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2015 ; 5
(1
): 233-245
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New Insights into Understanding Irreversible and Reversible Lithium Storage
within SiOC and SiCN Ceramics
#MMPMID28347008
Graczyk-Zajac M
; Reinold LM
; Kaspar J
; Sasikumar PV
; Soraru GD
; Riedel R
Nanomaterials (Basel)
2015[Feb]; 5
(1
): 233-245
PMID28347008
show ga
Within this work we define structural properties of the silicon carbonitride
(SiCN) and silicon oxycarbide (SiOC) ceramics which determine the reversible and
irreversible lithium storage capacities, long cycling stability and define the
major differences in the lithium storage in SiCN and SiOC. For both ceramics, we
correlate the first cycle lithiation or delithiation capacity and cycling
stability with the amount of SiCN/SiOC matrix or free carbon phase, respectively.
The first cycle lithiation and delithiation capacities of SiOC materials do not
depend on the amount of free carbon, while for SiCN the capacity increases with
the amount of carbon to reach a threshold value at ~50% of carbon phase.
Replacing oxygen with nitrogen renders the mixed bond Si-tetrahedra unable to
sequester lithium. Lithium is more attracted by oxygen in the SiOC network due to
the more ionic character of Si-O bonds. This brings about very high initial
lithiation capacities, even at low carbon content. If oxygen is replaced by
nitrogen, the ceramic network becomes less attractive for lithium ions due to the
more covalent character of Si-N bonds and lower electron density on the nitrogen
atom. This explains the significant difference in electrochemical behavior which
is observed for carbon-poor SiCN and SiOC materials.