present electrode materials. Unlike the lithium secondary batteries with lithium metal foil or lithium alloy as anode, this type of lithium ion batteries with LixCn as anode prohibit dendrite formation during charging-discharge process. The idea of lithium ion sources coming from the anode can come true successfully as a result that steady protecting solution be sought for LixCn.


1988 ◽  
Vol 126 ◽  
Author(s):  
P. Mel ◽  
S. A. Schwarz ◽  
T. Venkatesan ◽  
C. L. Schwartz ◽  
E. Colas

ABSTRACTTe enhanced mixing of AlAs/GaAs superlattice has been observed by secondary ion mass spectrometry. The superlattice sample was grown by organometallic chemical vapor deposition and doped with Te at concentrations of 2×1017 to 5×1018 cm−.3 In the temperature range from 700 to 1000 C, a single activation energy for the Al diffusion of 2.9 eV was observed. Furthermore, it has been found that the relationship between the Al diffusion coefficient and Te concentration is linear. Comparisons have been made between Si and Te induced superlattice mixing.


1998 ◽  
Vol 527 ◽  
Author(s):  
R. J. Hanrahan ◽  
S. P. Withrow ◽  
M. Puga-Lambers

ABSTRACTClassical diffusion measurements in intermetallic compounds are often complicated by low diffusivities or low solubilities of the elements of interest. Using secondary ion mass spectrometry for measurements over a relatively shallow spatial range may be used to solve the problem of low diffusivity. In order to simultaneously obtain measurements on important impurity elements with low solubilities we have used ion implantation to supersaturate a narrow layer near the surface. Single crystal NiAl was implanted with either 12C or both 56Fe and 12C in order to investigate the measurement of substitutional (Fe) versus interstitial (C) tracer diffusion and the cross effect of both substitutional and interstitial diffusion. When C alone was implanted negligible diffusion was observed over the range of times and temperatures investigated. When both Fe and C were implanted together significantly enhanced diffusion of the C was observed, which is apparently associated with the movement of Fe. This supports one theory of dynamic strain aging in Fe alloyed NiAl.


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