Amorphous silicon formed in situ as negative electrode reactant in lithium cells

Netz, Andreas; Huggins, Robert A.

doi:10.1016/j.ssi.2003.11.048

Cited by 48 publications

(33 citation statements)

References 12 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…10,11 Kim et al verified the above reaction mechanism by a solid-state 29 Si and 7 Li nuclear magnetic resonance technique, electrochemical dilatometry, and charge-discharge measurement. 12 A reaction at amorphous Si domains is an alloying reaction that occurs reversibly to give the charge-discharge capacity.…”

Section: Resultsmentioning

confidence: 90%

Kinetics of Electrochemical Insertion and Extraction of Lithium Ion at SiO

Yamada

Iriyama

Abe

et al. 2010

J. Electrochem. Soc.

135

View full text Add to dashboard Cite

The kinetics of the electrochemical insertion and extraction of lithium ion at silicon monoxide ͑SiO͒ were investigated by ac impedance spectroscopy. The resultant Nyquist plots showed two semicircles at high and middle frequency regions. These two semicircles were attributed to lithium-ion transport resistance in a surface film and alloying reaction resistance ͑charge-transfer resistance͒, respectively. We evaluated the activation energies of the charge-transfer reaction from the temperature dependences of the interfacial conductivities. When an ethylene-carbonate-based electrolyte was used, the activation energy of the charge transfer was 32 kJ mol −1 . This activation energy was much smaller than those at graphite electrode or positive electrode materials ͑around 50 kJ mol −1 or more͒. Based on these results, the charge transfer at SiO is exceptionally fast compared to those at other insertion materials. Furthermore, the activation energies of the charge transfer at SiO remained unchanged in various electrolytes. These results suggest that the charge-transfer kinetics at SiO is not influenced by the desolvation of lithium ion from solvent molecules. Lithium-ion batteries have recently attracted much attention as a power source for electric vehicles ͑EVs͒ and plug-in hybrid EVs. These applications of lithium-ion batteries give severe requirements to electrode materials. One such requirement is a significant improvement in the energy density of electrode materials. Therefore, an alternative electrode material has been explored for a much higher energy density. Among the candidates for a new negative electrode are alloying materials such as Si and Sn.1,2 These materials electrochemically react with lithium to form a lithium alloy that has an extremely high energy density compared to graphite. However, the alloying reaction shows a large volume change in the materials, 3 which leads to capacity fade during charge-discharge cycles. 4 To overcome the problem, silicon monoxide ͑SiO͒ has recently attracted much attention as a next generation negative electrode. 5-13SiO shows a small volume change because it contains a relatively small amount of Si element that is active for the alloying reaction. The discharge capacity of SiO electrodes was reported to be over 600 mAh g −1 in several papers, 9-12 which is much higher than that of a graphite electrode ͑372 mAh g −1 ͒. To commercialize the SiO electrode, we need to consider the rate performance in addition to the energy density. However, there are few reports on the kinetic aspect of alloying materials. Our group focused on the kinetics of charge ͑lithium ion͒-transfer reactions at a graphite/electrolyte interface 14,15 and other interfaces. [16][17][18][19] The activation energies of the charge-transfer reactions were around 50 kJ mol −1 or more, which were higher compared to those of lithium-ion transport in solid [20][21][22][23] or liquid [24][25][26] electrolytes. This is because the desolvation of lithium ion from solvents occurs during the charge transfer at the...

show abstract

Section: Resultsmentioning

confidence: 90%

Kinetics of Electrochemical Insertion and Extraction of Lithium Ion at SiO

Yamada

Iriyama

Abe

et al. 2010

J. Electrochem. Soc.

135

View full text Add to dashboard Cite

show abstract

“…In recent years, lots of efforts have been put in exploring anode materials with higher specific capacities over graphite. Silicon-based materials have attracted considerable research attentions as one of the most promising anode materials for lithium-ion batteries because of its highest theoretical capacity (4,200 mAh g −1 ) during the formation of Li4.4Si alloys (Netz and Huggins, 2004;Chan et al, 2008;Teki et al, 2009;Winter et al, 2010;Ji et al, 2011;Yue et al, 2013;Wang et al, 2015). However, the huge volume changes during lithiation and de-lithiation process always leads to poor cycle performance and electrical contact, which severely hinders the industrial applications of silicon-based anode materials (Candace et al, 2009;Hertzberg et al, 2010;Bo et al, 2016;Li et al, 2016Li et al, , 2017.…”

mentioning

confidence: 99%

Si@SiOx/Graphene Nanosheets Composite: Ball Milling Synthesis and Enhanced Lithium Storage Performance

Tie¹,

Han

Liang³

et al. 2018

Front. Mater.

View full text Add to dashboard Cite

“…Netz et al reported SiB 3 as a Li-ion anode, having 440 mAh/g reversible capacity. [18][19] However, there is no mention in the study by Netz et al of where the SiB 3 was obtained from, and diffraction patterns are not shown. Confirmation of their results is needed.…”

mentioning

confidence: 99%

The Electrochemistry of Amorphous Si-B Thin Film Electrodes in Li Cells

Liu

Zhu

et al. 2015

J. Electrochem. Soc.

View full text Add to dashboard Cite

Si1-xBx thin films of 0.071 ≤ x ≤ 0.950 have been synthesized using combinational sputtering. All Si1-xBx film compositions had a highly amorphous structure consisting of amorphous Si and B phases, as characterized by X-ray diffraction. In Li cells, it was found that all of the Si is active and the B is inactive with lithium. Otherwise, the Si1-xBx films have similar characteristics as pure Si film electrodes in Li cells, except with reduced capacity due to the added B. However, shifts in the voltage curves appear when the B content is increased that may be induced by stress-voltage coupling between the active Si and the inactive B phases.

show abstract

Amorphous silicon formed in situ as negative electrode reactant in lithium cells

Cited by 48 publications

References 12 publications

Kinetics of Electrochemical Insertion and Extraction of Lithium Ion at SiO

Kinetics of Electrochemical Insertion and Extraction of Lithium Ion at SiO

Si@SiOx/Graphene Nanosheets Composite: Ball Milling Synthesis and Enhanced Lithium Storage Performance

The Electrochemistry of Amorphous Si-B Thin Film Electrodes in Li Cells

Contact Info

Product

Resources

About