Journal of Power Sources 377 (2018) 7–11

Contents lists available at ScienceDirect

Journal of Power Sources

journal homepage: www.elsevier.com/locate/jpowsour

Correlating the interface resistance and surface adhesion of the Li metal- T

solid electrolyte interface
Michael Wanga, Jeff Sakamotoa,b,∗
a
Department of Materials Science & Engineering, University of Michigan, Ann Arbor, MI 48109, USA
b
Department of Mechanical Engineering, University of Michigan, Ann Arbor, MI 48109, USA

H I G H L I G H T S G RA P H I C A L AB S T R A C T

• Li-solid electrolyte interface strength

is correlated with interfacial re-
sistance.
• Low interfacial resistance is correlated
with a strong Li-LLZO interface.
• The adhesion between Li-LLZO can
exceed the ultimate tensile strength of
Li.
• Presents a method of quantifying the
wettability of Li on LLZO at room
temperature.

A R T I C L E I N F O A B S T R A C T

Keywords: Solid electrolytes could enable stable cycling of metallic Li anodes, which can offer drastic increases to the
Solid-state electrolyte capacity of Li-ion batteries. However, little is known about the mechanics of the Li-solid electrolyte interface.
Li This study combines electrochemical and mechanical characterization to correlate interface kinetics with ad-
Buried interface hesive strength. Cubic garnet with the Li6·25Al0·25La3Zr2O12 (LLZO) formulation was selected as a model solid
Interface adhesion
electrolyte based on its high conductivity and stability against Li metal. Symmetric Li-LLZO cells were tested
using electrochemical impedance spectroscopy to determine the interfacial resistance, Rint, and the adhesive
strength of the Li-LLZO interface, σadh, was measured using a unique tensile test in an inert atmosphere. It was
determined that the Rint is directly correlated to the adhesive strength of Li on LLZO. At the highest Rint in this
study, 330 k·cm2 the σadh was 1.1 kPa and at the lowest Rint in this study, 7 ·cm2, σadh was 8 MPa. Furthermore,
by optimizing the surface chemistry the wettability of LLZO was enhanced resulting in σadh exceeding the ul-
timate tensile strength of Li metal. The relationship demonstrated provides a deeper understanding of the me-
chanical properties of the Li-electrolyte interface, which will play an important role in the design of batteries
employing metallic Li anodes.

1. Introduction
In recent years, solid state electrolytes have garnered interest as
potential materials to enable the usage of Li metal anodes for high
energy density batteries [1,2]. Unlike in conventional liquid electro-
lytes, solid state electrolytes not only offer the ability to conduct Li ions
but also act as a physical barrier to prevent dendrite penetration and
parasitic SEI side reactions, which limit the use of Li metal in state-of-
the-art cells [3,4]. The family of ceramic oxides with the garnet struc-
ture has shown promise as candidates for a solid electrolyte to use with
Li metal. The cubic phase of Li7La3Zr2O12 (LLZO) in particular has
shown potential due to its high ionic conductivity (∼1 mS/cm2) and

∗
Corresponding author. Department of Materials Science & Engineering, University of Michigan, Ann Arbor, MI 48109, USA.
E-mail address: jeffsaka@umich.edu (J. Sakamoto).

https://doi.org/10.1016/j.jpowsour.2017.11.078
Received 12 August 2017; Received in revised form 13 November 2017; Accepted 25 November 2017
0378-7753/ © 2017 Elsevier B.V. All rights reserved.
M. Wang, J. Sakamoto
stability against Li metal [5–8]. In order to successfully incorporate Li
metal anodes into solid state batteries, it is imperative that the interface
is sufficiently stable and the charge transfer kinetics are sufficiently fast
for facile stripping and plating of Li metal. Currently there is a
knowledge gap in the understanding of the mechanical behavior of Li
metal, as well as the mechanics and properties at the LLZO-Li metal
interface. Because of its instability in air, it is difficult to characterize Li
metal using conventional techniques and even more difficult to char-
acterize the mechanics of the metal-solid electrolyte interface since it is
buried. Computational methods have been used to study the mechan-
ical properties of Li metal [9], but few experiments have been able to
verify these calculations. One study in particular was able to investigate
the mechanical behavior of nanoscale Li pillars [10], however there
have not been many other studies that have been able to determine the
mechanical properties of Li metal. It is clear by the lack of experimental
data on pure Li metal that there are many challenges in thoroughly
studying the mechanics of the Li-electrolyte interface. However, in
order to mature Li metal electrode technology, a deeper understanding
of the relationship between electrochemical and mechanical properties
of this metal-electrolyte interface is needed.
One of the biggest challenges in pairing most oxide electrolytes with
metallic Li has been high interfacial resistance [11,12]. Recently, it was
demonstrated that layers of Li2CO3 spontaneously form on the surface
of the LLZO in humid air, which results in significant increases in the
interfacial impedance [13]. Furthermore, a recent study compared the
wettability of LLZO to the wettability of Li2CO3 and showed that the
wettability of LLZO can be greatly improved by removing Li2CO3 con-
tamination from the surface [14]. It is clear from these two studies that
the degree of surface chemistry between Li metal and LLZO is not only
related to the morphology of the LLZO surface features, but is also
strongly related to the degree of contamination on the LLZO surface.
However, currently there are no known methods of quantifying the
wettability of a surface at room temperature. Since the wettability is
typically measured for liquids or molten materials, the wettability of Li
metal on a surface must be measured at temperatures above the melting
point. This not only presents experimental challenges, but can also only
provide information on the behavior of the liquid-solid interface and
not a solid-solid interface, which is not representative of typical oper-
ating conditions. Since the wettability of Li on LLZO is an indication of
chemistry at the interface, which not only correlates to low impedances,
it should also correlate to a strong interfacial bond between the two
surfaces. This leads to the hypothesis that the Li-LLZO interfacial re-
sistance, Rint, should be intrinsically linked to the strength of the Li-
LLZO adhesive bond, σadh. The goal of this work is to explore this re-
lationship between the interfacial resistance and the mechanical
strength of the interface to demonstrate intrinsic links between the
electrochemical and physical properties of the Li-LLZO interface at
room temperature.
To correlate Rint, with σadh, all solid-state Li-LLZO-Li cells were
fabricated and characterized using conventional electrochemical tech-
niques and a mechanical testing apparatus. Rint was measured using
electrochemical impedance spectroscopy (EIS) as a function of surface
treatment, which affected the surface chemistry. σadh was measured
with a unique tensile tester in an inert gas atmosphere. The observed
correlation agrees with the hypothesized relationship between the in-
terfacial resistance and interfacial strength and may provide further
insight into the interactions between Li metal and oxide electrolytes.
2. Experimental
2.1. Material synthesis and processing
Al-stabilized cubic LLZO with nominal composition
Li6·25La3Zr2Al0·25O12 was prepared by a solid state synthetic method.
The starting precursors, Li2CO3 (1 μm, Alfa Aesar, Ward Hill, MA), La
(OH)3 (1 μm, Alfa Aesar, Ward Hill, MA), Al2O3 (0.05 μm, Mager
8
Journal of Power Sources 377 (2018) 7–11
Scientific Inc. Dexter, MI), and ZrO2 (30–60 nm, Inframat, Advanced
Materials, Manchester, CT) were weighed with the appropriate stoi-
chiometry and were milled in ethanol on a roller mill for 20 h s. A 5 wt
% excess amount of Li2CO3 was added to the precursors to account for
volatilization during the calcination process. The powders were dried,
cold-pressed, and calcined at 1000 °C for 4 h s in dry air. The resulting
pellets were ground into powders and then hot-pressed at 1100 °C
under 47 MPa for one hour, using a rapid-induction hot-pressing
technique as described by Rangasamy et al. [15]. The resulting pellet
was then cut into 1.5 ± 0.2 mm thick samples using a diamond saw
and polished with sandpapers and diamond pastes of varying degree,
ranging between a final polish of 1200grit to a 1 μm polish. In order to
minimize the exposure to air, the LLZO specimens were stored in an Ar-
filled glovebox. Before testing, some LLZO samples were heat treated at
400 °C temperature for 3 h s inside the glovebox in order to remove the
Li2CO3 surface layers.
2.2. Solid-state cell assembly
Symmetric Li-LLZO-Li cells were fabricated using the same proce-
dure reported by Sharafi et al. [11]. Li foils (Alfa Aesar), 750 μm thick,
were scraped to remove any oxide layers from the surface and then
pressed onto each side of the LLZO disc. To fabricate cells with high
Rint, the Li foil was simply pressed onto the LLZO by hand at room
temperature and then tested. To fabricate cells with lower Rint, the Li
foil was pressed onto the LLZO and then preconditioned at ∼170 °C
under a load of ∼1 MPa for 4 h s. To fabricate cells with the lowest Rint
achievable, the LLZO was heat-treated at 400 °C for 3 h s in an inert
atmosphere before attaching the Li foil and preconditioning at ∼170 °C
with a load of ∼1 MPa for 4 h s.
2.3. Electrochemical testing
The interfacial resistance of the cell was measured with electro-
chemical impedance spectroscopy (EIS) using a Biologic VMP-300
galvanostat/potentiostat. EIS was performed after the samples had
cooled to room temperature and was conducted from 1Hz to 7 MHz
with a perturbation of 100 mV. The obtained spectra were fit to a
modified version of the model proposed by Huggins [16]. In the Hug-
gins model, three parallel elements, representing the bulk, grain
boundary, and interfacial impedances, are connected in series, with
each element containing a resistor and capacitor in parallel. In the
model used, the capacitors are replaced with constant phase elements to
account for variations in the time constants. It is well known that the
interfacial impedance corresponds to the lower frequencies in the EIS
spectra and corresponds to Q values of ∼10−6 F. These impedances
corresponding to Q values close to 10−6 F were taken to be the total
interfacial impedance and were multiplied by the area of the Li foil to
obtain the Rint.
2.4. Mechanical testing
For measuring the adhesive strength of the Li-LLZO interface, σadh,
an Instron 5944 tension/compression testing unit was integrated inside
a custom designed Ar-filled glovebox. Measuring the shear strength of
the interface was initially considered, but minor misalignments in the
test set-up led to dramatic variability in the results. After pre-
conditioning, the cells were cooled to room temperature and one side of
the cell was attached to a steel pin using an acrylic based adhesive
(Loctite Super Glue Gel). The pin was mounted in one of the tension
fixtures of the Instron, while another pin was mounted in the opposite
fixture. The two pins were aligned in the tension grips and then the
other side of the cell was adhered to the other pin. This method of
alignment minimized the loads applied by the Instron grips, perpendi-
cular to the tensile axis. Fig. 1 shows a schematic of the experimental
setup. The strength of the Li-LLZO interface was measured using a
M. Wang, J. Sakamoto
Fig. 1. Schematic of the tensile testing set-up for measuring the interfacial strength of Li
on LLZO. The set-up is contained in an Ar-filled glovebox.
standard tension test with a strain rate of 1 mm·min−1. As a control,
the same tension test was performed on a single piece of Li foil that was
subjected to the same preconditioning method as the Li-LLZO-Li cells.
All Li-LLZO-Li cells were tested until rupture occurred. Fractured cell
components were stored in Ar for subsequent analysis.
2.5. Surface characterization
The fracture surfaces of the Li-LLZO interfaces were imaged using a
Meiji Techno EMZ-13TR optical light microscope. Scanning electron
microscopy (SEM) was performed with a FEI Nova 200 Nanolab SEM. A
custom sample holder was used to protect the Li from air exposure
during the transport and sample loading process.
3. Results and discussion
3.1. Electrochemical characterization
Fig. 2 shows two representative examples of measured EIS spectra
corresponding to one of the lowest Rint measured and one of the higher
Rint measured in this study. It can be seen that the main difference is the
diameter of the low frequency semicircle, which is representative of the
interfacial impedance Rint. It is known to be charge transfer resistance
based on the capacitance values [17]. Samples with intermediate Rint
exhibit low frequency semicircles with diameters in between the two
extremes shown in Fig. 2a.
3.2. Mechanical testing
Li-LLZO-Li and Li metal stress-stain behavior was characterized in
uniaxial tension (Fig. 3). Representative data for low and high Rint cells
and Li metal are shown. Because Li metal is known to have a sig-
nificantly lower elastic modulus and high degree of ductility compared
to LLZO, the mechanical properties of Li metal were characterized to
determine its contribution to the stress-strain behavior of Li-LLZO-Li
cells. The yield strength of Li metal was measured to be 2.0 MPa and the
ultimate tensile strength was measured to be 8.0 MPa (Fig. 3). The yield
9
Journal of Power Sources 377 (2018) 7–11
strength measured is higher than previous reports for polycrystalline Li
(0.41–0.89 MPa) [10,18,19] which may be due to the degree of cold-
working of the Li foils that were used in this study. However, the effects
of dislocation density and grain size on the yield strength are beyond
the scope of this work. In addition, the elastic modulus of Li was de-
termined to be 3.4 GPa, which falls in the range of elastic moduli for
polycrystalline Li, reported to range from 1.9 GPa to 7.9 GPa [18–21].
The stress-strain behavior of Li-LLZO-Li cells with the high Rint exhibit
similar elastic moduli compared to Li metal, however the ultimate
tensile strength is considerably lower, below 5 MPa. In contrast, the
stress-strain behavior of Li-LLZO-Li cells with low Rint exhibit nearly
identical behavior compared to Li metal.
Fracture surface analysis was conducted after tensile testing.
Primarily two types of mechanical behavior were observed (Fig. 4). At
lower Rint, no sharp drop-off in the load is observed but rather a slow
drop in the load. Analysis of the fracture surfaces show that this type of
load profile correlates to yielding of the Li foil (Fig. 4a). It can be seen
that a significant amount of Li remains stuck to the LLZO surface and
the “cup & cone” features are signs that the slow drop in the loading
profile can be attributed to necking and eventual failure of the Li metal,
rather than the Li-LLZO interface. At higher Rint (> ∼5000 ·cm2), a
sharp drop-off in the load is observed at the failure stress. This type of
stress-strain behavior correlates to a clean separation of the Li metal
from the LLZO surface with no noticeable deformation of the Li foil and
negligible Li residue on the LLZO surface (Fig. 4b).
For the lowest interfacial resistances reported, the Li metal alone
seems to be the weakest load bearing element in the stack, but there
does exist a regime of slightly higher interfacial resistances (∼50 ·cm2 -
∼5000 ·cm2) where a combination of Li separation and yielding is
observed. In these cases, the shape of the loading profile is the same as
the yielding of Li, although the ultimate tensile strength of the stack is
below that of the Li. This can be attributed to small isolated regions
where the Li separates from the surface, effectively reducing the area of
the Li. This is evident in the fracture surface, which shows isolated
areas of negligible Li residue and other areas of heavily deformed Li.
The SEM images in Fig. 4d show a closer look of the “cup & cone”
fracture of the yielded Li, which is an indication of severe plastic de-
formation. In comparison, Fig. 4e shows an SEM image of a region on
the LLZO surface where the Li metal has separated from the LLZO.
Despite what seems like a clean separation of the interface, it can be
seen that that small pieces of Li residue, a few microns large, remain on
the surface. This may suggest that even when clean separation occurs,
there is still some surface chemistry that adheres the Li to the LLZO.
3.3. Correlating Rint with σadh
For each cell, the Rint and σadh are plotted in Figure 5. Consistent
with the EIS and mechanical testing discussion above, it was apparent
that when Rint was high the Li-LLZO interface adhesion was low and
when the Rint is low the Li-LLZO interface adhesion was high. At the
lowest Rint value, the σadh of the Li-LLZO interface adhesion strength
nearly matched the tensile strength of Li metal. In other words, the
stress-strain behavior was primarily controlled by the tensile strength of
Li rather than the Li-LLZO interface adhesion strength when Rint is
minimized. The fact that the interface strength can match the ultimate
tensile strength of the Li metal suggests that the Li-LLZO interface bond
is more chemical than physical in nature. As seen in the SEM images of
the LLZO surface, there are few pores or surface features that can lead
to strong mechanical or van der Waals bonds. Instead it seems more
likely that Li is chemically bonded to the LLZO surface, which has been
cleaned by heating at higher temperatures as reported by Sharafi et al.
[14]. Sharafi et al. recently demonstrated that the wettability of Li on
LLZO is drastically improved by removing Li2CO3 surface contamina-
tion by heat treating in an inert atmosphere as was done in this study. It
is believable that previous reports of poor wettability are actually due
to the Li2CO3 layers on the oxide surface rather than poor wettability
M. Wang, J. Sakamoto Journal of Power Sources 377 (2018) 7–11

Fig. 2. (a) Impedance spectra for representative

Li-LLZO-Li cells with high Rint and low Rint. The
inset shows the spectrum for a low Rint cell. (b)
The equivalent circuit schematic used for mod-
eling of the impedance spectra. (c) Summary of
fitted data for the representative spectra shown in
(a).

Fig. 5. The relationship between the logarithm of the interfacial resistance, Rint, and σadh
Fig. 3. Representative stress-strain curves for a Li-LLZO-Li cell with high Rint
of the Li-LLZO-Li cell. Markers indicate the observed failure mechanism for each sample.
(330 k·cm2), a cell with intermediate Rint (446 ·cm2), a cell with low Rint (7.2 ·cm2), and a
The experimentally determined ultimate tensile strength of the Li metal is indicated by a
single Li foil. The profile of the Li foil is almost identical to the profile of the low Rint
dashed line.
sample.

Fig. 4. Optical microscope images of a sample where the mode of

failure of the cell is caused by (a) the failure of the Li metal, (b)
complete separation of the Li from the LLZO, and (c) a mix of se-
paration and Li failure. SEM images of (d) the fracture surface of the
yielded Li on the surface of a low Rint sample and (e) the LLZO
surface of a high Rint sample after the separation of the Li from the
surface.

10
M. Wang, J. Sakamoto
properties of LLZO. This observation is consistent with the pioneering
work done by Humenik and Kingery, who found that wetting of metals
on metal oxides was highly sensitive to surface contaminants [22].
Furthermore, DFT calculations report that the work of adhesion Wad is
0.1 J m−2 for Li on Li2CO3 and 0.67J.m−2 for Li on LLZO [13]. Al-
though the exact work of adhesion could not be determined here due to
the degree of work that occurred during plastic deformation of the Li
metal, the relationship observed here is in good agreement with these
findings. The samples fabricated with high interfacial resistances, had
no heat treatment to remove Li2CO3 from the surface and consequently
exhibited low adhesive strengths, while the samples that were heat-
treated consequently exhibited the highest adhesive strengths, the
lowest interfacial resistances, and primarily Li yielding as the fracture
mechanism. Comparing these findings to previously reported works of
adhesion, it can be concluded that high interfacial resistance is a result
of Li2CO3 contamination layers, which drastically decreases the ad-
hesive strength. In this case, the adhesion is mainly governed by the
surface chemistry and wettability of the Li metal. It has been shown that
Li2CO3 growth on the LLZO surface is non-uniform, and so it is likely
that there is an increasing area fraction of Li2CO3 on the LLZO surface
with decreasing adhesion strength [13]. Using the adhesion strength as
a proxy for contact area, this would suggest that the decrease in ad-
hesion strength is caused by an increase in the area fraction of the Li-
Li2CO3 interface and a corresponding decrease in the area fraction of
the Li-LLZO interface, rather than a varying thickness of Li2CO3.
However, since a non-destructive method of elemental mapping of the
buried interface continues to be a challenge, this hypothesis cannot be
validated at the time.
It is clear that the adhesion strength is intrinsically related to the
wettability of the surface. Even though there have been previous re-
ports of the wettability of Li metal on oxide surfaces, the only well-
defined metric of quantifying the wettability is the contact angle.
However, methods of experimentally determining the contact angle,
like the sessile drop test, require testing conditions above the melting
temperature of Li and therefore are not indicative of a solid-solid in-
terface. The method demonstrated here presents a simple method of
quantifying the wettability of Li metal on solid electrolytes at room
temperature by using the adhesion strength. Since both the adhesion
strength and the wettability of the surface are dependent on the surface
chemistry, the adhesion strength can be used as a metric to quantify the
wettability of the solid-solid interface at room temperature. In future
studies, this method may present a simpler alternative to quantifying
the quality of contact between solid Li metal and solid electrolytes at
room temperature.
4. Conclusions
This study correlated the electrochemical and mechanical properties
of the Li-LLZO interface. We demonstrated a strong relationship be-
tween the interfacial resistance and the tensile adhesion strength of the
Li metal on the LLZO surface. It was determined that when Rint was
330 k·cm2, σadh was 1.1 kPa. Conversely when Rint was 7 ·cm2, σadh was
8 MPa. This study also presented one of the first experimental mea-
surements of the stress-strain behavior of Li metal. It was determined
that the yield strength of Li metal is approximately 2.0 MPa and the
ultimate tensile strength to be 8.0 MPa. Analysis of the fracture surfaces
indicated that at the lowest Rint measured, the interfacial strength is
stronger than the ultimate tensile strength of the Li metal itself, in
which case the Li metal is the weakest load-bearing element. The results
presented in this study are also in good agreement with previous studies
that investigated the wettability of Li metal on Li2CO3and LLZO. It
follows that the absence of Li2CO3 on the surface improves the surface
chemistry and wettability of the Li metal on LLZO, which provides good
interfacial contact and results in a high adhesive strength. It is also
demonstrated that the heat treatment method used by Sharafi et al. is a
reliable method for achieving consistently low interfacial resistances
11
Journal of Power Sources 377 (2018) 7–11
and consistently high interfacial strengths. Furthermore, the method of
tensile testing conducted in this study presents a novel, yet simple
method of quantifying the wettability of the solid-solid Li-LLZO inter-
face. The results of this study can help elucidate the mechanics of the Li
metal-electrolyte interface to facilitate the development of solid-state
batteries using Li metal electrodes.
Acknowledgements
This work was supported by the U.S. Department of Energy
Advanced Battery Material Research (BMR) programs Grant No. DE-
EE0991-1663. MW and JS would also like to acknowledge Dr. Nancy
Dudney at the Oak Ridge National Laboratory for her helpful insights.
References
[1] J.B. Goodenough, Y. Kim, Challenges for rechargeable Li batteries †, Chem. Mater 22
(2010) 587–603, http://dx.doi.org/10.1021/cm901452z.
[2] J.-M. Tarascon, M. Armand, Issues and challenges facing rechargeable lithium batteries,
Nature 414 (2001) 359–367, http://dx.doi.org/10.1038/35104644.
[3] C. Monroe, J. Newman, The impact of elastic deformation on deposition kinetics at li-
thium/polymer interfaces, J. Electrochem. Soc. 152 (2005), http://dx.doi.org/10.1149/
1.1850854 A396.
[4] E.J. Cheng, A. Sharafi, J. Sakamoto, Intergranular Li metal propagation through poly-
crystalline Li6.25Al0.25La3Zr2O12 ceramic electrolyte, Electrochimica Acta 223 (2017)
85–91, http://dx.doi.org/10.1016/j.electacta.2016.12.018.
[5] R. Murugan, V. Thangadurai, W. Weppner, Fast lithium ion conduction in garnet-type
Li7La3Zr2O12, Angew. Chem. Int. Ed. 46 (2007) 7778–7781, http://dx.doi.org/10.1002/
anie.200701144.
[6] T. Thompson, A. Sharafi, M.D. Johannes, A. Huq, J.L. Allen, J. Wolfenstine, J. Sakamoto,
A tale of two sites: on defining the carrier concentration in garnet-based ionic conductors
for advanced Li batteries, Adv. Energy Mater 5 (2015) 1500096, http://dx.doi.org/10.
1002/aenm.201500096.
[7] T. Thompson, J. Wolfenstine, J.L. Allen, M. Johannes, A. Huq, I.N. David, J. Sakamoto,
Tetragonal vs. cubic phase stability in Al – free Ta doped Li7La3Zr2O12 (LLZO), J. Mat.
Chem. A 2 (2014) 13431–13436, http://dx.doi.org/10.1039/C4TA02099E.
[8] I.N. David, T. Thompson, J. Wolfenstine, J.L. Allen, J. Sakamoto, Microstructure, Li-
Ion Conductivity, Of hot-pressed cubic Li7La3Zr2O12, J. Am. Ceram. Soc. 98 (2015)
1209–1214, http://dx.doi.org/10.1111/jace.13455.
[9] S. Yu, R.D. Schmidt, R. Garcia-Mendez, E. Herbert, N.J. Dudney, J.B. Wolfenstine,
J. Sakamoto, D.J. Siegel, Elastic properties of the solid electrolyte Li 7 La 3 Zr 2 O 12
(LLZO), Chem. Mater 28 (2016) 197–206, http://dx.doi.org/10.1021/acs.chemmater.
5b03854.
[10] C. Xu, Z. Ahmad, A. Aryanfar, V. Viswanathan, J.R. Greer, Enhanced strength and tem-
perature dependence of mechanical properties of Li at small scales and its implications for
Li metal anodes, Proc. Natl. Acad. Sci. 114 (2017) 57–61.
[11] A. Sharafi, H.M. Meyer, J. Nanda, J. Wolfenstine, J. Sakamoto, Characterizing the Li–Li 7
La 3 Zr 2 O 12 interface stability and kinetics as a function of temperature and current
density, J. Power Sources 302 (2016) 135–139, http://dx.doi.org/10.1016/j.jpowsour.
2015.10.053.
[12] Y. Zhu, X. He, Y. Mo, First principles study on electrochemical and chemical stability of
solid electrolyte–electrode interfaces in all-solid-state Li-ion batteries, J. Mater Chem. A 4
(2016) 3253–3266, http://dx.doi.org/10.1039/C5TA08574H.
[13] A. Sharafi, S. Yu, M. Naguib, M. Lee, C. Ma, H.M. Meyer, J. Nanda, M. Chi, D.J. Siegel,
J. Sakamoto, Impact of air exposure and surface chemistry on Li–Li7La3Zr2O12 inter-
facial resistance, J. Mat. Chem. A 5 (2017) 13475–13487, http://dx.doi.org/10.1039/
C7TA03162A.
[14] A. Sharafi, E. Kazyak, A.L. Davis, S. Yu, T. Thompson, D.J. Siegel, N.P. Dasgupta,
J. Sakamoto, Surface chemistry mechanism of ultra-low interfacial resistance in the solid-
state electrolyte Li 7 La 3 Zr 2 O 12, Chem. Mater (2017), http://dx.doi.org/10.1021/acs.
chemmater.7b03002.
[15] E. Rangasamy, J. Wolfenstine, J. Sakamoto, The role of Al and Li concentration on the
formation of cubic garnet solid electrolyte of nominal composition Li7La3Zr2O12, Solid
State Ion. 206 (2012) 28–32, http://dx.doi.org/10.1016/j.ssi.2011.10.022.
[16] R.A. Huggins, Simple method to determine electronic and ionic components of the con-
ductivity in mixed conductors a review, Ionics 8 (2002) 300–313.
[17] J.T.S. Irvine, D.C. Sinclair, A.R. West, Electroceramics: characterization by impedance
spectroscopy, Adv. Mater 2 (1990) 132–138, http://dx.doi.org/10.1002/adma.
19900020304.
[18] R.P. Schultz, Lithium: Measurement of Young's Modulus and Yield Strength, Fermi
National Accelerator Lab., Batavia, IL (US), 2002http://lss.fnal.gov/cgi-bin/find_paper.
pl?tm-2191 (accessed August 6, 2017).
[19] S. Tariq, K. Ammigan, P. Hurh, R. Schultz, P. Liu, J. Shang, Li material testing - fermilab
Antiproton Source lithium collection lens, Proc. 2003 Part. Accel. Conf. 3 (2003)
1452–1454, http://dx.doi.org/10.1109/PAC.2003.1288558.
[20] W.M. Robertson, D.J. Montgomery, Elastic modulus of isotopically-concentrated lithium,
Phys. Rev. 117 (1960) 440–442, http://dx.doi.org/10.1103/PhysRev.117.440.
[21] P.W. Bridgman, The effect of tension on the electrical resistance of certain abnormal
metals, Proc. Am. Acad. Arts Sci. 57 (1922) 41–66, http://dx.doi.org/10.2307/20025885.
[22] M. Humenik, W.D. Kingery, Metal-ceramic interactions: III, surface tension and wett-
ability of metal-ceramic systems, J. Am. Ceram. Soc. 37 (1954) 18–23, http://dx.doi.org/
10.1111/j.1151-2916.1954.tb13972.x.