Supporting Information

Solid-State Li-Ion Batteries Using Fast, Stable, Glassy

Nanocomposite Electrolytes for Good Safety and Long Cycle-Life

Guoqiang Tan1,2, Feng Wu*1,3, Chun Zhan2, Jing Wang1,3, Daobin Mu1,3, Jun Lu*2 and Khalil
Amine2

1 School of Materials Science and Engineering, Beijing Institute of Technology, Beijing Key
Laboratory of Environmental Science and Engineering, Beijing, 100081, China
2 Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 S. Cass
Avenue, Lemont, Illinois 60439, United States
3 Collaborative Innovation Center of Electric Vehicles in Beijing, Beijing, 100081, China

Correspondence and requests for materials should be adressed to F.W. (email:

wufeng863@bit.edu.cn) or to J.L. (email: junlu@anl.gov)

1
Experimental Methods

NE preparation. NEs were synthesized using a nonaqueous sol-gel procedure. First, add 1 g
LiTFSI (3M Inc, 99%) into [BMI][TFSI] (Shanghai Cheng Jie, 99%) completely dissolved to
form ILE (see Table 1 for the molar ratios). Add 2.75 mL TEOS (Aldrich, 99%) into 4 mL
HCOOH (Aldrich, 99%) under mild stirring for 10 min to form a clear solution. Pour the clear
solution into ILE and let stand 30 min for gelation. Let dry at 110 °C under vacuum over 3
days, resulting in a transparent glass monolith. For preparing thin films, immediately after the
clear solution is mixed with ILE, pour the resulting mixture into a stainless steel mould to
form NE thin films. The thin films were then dried at 110 °C under vacuum over 3 days prior
to electrochemical and battery tests. The whole procedure was conducted at room temperature
under an argon atmosphere.

Electrode preparation. Commercially available LCO (Beijing Easpring Material Technology

Co., China), LFP (Pulead Technology Industry Co., China), and NCM powders (Shanshan
Group Co., China) were used as cathode materials, and MCMB (BTR New Energy Materials
Inc., China) was used as anode material. The cathodes were prepared by pasting a mixture of
80 wt % active materials (LCO, or LFP, or NCM), 10 wt % acetylene black, and 10 wt %
poly(vinylidene fluoride) (PVDF) onto an aluminum foil current collector. The anodes were
formed by pasting a mixture of 80 wt % MCMB, 10 wt % acetylene black, and 10 wt %
PVDF onto a copper foil current collector.

Electrochemical methods. Ionic conductivities of NEs were calculated from EIS

measurements using an electrochemical cell equipped with two Pt electrodes. The cell
constant was determined with a standard KCl solution (0.01M) at 25 °C. The EIS data were
collected in a frequency range of 10−100 kHz, and the measurements were performed in a
temperature range of -40−200 °C in a stepwise manner of 5 °C. The electrochemical stabilities
of the NEs were determined by LSV and CV tests using a Swagelok-type cell composed of a
lithium metal anode, a NE thin film, and a stainless steel cathode. The scan rate was set at 0.1
mV s−1 at room temperature. The battery performance was investigated for half cells and full
cells.
The 2032 coin cells were made up of lithium transition metal oxides (LCO, NCM, or
LFP) as the cathode, NE thin film as the solid electrolyte, and lithium metal or MCMB as the
anode. All cells were assembled in an argon-filled glove box and then aged at 35 °C for 24 h

2
before the electrochemical tests. EIS, LSV, and CV tests were performed on a CHI 604D
electrochemical workstation. Galvanostatic charge−discharge measurements were carried out
on a Land CT2001A battery tester.

Material characterization. The mechanical characterization of the NEs was measured by

three-points’ bending technique on a DMA TA Q800 analyzer at room temperature, the size
of samples was 35×10×3 mm. In order to observe the NE pore structure, we washed the NE
powders and thin films with acetonitrile to remove the ILE, then outgassed under vacuum at
120 °C overnight. SEM and TEM were used to observe the structure and morphology of the
silica matrix, and isothermal N2 adsorption–desorption measurements were employed to
evaluate its specific surface area and porosity. SEM images were recorded at 20 kV on a FEI
Quanta 600, and TEM images were acquired at 120 kV on a JEOL JEM-2100. A
Quantachrome NOVA1200e analyzer was used to generate 77 K N2 adsorption–desorption
curves, using the desorption isotherms with 0.6 < P/Po < 0.95. The pore size distribution was
determined by Barrett–Joyner–Halenda (BJH) analysis. To analyze the strutural compositions
and dynamics features of the NEs, XRD tests were performed on a Rigaku Ultima IV X-ray
diffractometer using Cu Kα radiation (40 mA, 40 kV) over a 2θ range of 8°–40° at a rate of 1°
min−1. The FT-IR spectra were obtained on a Nicolet 6700 spectrometer. Solid-state 7Li-MAS
NMR measurements were carried out on a Bruker AV 300 spectrometer with a resonance
frequency of 116.6 MHz for 7Li. The spectral width was set to 73.5 kHz. TGA was performed
on a Netzsch TG209F1 analyzer. The samples were heated from 25 to 600 °C at a rate of
10 °C min−1. DSC was performed on a MDC290 analyzer. The samples were heated from -90
to 200 °C at a rate of 10 °C min−1. To observe structural changes of electrodes after cell
cycling, we disassembled the cycled cells in an argon glovebox, rinsed electrodes with
dimethyl carbonate (DMC) solvent, then evacuated them overnight. The final electrodes were
examined by SEM and EDX.

3
 Table S1 The mechanical characterization of the NEsα

Samples
Parameters
NE-1 NE-2 NE-3 NE-4
Fracture strength
0.85 0.80 0.76 0.69
(MPa)
Young modulus
63.8 62.2 60.4 57.3
(MPa)

4
 Table S2 The main FT-IR bands of the pristine [BMI][TFSI]α 1−3

Wavelength of
Vibration
the bands [cm-1]

3157 3120 ν(C-H) aromatic, str

2967 2940 2880 ν(C-H) aliphatic, str
1573 1467 ν(ring, C-N), str sym
1347 ν(SO2), str asym
1178 ring, str sym
1120 ring, C-H, i/p, bend
1056 ν(S=O), str
789 ν( C-S, S-N), str
747 ring, o/p, b, asym
739 ν( -CF3), str
α
Abbreviations for the tables: str, stretching; b, bending; i/p, in plane; o/p, out of plane; sym,
symmetrical; asym, asymmetrical; as, association.

5
Table S3 Comparison of electrochemical performance for all half cells cycling at 1/10 C rateα

LCO NCM LFP

Samples
1st dc 51th dc cr 1st dc 51th dc cr 1st dc 51th dc cr
NE-1 128.0 106.7 83.3% 132.0 121.3 91.9% 135.6 126.8 93.5%
NE-2 133.2 118.2 88.7% 139.5 132.8 95.2% 142.7 135.3 94.8%
NE-3 136.8 123.0 89.9% 143.9 137.5 95.6% 146.7 140.5 95.8%
NE-4 140.9 127.2 90.3% 147.7 143.5 97.2% 149.6 145.7 97.4%
α
Abbreviations for the tables: dc, discharge capacity (mAh/g); cr, capacity retention.

6
Fig. S1 (A) Scheme of the sol-gel formation and the extraction of ILE; (B−F) SEM images of
silica matrices for the NEs after remove the ILE; (G) Nitrogen adsorption−desorption
isotherms for these silica matrices (insert: pore diameter distributions, which were calculated
from the desorption branch of the isotherm using the BJH method); and (H) Photograph of the
glass monoliths corresponding to images C−F.

7
 1056

612
A B C

1347
NE-4

789
IL

1573
Intensity / a. u.

2967
3157
IL
NE-3

Absorbance
NE-4

1056
1347
NE-3 NE-2

1569
2967
NE-2

3157
NE-2

1060
90 80
NE-1 NE-1 85

960
797
Silica
Silica LiTFSI 10 0 -10

10 15 20 25 30 35 40 4000 3500 3000 2500 2000 1500 1000 200 100 0 -100 -200
7
2θ / degree Wavenumbers / cm δ ( Li) / ppm

100 o
F − 19.88 C
o
Tc crystalline temperature E Tc T5%=390 C D
exo

exo
o
−28.2 C NE-1
80 100

Weight loss / %
T5%
IL −28.9 C
o
T10%
NE-2 90
-1

-1
− 87.12 C 60
Heat flow / w g

Heat flow / w g
o
−29.3 C −18.3oC
80
wt% of IL
Tg glass-transition −31.8 C
o NE-3 40
o 550 600 650 700 750
−16.4 C
temperature 77%
NE-4 20 NE-1 NE-2 80%
Tm melting temperature 85%
NE-3 NE-4
o
Tm IL
88%
−2.69 C 0
o
−87.5 C Tg −6.87 C
o

200 240 280 320 360 200 240 280 320 300 400 500 600 700 800 900
Temperature / K Temperature / K Temperature / K

Fig. S2 (A) XRD patterns and (B) FT-IR spectra of the pristine IL ([BMI][TFSI]), NEs and
remnant silica; (C) 7Li-MAS NMR spectra for the NEs and the pristine LiTFSI incorporated
for comparison (experimental details: νMAS = 10 kHz; pulse length = 0.5 µs; repetition time =
5 s); (D) TGA and (E,F) DSC traces of the IL and NEs.

8
 0.08 A B

−1
cm
1

log[(σ T)/(S K cm )]
o

Conductivity / S
200 C

−1
0.06
0 o
100 C
0.04
o
50 C
-1
o
0.02 20 C
-2
500 NE-1 NE-2
0.00
ILE 450 NE-3 NE-4 ILE-3
/K
o
400 -20 C
NE-4 -3
NE-3 350 re
S am NE-2 300 a tu
250 er
ple mp
NE-1 2.0 2.5 3.0 3.5 4.0 4.5
s 200
Te
−1
1000/T / K

C 0.74V 1st cycle D

-2

−2
Current density / mA cm

0.6 2th cycle NE-2 5.10V

Current Density / mA cm−

1.13V
3rd cycle
0
0.4 -2 1.05V
-0.32V
5.0 V
0.2 4 0.73V 1st cycle
2 2th cycle NE-3 5.05V
1.16V
0.0 3rd cycle
0
NE-1 NE-2 5.2 V
-0.2 NE-3 NE-4 ILE-3 -2 1.04V
-0.33V
-4
3.5 4.0 4.5 5.0 5.5 -1 0 1 2 3 4 5
+ +
Potential / V vs Li /Li Potential / V vs Li /Li

Fig. S3 (A) Conductivities of the ILE−3 and NEs measured at various temperatures; (B)
Conductivity over temperature dependence of the ILE−3 and NEs; (C) Linear sweep
voltammograms of the ILE−3 and NEs; (D) Cyclic voltammograms of the NE−2 and
NE−3.

9
Fig. S4 (A,B) SEM morphologies of the surface (A) and cross-section (B) of the NCM
electrode; and (C) EDX elemental mapping of the cross-section (B) of the electrode.

10
Fig. S5 (A,B) SEM morphologies of the cycled NCM electrode (A) and the NE−3 electrolyte
(B) after 100 cycles and removing the ILE; (C) TEM image of the cycled NE−3 electrolyte
after 100 cycles.

References

1 Liu, Y.; Wang, M.; Li, Z.; Liu, H.; He, P.; Li, J. Langmuir 2005, 21, 1618.
2 Blokhin, A. V.; Paulechka, Y. U., Strechan, A. A.; Kabo, G. J. The Journal of Physical
Chemistry B 2008, 112, 4357.
3 Yu, L., Pizio, B. S., Vaden, T. D. The Journal of Physical Chemistry B 2012, 116, 6553.

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