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Article history:
Received 23 May 2014
Received in revised form
22 July 2014
Accepted 23 July 2014
Available online 1 August 2014
Silicon is a promising anode material for lithium-ion batteries due to its enormous theoretical energy
density. Fracture during electrochemical cycling has limited the practical viability of silicon electrodes,
but recent studies indicate that fracture can be prevented by taking advantage of lithiation-induced
plasticity. In this paper, we provide experimental insight into the nature of plasticity in amorphous
LixSi thin lms. To do so, we vary the rate of lithiation of amorphous silicon thin lms and simultaneously
measure stresses. An increase in the rate of lithiation results in a corresponding increase in the ow
stress. These observations indicate that rate-sensitive plasticity occurs in a-LixSi electrodes at room
temperature and at charging rates typically used in lithium-ion batteries. Using a simple mechanical
model, we extract material parameters from our experiments, nding a good t to a power law relationship between the plastic strain rate and the stress. These observations provide insight into the unusual ability of a-LixSi to ow plastically, but fracture in a brittle manner. Moreover, the results have
direct ramications concerning the rate-capabilities of silicon electrodes: faster charging rates (i.e., strain
rates) result in larger stresses and hence larger driving forces for fracture.
2014 Elsevier B.V. All rights reserved.
Keywords:
Lithium-ion batteries
Silicon
Plasticity
Fracture
Strain rate sensitivity
Creep
1. Introduction
Silicon has been identied as a promising anode material for
lithium-ion batteries due to its ability to host a large amount of
lithium [1]. Lithiation of silicon, however, causes an enormous
* Corresponding author. Tel.: 1 617 496 0424; fax: 1 617 495 9837.
E-mail address: vlassak@seas.harvard.edu (J.J. Vlassak).
http://dx.doi.org/10.1016/j.jpowsour.2014.07.153
0378-7753/ 2014 Elsevier B.V. All rights reserved.
570
2. Experimental results
Using the substrate curvature technique, we measure stresses in
thin-lm electrodes of amorphous silicon during electrochemical
testing. Details can be found in the Experimental procedure section.
As a brief summary, 100 nm lms of amorphous silicon on a glass
substrate are lithiated and delithiated galvanostatically at a C/8 rate
571
Fig. 3. Components of the strain rate in the 100 nm thin-lm Si electrode subject to
the electrochemical cycling conditions shown in Fig. 1. The thick blue line indicates the
prescribed lithiation-induced strain rate, L b/[3(1 bs)],ds/dt. The thin purple line
indicates the elastic component of the strain rate, E (1 nf)/Ef,ds/dt. The thin orange
line represents the plastic component of the strain rate, P 1/lP,dlP/dt, as calculated
from Eq. (7). (For interpretation of the references to colour in this gure legend, the
reader is referred to the web version of this article.)
Fig. 2. (a) Stress measured in the 100 nm thin-lm Si electrode subject to the electrochemical cycling conditions shown in Fig. 1. (b) A zoomed-in view that focuses on
the second cycle. The line thickness increases with the charging rate. The vertical
dashed line indicates the point at which the set of charging rates is repeated. A change
in the charging rate results in a signicant change in the stress.
ij
Lij
Eij
Pij ;
(3)
where Vf0 is the initial volume of the lm, b is related to the atomic
volumes (U) by b ULi15 Si4 USi =USi, and s is the state of charge,
with a value of 0 representing pure silicon and a value of 1 representing the fully lithiated state (assumed to be a-Li15Si4 with a
capacity of 3579 mAh g1) [36]. Obrovac et al. found a 280% increase in the volume of silicon upon reaching the fully lithiated
state of Li15Si4 [36], i.e., b 2.8. Using atomic force microscopy, He
et al. and Beaulieu et al. measured similar values in patterned
amorphous silicon lms [37,38]. Both groups found that the volume
increased linearly with lithium concentration [37,38].
Due to the amorphous nature of LixSi, the lithiation-induced
deformation is assumed to be isotropic, such that the stretch ratios are equal, lL1 lL2 lL3 lL . As in Ref. [5], we take
lL (1 bs)1/3. By denition, the in-plane component of the true
lithiation-induced strain is L ln(lL), such that.
L
(1)
1
ln1 bs:
3
(4)
where Lij represents the true lithiation-induced strain, Eij represents the true elastic strain, and Pij represents the true plastic strain.
For a thin lm on a thick substrate, the state of stress is equi-biaxial,
s11 s22 s, with all other components of the stress vanishing.
Due to the constraint of the substrate, the total in-plane components of the strain vanish, 11 22 0. Eq. (1) becomes
L E P 0;
Vf Vf0 1 bs;
(2)
1 nf
s;
Ef
(5)
P ln lP :
(6)
572
"
1 dlP
d 1 nf
b
ds
:
P
s
dt
31
bs
dt
dt
E
l
f
(7)
1 dlP
b
ds
:
P
31 bs dt
l dt
(8)
1 dlP
s sY m
A
P
;
sY
l dt
(9)
3m
s
s
s
s
Y
C=8
C=8
1 dl
5 ;
A4
P
l dt
sC=8 sC=8 sY
P
2
(10)
where sC/8 represents the stress at the nominal charging rate of C/8,
and all of the stresses represent the magnitude of the measured
stresses (positive quantities). We assume that (sC/8 sY) is constant, independent of the lithium concentration over the range of
concentrations considered in the experiments. After each change in
the charging rate, we measure the quantity (s sC/8). We also
Fig. 4. Plastic strain rate (in units of s1) versus the change in measured stress relative
to the C/8 rate (in units of MPa). The solid red circles represent the experimental data
and the open black circles represent the phenomenological model presented in Eq.
(10). (For interpretation of the references to colour in this gure legend, the reader is
referred to the web version of this article.)
sC/8 e sY (MPa)
R2
0.00175
0.00230
0.00168
4.07
2.94
2.58
130
94.1
82.9
0.947
0.937
0.892
573
574
s sr
Es h2s
DK;
6hf 1 ns
(11)
hf h0f 1 bs;
(12)
DK
d0 d hcos ai na
;
d0
2L
ne
(13)
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