Journal of Power Sources 306 (2016) 258e267

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Journal of Power Sources

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

Thermally cured semi-interpenetrating electrolyte networks (s-IPN)

for safe and aging-resistant secondary lithium polymer batteries
Jijeesh R. Nair a, **, Matteo Destro a, b, Federico Bella a, Giovanni B. Appetecchi c,
Claudio Gerbaldi a, *
a
GAME lab, CHENERGY Group, Department of Applied Science and Technology (DISAT), Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129 Torino,
Italy
b
LITHOPS Batteries S.r.l., Via della Rocca 27, 10123 Torino, Italy
c
ENEA, Agency for New Technologies, Energy and Sustainable Economic Development, SSPT-PROMAS-MATPRO, Via Anguillarese 301, 00123 Roma, Italy

h i g h l i g h t s

Thermally cured semi-interpenetrated solid electrolyte networks.

Simple, cheap thermal polymerisation approach for Li polymer batteries.

Green polymer electrolytes with safe and aging-resistant characteristics.

Stable cycling in Li/LiFePO4 cells at 70  C for >2000 cycles.

a r t i c l e i n f o a b s t r a c t

Article history: Truly solid polymer electrolyte membranes are designed by thermally induced free radical polymeri-
Received 25 July 2015 sation. The overall membrane architecture is built on a semi-interpenetrating polymer network (s-IPN)
Received in revised form structure, where a di-methacrylate oligomer is cross-linked (in situ) in the presence of a long thermo-
14 November 2015
plastic linear PEO chain and a supporting lithium salt to obtain a freestanding, exible and non-tacky
Accepted 1 December 2015
Available online 18 December 2015
lm. In the envisaged systems, the di-methacrylate functions as a soft cross-linker, thus avoiding
physico-mechanical deformation of the s-IPNs at elevated temperature, without hampering the ionic
conductivity. s-IPNs exhibit remarkable stability towards lithium metal and no traces of impurity are
Keywords:
Interpenetrating polymer network
detected while testing their oxidation stability (4.7 V vs. Li/Li) towards anodic potential. The newly
Thermal polymerization elaborated system is also successfully tested at moderately high temperature in Li metal cells in which
Polymer electrolyte LiFePO4/C is used as the cathode active material, showing excellent indications of safe and highly durable
Lithium battery electrolyte separator (i.e., 2000 cycles at reasonably high 1C rate).
Aging resistance 2015 Elsevier B.V. All rights reserved.

1. Introduction
Energy economy and related complications are the everlasting
phobia of 21st century [1e3]. Even though many means of pro-
ducing energy are established, effectively using them by efcient
storage remains one of the biggest concerns of present and future
generations [4,5]. An efcient storage system can effectively
improve our lifestyle, cultural integration and transportation
* Corresponding author.
** Corresponding author.
E-mail addresses: jijeesh.nair@polito.it (J.R. Nair), claudio.gerbaldi@polito.it
(C. Gerbaldi).
system. Unfortunately, the worries are still worries and options are
still immature. Among the existing energy storage options, lithium-
ion batteries (LiBs) have cultivated the benets and still lead the
market [6,7]. Even though other innovative approaches are getting
closer to the reality, their stability and adaptability are yet to be
quantied [8,9]. Thus, the present scenario demands better per-
forming materials that can compensate the troubles existing in the
current technology such as safety, heavy packaging materials,
ageing stability, ecocompatibility and cost [10e12].
Many of the above mentioned issues related to LiBs can be
overcome by moving to an all-solid conguration [13,14]. Moreover,
another drawback is the use of solvents in most of the preparation
procedures, thus increasing the concerns related to high impact
processes and disposal of organic (most often halogenated)

http://dx.doi.org/10.1016/j.jpowsour.2015.12.001
0378-7753/ 2015 Elsevier B.V. All rights reserved.
 J.R. Nair et al. / Journal of Power Sources 306 (2016) 258e267
solvents. On the contrary, the use of water as solvent in different
preparation procedures should be one of the main objectives of the
scientic community in view of the assessment of the next-
generation of large-scale energy storage systems [15]. However,
the scientic activity in this direction is rather scarce, and most of
the cell components reported in the literature are prepared in
hazardous conditions, by means of processes including many
expensive heat treatments and prolonged separation/purication
steps [16,17].
The choice of the preparation conditions becomes even more
relevant when coupled with the disposal of conventional liquid
organic electrolyte solutions, made of a lithium salt dissolved in
organic carbonates. Indeed, all-solid state batteries can lead to
substantial benets, such as excellent processability and exibility,
higher safety, minimization/prevention of short circuits due to
lithium dendrite crystals growth upon cycling and ease of handling
[18,19]. Moreover, solid-sate electrolytes also act as separators
insulating the positive electrode from the negative one. To this
purpose, they are requested to possess suitable physical properties
in terms of mechanical robustness, elasticity and thermal stability
[20,21].
We recently proposed various polymeric matrices suitable as LiB
solid electrolytes [22e26]. However, a relevant limit is the absence
of a polymeric matrix capable of providing all the required pecu-
liarities cited above. To this purpose, a promising solution could be
given by interpenetrating polymer networks (IPNs). Indeed, by
taking monomers or oligomers that polymerize by different
mechanisms, two IPNs having contrasting or complementary
properties can be produced. The major advantage of these hybrid
systems lies in their superior combination of physical, chemical,
thermal, mechanical and electrical properties, which can be ach-
ieved by appropriately selecting these components and by adjust-
ing their relative proportions [27]. Despite their potential interest,
as being often used in the eld of fuel cells [28] or in the prepa-
ration of special binders for electrodes in energy storage systems
[29,30], to the best of our knowledge only a few groups proposed
IPN-based polymer electrolyte for lithium batteries. Passerini et al.
[31] and Momma et al. [32] prepared a PEO-PS di-block copolymer
gel electrolyte that showed high ionic conductivity (1 mS cm1 at
ambient temperature) and kept a discharge capacity of 124 mAh
g1 during 30 cycles. However, this system still contained a high
quantity of solvent within the polymeric network; moreover, a
study of prolonged cycling was not proposed.
In general, accordingly to the IUPAC denition [33], systems
comprising one or more polymer networks and one or more linear
polymers characterized by molecular scale penetration of at least
one of the networks by a linear macromolecule are generally clas-
sied as semi-interpenetrating polymer networks (s-IPNs). A s-IPN
[34] is identied from an IPN due to the presence of linear mac-
romolecules that can be separated from the constituent polymer
network without breaking any chemical bonds. The most inter-
esting semi-interpenetrating networks reported in the literature so
far include: PEO-PU-PAN [35], PMMA/PEGDA [36], PEGDMA/pol-
y(siloxane-g-allyl cyanide)/PEGDME [37], TMPTA/PVDF-co-HFP
[38], PEG/PMMA [39], multi-armed oligo(ethyleneoxy)phosphate
[40], PEO-co-EC/POSS-A/ETPTA [41], PMMA/polysiloxane-co-pro-
pyloxymethoxytriglycol [42], and PEGDA-co-PVC/PVDF-co-HFP
[43]. Interestingly, recent results concerning the preparation of
polymer electrolytes incorporating polymerised ionic liquids or
other polymer systems having linear chains in semi-
interpenetrating network-like architecture is also pacing up
[43e45]. Shaplov et al. [46] reported high ionic conductivity
(>104 S cm1 at 25  C), excellent mechanical properties and stable
interfacial properties for a s-IPN-based system that contains reac-
tive ionic liquid, nitrile butadiene rubber and methacrylate-based
259
oligomers. In general, in all the above reported results, the role of
linear chain is to impart ionic conductivity and/or mechanical
properties.
Considering the existing know how, in the present work we
propose newly elaborated truly-solid s-IPN-based polymer elec-
trolyte membranes. The samples are prepared by thermally-
induced free radical polymerisation and thoroughly characterised
in terms of their physical, chemical and electrochemical properties.
The best performing sample is assembled in lithium pouch cells
exploiting a composite LiFePO4 cathode and a suitable in situ
polymerization procedure directly on the surface of the electrode
lm, fundamental to obtain an intimate interfacial adhesion. The
process is simple, eco-friendly and even adaptable to battery pro-
cessing methods to improve the interfacial properties. The truly
solid polymer cell demonstrates for the rst time very long-term
charge/discharge cycling for thousands of cycles. The results
regarding stability and aging resistance are motivating, and a good
insight is provided for the materials that can be pursued by such
polymerisation procedures. In addition, the simplicity of the pro-
posed process and the wide availability of the materials used make
this system very promising and ready to be industrially scaled-up
following the main principles of green chemistry.
2. Experimental
2.1. Materials
Unless otherwise mentioned separately, all starting materials
and reagents were purchased from commercial supplier Sigma
Aldrich and used without further purication. The experiments
were repeated two to three times and found to be reproducible. All
samples were stored in an environmentally controlled dry-room
(10 m2, R.H. <2% 1 at 20  C) produced by SOIMAR (Caluso, Italy).
The reactive formulation for the preparation of the all solid
semi-IPN-based polymer electrolyte membranes was based on
bisphenol A ethoxylate (15 EO/phenol) dimethacrylate (BEMA), a
methacrylate based di-functional oligomer having an average mo-
lecular weight of 1700. Poly(ethylene oxide) (PEO, Mw 200,000)
was used as long chain polymer, which can enhance the mobility of
Li ions. Bis(triuoromethane)sulfonimide lithium salt (LiTFSI,
CF3SO2NLieSO2CF3, battery grade) was obtained from Solvionic and
used as the source of Li ions. 2-20 -azoisobutyronitrile (AIBN) was
used as free radical initiator when acetonitrile (ACN) was used as
the solvent; 2,20 -azobis(2-methylpropionamidine) dihydrochloride
(AAPH) was used as the initiator when water was used as the sol-
vent. Before use, BEMA and PEO were dried for few days under
vacuum (BUCHI Glass Oven B-585 Drying), and ACN was treated
with molecular sieves (4 ).
2.2. Preparation of the semi-IPN-based polymer electrolyte
membranes
The reactive mixtures were prepared by mixing known quantity
of dimethacrylate monomer, polyethylene oxide and lithium salt in
ACN along with 2 wt. % of free radical thermal initiator AIBN. The
ratio of active components to ACN was 1:3 (in weight). The exact
formulation of the series of samples prepared (namely, TBP-1 to
TBP-3) is given in details in Section 3. The reactive mixture was
later drawn into a lm by coating it onto a releasing paper pur-
chased from LENETA, USA. Then, the set up was kept for drying
under a fume hood. Later, the precursor membrane over LENETA
sheet was kept in an oven under N2 ux at 90  C for 1 h to complete
the thermal polymerization. Mechanically stable, free-standing
lms were easily peeled off from LENETA sheets. The average
thickness of the nal polymer electrolyte membrane was around
260 J.R. Nair et al. / Journal of Power Sources 306 (2016) 258e267
80 mm. The complete process usually takes less than 3 h for the
production of ready-to-use all solid polymer electrolyte mem-
branes. For electrochemical testing in lithium cells, the reactive
solution was prepared using water as the solvent and sprayed over
the electrode surface to form a thin lm that successively under-
went thermal polymerisation.
2.3. Instrumental techniques and polymer electrolyte
characterization
The insoluble fraction (gel content) of the thermally cured
products was determined as follows: the samples were kept in a
stainless steel metal net, accurately weighed and, subsequently,
extracted with CHCl3 to dissolve the non-cross-linked polymer
chains. Extraction included 18 h of residence time for the solvents
in order to remove the soluble content from the sample at ambient
temperature. The cross-linked (insoluble) fraction was then calcu-
lated by dividing the mass of the dry sample left after the extraction
by the mass of the original sample (relative error 1%).
The surface morphology study was performed using Field
Emission Scanning Electron Microscope (FESEM, ZEISS Supra 40),
equipped with an energy dispersive X-ray spectrometer (EDX). For
analysis, the samples were subjected to metallization by sputtering
a very thin Cr layer (around 10 nm maximum) to minimize the
effect of the electron beam irradiation that might lead to charging
and burning of the polymer network.
The glass transition temperature (Tg) was evaluated by differ-
ential scanning calorimetry (DSC) using a DSC 204 F1 Phoenix
(Netzsch) instrument. Samples were housed in aluminium pans in a
dry room under controlled atmosphere. In a typical measurement,
the electrolyte samples were cooled from ambient temperature
to 85  C and then heated at 10  C min1 up to 120  C under N2
ux. The Tg was calculated as the midpoint of the heat capacity
change observed in the DSC trace during the transition from glassy
to rubbery state. The thermal stability of the samples was tested by
thermo-gravimetric analysis (TGA) with a TG 209 F1 Libra in-
strument from Netzsch over the temperature range of 25e600  C
under N2 ux at a heating rate of 10  C min1.
The ionic conductivity of the s-IPNs was determined by elec-
trochemical impedance spectroscopy (EIS) analysis of two-
electrodes test cells (ECC-Std purchased from EL-Cell, Germany)
assembled by sandwiching the electrolyte sample between two
stainless steel (SS-316) blocking electrodes (area 2.54 cm2). A
PARSTAT-2273 potentiostat/galvanostat/F.R.A. (Frequency
Response Analyzer) instrument (Princeton Applied Research, USA)
was used for measurements at various temperatures in the 1 Hz to
100 kHz frequency range at the open circuit potential (OCV). The
cells were assembled in the dry room and housed in an environ-
mental simulation chamber (BINDER model MK-53, with a tem-
perature control of 1  C). They were kept at 80  C overnight and,
then, tested from 20 to 80  C at a temperature interval of 10  C (the
samples were kept at each intervals for about 1 h before mea-
surement, to allow an optimum thermal equilibrium). The ionic
conductivity was calculated based on the following equation:
s ([ / A) / Rb
where s is the ionic conductivity (S cm1), Rb the bulk resistance, [
and A are the thickness and area of the test sample, respectively. Rb
was given by the high frequency intercept of the Nyquist plot by
analysing the impedance prole using a suitable tting program
(Electrochemistry Power Suite software, version 2.58, Princeton
Applied Research).
The compatibility of the s-IPNs with the lithium metal anode
was tested by monitoring the time evolution of the impedance
response of a non-blocking Li/s-IPN/Li symmetrical cell under open
circuit conditions (OCV) at 70  C. The electrochemical stability
window (ESW) was evaluated at 70  C by linear sweep voltam-
metry (LSV) in three electrodes test cells (ECC-Std purchased from
EL-Cell, Germany) using a PARSTAT-2273 instrument. Separate LSV
tests were carried out on each polymer electrolyte sample to
separately determine the cathodic and anodic stability limits. The
measurements were performed by scanning the cell potential from
the OCV towards more negative (cathodic limit) or positive (anodic
limit) potential values. The following cell congurations were
adopted for the anodic (potential scan range from OCV to 6 V vs. Li/
Li) and cathodic (from OCV to 0.2 V vs. Li/Li) scans, respectively:
i) stainless steel (SS, working) and Li metal (counter) as the elec-
trodes and the given s-IPN as the electrolyte; ii) Cu foil (working)
and Li metal (counter) as the electrodes and the given s-IPN as the
electrolyte. In both cases, the active area of both the electrodes and
the electrolyte was equal to 2.54 cm2. The potential was scanned at
a rate of 0.1 mV s1. The current onset of the cell was associated
with the decomposition (oxidation or reduction) of the electrolyte.
Clean electrodes and fresh samples were used for each test.
2.4. Fabrication and electrochemical characterization of LiB
components and test cells
Laboratory-scale lithium cells were assembled using a carbon
coated LiFePO4-based composite cathode and a lithium metal
anode. The average composition of the cathode was in the ratio of
87:8:5 wt.%, where the active material was commercial LiFePO4
(Clariant LP20), conductive carbon was Shawinigan Black AB50
(Chevron Corp., USA) and sodium carboxymethyl cellulose (Na-
CMC) was the binder [47]. Na-CMC was initially dissolved in
deionized water followed by the addition of conductive carbon and
active material nanoparticles under continuous stirring (~3 h). The
obtained slurry was then spray-coated onto a hot aluminium cur-
rent collector foil (70  C), dried under a fume hood at ambient
conditions and later vacuum dried overnight at 120  C. Later,
electrode foils were cut in 2.5 cm  2.5 cm pieces and prepared in
the form of an electrodeelectrolyte composite by thermally curing
the s-IPN polymer electrolyte directly onto the surface of the
electrode lm. In a typical preparation, a blend of the thermally-
cured polymer electrolyte was prepared following the procedure
described in Section 2.2 but using water instead of ACN as the
solvent. The mixture was spray-coated over the electrode surface to
form a thin lm (max 30 mm) and followed up with a thermal-
induced polymerization directly over the electrode. Then, the
electrolyte/electrode lms were dried under high vacuum over-
night at 90  C prior to cell assembly to assure complete water
removal. The all-solid-state test cells were fabricated by laminating
a lithium foil over the multiphase composite electrode/electrolyte
tape. The assemblies were housed in a coffee bag envelope (pouch
cell) and, successively, sealed by hot pressing at about 100  C. The
electrochemical active area of the laminated cells was approxi-
mately 6 cm2. The electrochemical behaviour and characteristics of
the cells were investigated at 70  C in terms of constant current
charge/discharge cycling at different current regimes using an
Arbin Instrument Testing System model BT-2000. The performance
was evaluated in terms of rate capability, charge/discharge ef-
ciency and specic capacity retention upon very long-term cycling
at 70  C. The potential cut-offs were xed at 4.0 V vs. Li/Li (charge
step, lithium deinsertion) and 2.5 V vs. Li/Li (discharge step,
lithium insertion). Prior to testing, all cells were kept at 70  C for at
least 5 h to achieve the thermal equilibrium and the effective
contact between the electrodes and electrolyte.
 J.R. Nair et al. / Journal of Power Sources 306 (2016) 258e267
3. Results and discussion
3.1. Solid polymer electrolyte preparation and physicochemical
characterisation
Polymer electrolyte membranes were prepared by thermally
induced free radical polymerisation of a reactive mixture under
inert conditions. The typical reactive mixture formulation consists
of four components, namely, a dimethacrylate oligomer BEMA, a
high molecular weight PEO, LiTFSI as the lithium ion source and a
thermal initiator, thoroughly dissolved in a proper solvent. BEMA
was selected as the multifunctional oligomer as it can function as a
soft crosslinking agent due to its well-known characteristics such
as low Tg, solubility in various solvents, fast reaction kinetics and
compatibility with PEO chains and lithium salt [48]. Moreover, it
can readily form cross-linked networks thus keeping the electrolyte
components intact. Under temperature, the thermal initiator de-
composes into free radicals, which react with the dimethacrylate
groups to form three dimensional networks. Before polymerisation
reaction, the precursor solution was poured into a Teon dish and
kept under a fume hood for evaporation. This process allows the
PEO chains to distribute uniformly over the surface. Then, once
transferred in an oven under controlled atmosphere at 80  C, the
di-methacrylates react themselves to form a three dimensional
network. This overall step forms the backbone of the polymer
electrolyte, which is similar to the matrices being formed in the
form of a semi interpenetrating polymer network. A s-IPN [38] is
generally characterized by the presence of a heterogeneous phase
structure that is formed by a chemically cross-linked polymer
matrix and a linear thermoplastic chain. It is efcient and easy to
produce with tailored structural/physicochemical characteristics
and it is used for a wide variety of applications [49].
Various physical and chemical characterisation methods such as
gel content studies, FESEM analyses, differential scanning calo-
rimetry (DSC) and thermo-gravimetric analyses (TGA) were per-
formed on the thermally cured polymer electrolytes. The BEMA to
PEO ratio was kept at 40:60 as it was found to be the optimal bal-
ance between the soft cross-linker to linear thermoplastic polymer
content. Before arriving to the reported formulation, several tests
were performed to understand the fundamental aspects of the
polymer electrolytes, to decide the quantity and type of photo-
initiator, as well as the suitable molecular weight of PEO depending
on the easiness in processing, solubility of salt, ionic mobility in
terms of [EO]/[Li] ratio and mechanical integrity. Thus, here the
focus was on varying the salt content and pursuing the in-
vestigations of the different samples resulting from such
combinations.
Table 1 shows the composition of the solid polymer electrolytes
under study along with the insoluble fraction (gel content), thermal
stability and glass transition temperature values. As seen in Fig. 1,
after solvent evaporation and thermally induced crosslinking, the
polymer electrolytes obtained by copolymerisation of the various
components are rather thin (~80 mm), non-tacky, translucent,
freestanding, extremely exible and easy to manipulate. A multi-
media illustration of the mechanical integrity of the representative
Table 1
List of the different s-IPNs under study, amount of the various components used in the polymer electrolyte preparation along with the relevant thermal and physical
characteristics.
Name BEMA (wt. %) PEO (wt. %) LiTFSI (wt. %)
TBP-1 36 54 10
TBP-2 34 51 15
TBP-3 32 48 20
In all cases the initiator content was 2% by weight with respect to the total weight.
261
s-IPN, namely TBP-1, is shown in the supported video in which the
nal polymer electrolyte was folded in half multiple times, and
recovered to its original shape without any damage or tackiness.
This indicates that the prepared solid electrolyte material is me-
chanically stable and robust even if the thickness is rather low;
similar features are also visible in Fig. 1.
Supplementary video related to this article can be found at
http://dx.doi.org/10.1016/j.jpowsour.2015.12.001.
The conversion of the di-functional oligomer to cross-linked
network after thermal polymerisation was evaluated by
measuring the insoluble fraction content. The obtained values are
listed in Table 1. It was observed that an increase in salt content
slightly reduced the insoluble one. One possible explanation for
such a behaviour is the restricted mobility of the reactive meth-
acrylate groups to the reaction sites during the polymerisation
process where the propagation reaction is happening in an almost
solid like condition. Moreover, the addition of lithium salt further
increased the viscosity of the system. The gel content values (%)
were found to be well in accordance with the amount of BEMA used
in the matrix; indeed, a value higher than the theoretical was noted.
This result was also conrmed by FTIR measurements (data not
reported), that showed the absence of methacrylate groups at
1634 cm1. This may be ascribed to the PEO chains that, remaining
after extraction in CHCl3 solvent for 18 h, are trapped through the
polymerised BEMA (pBEMA) structures. Indeed, large number of
PEO chains came out of the three dimensional cages formed by
pBEMA structures during the extraction step in CHCl3 solvent,
which conrms the semi-IPN like characteristics of the nal poly-
mer electrolyte membrane.
The surface morphology of the polymer electrolyte was studied
by FESEM analysis. The topographic images are shown in
Fig. 2(AeD), which highlights the typical micro-phase heteroge-
neity characteristics of a s-IPN network structure. In particular, the
s-IPN based polymer matrix exhibited amorphous phases of
pBEMA, LiTFSI coordinated PEO and crystalline PEO phases. Some
voids or pores are visible in the images, which are most likely
formed during the evaporation of the solvent from the polymer
matrix along with the evolution of N2 gas during the polymerisa-
tion process that involves the decomposition of AIBN molecules. At
very high magnication (see image D of Fig. 2), the overall homo-
geneity and smooth surface of the s-IPNs under study are well
evidenced.
The glass transition temperature (Tg) was evaluated by differ-
ential scanning calorimetry (DSC) analysis and the resulting ther-
mograms are shown in Fig. 3A. DSC measurements were performed
on the series of polymer electrolytes TBP-1 to TBP-3. The corre-
sponding Tg values are also listed in Table 1. The Tg was dened as
the midpoint of the heat capacity change observed in the DSC trace
during the transition from glassy to rubbery state. The analyses
evidenced an increase in Tg values with increasing the salt content.
This effect may result from the coordination of lithium salt with
PEO chains, which may increase the viscosity, thus restricting the
segmental mobility. For comparison purposes, a reference polymer
electrolyte was prepared by mixing PEO (85 wt. %) of same mo-
lecular weight and 15 wt. % of LiTFSI (namely, PEO-15Li). A Tg value
Insoluble content (wt. %) T5 ( C) Tg ( C) EOm/Li Xc (%)
40 3 330 33.2 35:1 36.2
39 2 330 29.2 21:1 29.7
35 2 330 25.3 16:1 25.8
262 J.R. Nair et al. / Journal of Power Sources 306 (2016) 258e267
Fig. 1. Non-sticky and exible nature of a typical TBP-1 based s-IPN (top left image), which was folded multiple times, and recovered (bottom left) to the rst shape without any
damage.
of 47  C was evidenced, which is much lower than the TBP series
of s-IPN electrolytes. Comparing the EOm/Li ratio of PEO-15Li with
that of the s-IPNs, it is observed that it matches with TBP-1. Note
that EOm indicates the number of eEOe moieties of the PEO chains,
which possess the segmental mobility characteristics compared to
the restricted eEOe moieties from the crosslinker BEMA. More-
over, if one calculates the amount of LiTFSI in weight percentage
with the reference electrolyte (PEO-15Li), it matches with TBP-2
electrolyte. However, in both cases the Tg was higher than the
PEO-15Li reference sample, which is an indication that the soft
crosslinker BEMA inuences the mobility of the PEO chains. This
may account for an increase in the overall Tg of the TBP series of
electrolytes. The crystallinity percentage (Xc %) calculated from the
DSC curves using the PEO heat of melting (Enthalpy 197 J g1) [50]
conrmed that the Xc of PEO-15Li (graphs not reported here) is 55%,
which is much higher than the TBP series of electrolytes, both if
calculated in EO/Li ratio and/or LiTFSI wt. %. This further conrms
that the crosslinking process (induced by BEMA) helps the PEO
chains to pack properly within the polymer network. The different
percentage of lithium salt in the polymer matrix signicantly
inuenced the size and nature of the crystalline peaks at around
50  C. It is also worth noting that the melting temperature (Tm) of
the s-IPNs was decreased from 56  C (TBP-1) to 47  C (TBP-3). The
melting peak was also broadened with an increase in the LiTFSI
concentration, indicating that the salt interacted with the PEO
chains, thus hindering the formation of crystallites in the polymer
matrix. It can be eluded from the DSC studies that the TBP mem-
brane series is in the rubbery state at ambient temperature and
dominated by amorphous phase, especially if compared with the
pristine PEO-15Li reference sample (e.g., the amorphous nature of
TBP-2 exceeds 70%).
The thermal stability of the samples was assessed by thermo-
gravimetric analysis (TGA). The resulting thermograms are shown
in Fig. 3B. A high temperature single step weight loss is evidenced,
which accounts for the profound homogeneity of the semi-
interpenetrating solid electrolytes with noticeable deection only
above 300  C. The thermal stability of the samples, corresponding
to the temperature where 5% of weight is lost, is denoted as T5, and
the corresponding values are listed in Table 1. The T5 values for the
s-IPNs under study are well above 330  C, indicating that the
polymer electrolytes are highly stable and safe to use up to very
high temperatures. The shoulder peak at above 400  C likely cor-
responds to the decomposition of the LiTFSI incorporated in the
polymer electrolyte. The initial 1e2% dip before 100  C is ascribable
to the loss of humidity that is absorbed during the handling of the
sample for testing [51,52].
The ionic conductivity of the s-IPN series of polymer electrolytes
was calculated from the response of electrochemical impedance
spectroscopy (EIS) analysis. Lithium salt is directly incorporated
into the polymer electrolyte during thermal polymerisation, thus
no additional steps were performed (to incorporate salts and/or
plasticisers). Fig. 4A shows the Arrhenius plot, reporting the ionic
conductivity versus the temperature inverse of the s-IPNs prepared
by thermal curing. A typical ionic conductivity increase with
elevating temperature was observed, at least in the range of EO/Li
ratio investigated in the study. In addition, it was also observed that
an increase in lithium salt concentration increases the ionic con-
ductivity, which indirectly means that a lower EOm/Li ratio is
 J.R. Nair et al. / Journal of Power Sources 306 (2016) 258e267 263

Fig. 2. A) FESEM image of the representative TBP-3 polymer electrolyte at 5K magnication; BeD) images at various locations (marked in yellow circles) and at different mag-
nications. (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

Fig. 3. A) DSC curves and B) TGA thermogram obtained for the TBP series of s-IPNs prepared with various amount of LiTFSI.

benecial for higher ionic conduction. That means, when the EOm/
Li ratio was changed from 35:1 to 16:1, the conductivity corre-
spondingly enhanced. A further increase in salt concentration was
not attempted, as it will decrease the EOm/Li ratio to unfavourable
values [53]. Further increase in salt concentration may create
problems related to TFSI anions where conductivity will dampen
by salt precipitation and/or formation of aggregates [54]. In the TBP
series of polymer electrolytes two kinds of eEOe moieties are
present: i) the ethoxy group that is present in the BEMA molecule,
which is static (EOs) or mobility restricted due to the participation
in chemical crosslinking, and ii) the mobile eEOe moieties (EOm) of
PEO chains, which can exhibit sufcient segmental motion. Also,
EOm responds very well to temperature change and salt concen-
tration, as it can inuence the crystallinity of the overall polymer
matrix. In the present case we reported the EO/Li ratio with respect
to EOm as it is the most inuencing moiety. TBP-3 sample displays
the highest conductivity in the whole temperature range, reaching
values of the order of 105 S cm1 at 20  C and exceeding
103 S cm1 at 80  C. Thus, sample TBP-3 having the lowest EOm/Li
ratio (16:1, see Table 1) showed the highest ionic conductivity if
compared to those having a higher EOm/Li ratio. The large deec-
tion in ionic conductivity upon heating is observed around 50  C for
all the electrolytes, and conrmed that the physical transitions
related to the melting of the crystalline peaks are in agreement
with the melting temperature values obtained from DSC analysis. It
is worth noting that the PEO-15Li sample, obtained without cross-
linker and with the same amount of lithium salt (in wt. %) as for
TBP-2, exhibits lower ionic conductivity in the whole temperature
264 J.R. Nair et al. / Journal of Power Sources 306 (2016) 258e267

Fig. 4. A) Arrhenius plot showing the ionic conductivity vs. temperature for s-IPNs prepared with various LiTFSI content, but keeping the BEMA to PEO ratio xed at 40:60; B)
VogeleTammaneFulcher (VTF) dependence of the s-IPNs tted between 50 and 80  C (i.e., above the deection point).

range. This is well in agreement with the DSC studies and the
resulting percentage of crystallinity (Xc %) calculations, which is
induced by the pBEMA networks.
In polymer electrolytes, the dependence of the ionic conduc-
tivity towards temperature increase is not a linear relation.
Generally, the ion conduction mechanism can be elucidated from
the activation energy calculations. A complete tting at a full range
of testing temperature may not be possible due to the phase
transitions occurring from the melting of the crystalline regions or
the rearrangement of the eEOe moieties in a PEO-based system. In
the present case, the ionic conductivity vs. temperature curve was
not tting with the Arrhenius equation as well as with the
VogeleTammaneFulcher (VTF) equation [55]. The optimal tting
(i.e., regression analysis R2 values above 0.999) was obtained using
VTF equation when the calculations were carried out between 50
and 80  C. Thus, the activation energy (Ea) of the electrolyte systems
was calculated by tting the values with the VTF equation, using
the slopes of the resulting plots. Fig. 4B shows the relationship (see
equation below) between ln s and 1/(TeT0):
Fig. 5. A. Nyquist plot representing the evolution of the interfacial resistance versus
  time at open circuit conditions, using the Li/TBP-3/Li symmetric cell conguration at
Ea
s s0 T 2 70  C; B: change in resistance (high Hz and low Hz) along with the evolution of the
1
exp 
RT  T0 charge transfer resistance (diameter of semi-circle) with time.

where T0 is a parameter related to the glass transition temperature,

Ea is the activation energy, s0 is the pre-exponential factor and R is
the ideal gas constant. Generally, the VTF equation is believed to
describe the conduction behaviour of highly concentrated liquid
electrolytes and molten salts [56,57]. As listed in Fig. 4B, Ea values
varied from 4.9 to 6.7 kJ mol1 from TBP-1 to TBP-3, indicating a
corresponding viscosity increase with the EOm/Li ratio. This will
enforce the ions to move slowly at a given energy, demonstrating
that the ionic moment in a polymer electrolyte above the melting
point is largely contributed by the melted eEOm moieties (i.e.,
segmental motion).
A deep understanding of the interfacial properties between the
lithium metal electrode and the polymer electrolyte is necessary for
interpreting and nely tuning the factors that control the recharge
ability of lithium-based polymer batteries. Thus, the highly con-
ducting TBP-3 sample was examined in terms of compatibility
(interfacial stability) with the lithium metal electrode. As shown in
Fig. 5 (A and B), a TBP-3-based lithium symmetric cell showed
stable resistance after few days of testing at 70  C. Indeed, the
resistance increased during the initial days of storage indicating the
formation of a thin and homogeneous solid electrolyte interface
(SEI) layer onto the surface of the lithium metal electrode, which is
clearly showed in Fig. 5B. The overall resistance rapidly decreased
and stabilized at around 100 U after few days, accounting for stable
interfacial characteristics. It is worth noting that the change in bulk
resistance was limited within the range of 32 4 U (Fig. 5B),
indicating that no vigorous reactions were taking place as resulting
from any unavoidable impurities that might be present in the
polymer matrix due to synthesis procedure, sample transfer/
handling or cell assembly (note that impedance measurements
exhibit an error bar from 5 to 10%).
3.2. Electrochemical characterisation, constant current lithium cell
testing
In general, for a lithium-based battery, the anode reactions
occur in the vicinity of 0 V vs. Li/Li, while the cathode potential
may exceed 4.5 V vs. Li/Li, implying that the electrochemical
stability window (ESW) is a fundamental parameter that de-
termines the reversibility of plating/stripping and de-intercalation/
intercalation processes.
 J.R. Nair et al. / Journal of Power Sources 306 (2016) 258e267 265

in lithium cell as well as the presence of a porous and ion-

transporting interface. During the initial anodic sweep towards
higher potential values, the onset of a current peak at approx. 4.7 V
vs. Li/Li is generally related to the decomposition (oxidation) of
the electrolyte. No other features are observed, conrming the high
purity of the polymer electrolyte. Thus, in summary, good thermal
stability, acceptable ionic conductivity, low activation energy and
wide electrochemical stability window are encouraging character-
istics for a polymer electrolyte that aspires to be tested in realistic
battery conguration.
In this respect, laboratory-scale lithium pouch cells were
assembled by combining a lithium metal anode with a composite
multiphase LiFePO4/TBP-3 electrode/electrolyte lm and tested in
order to evaluate the capability of the electrolyte to perform in real
battery conguration. Its electrochemical behaviour was investi-
gated in terms of constant current charge/discharge cycling per-
formed at 70  C. The electrochemical process of this battery is the
reversible insertion/de-insertion of lithium ions from and to
lithium iron phosphate following the typical reaction:
Fig. 6. Electrochemical stability window of sample TBP-3. The anodic and cathodic
scans were separately run at 70  C and then collected together.
LiFePO4 4 xLi Li(1x)FePO4

which is expected to operate at around 3.45 V vs. Li/Li with at

The ESW of the TBP-3 membrane (representative for all the
charge/discharge plateaus for a theoretical specic capacity of
samples) measured at 70  C is shown in Fig. 6. In the resulting
170 mAh g1. Fig. 7A shows the typical charge and discharge cycles
currentepotential traces, a clear and well-dened lithium deposi-
run at different current rates (i.e., from C/10 to 5C, note that 1C
tion/stripping couple of peaks at around 0 V vs. Li/Li was observed.
corresponds to ~ 3 mA with respect to an approximate LiFePO4
It conrms both the proper working of the solid polymer electrolyte

Fig. 7. Constant current charge/discharge cycling of the LiFePO4/TBP-3/Li truly solid lithium polymer cell at 70  C: A) potential vs. specic capacity proles and B) the specic
capacity at various current rates (C/10 to 5C) with respect to number of cycles.

Fig. 8. Constant current charge/discharge long-term cycling (up to 2000 cycles) of the LiFePO4/TBP-3/Li truly solid lithium polymer cell at 70  C: A) potential vs. specic capacity
proles and B) specic capacity vs. cycle number at 1C rate.
266 J.R. Nair et al. / Journal of Power Sources 306 (2016) 258e267
active mass of about 18 mg, corresponding to a mass loading of
approx. 3 mg cm2). Fig. 7B shows the specic capacity vs. cycle
number at different current rates. Reproducible potential proles
were obtained, in which the initial specic capacity approaches
160 mA h g1 at C/10 rate (i.e., the full capacity that the commercial
LiFePO4 cathode used in this study can deliver at the selected cur-
rent rate even in standard liquid electrolyte based conguration).
The rate capability and capacity retention were found to be satis-
factory: even after prolonged cycling at high 5 C current rate, the
cell was still able to deliver specic capacity values of around
120 mAh g1 (150th cycle at 1C rate) with a drop of less than 25%
with respect to the initial value at C/10. Such an excellent rate
capability is denitely a remarkable achievement for a fully solid
system. Thus, the cell operated with the expected potential proles
delivering a good fraction (>75%) of the theoretical capacity even at
rates as high as 1C. The cycling response was also encouraging since
no decay in capacity was shown during this initial test and the
chargeedischarge efciency following the initial cycles, where
rearrangements in the structure of the electrode took place, was
maintained to be always near to unity, with no abnormal drift even
at high regimes (see in Fig. 7B the complete restore of the specic
capacity values from 5C to 1C after >120 cycles).
The stability of the newly elaborated thermally cured s-IPN
polymer electrolyte upon prolonged aging in real cell conguration
was evaluated by a very long-term charge/discharge cycling test up
to >2000 cycles at 1 C rate. As shown in Fig. 8, the samples may
retain >70% of the initial specic capacity at the same current
regime. Moreover, the polarisation between the charge and
discharge plateaus was found to be reasonably limited if comparing
the potential vs. specic capacity proles at the 1st and 2000th
cycles, respectively (see Fig. 8A). Altogether, the cycling response is
highly encouraging, with an excellent efciency approaching 100%
after the initial cycles, that accounts for a high reversible cycling
stability upon the whole very long-term stress test.
The possibility of using the new elaborated polymer electrolyte
system with high potential cathodes such as mixed lithium nickel
manganese cobalt oxide (LiNiMnCoO2 or NMC) as well as nanosized
silicon-based anodes is under investigation in our Labs; the pre-
liminary results in this respect are highly encouraging and will be
presented in a forthcoming paper.
4. Conclusions
Exploiting a newly elaborated thermal induced free radical
polymerisation technique, we were able to produce highly robust
and thermally stable solid polymer membranes to be used as
electrolyte separators in aging resistant Li-ion batteries. The pro-
cess is very versatile, and easily permits to tailor a desired polymer
composition. The overall architecture is built on a semi-
interpenetrating polymer network (s-IPN) structure, where a di-
methacrylate oligomer is cross-linked (in situ) in the presence of
a long thermoplastic linear PEO chain and supporting lithium salt
to obtain a freestanding, exible and non-tacky lm. In the envis-
aged systems, the di-methacrylate functions as a soft cross-linker,
thus avoiding physical mechanical deformation of the s-IPNs at
elevated temperature, without hampering the ionic mobility.
The analysis of the electrochemical behaviour evidenced a wide
stability window and excellent performance in real battery
conguration. In this respect, a truly solid-state polymer lithium
cell was assembled using a commercial LiFePO4 cathode with an in-
situ deposited thin polymer electrolyte lm and a lithium metal
anode, which upon constant-current charge/discharge cycling at
70  C showed full specic capacity recovery at low current regimes
and excellent rate capability up to 5C rate. Moreover, outstanding
aging resistance was demonstrated, as for the very high capacity
retention after very long-term cycling (up to > 2000 constant
current charge/discharge cycles), which is utmost important when
stationary or highly stressful applications are envisaged.
Acknowledgement
The support from the European Commission under the MARS-
EV (Grant agreement no. 609201) project is gratefully
acknowledged.
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