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A New, Safe, High-Rate and High-Energy Polymer
Lithium-Ion Battery
By Jusef Hassoun, Stefania Panero, Priscilla Reale, and Bruno Scrosati*
Lithium-ion batteries are light and compact and operate using
voltages on the order of 4 V and with energy densities ranging
between 150 W h kg
1 and 250 W h kg
1.[1] Due to their high-
capacity of energy storage, lithium-ion batteries have triggered
the growth of the consumer electronics market and now are the
power sources of choice for many popular devices, including
mobile phones, laptop computers, and Mp3 players. Accordingly,
lithium ion batteries are today produced in billions of units per
year.[2]
Although already a commercial reality, lithium-ion batteries
are expected to enter into markets beyond the consumer, portable
electronic sector. The main drivers for this market evolution are:
i) the concern regarding global warming, which urgently requires
a much greater proportion of clean, renewable energy sources
than are used at present; and ii) the continuously growing
interest, both ecological and industrial, in moving from
gasoline-powered internal combustion engine cars to low-
emission electric or hybrid vehicles.
Systems such as lithium batteries that can efficiently store
and deliver energy on demand in stand-alone or grid-connected
renewable power plants (REPs) and provide power quality and
load-levelling of the electrical grid in the case of integrated
systems, are playing, at different time scales, a crucial role in this
field.[3–5] Another important prospective market for lithium
batteries is sustainable transportation. Low-emission cars, such
as Hybrid Electric Vehicles, HEVs, and Plug-in Hybrid Electric
Vehicles, PHEVs, are already on the road and it is expected that
their penetration into the automobile market will continuously
grow. In addition, zero-emission, full-electric vehicles, EVs, are
also expected to be a commercial reality in a not-too-distant
future. This potential gives great incentives for battery technology
breakthroughs aimed at optimization of their performance and
thus, enhancing their market competitiveness and penetration.
Lithium-ion batteries are identified as the power systems of
choice for such applications because they are considered the only
solution able to guarantee a wide diffusion of HEVs at high level
of hybridization.[6]
However, scaling up the chemistry used in the available
lithium batteries for vehicles or for renewable energy plants is
problematic. Barriers of various natures still prevent this step.
They include safety, cycle-life, energy density, performance over
wide temperature ranges, and materials availability. The
[*] Prof. B. Scrosati, Dr. J. Hassoun, Prof. S. Panero, Dr. P. Reale
Department of Chemistry, University of Rome ‘‘La Sapienza’’
Piazza Aldo Moro 5, 00185 Rome (Italy)
E-mail: bruno.scrosati@uniroma1.it
DOI: 10.1002/adma.200900470
Adv. Mater. 2009, 21, 4807–4810 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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chemistry of lithium-ion batteries has not significantly changed
since their introduction in the market in the early Nineties. Most
production still relies on a graphite anode and a lithium cobalt
oxide cathode, separated by a liquid solution of a lithium salt in an
organic solvent mixture soaked in a polypropylene separator. It is
now universally accepted that breakthroughs in lithium battery
technology require the passage to innovative chemistries,
including both electrode and electrolyte components, involving
materials having higher performance than the ones presently
used in common batteries. This is an ambitious goal; however,
the intrinsic benefit of lithium battery technology, and its
reflection in the evolving markets, have triggered tremendous
world-wide efforts to place lithium-ion batteries in a dominant
position in both the HEV and REP sectors.[7]
We too have taken part in this race by investigating new
electrode and electrolyte materials designed for advanced
lithium ion battery configurations. In this work we report the
properties and characteristics of a lithium-ion battery based on
an original combination of these new materials. We demon-
strate that this totally renewed battery has unique performances
in terms of energy density, power capability, cycle-life, and
safety.
Battery Configuration: In this work we describe and evaluate a
lithium ion battery having a chemistry totally renewed with
respect to the conventional configuration.[8] In our battery, the
anode material is chosen from the family of lithium metal alloys.
These are the most appealing materials for anode development
since their specific capacity largely exceeds that of common
graphite, i.e., 4,000 mA h g
1 (Li
Si) and 993 mA h g
1 (Li
Sn)
versus 370 mA h g
1 (Li
C). The main issue with using metal
alloys is in the large volume expansion/contraction that they
experience during the charge/discharge cycling process which in
turn induces mechanical disintegration and thus, electrode
failure after relatively few cycles.[9] We have circumvented this
issue by optimizing the electrode morphology with the develop-
ment of metal (e.g., tin)–carbon nanocomposite configurations
capable of buffering the large volume changes and thus, of
assuring long cycle-life combined with high specific capacity.[10]
In this structure, the carbon matrix has a twofold, critical action; it
provides enough free volume to accommodate the tin’s
expansion/contraction, thus assuring the cycling stability, and
at the same it acts as a protective shell, assuring the safe handling
of the electrode powder.[11]
As the preferred anode for the new battery, we chose the Sn
C
(1:1) composite characterized by the following electrochemical
reaction:
Sn
C þ 4:4 Li ! Li4:4 Sn þ C (1)
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with an associated a specific capacity of 400–500 mAh g-1 (referred
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to the Sn
C content). As the preferred cathode to couple with the
Sn
C anode we selected lithium nickel manganese oxide,
LiNi0.5Mn1.5O4, which adopts a spinel structure characterized by
a two-phase electrochemical process:
LiNi0:5 Mn1:5 O4 ! Lið1
xÞ Ni0:5 Mn1:5 O4 þ xLi (2)
reflecting in a flat voltage profile evolving around 4.5 V versus
Li.[12] The theoretical specific capacity is 146 mA h g
1, i.e., on the
same order as the conventional lithium cobalt oxide, LiCoO2.
However, the key difference is in the high operational voltage,
which makes LiNi0.5Mn1.5O4 a very competitive cathode material.
Being aware that a quantum leap in lithium-ion technology
can only be achieved by discarding the unsafe, liquid organic
solutions and moving to more inert systems, we devoted
particular attention to the choice of the electrolyte. A very
appealing option is obviously one which sees the use of a fully
solid, solvent-free membrane, such as those formed by
combining poly(ethylene oxide), PEO, and a lithium salt.[13]
Unfortunately, wide use of such membranes is still prevented by
decay in ionic conductivity at temperatures below 70 8C. We have
also considered a polymerlike electrolyte formed by trapping a
typical lithium-ion solution, e.g., LiPF6, in a carbonate solvent
mixture in a poly(vinylidene fluoride), PVdF, polymer matrix.
This is in fact a gel-type, hybrid membrane with a high
conductivity, i.e., approaching that typical of liquid solutions,
combined with good mechanical properties, i.e., those typical of a
polymer.[14]
In synthesis, the new battery discussed here uses a
configuration which exploits a Sn
C based anode, a PVdF-based
gel polymer electrolyte (GPE) and a LiNi0.5Mn1.5O4 cathode.
Battery Performances: Figure 1 shows typical voltage profiles of
the charge/discharge process of the Sn
C/GPE/LiNi0.5Mn1.5O4
battery at room temperature and at various rates. The process
basically involves the exchange of lithium ions between the two
electrodes. We see that the battery, which is cathode-limited,
operates at around 4.0 V and delivers at a C/3 rate a capacity of
120 mA h g
1, i.e., 82% of the theoretical value. These high
capacity and voltage values reflect an energy density as high as
480 W h kg
1. This value is only indicative since it does not take
Figure 1. Voltage profiles of the Sn
C/GPE/LiNi0.5Mn1.5O4 battery at
various rates (1C about 0.2 A cm
2 g
1 respect the cathode mass) and
at room temperature.
4808 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advmat.de
Figure 2. Capacity delivery versus cycle number for the Sn
C/GPE/
LiNi0.5Mn1.5O4 battery at 1C rate and at room temperature. The inset
shows the cycling response at various rates.
into account the weight of the battery ancillary components, such
as electrolyte, current collectors, and case. Thus, the practical
value is certainly lower; we are, however, confident that by
optimizing the cell design and structure, achievement of an
effective energy density approaching 180 W h kg
1 is a reasonable
assumption. The results shown in the figure also demonstrate
that the battery combines high energy with high rate capability.
Indeed, we see that even at a rate as high as 3C, the battery is
capable of delivering 80 mA h g
1, which is still 55% of the
theoretical value.
Cycle-life is also an important evaluation parameter for rating
lithium-ion batteries. Accordingly, we monitored the battery
response for over 400 charge/discharge cycles at room tempera-
ture and at 1C rate. Figure 2, which shows the capacity evolution
during the cycling test, demonstrates very stable behavior with
capacity decay limited to only 0.06 mA h g
1 per cycle. The cycling
response at various rates is also shown (see inset). The trends
clearly reveal that the battery can cycle at high rates with a very
contained capacity decay that is mainly due to Ohmic polariza-
tion. Indeed, when changing from a high to a low rate (e.g., from
3C back to 1C), the capacity reassumes its original value; this
suggests that by optimizing the cell geometry, such as by reducing
its overall resistance, one could achieve even better performances
that those reported here.
High energy, high rate, and long life, although important
features, are still not sufficient to assure the application of the
battery in sectors such as energy storage and sustainable
transportation. In these fields, safety is a key parameter.
Accordingly, we controlled the battery behavior by running a
specific test based on thermal analyses (differential scanning
calorimetry, DSC plus thermogravimetric analysis, TGA) com-
bined with mass spectrometry (MS). The objective was to evaluate
the thermal effects in terms of mass evolution and detect any
decomposition products at the same time.[15] We carried out this
analysis at both the anode and cathode sides in different states
under different conditions, i.e., in a pristine state as well as after
full charge and after full discharge (see Experimental for details).
Figure 3A shows the DSC-TGA analysis of the GPE/
LiNi0.5Mn1.5O4 cathode side of the battery, run in the pristine,
charged, and discharged states. The traces reveal for all states a
first endothermic peak at 100 8C, which, as detected by MS, may
be associated with the evaporation of that small portion of the
electrolyte solvent which remains unlinked with the PVdF matrix
Adv. Mater. 2009, 21, 4807–4810
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Figure 3. Combined Differential Scanning Calorimetry (DSC) and Thermal
Gravimetric Analysis (TG) of the GPE/LiNi0.5Mn1.5O4 half battery cathode
side (A) and of the Sn
C/GPE half battery anode side (B), at pristine fully
charged and fully discharged states.
of the GPE. The mass involved is less than 1% of the overall
electrolyte mass. The traces show no peaks up to 200–300 8C,
where the evolution of a complex peak is clearly observed. The MS
analysis (data not shown) indicates that this peak is representative
of the evaporation/decomposition of the GPE. The mass change
associated with this process is approximately 70–75% of the
overall GPE mass. No other thermal effects are noticed up to
400 8C, where the PVdF decomposition starts with a mass change
of approximately 6–7% of the overall GPE mass. We may then
conclude that no serious thermal effects occur below to
200–300 8C.
Similar results were obtained by DSC-TGA analysis run on
the of Sn
C/GPE anode side of the battery, see Figure 3B. Again
we noticed a small peak at 100 8C without significant mass
change, which is related to the evaporation of a small amount of
unlinked solvent. The following peaks in the 200–300 8C region,
with an accompanying mass change of 50–60%, are related to
GPE evaporation/decomposition, while those in the 400–500 8C
region, with a mass change of the order of 4–6%, relate to the
PVdF decomposition. The latter is more complex in this case
since it shows kinetics that are more dependent on the charge
state than in the previous half-cathode cell case; this difference is
likely associated with the carbon content being higher in the
Sn
C anode than in the cathode. This extra amount of carbon
may more significantly affect the decomposition reaction
mechanism.
The DSC-TGA-MS analysis demonstrates that both anode and
cathode sides and thus, the overall cell, can withstand temperatures
Adv. Mater. 2009, 21, 4807–4810 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
of up to 200–300 8C without undergoing thermal decomposition.
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This is convincing evidence that the Sn
C/LiNi0.5Mn1.5O4
polymer battery disclosed here is intrinsically safe.
Lithium batteries are one of the great successes of modern
electrochemistry. These batteries have an established role in the
consumer electronic market with no current risk of being
replaced by any other contender. They are expected to soon
dominate the electric automotive transportation and renewable
energy storage sectors as well as other revolutionary technologies
in medicine, robotics, and space applications, making lithium
batteries the batteries of the future. However, further advances in
the science and technology of lithium batteries require
modification of electrodes and electrolytes. The goal is to achieve
new configurations that can assure environmental sustainability,
high energy content, and low safety hazard. In this work we
present one possible candidate, formed by the combination of a
novel electrode couple separate by a gel-type polymer electrolyte.
We show that this combination results in a new polymer
lithium-ion battery having unique performances in terms of
energy density, rate capability, cycle-life, and safety.
One aspect that is still to be checked is the influence of
temperature on the battery performance. There are no
components that are expected to be critically affected by large
temperature fluctuations. The electrodes have fast kinetics and
the electrolyte has a conductivity that remains high across a wide
temperature range.[14] Therefore, no severe temperature limita-
tions are foreseen. However, considering the practical relevance
of this aspect, work is in progress to clearly determine the
effective role of the temperature on the operation of this new
lithium-ion battery.
Experimental
The gel-polymer electrolyte (GPE) was formed by trapping a LiPF6 ethylene
carbonate (EC) and propylene carbonate (PC) (20:40:40 by weight) solution
in a PVdF matrix. The electrolyte was prepared in an Ar-filled glovebox
according to a consolidated procedure developed in our laboratory and
described in a previous paper [14].
The nickel–manganese LiNi0.5Mn1.5O4 cathode material was obtained
by following a wet chemistry route described in detail in a previous work
[12]. The LiNO3, Ni(NO3)2  H2O, and Mn(NO3)2  H2O reagents were
dissolved in water and mixed in a stoichiometric ratio; the mixture was then
dried and finally thermally treated in air at 800 8C for 24 h followed by slow
cooling at a 0.5 8C min
1 rate. The synthesis of the Sn
C nanostructured
composite material was based on the infiltration of an organometallic tin
precursor in an organic resorcinol (benzene-1,3-diol)-formaldehyde
(methanal) gel, followed by calcination under argon, according to a
procedure already described in previous works [10,11].
The positive and the negative electrodes were prepared as thin films by
doctor-blade deposition on an aluminium or copper substrate, respectively,
of a slurry composed of 80% active material, 10% PVdF 6020, Solef Solvay
(binder) and 10% SP carbon, MMM Belgium (electron conductor additive).
Prior to cell testing, the Sn
C anode was activated using a procedure
originally developed in our laboratory that involves direct contact with
electrolyte-wetted metallic lithium [10]. More details are reported in the
Supporting Information.
Complete lithium-ion cells were assembled using the nanostructured
Sn
C composite as the anode, LiNi0.5Mn1.5O4 as the cathode and a LiPF6
EC:PC GPE as the electrolyte. The lithium ion cells were cycled at various
C-rates (1C corresponding to about 0.2 A cm
2 g
1 with respect to the
cathode mass) and within a 3.0–4.9 V voltage range, using a Maccor
Series 4000 Battery Test System as the driving and controlling
instrument.
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Thermal and mass spectrometry measurements were carried out on
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half-cell assemblies, i.e., anode/GPE and GPE/cathode, respectively. In
both cases, the test was run in the pristine state, as well as at full charge and
full discharge states. The samples for these tests were prepared by
dismounting pristine, discharged, and charged, cells in argon-atmosphere
dry boxes; proper portions of the cells were then sealed in suitable crucibles
before removing them from the dry box and opened just before running the
measurement.
The TGA-DSC studies were performed using a NETZCH STA 449C
Jupiter instrument at a scan rate of 10 8C min
1 in the 25–550 8C
temperature range, under argon flux; Mass Spectrometry was performed
using a NETZCH QMS 403C Aëolos mass spectrometer coupled with the
previously described TGA-DSC instrument.
Acknowledgements
The authors wish to thank Dr. Mario Wachtler for the assistance and helpful
discussion in performing the DSC-TGA-MS measurements and ZSW
(Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-
Württemberg, Ulm, Germany) for hosting one of us (J. H) and providing
the facilities for these measurements. Supporting Information is available
online from Wiley InterScience or from the author.
Received: February 10, 2009
Revised: May 5, 2009
Published online: August 15, 2009
4810 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advmat.de
[1] Advances in Lithium-Ion Batteries (Eds: W. van Schalkwijk, B. Scrosati),
Kluwer Academic/Plenum, Boston 2004.
[2] Report of the Basic Energy Sciences Workshop on Electrical Energy
Storage, US Department of Energy, Washington, July 2007.
[3] Global Trends in Sustainable Energy Investment 2007, UNEP, United
Nations Environment Programme, Source: Sustainable Energy Finance
Initiative, New Energy Finance, http://www.unep.org.
[4] C. J. Rydh, B. A. Sandén, Eng. Convers. Manag. 2005, 46, 1957.
[5] C. J. Rydh, B. A. Sandén, Eng. Convers. Manag. 2005, 46, 1980.
[6] E. Karden, S. Ploumen, B. Fricke, T. Miller, K. Snyder, J. Power Sources 2007,
168, 2.
[7] Editorial, Nature 2008, 436.
[8] J. Hassoun, S. Panero, P. Reale, B. Scrosati, Italian Patent
RM2008A000381, 2008.
[9] M. Winter, J. O. Besenhard, Electrochim. Acta 1999, 45, 31.
[10] G. Derrien, J. Hassoun, S. Panero, B. Scrosati, Adv. Mater. 2007, 19,
2336.
[11] J. Hassoun, G. Derrien, S. Panero, B. Scrosati, Adv. Mater. 2008, 20,
3169.
[12] P. Reale, S. Panero, B. Scrosati, J. Electrochem. Soc. 2005, 152, A1949.
[13] F. Gray, Solid Polymer Electrolytes, VCH, Weinheim 1991.
[14] F. Croce, A. D’Epifanio, J. Hassoun, P. Reale, B. Scrosati, J. Power Sources
2003, 119–121, 399.
[15] J. Hassoun, P. Reale, B. Scrosati, M. Wachtler, M. Fleischammer,
M. Kasper, unpublished.
Adv. Mater. 2009, 21, 4807–4810