Supporting Information

Single Lithium-Ion Conducting Polymer Electrolytes Based on a Super-

Delocalized Polyanion
Qiang Ma, Heng Zhang, Chongwang Zhou, Liping Zheng, Pengfei Cheng, Jin Nie,
Wenfang Feng, Yong-Sheng Hu,* Hong Li, Xuejie Huang, Liquan Chen, Michel Armand, and
Zhibin Zhou*

anie_201509299_sm_miscellaneous_information.pdf
 Supporting Information

Experimental Section

Instrumentation
1
H (399.65 MHz), and 19F (376.05 MHz) NMR spectra were recorded on a Bruker AV400 spectrometer.
Chemical shift values are reported in ppm relative to TMS for 1H, and external references CCl3F for 19F.
Element analyses (C, H, and N) were performed on an Elementar Vario Micro Cube elemental analyzer.

The calorimetric measurements were performed on a differential scanning calorimeter (Netzsch 200 F3). A
sample of average weight of ca. 5−10 mg was hermetically sealed in an aluminum pan and stored at room
temperature for 10 days prior to measurement in a glove box (H2O and O2 < 1 ppm). The sample was
measured using two successive cooling-heating scans at a rate of 10 ºC min−1 in the range of −150 to 150 ºC
under nitrogen flow, except for the initial cooling scan from room temperature. The glass transition temperature
(Tg) was taken at the onset of the heat capacity change, while melting point (Tm) was taken at the peak of the
heat capacity change at the heating scan.

Thermal gravimetric analysis (TGA) was performed on a NETZSCH STA 449C thermoanalyzer. Samples
of average weight of ca. 5−10 mg were placed in an aluminum pan and heated at a ratio of 10 ºC min−1 from 30
to 600 ºC under a flow of argon. The temperature at which 5 % weight loss was defined as the decomposition
temperature (Td).

The number-average molecular weight (Mn) and polydispersity indices (PDI) of the prepared polymers
were determined by gel permeation chromatography (GPC) using an Agilent 1100 GPC equipped with a PLgel
10 μm MIXED-B column and an RI detector. DMF (0.5% LiCl) was used as the eluent with a flow rate of 1.0 mL
min−1 at 50 ºC. Polystyrene was used as an internal standard.

XRD patterns of the polymers were recorded on a X' Pert Pro diffractometer (PA Nalytical B.V.). The
diffraction data were collected using Cu Kα radiation at a scan step of 0.017ºin the 2θ range from 5 to 95ºat 40
mA and 40 kV.

The electrochemical measurements of ionic conductivities (σ, in S cm−1) of the blended polymer
electrolytes were carried out on an Autolab PGSTAT302N workstation (Eco Chemie, Netherland) using AC
impedance spectroscopic technique. The membranes of blended polymer electrolytes were sandwiched
between a pair of stainless steel blocking electrodes. Before being measured, the cell was first heated at 60 ºC
for 4 h for obtaining good contact between the electrolytes and electrodes followed by slow cooling to room
temperature. The cell was allowed to stand at room temperature for 10 days prior to measurement. Afterwards,
the measurements were performed in the temperature range from 25 to 90 ºC for the heating scan. The cell
was thermally equilibrated for at least 1 h at each temperature prior to measurement. The AC impedance
spectra were recorded over the frequency range from 0.01 to 106 Hz. The values of ionic conductivity (σ, in S
cm−1) were derived from the measured resistance by using the equation of σ = l/SR, where l (cm) is the
thickness of membrane of blended polymer electrolytes, A (cm2) is the area of the membrane, and R (Ω) is the
resistance determined from the Nyquist plot.

The lithium-ion transference number (tLi+) of the blended polymer electrolytes was obtained by combining
AC impedance and DC polarization measurements using a symmetric cell of [Li metal | polymer electrolytes | Li
metal] at 60 ºC, which had been described by Bruce and Abraham. [1,2] The surface of lithium metal was shaved
with a scalpel before use. The cell was assembled in a glove box (H2O and O2 < 1 ppm). Before measurement,
the cell was heated at 60 ºC for 2 h for obtaining good contact, as well as for forming a stable interface,
between the electrolytes and electrodes. Then, the cell was applied a DC voltage of 10 mV until a steady
current was obtained (usually 1−2 hours in this study), and the initial and steady currents, which flow through
the cell, were measured. Simultaneously, the cell was also monitored in the frequency range from 0.01 to 106
Hz, by using AC impedance with an oscillation voltage of 5 mV to measure the resistance of the electrolytes
and the interface of electrolytes/Li metal electrodes, before and after the DC polarization. The temperature of
the cell was accurately controlled at 60 ± 0.1 ºC by using a JULABO F12 oil bath.
Materials

Poly(ethylene oxide) (PEO, Mw = 4 × 106 g mol−1, Huagao Fine Chemicals, China) was dried at 50 ºC for 10
h under vacuum conditions before use. Azodiisobutyronitrile (AIBN, Shanghai Reagent, China) was
recrystallized twice from methanol before use. 4-Vinylbenzenesulfonyl amine and
N-(trifluoromethylsulfonyl)trifluoromethanesulfonimidoyl fluoride were synthesized according to the reported
procedures in the literature.[3-5] All other reagents and solvents were dried and purified using standard
procedures before use. All the procedures related to handling moisture and oxygen sensitive reagents were
performed under a dry argon atmosphere, or in a glove box (Mikrouna, H 2O and O2 < 1 ppm).

Synthesis

1. Potassium
[(4-styrenesulfonyl)(trifluoromethyl(S-trifluoromethylsulfonylimino)sulfonyl)imide] (KSsTFSI)
4-vinylbenzenesulfonyl amine (18.32 g, 0.10 mol), K2HPO4 (38.32 g, 0.22 mmol), 4-t-butylcatechol (0.17 g,
TBC, as inhibitor) and dimethylaminopyridine (0.24 g, DMAP, as catalyst) were mixed and dissolved in CH 3CN
(100 mL) at 0 ºC under stirring conditions, and then N-(trifluoromethylsulfonyl)trifluoromethanesulfonimidoyl
fluoride (28.32 g, 0.10 mol) was added dropwise under a dry argon atmosphere. The mixture was stirred at 0 ºC
for 30 min, and then maintained at 25 ºC for 48 h. The crude product was isolated by filtration and then filtrate
was evaporated under reduced pressure to remove solvent, the residue was successively purified by columm
chromatography (silica, hexane/ethylacetate, 1:2, Rf = 0.40) to afford the desired product after rotary
evaporation of all solvents. The pure product was then dried at 25 ºC for 48 h under high vacuum, affording
potassium [(4-styrenesulfonyl)(trifluoromethyl(S-trifluoromethylsulfonylimino)sulfonyl)imide] (KSsTFSI) (22.28 g,
yield 46%) as a yellow gummy compound. 1H NMR (399.65 MHz; Acetone-d6; TMS; ppm): δ = 7.90 (d, J = 8.4
Hz, 2H), 7.60 (d, J = 8.4 Hz, 2H), 6.84 (q, J = 17.7 Hz, 11.0 Hz, 1H), 5.98 (d, J = 17.7 Hz, 1H), 5.39 (d, J = 11.0
Hz, 1H). 19F NMR (376.05 MHz; Acetone-d6; CCl3F; ppm): δ = −79.27 (s, 3F), −79.54 (s, 3F). Elemental
analysis calcd (%) for C10H7F6KN2O5S3: C, 24.79; H, 1.46; N, 5.78; found: C, 24.45; H, 1.52; N, 5.86. ESI-MS:
ESI+ m/z 39 (100%, K+); ESI− m/z 445 (100%, [CH2=CH-C6H4-SO2-N-S(O)=NSO2CF3]−).

2. Potassium
poly[(4-styrenesulfonyl)(trifluoromethyl(S-trifluoromethylsulfonylimino)sulfonyl)imide] (KPSsTFSI)
KPSsTFSI was synthesized by free radical polymerization of KSsTFSI (9.69 g, 0.02 mol) in CH3OH (25 mL)
with AIBN (0.07 g, 0.37 mmol) as an initiator. The solution was heated at 65 ºC for 12 h under a dry argon
atmosphere. The raw polymer was precipitated by pouring the solutions into a large excess of ether (200 mL).
The gummy residue obtained was washed with excess ether three times (3 × 100 mL) and then dried at 80 ºC
for 12 h under high vacuum, affording potassium poly[(4-styrenesulfonyl)(trifluoromethyl(S-trifluoromethylsulfo-
nylimino)sulfonyl)imide] (KPSsTFSI) (6.28 g, yield 65%) as a yellow powder. 1H NMR (399.65 MHz; Acetone-d6;
TMS; ppm): δ = 7.72 (broad, 2H), 6.62 (broad, 2H), 1.62 (broad, 2H). 19F NMR (376.05 MHz; Acetone-d6; CCl3F;
ppm): δ = −79.34 (broad, 6F).

3. Lithium
poly[(4-styrenesulfonyl)(trifluoromethyl(S-trifluoromethylsulfonylimino)sulfonyl)imide] (LiPSsTFSI)
LiPSsTFSI was synthesized by a metathesis reaction between KPSsTFSI and LiClO4 in CH3CN in nearly
quantitative yield, in a glove box specialized for preparing electrolyte salts, which is similar to the preparation of
lithium (fluorosulfonyl)(pentafluoroethanesulfonyl)imide, as described in the literature.[6]

4. Elaboration of polymer electrolyte membrane

The blended polymer electrolyte of lithium salt (LiPSsTFSI)/PEO was prepared by mixing and dissolving
pre-weighed amounts of PEO and LiPSsTFSI in purified DMF in a glove box under argon atmosphere. The
membrane of the blended polymer electrolyte was prepared by solution casting method. The resulting viscous
solution was cast with a doctor blade onto Teflon plat and left to evaporate the solvent slowly for 12 h at room
temperature. The obtained self-standing film was dried under high vacuum at 60 ºC for 48 h to remove any
residual solvent. Film thickness was accurately controlled in the range of 100−200 μm.
Table S1. The characterization data for GPC of the prepared polymers
Samples Mn[a] ( × 104) PDI[b] Appearance

LiPSS 7.50 / yellow power

LiPSTFSI 5.28[7] 1.27 yellow power

LiPSsTFSI 18.92 2.21 yellow power

[a] Molecular weight, which was determined by GPC calibrated with polystyrene as an internal
standards.
[b] Polydispersity indices (Mw/Mn) of the prepared polymers, which was determined by GPC
calibrated with polystyrene as an internal standards.

Table S2. The characterization data for phase transition behaviors of the blended polymer electrolytes of the
LiX/PEO (X = PSS, PSTFSI and PSsTFSI) with a molar ratio EO/Li+ = 20, and for neat PEO and LiPSsTFSI.

Samples Tg[a] (ºC) Tm[b] (ºC) Hm[c] (J g−1) χc[d] (%)

LiPSsTFSI 44.3
LiPSS/PEO (20) 73.3 101.2 50
First heating 68.5 71.8
Second heating
LiPSTFSI/PEO (20)
First heating 70.3 71.9 35
Second heating 66.6 59.1
LiPSsTFSI/PEO (20)
First heating −15.1 70.0 58.3 29
Second heating −15.3 63.9 49.8
PEO 70.1 122.2 60
[a] Glass transition temperature.
[b] Melting point.
[c] Enthalpy of melting.
[d] The crystallinity of the blended polymer electrolytes is calculated by: Crystallinity = (Hm/Ho) ×
100%, where ∆Hm is the melting enthalpy of per unit mass of PEO, and ∆Ho is the value of 203.0 J g−1
reported in the literature[8] for the melting enthalpy of 100 % crystalline PEO.

Table S3. The characterization data for the ionic conductivities of blended polymer electrolytes of the LiX/PEO
(X=PSS, PSTFSI, PSsTFSI and TFSI) with a molar ratio EO/Li+ = 20.

Samples σ (S cm−1)
(EO/Li+ = 20) 25 ºC 70 ºC 90 ºC
LiPSS/PEO 3.59 × 10−10 8.35 × 10−8 1.90 × 10−7
LiPSTFSI/PEO 2.09 × 10−9 8.42 × 10−6 3.23 × 10−5
LiPSsTFSI/PEO 7.82 × 10−9 7.61 × 10−5 1.48 × 10−4
LiTFSI/PEO 2.01 × 10−5 6.41 × 10−4 1.33 × 10−3
Table S4. Measured values for the parameters in Equation (S1) and the corresponding calculated values of
lithium-ion transference number (tLi+) at 60 ºC.

Samples Ri Rf Rlo Rls ∆V

Io (μA) Is (μA) tLi+
(EO/Li+ ratio by mole) (kΩ) (kΩ) (kΩ) (kΩ) (mV)
LiPSsTFSI/PEO (20) 1.17 1.03 0.259 0.267 7.169 8.155 10 0.91
LiTFSI/PEO (20) 2.66 1.86 0.156 0.152 3.344 3.382 10 0.22
LiPSTFSI/PEO (20) / / / / / / / 0.92[7]
LiPSS/PEO (20) / / / / / / / 0.85[9]

I s R f [V  I o R1o ]
t Li  (S1)
I o Ri [V  I s R1s ]
Where ∆V is the DC potential applied across the cell; Is and Io are the steady-state and the initial current
determined by the DC polarization, respectively; Rlo and Rls are the interface resistance measured by the AC
impedance method before and after polarization; Ri and Rf are the initial and final resistances of the
electrolytes.

Table S5. The characterization data for the ionic conductivities of individual Li+ cations of blended polymer
electrolytes of the LiX/PEO (X=PSS, PSTFSI, PSsTFSI and TFSI) with a molar ratio EO/Li+ = 20.

Samples σLi+ (S cm−1)

(EO/Li+ = 20) 25 ºC 70 ºC 90 ºC
LiPSS/PEO 3.05 × 10−10 7.10 × 10−8 1.61 × 10−7
LiPSTFSI/PEO 1.92 × 10−9 7.75 × 10−6 2.97 × 10−5
LiPSsTFSI/PEO 7.11 × 10−9 6.92 × 10−5 1.35 × 10−4
LiTFSI/PEO 4.41 × 10−6 1.41 × 10−4 2.94 × 10−4
 1
H and 19F NMR spectra of the monomer (KSsTFSI) and its polymer (KPSsTFSI) are shown in Figure S1.
The successful preparation of the polymer salts (MPSsTFSI, M = K and Li) is well confirmed by comparing the
characteristic peaks in 1H and 19F NMR for the monomer (KSsTFSI) before and after polymerization reaction.
For example, in the 1H NMR spectra, the characteristic peaks for the monomer (KSsTFSI) at 5.38−6.88 ppm for
the protons of −CH=CH2 group (7.59−7.91 ppm for the phenyl protons) (Figure S1a) disappeared completely in
those of the corresponding products after polymerization (KPSsTFSI) (Figure S1c), and new broad peaks at
1.25−1.90 ppm corresponding to saturated hydrocarbon alkyl are observed, which displays the polymerization
occurring at double bonds.[10] Besides, the remarkable differences of 19F NMR spectra between the monomer
(two sharp peaks) and polymerized products (a broad peak) are also well observed, indicating that the polymer
salts (MPSsTFSI, M = K and Li) are successfully prepared.

Figure S1. Comparison of 1H and 19F NMR spectra of KSsTFSI and KPSsTFSI.
 The anodic electrochemical stability of the LiPSsTFSI/PEO blended polymer electrolyte was investigated
by linear sweep voltammetry. Figure S2 shows the polarization curve for the LiPSsTFSI/PEO blended polymer
electrolyte on Li/SPEs/SS coin type cells over a wide range of potentials at a sweep rate of 1 mV s−1 at 70 ºC.
As seen from Figure S2, a small anodic current (but below 5 µA cm−2) at ca. 4 V vs. Li+/Li is observed, which
would be attributed to the initializing oxidative decomposition of PEO. The anodic current is enhanced abruptly
from ca. 4.5 V vs. Li+/Li (above 10 µA cm−2). This would be explained by the concurrent oxidative
decomposition of both the PSsTFSI− anions and PEO matrix.[11] This result indicates that the anodic stability of
LiPSsTFSI/PEO blended polymer electrolyte would satisfy the requirements for application in 4 V-Li batteries.

Figure S2. Linear sweep voltammogram of the complex of LiPSsTFSI/PEO (EO/Li+ = 20) on Li/SPEs/SS coin
type cells, measured over a wide range of potentials from 2.7 to 6.0 V vs. Li+/Li.

Figure S3 shows the TGA traces of the polymer salt (LiPSsTFSI), and the LiX/PEO (X = PSS, PSTFSI,
PSsTFSI) blended polymer electrolytes (EO/Li+ = 20). As shown in Figure S3, the neat LiPSsTFSI salt is
thermally stable up to 290 ºC, which is well enough for its use as a conducting salt. Meanwhile, the
decomposition temperature of the LiPSsTFSI/PEO blended electrolyte at 337.2 ºC is observed, which is slightly
lower than that of both the LiPSTFSI/PEO and LiPSS/PEO ones. But it still meets the requirements for
application in Li batteries in ambient temperature region.

Figure S3. TGA traces of the polymer salt (LiPSsTFSI), and the LiX/PEO (X = PSS, PSTFSI, PSsTFSI) blended
polymer electrolytes (EO/Li+ = 20).
Figure S4. The representative structure of neat LiX (X = PSS, PSTFSI, PSsTFSI).

Figure S5 compares the DSC traces of the monomer (KSsTFSI) and the polymer salts (MPSsTFSI, M = K
and Li) at the first heating scan. It can be seen that a small broad endothermic peak is observed at −5.0 ºC
(Figure S5), corresponding to a glass transition. With further increasing the temperature, a large broad
exothermic peak appears at 122.8 ºC, which can be ascribed to a thermal polymerization of the KSsTFSI
monomer,[7] as this peak vanished at the second heating scan (The data are not shown).
It is important to note that glass transitions (Tg) are also observed for the two polymer salts, at the
temperature of 75.1 ºC for KPSsTFSI, and at 44.3 ºC for LiPSsTFSI (Figure S5), respectively. In contrast, glass
transitions below 50 ºC have not observed for any neat Li ionomer based on lesser delocalized anions (e.g.,
−CO2−, −SO3− and −SO2-N(−)-SO2-CF3) without PEO blending.[7] Such an unusual behavior for the neat polymer
salts (KPSsTFSI and LiPSsTFSI) would thank for the high flexibility and super-delocalized negative charge
distribution of the −SO2-N(−)-SO(=NSO2CF3)-CF3 structure in PSsTFSI− anion, is a signature of strongly
plasticizing effect for creating high degrees of amorphous phase when dissolved in PEO. This is key for
effectively enhancing ionic conductivities of SPEs, as ion transports in SPEs with high molecular weight PEO
as host mainly occur in amorphous phase.[12] Additionally, the glass transition temperature is lower for
LiPSsTFSI than for KPSsTFSI, presumably due to the better mobility for smaller Li+ cations in the former.

Figure S5. DSC traces of the monomer (KSsTFSI) and the polymers (KPSsTFSI and LiPSsTFSI) at the first
heating scan.
 Figure S6 shows the DSC traces of the LiPSsTFSI/PEO blended polymer electrolyte (EO/Li+ = 20),
wherein the DSC traces for two successive heating scans are presented. As seen from Figure S6, two
endothermic peaks are observed at both the first heating scan and the second heating scan. The former
endothermic peaks (Tg) at −15.1 ºC and −15.3 ºC (Table S2) correspond to the onset of polymeric motions in a
minority amorphous phase for the first heating scan and the second heating scan, respectively. The latter
endothermic peaks (Tm) at 70.0 ºC and 63.9 ºC could be gradual melting of crystalline PEO for the first heating
scan and the second heating scan, respectively.[11] Important note is that crystallite melting temperature (Tm)
decreases from 70.0 ºC to 63.9 ºC and the value of melting enthalpy (∆Hm) decreases from 58.3 J g−1 to 49.8 J
g−1 by comparing the first heating scan with the second heating scan. This is presumably due to the slow kinetic
rate of the recrystallization of PEO, as described in the literature. [13]

Figure S6. DSC traces of the LiPSsTFSI/PEO blended polymer electrolyte (EO/Li+ = 20 by mole).

Li-ion transference number (tLi+) is a key parameter for evaluating the performance of SPEs. The tLi+ for all
these four blended polymer electrolytes in Figure 3b were measured by a combining AC impedance and DC
polarization method (Figure S7), and are summarized in Table S4. The value of tLi+ for the classic ambipolar
LiTFSI/PEO (EO/Li+ = 20) blended electrolyte is 0.22 at 60 ºC, which is comparable to that of 0.29 reported in
the literature.[14] It is noticeable that the value of tLi+ for the complex of LiPSsTFSI/PEO is as high as 0.91 at 60
ºC, indicating that this blended polymer electrolyte based on the super-delocalized polyanion exhibits single
Li-ion conducting behavior, which is essentially due to the huge volume of the polyanion. Additionally, single
Li-ion conducting behaviors were also observed for the two lesser conductive blended electrolytes, LiPSS/PEO
and LiPSTFSI/PEO (e.g., 0.85 for the former and 0.92 for the latter at 60 ºC, Table S4).

Figure S7. Impedance spectra (a) and time-dependence response of DC polarization (b) for the complex of
LiPSsTFSI/PEO (EO/Li+ = 20) on the [Li metal | SPEs | Li metal] symmetric cell at 60 ºC, polarized with a
potential of 10 mV.
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