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Polymerized Ionic Networks with High Charge Density:

Quasi-Solid Electrolytes in Lithium-Metal Batteries
Pengfei Zhang, Mingtao Li,* Bolun Yang, Youxing Fang, Xueguang Jiang,
Gabriel M. Veith, Xiao-Guang Sun, and Sheng Dai*

In the past two decades, poly(ionic liquid)s (PILs), a new family

of functional polymers, have attracted increasing interest owing
to their promising performance in various fields such as membrane science, catalysis, analytical chemistry, CO2 capture, and
electrochemistry.[1] In general, PILs are prepared by conventional or controlled radical polymerization of ionic liquid (IL)
monomers bearing vinyl groups.[2] PILs with designable cations
and anions afford several unique properties, such as ionic conductivity, processability, self-assembly to colloidal nanoparticles,
and controllable porosity.[3] For instance, a family of porous PIL
membranes have been fabricated by a template-free strategy.[3d,e]
Actually, PILs were originally designed as solid ionic conductors
by the Ohno group in 1998.[4] The rationale behind the above
strategy is that the presence of an IL moiety in the repeating unit
of the PIL chains can integrate some desirable IL characteristics
(e.g., high ionic conductivity) into the polymeric architecture.[5]
Therefore, PILs could be considered potential solid electrolytes,
a topic of significant interest in the field of electrochemistry.
Meanwhile, lithium (Li) metal batteries are considered as
one of the most attractive candidates for next-generation energy
storage systems.[6] For battery applications, Li metal possesses
a number of advantages, such as high theoretical capacity
(3860 mA h g1), and the lowest negative electrochemical potential (3.04 V vs a standard hydrogen electrode).[7] However,
several issues, such as serious safety and/or cell lifetime problems induced by dendrite formation or the instability of the
electrolyte (e.g., leakage of liquid electrolytes), continue to
obstruct the development of the Li metal batteries for practical
applications. It is widely acknowledged that the uneven
Dr. P. Zhang, Prof. M. Li, Dr. X.-G. Sun, Prof. S. Dai
Chemical Sciences Division
Oak Ridge National Laboratory
Oak Ridge, TN 37831, USA
E-mail: lmt01558@mail.xjtu.edu.cn; dais@ornl.gov
Prof. M. Li, Prof. B. Yang
School of Chemical Engineering and Technology
Xian Jiaotong University
Xian, Shaanxi 710049, China
Dr. Y. Fang, Dr. X. Jiang, Prof. S. Dai
Department of Chemistry
University of Tennessee
Knoxville, TN 37996, USA
Dr. G. M. Veith
Materials Science and Technology Division
Oak Ridge National Laboratory
Oak Ridge, TN 37831, USA

DOI: 10.1002/adma.201502855

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electrodeposition of Li during repeated chargedischarge cycles

leads to the formation and proliferation of dendrites from
the anode to the cathode, which could cause catastrophic cell
failure with the risk of thermal runaway-induced fire if a flammable electrolyte is employed.[8]
To address these issues, various solid electrolytes (e.g., Li
nitride, polymer electrolyte) have been widely investigated as
alternatives for organic liquid electrolytes.[9] Polymer electrolytes are one of the promising classes; however, the popular
complexes of an Li salt and polyethylene oxide have very low
conductivities at room temperature (<105 S cm1).[10] In solid
polymer electrolytes, ionic conductivities are governed by
both the segmental motion of the chains and the number of
dissociated carrier ions and their mobility.[11] As was noted
earlier, PILs may have the potential to serve as polymer electrolytes for advanced batteries, and the charge density of the
PILs is an important factor controlling ionic conductivity. For
example, Yang and co-workers illustrated that gel polymer
electrolytes based on dicationic PILs showed an ionic conductivity of around 4.6 105 S cm1 at 25 C, which was superior
to the performance of the composite electrolytes containing
monocationic PILs (e.g., 105 S cm1 at 25 C).[12] Recently,
Drockenmuller and co-workers demonstrated the facile synthesis of 1,2,3-triazolium-based PIL networks with an anhydrous ionic conductivity of 2 108 S cm1 at 30 C.[13] Unfortunately, there is still a large difference between these polymer
materials and the state-of-the-art organic liquid electrolytes
in Li-ion batteries (around 102 S cm1 at room temperature)
with respect to ionic conductivity. To design high ion conductivity polymers, the density of ion pairs must be increased.
In this contribution, we demonstrate an interesting class
of PILs with a high charge density (six ion pairs per repeating
unit)polymerized ionic networks (PINs). Their macromolecular backbones build on two simple and efficient pathways (Scheme 1): (1) a direct nucleophilic substitution reaction
between hexakis(bromomethyl)benzene and 4,4-bipyridine,
which enables ionization and polymerization in one process, and
(2) a free radical polymerization of the ionic monomer bearing
six 1-vinylimidazolium cations. Solid-like ternary electrolytes
with PINs as the polymer hosts and LiTFSI in 1-ethyl-3-methylimidazolium bis(trifluoromethane)sulfonimide (EMIM-TFSI)
(0.5 mol kg1) as the plasticizer exhibit good ionic conductivities (up to 5.32 103 S cm1 at 22 C), wide electrochemical
stability windows (up to 5.6 V), and good interfacial compatibility with the electrodes. Moreover, an Li/LiFePO4 battery
assembled with the PIN-based electrolytes possesses an initial
high discharge capacity of 146 mA h g1 at 25 C.

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Scheme 1. The reaction route to obtain polymeric ionic networks (PINs): a) PIN-1. b) PIN-2. c) PIN-3. d) PIN-4.

The synthesis of PIN-1 involved the cross-linking of a

hexakis(bromomethyl)benzene tecton with a 4,4-bipyridine
linker via a nucleophilic substitution mechanism,[14] followed
by an ion-exchange process to introduce TFSI anions into the
matrix. This pathway coupled alkylation and polymerization in
one reaction and proceeded under mild conditions. At 80 C,
the solution became yellow and precipitated in several minutes. The other route for synthesizing PIN-3-Br proceeded
by the polymerization of monomers densely substituted by
1-vinylimidazolium cations, a precursor recently developed by
the Poly(ionic liquid)s Group in Germany.[15] The temperature
required for current radical polymerization (120 C) is higher
than that used for the synthesis of polyvinylimidazolium

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nanoparticles (65 C). The current reaction was performed

in solvothermal conditions with autogenic pressure, thereby
leading to a solid electrolyte material with a higher degree of
cross-linking. All the PIN samples are insoluble in organic
solvents (e.g., ethanol, tetrahydrofuran, and N,N-dimethylformaldehyde) or water, possibly owing to the formation of 3D
networks. The anion exchange from Br to TFSI was aimed
at achieving a wider electrochemical voltage window and better
compatibility with EMIM-TFSI and the electrodes. The anion
exchange process of PINs was carried out in a 15 wt% LiTFSI
aqueous solution at 50 C for easier accessibility of the Br
anions trapped in the highly cross-linked networks. After the
anion exchange, four peaks in the Fourier transform infrared

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Figure 1. ac) Fourier transform infrared spectra of PIN samples. d) 1H nuclear magnetic resonance (NMR) spectra of samples (in D6-DMSO) during
the synthesis of PIN-2-Br, reaction condition: 1,3,5-tris(bromomethyl)benzene (1 mmol), 4,4-dipyridyl (1.5 mmol), N-methyl-2-pyrrolidinone (15 mL)
solvent, stirring at room temperature for 165 min and at 40 C for 140 min. e) Solid-state 13C NMR spectrum of the PIN-1-Br sample. f) Solid-state
13C NMR spectrum of the PIN-3-Br sample.

(FTIR) spectra appeared (1344, 1177, 1128, and 1050 cm1)

that could be assigned to the vibration sorption of TFSI
anions (a(SO2), a(CF3), s(SO2), and a(SNS), respectively
(Figure 1a,b).
The radical polymerization of PIN-3-mono was also characterized by FTIR, during which the intensity of the characteristic
peak for the vinyl group (1654 cm1) significantly decreased
(Figure 1b). Based on the integrated signal areas, the ratio of vinyl
group before and after polymerization is 4.43:1, and the degree of
polymerization of PIN-3 (the fraction of reacted repeating units)
is around 77.4% (Figure 1c). A higher degree of polymerization
was observed (93.1%) in the PIN-4 sample, suggesting that most
vinyl moieties had already been incorporated into the crosslinked polymer network (Figures S1 and S2, Supporting Information). The monomer conversion of PIN-2 was also investigated by nuclear magnetic resonance (NMR) measurements
(note that the hexakis(bromomethyl)benzene monomer cannot
be completely dissolved in N-methyl-2-pyrrolidinone, resulting
in the study of PIN-1 synthesis by NMR impossible). The peak
at = 4.7 ppm (for CH2Br in 1,3,5-tris(bromomethyl)benzene)
shifts to 6.0 ppm after the nucleophilic substitution by 4,4-bipyridine, and the ratio of reacted CH2Br can be used to estimate the degree of cross-linking (Figure 1d and Figure S3S6,

Adv. Mater. 2015,

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Supporting Information). The degree of polymerization reached

49.2% in 5 h at room temperature, after when a lot of solids
were formed in the solution.
The structure of the PINs was investigated at the molecular
level by solid-state 13C cross-polarization magic angle spinning
nuclear NMR spectroscopy.[14a,b,e] In PIN-1-Br, the signal at
145.7 ppm (Figure 1e) is attributed to the pyridinium carbon
(C-2, C-4, and C-6 positions) bearing the positive charge, and
peak C (128.1 ppm) is assigned to the carbons at the C-3 and C-5
positions. The B peak at 135.5 ppm is ascribed to the substituted
phenyl carbons. The peak at 63.7 ppm should be the result of the
benzylic carbon atom close to the positive unit. The NMR spectrum of PIN-3-Br is shown in Figure 1f. The high-intensity peak
at 138.2 ppm is considered the overlapped contribution of the
phenyl carbons and the imidazolium carbon at the C-2 position,
and the carbon atoms at the C-4 and C-5 positions of the imidazolium ring lead to the peak at 124.9 ppm. The broad signal
from 22.5 to 64.0 ppm consists of three peaks at 55.4, 49.9, and
40.2 ppm, which can be induced by the benzylic carbon atoms
and the 1-ethyl group of the imidazolium ring, respectively.
Figure 2a illustrates the thermogravimetric analysis curves
of the PIN samples, which are thermally stable up to 250 C,
well above the melting point of Li metal. X-ray diffraction

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microscopy (SEM) image that the PIN

samples are made of secondary irregular particles with rough surfaces (Figure 2c,d). The
particle size of PIN-1 (21.0 m) is much
bigger than that of PIN-3 (300600 nm)
(Figure S7, Supporting Information).
Predetermined amounts of the as-prepared PINs were directly blended with
LiTFSI or LiTFSI in an EMIM-TFSI solution
(0.5 mol kg1) to produce hybrid electrolytes
(Figure 3a, Table S1, Supporting Information). As shown in the photographs, the
PIN-1@LiTFSI sample was processed into a
solid electrolyte membrane, which exhibited
moderate ionic conductivity at room temperature (1.17 104 S cm1) (Figure 3b). The
positively charged backbone of the PINs was
expected to interact with TFSI anions by electrostatic force and thus liberates Li+ for faster
mobility along the highly charged channels
(Figure 3a). To understand the coupled structure, XRD patterns of PINs@LiTFSI samples
were collected. It is interesting that the crysFigure 2. a) Thermogravimetric analysis curves of PIN samples in an N2 atmosphere; heating talline peak of LiTFSI disappeared after it was
rate: 10 C min1. b) X-ray diffraction patterns of PIN samples. c) Scanning electron microscopy loaded into the PIN hosts (Figure 3c). All the
(SEM) image of PIN-1. d) SEM image of the PIN-3 sample.
PINs@LiTFSI samples afforded extremely
broad peaks, similar to those of amorphous PINs. It seems that
(XRD) measurements of PINs exhibited two broad reflections
the strong electrostatic interaction and the sharing of the same
around 22 and 40; thus, these polymers were in an amoranion between the LiTFSI and the PINs may restructure the
phous state (Figure 2b). It can be seen in the scanning electron

Figure 3. a) Schematic representation of the PIN-1@LiTFSI-EMIMTFSI hybrid electrolyte used in the study. b) A photograph of a PIN-3@LiTFSI solid
membrane. c) X-ray diffraction patterns of PIN@LiTFSI samples. d) N1s X-ray photoelectron spectroscopy curves of PIN-3 and controlled samples
with LiTFSI (28.7 wt%) or EMIM-TFSI (190 wt%) additives. e) A photograph of PIN-3@LiTFSI-EMIMTFSI.

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ion pair structure of LiTFSI. Because both positive and negative charges are borne on the nitrogen atoms of PINs, N1s X-ray
photoelectron spectroscopy (XPS) measurements were then
carried out to investigate the electrostatic interaction. The N1s
peaks of the PIN samples were broad, suggesting the coexistence of different nitrogen species. The peak was fitted with a
Shirley background and GaussianLorenz model functions, and
two peaks at 399.2 and 401.5 eV were obtained, which could
be assigned to the pyridinum N+ form and N species in the
TFSI anion, respectively (Figure 3d).[16] The N1s XPS spectra
of PIN-3@LiTFSI (1/0.287, wt/wt) with more TFSI anions
afforded a higher intensity of peak for N atoms; and only
one peak corresponding to the N species in TFSI anion was
observed, indicating the homogeneous distribution of LiTFSI
anions in the PIN-3 host. Similar results were also collected for
the PIN-3@EMIMTFSI sample (1/1.9, wt/wt). Thus, it is concluded that PINs with highly charged structures can provide a
solid, mechanically strong matrix alone or together with other
ionic compounds for the fabrication of solid electrolytes.
In consideration of the interfacial property toward the electrode material and the desired ionic conductivity, 0.5 mol kg1
LiTFSI in EMIM-TFSI was incorporated into PINs to fabricate
solid-like electrolytes (Figure 3e, PIN@LiTFSI-EMIMTFSI).
Compared with the ratio of ILs doped in the monocationic PIL
(e.g., 65 wt%) or the dicationic PIL (e.g., 95 wt%), a significantly
enhanced value was observed in PINs (up to 190 wt%) as the
polymer host (Table S1, Supporting Information).[12] Such a large
difference in the IL incorporation capability can be attributed
to the stronger intermolecular interaction between ILs and the
highly charged PINs, which has also been observed by Yang and
co-workers.[12a] Initially, the electrochemical stability of the PIN@
LiTFSI-EMIMTFSI electrolytes at 25 C was studied by linear
sweep voltammetry, as shown in Figure 4a. Except for PIN-3
(4.7 V vs Li/Li+), all other PIN-based electrolytes are stable above
5.0 V versus Li/Li+. In particular, the decomposition of PIN-2
occurs around 5.6 V versus Li/Li+, which makes it suitable for
application in high-voltage batteries. Based on the decomposing
voltage, it can be concluded that PINs linked by 4,4-bipyridine
(PIN-1 and PIN-2) are more stable than those from the polymerized vinyl groups (PIN-3 and PIN-4). It seems reasonable since
the backbone with bipyridine linker is more stable than that
linked by the CC bond. It can also be observed that PINs with
three substitution groups are more stable than the PINs with six
substitutions (PIN-2 > PIN-1, PIN-4 > PIN-3). The steric hindrance of PIN-1 and PIN-3 with six big substituted groups makes
them more decomposable, in comparison with PIN-2 and PIN-4.
Ion-conducting properties of PIN@LiTFSI-EMIMTFSI electrolytes under hydrous conditions were assessed by AC impedance techniques, and the ionic conductivities as a function of
temperature for those samples are presented in Figure 4b. As
expected, the PIN samples with a higher charge density (PIN-1 vs
PIN-2 and PIN-3 vs PIN-4) afforded a higher ionic conductivity;
the charge density of the polymer might be a factor affecting
the transport of Li+ ions. It is understandable that the ionic
conductivities of the PIN-based samples increase under higher
temperatures, roughly following VogelTammanFulcher-type
behavior. The increase indicates that the ionic conductivity of
the electrolytes is closely correlated with the viscosity of the
solution, and the ion mobilities in the electrolytes are mainly

determined by the property of the LiTFSI-EMIMTFSI electrolytes. It is important that all the solid-like electrolytes possess
good ionic conductivities on the order of 102103 S cm1 at
22 C, and the optimized sample of PIN-3@LiTFSI-EMIMTFSI
exhibits an ionic conductivity of 5.32 103 S cm1 at 22 C, a
very high value for a polymer-based solid electrolyte.
Lithium redox in the PIN@LiTFSI-EMIMTFSI electrolytes was
characterized by cyclic voltammograms (CVs) with an Li/electrolyte/Pt cell, as shown in Figure 4c,d and in Figure S8 (Supporting
Information). The plating and stripping of Li on the nickel electrode can be clearly observed, as in the EMIM-TFSI IL electrolytes.[17] In the first cycle for the PIN-1-based electrolyte and the
PIN-3-based electrolyte, the cathodic peaks corresponding to the
plating of Li are about 0.5 and 0.38 V versus Li/Li+, respectively;
and in the anodic scan, the peaks corresponding to the stripping
of Li are around 0.14 and 0.10 V versus Li/Li+, respectively. It
is noteworthy that in case of the Pt electrode, many peaks due
to the formation of LiPt alloys are observed, such as 0.62 and
0.70 V versus Li/Li+ in Figure 4c,d, respectively.[17b,c] The Li redox
in the PIN@LiTFSI-EMIMTFSI electrolytes could be generated
by forming a solid electrolyte interface (SEI) on the platinum
electrode; the CV curves do not change obviously in the following
cycles, suggesting that the SEI film formed is stable. The reversible plating and stripping of Li in the electrolytes and the stable
SEI film generated indicate the PIN@LiTFSI-EMIMTFSI electrolytes are suitable for application in Li batteries.
As an example, Li/LiFePO4 batteries with the electrolyte
PIN-1@LiTFSI-EMIMTFSI
or
PIN-3@LiTFSI-EMIMTFSI
were assembled, and their cycling performances were characterized at room temperature (Figure 4e,f). The batteries with
PIN-1 and PIN-3 show good initial discharge capacity of 146 and
143 mA h g1, respectively, and their corresponding Coulombic
efficiencies reach 97.5% and 96.3%. These results indicate that
the PIN-based solid-like electrolytes are promising candidates
for use in Li metal batteries. However, subsequently, the battery
capacity decreases slowly with cycling (Figure 4gh, Figure S9,
Supporting Information). It is noted that the solid-like electrolytes
are different from the traditional sticky polymer electrolytes. It is
found that our battery performance is closely associated with the
thickness of the solid-like electrolyte wafer and the wafer-shaped
stress. The optimization of the PIN-based electrolytes is ongoing.
Anyway, these results indicate that the PIN-based solid-like electrolytes are potential candidates for use in Li metal batteries.
In summary, PINs, an interesting class of charged frameworks,
were designed using two easy strategies, extending the scope of the
ionic polymer library from one charge per unit to densely charged
networks. Nucleophilic-substitution-mediated polymerization,
particularly, provides a direct, effective, versatile pathway to obtain
ionic polymers. Moreover, it has been shown that it is possible to
create solid-like polymer electrolytes with acceptable ionic conductivities at room temperature (5.32 103 S cm1). The key point of
this strategy is that a facile channel for Li+ mobility in a solid-like
condition can be easily achieved via the introduction of PINs as the
electrolyte matrix. The high charge density of PINs provides abundant, weakly coordinating sites during Li+ movement via electrostatic interaction. Meanwhile, their hierarchical and robust backbone not only provides a rich void for Li+ mobility, but also contributes to the mechanical strength of the electrolyte membrane.
We believe that PIN-based solids or solid-like electrolytes might

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Figure 4. a) Linear sweep voltammetry plots of a Li cell with PIN@LiTFSI-EMIMTFSI solid-like electrolytes. b) Temperature dependence of the ionic
conductivity of PIN@LiTFSI-EMIMTFSI solid electrolytes. c,d) Cyclic voltammograms for PIN@LiTFSI-EMIMTFSI electrolytes. Working electrode:
platinum; counter electrode and reference electrode: lithium; scan rate: 10 mV s1. e,f) Chargedischarge curves of Li/PIN@LiTFSI-EMIMTFSI/LiFePO4
cells at room temperature. g,h) Discharge capacity versus cycle number of the two hybrid electrolyte systems.

provide an alternative route for safe Li batteries. PILs were

unveiled around 17 years ago, but their unexpected potentials in
material science are a young topic, full of promise. In principle,
the present findings (PINs and nucleophilic-substitution-mediated
polymerization) can be extended to a number of ionic organic
materials for specific tasks by careful selection of monomers.

(FIRST) Center, an Energy Frontier Research Center funded by the

US Department of Energy, Office of Science, Office of Basic Energy
Sciences. Y.F., G.V., X.S., and S.D. (XPS and battery characterizations)
were supported by the U.S. Department of Energy (DOE), Basic Energy
Sciences (BES), Materials Sciences and Engineering Division. M.L.
appreciates the financial support from the National Natural Science
Foundation of China (21303132).
Received: June 13, 2015
Revised: August 7, 2015
Published online:

Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.

Acknowledgements
P.Z. and X.J. (polymer synthesis and characterization) were supported
as part of the Fluid Interface Reactions, Structures and Transport

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