Ni<sub>x</sub>Si<sub>1-x</sub>Alloys Prepared by Mechanical Milling as Negative Electrode Materials for Lithium Ion Batteries

Du, Zhijia; Ellis, Sarah N.; Dunlap, R. A.; Obrovac, M. N.

doi:10.1149/2.0011602jes

Cited by 53 publications

(70 citation statements)

References 26 publications

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“…The differential capacity curves are very similar to the ball milled Ni 0.35 Si 0.65 samples in our previous study. 13 In our recent papers on sputtered and ball milled NiSi alloys, 13,14 we have found that inactive alloy components depress the lithiation voltage of Si. We suggested that this was because these inactive components applied stress to the active Si phase as it expands during lithiation.…”

Section: Resultsmentioning

confidence: 99%

“…Similarly, Park et al reported that the NiSi 2 phase was also inactive because its XRD peaks were unchanged during cycling between 5 mV and 1.5 V. 12 Recently, we have studied the electrochemical behavior of ball milled Ni x Si 1-x alloys. 13 These alloys were found to consist of nanocrystalline Si and NiSi 2 for 0 < x ≤ 0.30. However, the reversible capacity dependence on x is not consistent with the hypothesis that NiSi 2 is inactive.…”

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confidence: 99%

“…In these alloys capacity was further reduced by the depression of the voltage curve, which we suggested was due to stress-voltage coupling. 13 The different preparation methods in the above studies result in different microstructures and are likely the cause of the disparate reaction mechanisms. In the present study, crystalline NiSi 2 (c-NiSi 2 ) and nanocrystalline NiSi 2 (n-NiSi 2 ) are prepared and their behavior as anodes in Li-ion cells is studied to better understand the effect of microstructure on their electrochemistry.…”

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confidence: 99%

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Electrochemical Activity of Nano-NiSi₂in Li Cells

Hatchard

Bissonnette

et al. 2016

J. Electrochem. Soc.

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Crystalline and nanocrystalline NiSi 2 were studied as negative electrode materials in Li cells. Crystalline NiSi 2 was found to be inactive toward lithiation/delithiation. However, it was found that NiSi 2 becomes active toward lithium when made nanocrystalline by ball milling. X-ray diffraction peaks from nanocrystalline NiSi 2 disappear after the first lithiation process, confirming its electrochemical activity. In subsequent cycles, the voltage curve of nanocrystalline NiSi 2 is similar to that of amorphous Si, excepting that there is significant depression of the lithiation potential, which may arise from internal stress.

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Section: Resultsmentioning

confidence: 99%

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Electrochemical Activity of Nano-NiSi₂in Li Cells

Hatchard

Bissonnette

et al. 2016

J. Electrochem. Soc.

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“…12 In contrast to SPEX milling in which products can reach a steady state in hours/days, steady state conditions are typically achieved only after weeks of roller milling. [12][13][14] It occurred to us that the low energy milling regime was not fully explored for the SPEX milling method because it is generally believed that only high energy impacts contribute to alloying, as discussed above. By making the ball size substantially smaller than what is typically used, the impact energy in a SPEX mill could be greatly reduced.…”

Section: Introductionmentioning

confidence: 99%

Rapid mechanochemical synthesis of amorphous alloys

2017

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A rapid method for preparing amorphous alloys has been developed utilizing a SPEX high energy ball mill. Parameters such as ball size, mass of balls and milling time, were systematically optimized to prepare amorphous alloys quickly. Amorphous alloys previously not thought possible to synthesize by means of SPEX milling were made amorphous by the new method. When applied to the preparation of Sn-Co-C and Si-Fe alloys, the method was found to produce fully amorphous alloys in a matter of hours instead of days or weeks of milling by traditional techniques. Electrochemical performance of the alloys produced by the rapid milling technique in Li cells was found to be the same or superior to alloys produced by the more time consuming methods, confirming their amorphous microstructure.

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“…Reducing Li uptake and providing an inactive phase framework is one possible way to alleviate the expansion problem. Some inactive M-Si alloys, such as Ni-Si, [2][3][4] Fe-Si, 5 Cu-Si, 6 B-Si, 7 have been extensively studied in the past two decades.…”

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Lithium Insertion in Nanostructured Si_1-xTi_xAlloys

Wang

Cao

Kalinina

et al. 2017

J. Electrochem. Soc.

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Nanostructured Si 1-x Ti x alloys (0 ≤ x ≤ 0.3) prepared by ball milling were studied as negative electrode materials in Li cells. The alloys comprised a nanocrystalline and amorphous Si phase and a nanocrystalline C49 TiSi 2 phase. When x ≥ 0.15 the nanocrystalline Si phase was completely eliminated and such alloys consisted only of amorphous Si and the C49 TiSi 2 phase. The alloys with x ≥ 0.15 also completely suppressed the formation of Li 15 Si 4 during cycling, resulting in good capacity retention, and, unlike other Si transition metal alloys, without introducing noticeable cell polarization. The observed capacity of the Si 1-x Ti x alloys suggested that the TiSi 2 is an inactive phase toward Li. Silicon-based materials are of high interest in the pursuit of obtaining higher energy density lithium ion batteries. Pure silicon has an outstanding theoretical capacity of 2194 Ah/L, which has been estimated to provide an increase in energy density of up to 34% in Li-ion cells, compared to cells with conventional graphite-based electrodes. However, the cycle life of Si electrodes is difficult to maintain because of its drastic volume expansion during lithiation (up to 280%). Reducing Li uptake and providing an inactive phase framework is one possible way to alleviate the expansion problem. Some inactive M-Si alloys, such as Ni-Si, 2-4 Fe-Si, 5 Cu-Si, 6 B-Si, 7 have been extensively studied in the past two decades.Si-Ti alloys are of interest as electrode materials for Li-ion batteries because of their thermal stability and because they are composed of high abundance elements. They also have low density and TiSi 2 has high electrical conductivity compared to other silicides. 8 Because of these favorable properties, this system has been studied by other groups in the past. Lee et al. synthesized Si-Ti alloys via melt spinning, forming alloys comprised of well crystallized Si and TiSi 2 phases. 9The observed capacities of these samples in Li cells were far less than expected from the amount of Si present. All the Si in these samples might not have been fully accessible to lithium ions because of the morphology that resulted from rapid solidification processing. Zhou et al. synthesized Si coated TiSi 2 nanonets via chemical vapor deposition.10 When the nanonets were cycled between 0.03-3.0 V, high capacity fade during cycling resulted because of the formation of Li 15 Si 4 . When cycling was conducted above 0.09 V, capacity retention was improved because the formation of Li 15 Si 4 was avoided. This indicates the importance of avoiding Li 15 Si 4 formation to obtain good cycling performance. Park et al. designed a TiSi 2 -coated Si anode via a silicothermic reduction process.11 The conductive silicide coating resulted in improved rate performance. It is apparent from these studies that microstructure and Li 15 Si 4 avoidance is important in obtaining good cycling in Si-Ti alloys. However, to our knowledge a systematic study of the effect of composition in the Si-Ti alloy system has not previously been reported.Here a...

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Ni_xSi_1-xAlloys Prepared by Mechanical Milling as Negative Electrode Materials for Lithium Ion Batteries

Cited by 53 publications

References 26 publications

Electrochemical Activity of Nano-NiSi₂in Li Cells

Electrochemical Activity of Nano-NiSi₂in Li Cells

Rapid mechanochemical synthesis of amorphous alloys

Lithium Insertion in Nanostructured Si_1-xTi_xAlloys

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NixSi1-xAlloys Prepared by Mechanical Milling as Negative Electrode Materials for Lithium Ion Batteries

Cited by 53 publications

References 26 publications

Electrochemical Activity of Nano-NiSi2in Li Cells

Electrochemical Activity of Nano-NiSi2in Li Cells

Rapid mechanochemical synthesis of amorphous alloys

Lithium Insertion in Nanostructured Si1-xTixAlloys

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Product

Resources

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Ni_xSi_1-xAlloys Prepared by Mechanical Milling as Negative Electrode Materials for Lithium Ion Batteries

Electrochemical Activity of Nano-NiSi₂in Li Cells

Electrochemical Activity of Nano-NiSi₂in Li Cells

Lithium Insertion in Nanostructured Si_1-xTi_xAlloys