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Li Permeability Increase in Nano-Sized Amorphous Silicon Layers Erwin Hüger, and Harald Schmidt J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.8b09719 • Publication Date (Web): 27 Nov 2018 Downloaded from http://pubs.acs.org on December 2, 2018
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The Journal of Physical Chemistry
Lithium Permeability Increase in Nano-Sized Amorphous Silicon Layers Erwin Hüger*,a, and Harald Schmidta,b a. Institut für Metallurgie, Abteilung Mikrokinetik, Technische Universität Clausthal, Robert-Koch-Str. 42, 38678 Clausthal Zellerfeld, Germany b. Clausthaler Zentrum für Materialtechnik (CZM), Technische Universität Clausthal, Leibnizstraße 9, 38678 Clausthal-Zellerfeld, Germany Abstract. Li permeation through nano-sized amorphous Si layers is investigated for temperatures up to 500°C (773 K) as a function of layer thickness between 12 and 95 nm. For the experiments the Si layers are embedded between 6Li and 7Li isotope enriched oxide based Li reservoirs and the thermally induced isotope exchange (through silicon layers and interfaces) is analyzed by Secondary Ion Mass Spectrometry in order to calculate Li permeabilities. The experiments reveal that the interface between silicon and the Li metal oxide does not hinder Li permeation and Li diffusion in silicon controls the overall process. The determined Li permeability increases drastically by orders of magnitude with decreasing silicon layer thickness, accompanied by a decrease in the activation enthalpy of Li permeation. These results can be explained by a gradual transition of trap-limited slow Li diffusion at high silicon thicknesses to interstitial fast Li diffusion at low Si thicknesses.
Introduction Ionic transport of lithium through thin layers and interfaces is an important topic of current academic and industrial research, especially in the field of Li-ion batteries (LIB).1-8 Interfaces as well as slow diffusion in layers can limit Li transport and consequently influence drastically the overall device performance. Consequently, it is of high interest to get fundamental insight into the nature of the limiting process. Recently, we introduced a new method which enables the measurement of Li permeation through nanosized layers.9-12 Reference 11 describes in detail how Li transport parameters can be determined using silicon as a model system. The aim of the present work is to study the influence of size reduction (layer thickness) and of interfaces on Li transport in amorphous silicon as a function of temperature. Figure 1 presents the basic principle of our method. Two isotope enriched 6LiNbO3 and 7LiNbO3 layers, as tracer reservoirs, are adjacent to a Si layer. Annealing leads to a dissolution of Li into silicon up to the maximum solubility limit ( 1.7) found an average activation enthalpy for Li diffusion of about 0.6 eV. This value is similar to that found in this work for Li diffusion in the thinnest amorphous Si layer (Figure 8(b)). Tracer diffusion investigations on amorphous LixSi with a lower Li content of x = 0.02 and 0.06 in 180 nm thick films gave a higher enthalpy of Li diffusion of 1.42 eV.93 This value is similar to that found in this work for the thickest amorphous Si layers (Figure 8(b)). The change of the activation enthalpy for Li diffusion in LixSi material for a different Li content can be attributed to a change in the diffusion mechanism.93 Trap-limited Li diffusion is present in low Li content material (H ~ 1.4 eV) and direct interstitial Li diffusion is present in high Li content material (H ~ 0.6 eV). These results from the literature confirm the findings
Figure 10: Sketch of Li permeation in Si layers. Li diffusion paths are indicated by curved lines. Black lines show diffusion paths where traps (black dotes) are touched and red lines represent trap-free fast Li diffusion paths which becomes predominant in thinner Si layer.
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The Journal of Physical Chemistry a decrease of the dimension of the material (here: silicon layer thickness) has an additional benefit for transport properties: It increases also the Li permeability, P.
of the present paper that diffusion takes place via a traplimited diffusion mechanism in thick amorphous silicon or LixSi layers with low x. The transition to a fast interstitial diffusion mechanism seems to be not only possible by reducing the film thickness but also by an increase in Li concentration.
In contrast to the experiments described here, during lithiation of silicon electrodes in LIBs an electrochemical driving force is present. This changes the Li content of the Si layer well above the Li solubility limit by alloy formation. Microscopy experiments as given in literature indicate that the electrochemical lithiation mechanism of crystalline101 and amorphous102,103 silicon electrodes may proceed by the movement of a reaction interface. The reaction front delimits a highly lithiated phase (LixSi, x>2) situated next to the electrolyte, from a (nearly) nonlithiated phase (silicon), situated next to the current collector (see Figure 12 of ref 11). As described in ref 11, it was found that the Li permeability in the non-lithiated phase is 23 orders of magnitude lower than that in the highly lithiated LixSi phase. This means that non-lithiated silicon actually blocks Li transport and reduces lithiation rates. Therefore, the higher Li permeability measured in this work for thin layers may contribute to a better and faster distribution of Li in nanosized silicon electrodes. This will give an additional benefit to the items discussed above.
Notice that although the described trap-free Li diffusion scenario is a very plausible explanation of the observed size effect, a layer thickness dependence of the Li solubility (content) in silicon would also explain the experimental findings. According to eq 1, the Li permeability increases also if the Li solubility increases in thinner Si layers for a constant diffusivity. An example of Li solid solubility enhancement by size reduction is given in literature for FePO4 (Li0.05FePO4). The Li solubility limit increases in FePO4 particles with sizes below 35 nm.94,95 The relevance of a dependence of Li solubility on Si layer thickness for the present results has to be further investigated in future. An increase of Li solubility may also imply accelerated Li diffusion. Li diffusion in amorphous LixSi material (for low Li concentration) becomes faster if Li concentration increases.93 Traps can be saturated by Li atoms, at least partly. The higher Li concentration has the consequence that the number of unsaturated traps is reduced and Li diffusion is accelerated.93 Hence both effects, i.e., an increase of Li solubility and of Li diffusivity, might contribute to the observed increased Li permeability in thinner Si layers. Theoretical work (calculations) for a fundamental understanding and support of the Li permeation size effect found in this experimental work would be highly desirable.
Experimental section ML films as sketched in Figure 2(a,f) were deposited using an ion-beam coater. The depositions were performed at room temperature. The MLs were stored in air also at room temperature. Annealing was performed in a commercial rapid thermal annealing setup in argon gas. SIMS was applied to determine the element and isotope resolved depth profiles of the ML species. Further investigations were done with X-ray reflectometry and Xray diffractometry. All measurements were performed at room temperature. More details are given in SI and ref 11.
Implication of the results for LIB design Silicon as a negative electrode material could play an important role for an increased Li storage capacity in LIBs. It can theoretically store 20 times more Li atoms per active host atom (Li21Si6) than graphite (LiC6), the active material of commercial negative electrodes.8,54-65
Conclusion
In comparison to bulky Si materials, nano-sized Si electrodes in LIBs composed of nanoparticles, thin layers or nanotubes possess a better electrochemical performance such as a higher capacity and better capacity retention during battery cycling.1-8,54-65,96-100 This can be traced back to a better mechanical stress tolerance and to shorter diffusion lengths and times for smaller sized materials.1-8,54-65,96-100 Materials with a shorter size (l) demand also shorter diffusion/permeation times (t) than larger sized materials for a given diffusivity according to t
l2 . 2D
Li permeation in amorphous silicon layers was experimentally determined at temperatures up to 500°C (773 K) of dependence on silicon layer thickness ranging from 12 to 95 nm. Silicon was embedded between 10 nm thin 6Li and 7Li enriched LiNbO3 layers and the exchange of the isotopes was monitored by secondary ion mass spectrometry. The LiNbO3 layers serve solely as solidstate Li reservoirs. The silicon layers effectively block Li permeation for more than four years at room temperature. At higher temperatures 6Li and 7Li isotope exchange through the silicon layer takes place. The overall process is not limited by the silicon / LiNbO3 interface but controlled by the diffusion in silicon. Thinner silicon layers behave differently compared to thicker silicon layers regarding Li permeation. Li
(6)
Consequently, the active material can be equilibrated with Li in shorter time periods. This work has shown that
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permeation through silicon and Li permeability of silicon is enhanced by orders of magnitude by reducing the silicon layer thickness. The activation enthalpy for Li permeation is also dependent on the silicon layer thickness. It increases from (1 ± 0.2) eV for the thinner silicon layers to (2 ± 0.2) eV for the thicker silicon layers. This can be explained by a gradual change of the associated Li diffusion behaviour from trap-free fast interstitial migration in thinner silicon layers to trapcontrolled slow diffusion in thicker silicon layers.
ASSOCIATED CONTENT Supporting Information. It contains details on layer thickness determination, Li solubility determination, additional SIMS data and details on error analysis. The Supporting Information is available free of charge on the ACS Publications website.
AUTHOR INFORMATION Corresponding Author * e-mail:
[email protected] Author Contributions The manuscript was written through contributions of all authors. / All authors have given approval to the final version of the manuscript.
COI Statement The authors declare no competing financial interest. Funding Sources Deutsche Forschungsgemeinschaft (DFG) under the contract HU 2170/2-1.
ACKNOWLEDGMENT Financial support from the Forschungsgemeinschaft (DFG) under the 2170/2-1 is gratefully acknowledged. Thanks Dörrer (TU Clausthal) for his assistance analyses and to E. Witt and P. Heitjans (U preparing the LiNbO3 sputter targets.
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Deutsche contract HU are due to L. during SIMS Hannover) for
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