Lithium batteries: a look into the
future.
Bruno Scrosati
Department of Chemistry,
University of Rome “Sapienza”
To fight the global warming a
large diffusion in the road of
low emission vehicles (HEVs)
or no emission vehicles (EVs)
is now mandatory
Electrified Vehicle sales forecast
for Asia Pacific countries
Source: The
Korean Times
1,400,000
1,200,000
Rest of Asia Pacific
Korea
China
Japan
( Vehlcles )
1,000,000
800,000
600,000
400,000
200,000
0
2010
2011
2012
2013
2014
2015
Source: http://aspoitalia.blogspot.com/2011/02/gli-scenari-dellagenziainternazionale.html
Will it be a tank of lithium to drive our next car?
Key requisite: availability of suitable energy storage,
power sources
Best candidates: lithium batteries
Where lithium is taking us?
Courtesy of Dr. Jürgen Deberitz
 Li-ion battery system: a scheme of operation
Electrochemical Reactions
• Cathode
LiCoO2
c
d
Li1-xCoO2 + xLi+ + x e-
• Anode
Cn + xLi+ + x e-
c
d
CnLix
• Overall
LiCoO2 + Cn
c
d
Li1-xCoO2 + CnLix
The present Li-ion batteries rely on intercalation chemistry!
(From: K. Xu, Encyclopedia of Power Sources, Elsevier, 2010)
7
Lithium Batteries
Although lithium batteries are established
commercial products
Further R&D is still required to improve
their performance especially in terms of
energy density to meet the HEV, PHEV,
EV requirement
Jumps in performance require the renewal
of the present lithium ion battery chemistry,
this involving all the components, i.e.,
anode, cathode and electrolyte
THE ENERGY ISSUE
Energy Density (Wh/kg) 
EV driving range (km)
Middle size car (about 1,100 kg) 
using presently available lithium
batteries (150 Wh/kg) 
driving 250 km with a single charge
  200 kg batteries
Enhancement of about 2-3 times in
energy density is needed!
Electric Vehicle ApplicationsThe energy issue
200 Wh/kg*
170 Wh/kg*
140 Wh/kg*
Present
Estimated
progress of the
conventional
Lithium-Ion
Technology in
terms of battery
weight in EVs
Li-ion Batteries
Near future
Modified by courtesy of Dr. Stefano Passerini, Munster University, Germany
Midterm evolution of the lithium
ion battery technology
Some examples of new-concept
batteries developed our
laboratory.
Main goal: complete the development of the battery starting from a further
optimization of the electrode and electrolyte materials, to continue with their
scaling up to large quantities and then on their utilization for the fabrication and
test of high capacity battery cells, to end with the definition and application of
their recycling process.
Collaborative participation of nine partners.
Consorzio Sapienza Innovazione (CSI), Italy,
managing coordinator
HydroEco Center at Sapienza including Dept Chemistry
(scientific coordinator) , Dept Physics,
Universities Camerino and Chieti;
Chalmers University of Technology
Ente Nazionale Idrocarburi ENI SpA
Chemetall
Zentrum für Sonnenenergie- und Wasserstoff-Forschung (ZSW)
SAES Getters SpA
ETC Battery and Fuel Cells Sweden AB
Stena Metall AB.
The APPLES SnC/ GPE / LiNi0.5Mn1.5O4
lithium ion polymer battery
anode
http://www.applesproject.eu
GPE
cathode
The Li[Ni0.45Co0.1Mn1.45]O4 / SnC lithium ion cell
1
μ
m
2 ,0
F irs t c y c le
S u b s e q u e n t c y c le s
C ell V oltage / V
1 ,5
1 ,0
0 ,5
0 ,0
0
50
100
150
200
250
300
S p e c ific C a p a c ity / m A h g
J.Hassoun, K-S. Lee, Y-K.Sun,B.Scrosati, JACS 133 (2011)3139
350
-1
400
450
The Li[Ni0.45Co0.1Mn1.45]O4 / SnC lithium ion battery
Li[Ni0.45Co0.1Mn1.45]O4 + SnC 
Li (1-x)[Ni0.45Co0.1Mn1.45]O4 + LixSnC
Projected
energy density:
170 Wh/kg
Li4Ti5O12 / Li[Ni0.45Co0.1Mn1.45]O4 lithium ion battery
B
Primary
particles
Crystallized
carbon
10 nm
500 nm
5.2
-1
3.0
Voltage / V
-1
0.5 C, 0.85 A g ,
-1
3 C, 0.51 A g ,
-1
10 C, 1.7 A g ,
1 C, 0.17 A g
-1
5 C, 0.85 A g
-1
20 C, 3.4 A g
2.5
2.0
1.5
A
1.0
0
1.0-3.0 V, 1 C charge
20
40
60
80
100 120 140 160
-1
Capacity / mAhg
Potential Vs. Li / V
3.5
A
4.8
4.4
4.0
3.6
3.2
2.8
0.0
0.2
0.4
0.6
0.8
X in Li1-x[Ni0.45Co0.1Mn1.45]O4
H-Gi Jung, M. W. Jang, J. Hassoun, Y-K. Sun, B. Scrosati,
Nature Communications, 2 (2011) 516
1.0
Li4Ti5O12 / Li[Ni0.45Co0.1Mn1.45]O4 lithium ion battery
4
A
Capacity / mAh g
3
2
0.2C
3C
10C
1
0
20
0.5C
5C
2C
40
60
1C
7C
80
100
120
140
-1
-1
Capacity / mAh g
Capacity / mAh g
Voltage / V
-1
2.0 - 3.4 V
140
C
2.0 - 3.4 V
0.1C 0.2C 0.5C 1C
2C
3C
120
5C
7C
10C
100
83.5%
80
60
0
4
8
12
Number of Cycle
16
100
80
60
40
20
0
0
100
200
300
Number of Cycle
20
Li4Ti5O12 + Li[Ni0.45Co0.1Mn1.45]O4 
Li4+xTi5O12 + Li (1-x) [Ni0.45Co0.1Mn1.45]O4
1C
120
B
140
400
500
Projected
energy density:
200 Wh/kg
Electric Vehicle Applications- The energy issue
Revolutionary
TechnologyChange
>500 Wh/kg
Super- Battery
200 Wh/kg*
< 100kg
Estimated
limit of
Lithium-Ion
Technology
170 Wh/kg*
140 Wh/kg*
Li-ion Batteries
Present
2012
2017
Year
Modified by courtesy of Dr. Stefano Passerini, Munster University, Germany
Cathode side: Li Metal Chemistries
Where should we go ?
Potential vs. Li/Li+
6
F2
Lithium-Element
Battery Cathodes
Li-Ion
Oxide
Cathodes
5
4
"4V"
O2 (Li2O2)
O2 (Li2O)
3
S
2
Intercalation
chemistry
Carbon
anodes
1
Li
metal
0
0
250
500
750
1000
1250
1500
1750
3750
4000
Capacity / Ah kg-1
Modified by courtesy of Dr. Stefano Passerini, Munster University, Germany
The lithium-sulfur battery
Anodic rxn.:
2Li
Cathodic rxn.:
S + 2e - → S2-
< Theoretical capacity of lithium polysulfides >
→ 2Li+ + 2e-
Li2S8 : 209 mAh/g-S, Li2S4 : 418 mAh/g-S
Li2S2 : 840 mAh/g-S, Li2S : 1675 mAh/g-S
Overall rxn.: 2Li + S → Li2S,
ΔG = - 439.084kJ/mol
Cobalt: 42,000 US$/ton
Sulfur: 30 US$/ton
OCV: 2.23V
Theoretical capacity : 1675mAh/g-sulfur
Cathode
e-
e-
Li+
Li+
Li+
Li+ + S
Li2S6
Li2S4
Li2S2
•Electrolyte
(polymer or liquid)
Li
Li2S8
Li2S
B. Scrosati, J. Hassoun, Y-K Sun, Energy &
Environmental Science, 2011
Li2S
Lithium
Sulfur
Discharge process
Anode
Charge process
S8
The lithium-sulfur battery
Major Issues:
 solubility of the polysulphides LixSy in the
electrolyte (loss of active mass  low utilization
of the sulphur cathode and in severe capacity
decay upon cycling)
 low electronic conductivity of S , Li2S and
intermediate Li-S products (low rate capability,
isolated active material)
 Reactivity of the lithium metal anode
(dendrite deposition, cell shorting, safety)
The lithium-sulfur battery
Sleeping for long time…….
booming in the most recent years…………
Ji, X., Lee, K.T., Nazar, L.F., Nat. Mater 8, 500 (2009)
Lai, C. Gao, X.P., Zhang, B., Yan, T.Y., Zhou, Z
J. Phys. Chem. C 113, 4712 (2009).
Ji, X., L.F. Nazar, J. Mat. Chem, ., 20, 9821 (2010)
Ji, X., S. Ever, R. Black, L.F. Nazar, Nat. Comm., 2, 325 (2011)
N. Jayprakash,J. Shen, S.S. Morganty, A. Corona, L.A. Archer,
Angew. Chemie Intern. Ed. 50, 5904 (2011)
E.J. Cairns et al, JACS, doi.org/10.1021/ja206955k
and others
……. however mainly focused on the
optimization of the sulfur cathode still
keeping Li metal anode
Our approach:
SnC nanocomposite / gel electrolyte/ Li2S-C cathode
sulfur lithium-ion polymer battery
ANODE
Conventional :Li metal

our work : Sn-C nanocomposite
(gain in reliability and in cycle life)
ELECTROLYTE
Conventional : liquid organic  our work : gel-polymer
membrane (gain in safety
and cell fabrication)
CATHODE
Conventional : sulfur-carbon  our work : C- Li2S composite
Conventional : liquid organic
(Li-metal-free battery )
(Li metal battery)
Jusef Hassoun and Bruno Scrosati, Angew. Chem. Int. Ed. 2010, 49, 2371
SnC/ Li2S lithium ion battery
2 ,0
F irs t c y c le
S u b s e q u e n t c y c le s
C ell V oltage / V
1 ,5
1 ,0
0 ,5
0 ,0
0
50
100
150
200
250
300
S p e c ific C a p a c ity / m A h g
350
400
450
-1
J. Hassoun & B. Scrosati, Angew. Chem. Int. Ed. 2010, 49, 2371
THE CATHODE
1
2
3
4
5
In te n sity / cp s
S u p p o rt
L i2 S
J C P D S -7 7 2 1 4 5
30
Potentiodynamic Cycling with
Galvanostatic Acceleration,
PGCA, response in the CPGE. Li
counter and reference electrode.
35
40
45
2  / d e g re e
50
55
In situ XRD analysis run on a
Li/CGPE/Li2S cell at various stages
of the Li2S → S+ 2Li charge
process.
Room temperature.
4 .8
2
3
4
300
450
5
Anode peak area = cathode
peak area (integration)
Reversibility of the overall
electrochemical reaction!
C e ll vo lta g e / V
4 .0
3 .2
2 .4 1
1 .6
0
150
C a p a city / m A h g
600
-1
Jusef Hassoun, Yang-Kook Sun and Bruno Scrosati, J. Power Sources, 196 (2011) 343
SnC/ Li2S lithium ion polymer
battery
1400
600
C /10 C /20
500
1200
1000
400
800
C /6
300
600
C /5
200
400
100
200
0
0
0
20
40
60
C ycle num ber
80
100
-1
C a p a c ity (L i 2 S -C m a s s ) / m A h g
700
C a p a c ity (L i 2 S -C m a s s ) / m A h g
-1
SnC+ 2.2Li2S  Li4.4SnC+ 2.2S
Projected
energy density:
400 Wh/kg
Safety
-1
600
C /10 C /20
500
1200
1000
400
800
C /6
300
600
C /5
200
400
100
200
0
0
0
20
40
60
80
100
The kinetics issue
Capacity decay upon rate
increase. Slow kinetics!
-1
C a p a c ity (L i 2 S -C m a s s ) / m A h g
1400
C a p a c ity (L i 2 S -C m a s s ) / m A h g
700
C ycle num ber
Some Li2S particles remain
uncoated by carbon
Optimization of the cathode material morphology is
needed. Work in progress in our laboratories
Improved sulfur-based cathode morphology
SEM
Scheme
FIB
EDX
Hard carbon spherule-sulfur (HCS-S) electrode morphology, showing the
homogeneous dispersion of the sulfur particles in the bulk and over the
surface of the HCS particles. The top right image illustrates the sample
morphology as derived from the SEM image (top left) and the EDX image
(bottom right) in which the green spots represent the sulfur
J.Hassoun, J. Kim, D-J. Lee, H.-Gi.Jung,S-M.Lee,Y-K.Sun, B. Scrosati, J.Power Sources,
Doi:10.1016/jpowsour.2011.11.60
Improved sulfur-based cathode morphology
Rate capability
Cycling response
room temperature
0C
J.Hassoun, J. Kim, D-J. Lee, H.-Gi.Jung,S-M.Lee,Y-K.Sun, B. Scrosati, J.Power Sources,
Doi:10.1016/jpowsour.2011.11.60
LiSiC/ S-C lithium ion battery
0.1 A g
2.0
-1
-1
-1
3 .0
(S )
800
-1
-1
1Ag
400
1.5
-1
2Ag
0.5 A g
-1
0.2 A g
0.1 A g
0
0
3
6
9 12 15
Cycle number
18
21
1.0
0.5
2 0 0 0.0
2 .5
2 .0
1 .5
1 .0
0
200
400
600
-1
Capacity (mAh g )
600
-1
V oltage (V )
Voltage (V)
2.5
800
1 A g
1200
Capacity (mAh g )
400
3.0
800
0
500
1000
1500
C a p a c ity (m A h g
-1
(S )
2000
)
J.Hassoun, J. Kim, D-J. Lee, H.-Gi.Jung,S-M.Lee,Y-K.Sun, B. Scrosati, J.Power Sources,
Doi:10.1016/jpowsour.2011.11.60
LiSiC/ S-C lithium ion battery
2000
-1
3 .0
2 .5
V oltage / V
C apacity (m A h g
-1
(S )
)
0 .5 A g
1500
2 .0
1 .5
1
1 .0
2
3
0 .5
1000
4
0
Projected energy
density: 400 Wh/kg
th
nd
th
th
250
C a p a c ity (m A h g
500
-1
(S )
)
500
0
0
10
C y c le n u m b e r
20
1800
1500
-1
(S )
C apacity (m A h g
-1
(S )
)
0 .5 A g
1200
900
600
300
0
0
20
40
60
C y c le n u m b e r
80
100
The lithium-air battery. The ultimate dream
Potential store 5-10 times more energy than
today best systems
Two battery versions under investigation
Lithium-air battery with protected
lithium metal anode and/or
protected cathode (aqueous
electrolyte)
2Li + ½ O2 + H2O 2LiOH
Theor. energy density : 5,800
Wh/kg
Lithium-air battery with
unprotected lithium metal anode
(non aqueous electrolyte)
Li + ½ O2  ½ Li2O2
Theor. energy density : 11,420
Wh/kg
Present Lithium Ion technology (C-LiCoO2:
Theor energy density: 420 Wh/kg
The lithium-air battery (organic electrolyte)
Unprotected electrode design
Organic electrolytes
Remaining issues:
high voltage
hysteresis loop,
limited cycle life,
stability of the organic
electrolytes, reactivity
of the lithium metal
anode…..
Courtesy of Prof O.Yamamoto, Mie University, Japan
Oxygen electrochemistry in the polymer electrolyte lithium cell at RT
Li / Polymer electrolyte / SP,O2 cell study by PCGA
Y-C. Lu, Z. Xu, H.A. Gasteiger, S. Chen, K. HamadSchifferli, Y. Shao-Horn, 2010, JACS, 132, 12170-12171
Lithium superoxide
formation
Y-C. Lu, H.A. Gasteiger, Y. Shao-Horn, Electrochem
Solid State Lett , 2011, 14, A70-A74
Lithium peroxide
formation
Lithium oxide
formation
Very low charge -discharge
hysteresis with efficiency
approaching 90% !
J. Hassoun, F. Croce, M. Armand & B. Scrosati,
Angew. Chem. Int. Ed., 2011, 50, 2999
Reaction mechanism
Oxygen electrochemistry in the polymer electrolyte lithium cell at RT
Polymer electrolyte
Electrolyte
decomposition !
EC:DMC, LiPF6
P.G. Bruce et al., IMLB, Montreal,
Canada, June 27-July 2, 2010
P.G. Bruce et al., ECS, Montreal,
Canada, May 01-06, 2011
J. Hassoun, F. Croce, M. Armand & B. Scrosati,
Angew. Chem. Int. Ed., 2011, 50, 2999
Oxygen electrochemistry in the polymer electrolyte lithium cell at RT
Reduction products
Li / polymer electrolyte / SP,O2 galvanostatic discharge
XRD of the SP electrode
The last concern:
are lithium metal
reserves sufficient for
allowing large electric
vehicle production?
Main Lithium Deposits
B.Scrosati, Nature, 473 (2011) 448
Laboratory structure
Principal investigator:
Prof Stefania Panero
Researchers:
Priscilla Reale
Sergio
Brutti
Maria
Assunta
Navarra
Jusef
Hassoun
Post Docs:
Inchul Hong
Graduate students: average 3
Visitors : average 2
Master students : average 4
Total : average 15
ACKNOWLEDGEMENT
This work was in part performed within the 7th Framework European
Project APPLES (Advanced, Performance, Polymer Lithium batteries
for Electrochemical Storage )