Single lithium-ion conducting polymer electrolytes based on a super-delocalized polyanion

Article abstract of DOI:10.1002/anie.201509299

A novel single lithium-ion (Li-ion) conducting polymer electrolyte is presented that is composed of the lithium salt of a polyanion, poly[(4-styrenesulfonyl)(trifluoromethyl(S-trifluoromethylsulfonylimino)sulfonyl)imide] (PSsTFSI^-), and high-mo

Full text of DOI:10.1002/anie.201509299

Angewandte
Communications
Chemie
International Edition: DOI: 10.1002/anie.201509299
German Edition: DOI: 10.1002/ange.201509299
Ion Conductors
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*
Abstract: A novel single lithium-ion (Li-ion) conducting
polymer electrolyte is presented that is composed of the lithium
salt of a polyanion, poly[(4-styrenesulfonyl)(trifluorometh-
gradients of the salt and cell polarization, which causes
premature battery failure.
[15,16]
One of the best solutions to the above-mentioned prob-
lem is to prepare single Li-ion conductors (SLICs), in which
the anions are immobilized by anion trapping agents or by
yl(S-trifluoromethylsulfonylimino)sulfonyl)imide]
À
(
(
PSsTFSI ), and high-molecular-weight poly(ethylene oxide)
PEO). The neat LiPSsTFSI ionomer displays a low glass-
[
17–20]
fixing the anions to the polymeric backbones,
so that the
+
+
transition temperature (44.38C; that is, strongly plasticizing
transference number (tLi ) of Li cations is close to one. Until
effect). The complex of LiPSsTFSI/PEO exhibits a high Li-ion
transference number (tLi = 0.91) and is thermally stable up to
now, most of SLICs have been synthesized by grafting
+
À
[17]
common alkyl carboxylate (RCO )
and/or sulfonate
2
À
[18]
3
1
008C. Meanwhile, it exhibits a Li-ion conductivity as high as
.35 ” 10 Scm at 908C, which is comparable to that for the
(RSO )
anions to the polymeric backbones. However,
3
À4
À1
the ion dissociation in polyether media is very limited, owing
to the low degrees of negative charge distribution in these
anions.
classic ambipolar LiTFSI/PEO SPEs at the same temperature.
These outstanding properties of the LiPSsTFSI/PEO blended
polymer electrolyte would make it promising as solid polymer
electrolytes for Li batteries.
[21]
Armand et al. have reported a new type of SLICs by
blending lithium poly[(4-styrenesulfonyl)(trifluoromethane-
sulfonyl)imide] (LiPSTFSI) with PEO. Owing to the
enhanced flexibility and improved negative charge distribu-
S
olid polymer electrolytes (SPEs) for solvent-free lithium
Li) rechargeable batteries have captured much attention
(
À)
À
(
tion of the ÀSO ÀN ÀSO ÀCF vs. common ÀCO and À
2
2
3
2
À
owing to their potential advantages, including safety, ease of
packaging, excellent flexibility and containment, and their
functioning as a separator compared with liquid or gel
SO structures, the relatively high ionic conductivity of about
3
À5
À1
10 Scm at 708C has been obtained for the blended
polymer electrolytes. Then, the conductivities were further
improved by elegantly preparing random and triblock
copolymers of LiPSTFSI through incorporating ethylene
[
1–8]
electrolytes.
To date, great progress has been made by
utilizing LiTFSI (Li[(CF SO ) N])/poly(ethylene oxide)
3
2 2
[22,23]
(
PEO) SPEs for Li/LiFePO batteries, which is being used
oxide (EO) units in side and main chains, respectively.
4
[
9]
as power source for an electric car, Autolib. However,
conventional SPEs formed by dissolving Li salt with a small
anion in a polymer host (usually high-molecular-weight
PEO), are dual-ion conductors, in which both cations and
A prototype Li battery using this triblock polymer electrolyte
exceeds a conventional battery based on a dual-ion polymer
electrolyte, suggesting the importance of single Li-ion nature
in improving the cycling performances. Inspired by these
results, we envisaged that it would be beneficial to further
enhance ionic conductivities of such imide anion-based SLICs
by increasing its negative charge distribution.
[
10–14]
anions are mobile.
This would generate the concentration
Herein, we report a new type of single Li-ion conducting
polymer electrolytes, which are prepared by simply dissolving
lithium salt of a super-delocalized polyanion, namely poly[(4-
styrenesulfonyl)(trifluoromethyl(S-trifluooromethylsulfony-
[
*] Q. Ma, H. Zhang, C. Zhou, L. Zheng, P. Cheng, Prof. J. Nie,
Prof. W. Feng, Prof. Z. Zhou
Key Laboratory for Large-Format Battery Materials and System,
Ministry of Education, School of Chemistry and Chemical Engineer-
ing, Huazhong University of Science and Technology
À
limino)sulfonyl)imide] (PSsTFSI ; Scheme 1) in PEO. We
1
037 Luoyu Road, Wuhan 430074 (China)
devised this kind of new anion structure on the base of
E-mail: zb-zhou@mail.hust.edu.cn
following consideration. Replacing a =O group in above À
(
À)
Prof. Y.-S. Hu, Prof. H. Li, Prof. X. Huang, Prof. L. Chen
Key Laboratory for Renewable Energy, Beijing Key Laboratory for New
Energy Materials and Devices, Beijing National Laboratory for
Condensed Matter Physics, Institute of Physics
Chinese Academy of Sciences, Beijing 100190 (China)
E-mail: yshu@aphy.iphy.ac.cn
SO ÀN ÀSO ÀCF structure by a strong electron-withdraw-
2
2
3
ing group, =NSO CF , can create much more delocalized
2
3
(À)
À
anion structure (ÀSO ÀN ÀSO(=NSO CF )ÀCF , sTFSI ),
2
2
3
3
+
in which the Li cations would be highly dissociated from this
super-delocalized anion when mixed with a polymer media
(
that is, PEO), so that conductivities can be further
Prof. M. Armand
CIC energigune, Alava Technology Park, Albert Einstein
[24]
improved.
4
801510 MIÑANO lava (Spain)
The procedures for preparing the monomeric and poly-
meric salts are detailed in the Supporting Information. The
structure and composition of the monomer (KSsTFSI),
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201509299.
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Scheme 1. The synthetic routes of a) monomer and b) polymers.
DMAP=dimethylaminopyridine, AIBN=azodiisobutyronitrile.
Figure 1. a) Photographs of membrane for the neat PEO and the LiX/
PEO (X=PSS, PSTFSI, and PSsTFSI) blended polymer electrolytes
intermediate (KPSsTFSI), and target salt (LiPSsTFSI) were
1
19
+
characterized by H and F NMR (Supporting Information,
Figure S1). The neat LiPSsTFSI salt has a number-average
(EO/Li =20). b) DSC traces of neat PEO, LiPSsTFSI, and the LiX/PEO
+
(
X=PSS, PSTFSI, PSsTFSI) blended polymer electrolytes (EO/Li =20)
5
À1
at the first heating scan.
molecular weight (M ) of about 2 ” 10 gmol with a polydis-
n
persity index (PDI) of 2.21 (Supporting Information,
Table S1), and its complex of LiPSsTFSI/PEO exhibits an
+
oxidation potential at ca. 4.0 V vs. Li /Li (Supporting
measurement data are summarized in the Supporting Infor-
mation, Table S2). The neat PEO shows a sharp melting
transition peak at 70.18C, which is consistent well with the
Information, Figure S2), and is thermally stable up to 3008C
(
Supporting Information, Figure S3).
[27,28]
To understand the impact of degree of negative charge
previous reports for neat PEO.
Important note is that the
distribution in anion on the ionic conductivity of SPEs
reliably, the two related lithium polymer salts, lithium
poly(4-styrenesulfonate) (LiPSS) and LiPSTFSI (Supporting
Information, Figure S4), were also synthesized using the same
neat LiPSsTFSI salt displays a low glass transition temper-
ature (T ) at 44.38C (Figure 1b; Supporting Information,
g
Figure S5). This would be attributable to highly flexibility and
super-delocalized negative charge distribution of the ÀSO À
2
[22,25]
(À)
À
methods as described previously.
The membranes of all of
N
ÀSO(=NSO CF )ÀCF structure in PSsTFSI , which
2
3
3
+
À
the blended polymer electrolytes were prepared by a solu-
tion-casting method (the procedures are detailed in Support-
ing Information).
impedes the motion of both Li cations and PSsTFSI
anions to rearrange orderly in space (that is, slow kinetics of
crystallization), thus making LiPSsTFSI glassformer at low
temperature. In contrast, glass transitions below 508C have
not observed for any neat Li ionomer based on lesser
Figure 1a shows the photographs of membrane for the
neat PEO and the LiX/PEO (X = PSS, PSTFSI, and PSsTFSI)
+
À
À
blended polymer electrolytes at a molar ratio of EO/Li = 20,
delocalized anions (for example, ÀCO , ÀSO3 , and ÀSO À
2
2
(
À)
[17,21,22,25]
as the concentration of lithium salt to EO unit in the classic
LiTFSI/PEO SPEs around this ratio region has been found to
afford relatively high ionic conductivities in medium high
temperatures, and its ionic conduction is little affected by its
N
ÀSO ÀCF ) without PEO blending.
It is interest-
2
3
ing to note that a glass transition at the low temperature of
À15.18C is also observed for the LiPSsTFSI/PEO blended
electrolyte (this glass transition at the low temperature of
À15.38C is repeatedly observed at the second heating scan;
Supporting Information, Figure S6), and is however not
detected for both the LiPSS/PEO and LiPSTFSI/PEO
electrolytes. This result clearly indicates the stronger plasti-
[26]
heat history. It can be seen that self-standing, translucent
membranes are obtained. It is worthy to note that the
membrane of LiPSsTFSI/PEO blended electrolyte has
a better mechanical ductility than both the corresponding
LiPSTFSI/PEO and LiPSS/PEO electrolytes, which is per-
ceptible from appreciable manual bending or stretching. This
would be attributed to the much better flexibility and greatest
À
À
À
cizing effect of the PSsTFSI vs. PSS and PSTFSI anions,
which is consistent with the glassformer nature of neat
LiPSsTFSI, and is favorable for enhancing segmental motions
of PEO in the blended electrolyte. The glass transition
temperature is a qualitative signature of ion mobility in SPEs,
and a low glass transition temperature for LiPSsTFSI/PEO is
a sign of high ion mobility in the blended electrolyte.
Moreover, the LiPSsTFSI/PEO blended electrolyte displays
(
À)
delocalized negative charge distribution of the ÀSO ÀN
À
2
À
SO(=NSO CF )ÀCF structure (in PSsTFSI ), among these
2
3
3
three polyanions.
Figure 1b comparatively shows the DSC traces of the neat
PEO, LiPSsTFSI, and the three blended polymer electrolytes
of LiX/PEO (X = PSS, PSTFSI, PSsTFSI) with the same
the lowest value of enthalpy of melting (that is, DH =
m
+
À1
molar ratio of EO/Li = 20 at the first heating scan (all the
58.3 Jg ; Supporting Information, Table S2), which is obvi-
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À
ously lower than that for the LiPSTFSI/PEO electrolyte (that
PSsTFSI . This is totally consistent with the degree of
À1
is, DH = 71.9 Jg ; Supporting Information, Table S2), and is
negative charge distribution and freedom (that is, structural
flexibility) of the anion. This trend in XRD patterns is also
well consistent with the DSC results in Figure 1b (Supporting
Information, Table S2), wherein the complex of LiPSsTFSI/
PEO shows low glass transition before melting (that is, low
tendency to crystallize), while the latter two complexes of
LiX/PEO (X = PSS, PSTFSI) only show melting with larger
values of enthalpy (that is, a higher degree of crystalline
phase) without glass transitions (Supporting Information,
Table S2).
m
significantly lower than that for the LiPSS/PEO electrolyte
À1
(
that is, DH = 101.2 Jg ; Supporting Information, Table S2).
m
This is a signature of a higher degree of amorphous phase in
the former (LiPSsTFSI/PEO) than in the latter two (LiPSS/
PEO and LiPSTFSI/PEO). All above results obtained from
DSC characterization suggest that the LiPSsTFSI/PEO
blended electrolyte has higher degrees of amorphous phases
and larger segmental motions than both the LiPSS/PEO and
LiPSTFSI/PEO electrolytes, which are beneficial for improv-
ing its ionic conductivities.
Figure 3a compares the temperature dependence of ionic
conductivities (s) for the LiX/PEO (X = PSS, PSTFSI,
PSsTFSI) blended polymer electrolytes with a molar ratio
Figure 2 comparatively displays the XRD patterns of the
LiX/PEO (X = PSS, PSTFSI, PSsTFSI) blended polymer
+
+
electrolytes with a molar ratio of EO/Li = 20, as well as the
of EO/Li = 20, as well as the classic LiTFSI/PEO blended
electrolyte for comparison, and some of the representative
data are presented in the Supporting Information, Table S3.
As seen from Figure 3a, our conductivity values for the classic
LiTFSI/PEO blended electrolyte are consistent with the
[26]
previous report,
indicating that our measurements are
[
29]
reliable. As a common feature for the PEO-based SPEs, an
increase in the ionic conductivity to a variable extent is
observed with increasing the temperature up to about 708C
for all the LiX/PEO (X = PSS, PSTFSI, PSsTFSI, TFSI)
blended electrolytes (Figure 3a), owing to a crystalline melt-
ing transition of the PEO host and/or the free-volume
activation. The ionic conductivities for all these four kinds
of blended electrolytes decrease in the order of LiTFSI/
PEO > LiPSsTFSI/PEO > LiPSTFSI/PEO > LiPSS/PEO in
the measured temperature range from 25 to 908C. It is
generally accepted that the ionic conductivity of SPEs is
mainly governed by the polymer crystallinity and/or glass
transition temperature, and the charge carrier concentra-
[2,22,25,30]
tion.
The highest ionic conductivities for the blended
electrolyte containing LiTFSI are observed, which is expected
+
À
from that both the Li cations and relatively small TFSI
anions are mobile in the complex of LiTFSI/PEO. By
contrast, the three blended electrolytes containing the
polymer salts show obviously lower ionic conductivities,
which is due to the huge volume of the polymeric anion.
Figure 2. XRD patterns of the LiX/PEO (X=PSS, PSTFSI, PSsTFSI)
blended polymer electrolytes (EO/Li =20), as well as the neat PEO
and LiPSsTFSI.
+
neat PEO and LiPSsTFSI for
comparison. As shown in
Figure 2, two sharp diffraction
peaks are observed at 2q =
1
9.28 and 23.38 for the neat
PEO, suggesting the nature of
[14]
highly crystalline phase. In
contrast, no characteristic dif-
fraction peak is observed for
the neat LiPSsTFSI salt, indi-
cating a mainly amorphous
phase. It is interesting to note
that the intensities of these
two representative XRD
peaks for neat PEO decrease
rapidly with addition of the
Figure 3. a) The temperature dependence of ionic conductivities for the LiX/PEO (X=PSS, PSTFSI,
+
PSsTFSI, TFSI) blended polymer electrolytes (EO/Li =20). b) The temperature dependence of ionic
+
polymer salts in the anion conductivities of Li cations for the LiX/PEO (X=PSS, PSTFSI, PSsTFSI, TFSI) blended polymer electrolytes
À
À
+
(
EO/Li =20).
order of PSS < PSTFSI <
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+
Among these three blended electrolytes containing polymeric
anions, the complex of LiPSsTFSI/PEO displays the highest
conductivities, and is higher by about one order in magnitude
than those of the previous state-of-the-art LiPSTFSI/PEO
electrolyte, and higher by 2–3 orders in magnitude than those
of LiPSS/PEO electrolyte in the whole temperature range.
This would be essentially attributed to more flexible and
an oxidation potential at ca. 4.0 V vs. Li /Li, and is thermally
stable up to 3008C. The ionic conductivities of the LiPSsTFSI/
PEO (EO/Li = 20) blended electrolyte are higher by about
one order in magnitude than those of the LiPSTFSI/PEO
(EO/Li = 20) electrolyte, and by 2–3 orders in magnitude
than those of LiPSS/PEO (EO/Li = 20) electrolyte over the
whole temperature range. This is essentially attributed to the
+
+
+
(
À)
(À)
super-delocalized nature of the ÀSO ÀN ÀSO(=NSO CF )À unique structure of ÀSO ÀN ÀSO(=NSO CF )ÀCF in the
2
2
3
2
2
3
3
À
À
CF structure (in PSsTFSI ) compared with both the ÀSO À PSsTFSI anion with both super-delocalized negative charge
3
À)
2
À
(
À
À
3
N
ÀSO ÀCF (in PSTFSI ) and ÀSO structures (in PSS ),
distribution and highly flexible features, which not only makes
2
3
+
which can not only further improve polymeric segmental
motions responsible for promoting Li-ion motion through the
chains of PEO in amorphous phase, but also increase degree
of dissociation of the Li salts. This anion-dependence trend in
conductivity concurs with the results in DSC and XRD
measurements (Figures 1b and 2), wherein a higher degree of
amorphous phase is observed in the complex of LiPSsTFSI/
PEO.
highly dissociation of Li ions from anions but also favorably
enhances the degrees of amorphous phases and the segmental
motions in SPEs required for ionic conduction. More
+
importantly, the ionic conductivities of individual Li cations
for the LiPSsTFSI/PEO blended electrolyte are comparable
to those for the classic ambipolar LiTFSI/PEO electrolyte
above the melting point of PEO. All of these preliminary
results suggest that the LiPSsTFSI would be a promising salt
of polymer electrolyte and would open the door to design new
highly conductive single lithium-ion conductors for lithium
batteries.
+
The lithium-ion transference number (tLi ) is a key
parameter for evaluating the performance of SPEs. The
+
value of tLi for the classic ambipolar LiTFSI/PEO blended
electrolyte is 0.22 at 608C, which is comparable to that of 0.29
[30]
+
reported previously. The value of tLi for the complex of
LiPSsTFSI/PEO is as high as 0.91 at 608C, indicative of single Acknowledgements
Li-ion conducting behavior, which is expected from the huge
volume of the polyanion (Supporting Information, Tables S4
and Figure S7).
This work was supported by the National Natural Science
Foundation of China (Nos. 51172083, 51222210, 51472268).
+
The ionic conductivities of individual Li cations in SPEs
play a paramount role in dictating the performance of Li
batteries, as Li cations are only active species needed during
Keywords: blended polymer electrolytes · ion conductors ·
lithium batteries · Li-ion conductivity
+
the cycling process of Li batteries; however, few work have
characterized the conduction behaviors of individual Li
+
How to cite: Angew. Chem. Int. Ed. 2016, 55, 2521–2525
Angew. Chem. 2016, 128, 2567–2571
cations. Figure 3b comparatively displays the temperature
+
dependence of ionic conductivities of individual Li cations
+
+
+
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+
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[
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À1
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À4
+
À1
+
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=
Li
À4
À1
+
1
1
.35 ” 10 Scm
0
(LiPSsTFSI/PEO)
(LiTFSI/PEO);
vs.
sLi = 2.94 ”
Information,
À4
À1
Scm
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ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
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