Bruno Scrosati
description
Transcript of Bruno Scrosati
Bruno Scrosati
Lithium batteries: a look into the future.
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 forecastfor Asia Pacific countries
20152014201320122011
1,400,000
1,200,000
800,000
1,000,000
600,000
400,000
( V
eh
lcle
s )
Rest of Asia Pacific Korea China Japan
0
200,000
2010
Source: The Korean Times
Source: http://aspoitalia.blogspot.com/2011/02/gli-scenari-dellagenzia-internazionale.html
Will it be a tank of lithium to drive our next car?
Key requisite: availability of suitable energy storage, power sourcesBest candidates: lithium batteries
Courtesy of Dr. Jürgen DeberitzCHEMETALL GmbH
Where lithium is taking us?
7
Li-ion battery system: a scheme of operation
Electrochemical Reactions
• CathodeLiCoO2 Li1-xCoO2 + xLi+ + x e-c
d
Cn + xLi+ + x e- CnLixcd
• Anode
• OverallLiCoO2 + Cn Li1-xCoO2 + CnLix
c
d
(From: K. Xu, Encyclopedia of Power Sources, Elsevier, 2010)
The present Li-ion batteries rely on intercalation chemistry!
Further R&D is still required to improve their performance especially in terms of energy density to meet the HEV, PHEV, EV requirement
Although lithium batteries are established commercial products
Lithium Batteries
Jumps in performance require the renewal of the present lithium ion battery chemistry, this involving all the components, i.e., anode, cathode and electrolyte
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!
THE ENERGY ISSUE
Electric Vehicle Applications- The energy issue
Li-ion Batteries
Present
140 Wh/kg*
170 Wh/kg*
200 Wh/kg*
Estimated progress of the conventional Lithium-Ion
Technology in terms of battery
weight in EVs
200kg
140 kg
200kg
140 kg
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.
Stena Metall AB.
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;
Chemetall
Chalmers University of Technology
Ente Nazionale Idrocarburi ENI SpA
Zentrum für Sonnenenergie- und Wasserstoff-Forschung (ZSW)
SAES Getters SpA
ETC Battery and Fuel Cells Sweden AB
The APPLES SnC/ GPE / LiNi0.5Mn1.5O4
lithium ion polymer battery
anode GPE cathode
http://www.applesproject.eu
1 μm
The Li[Ni0.45Co0.1Mn1.45]O4 / SnC lithium ion cell
J.Hassoun, K-S. Lee, Y-K.Sun,B.Scrosati, JACS 133 (2011)3139
The Li[Ni0.45Co0.1Mn1.45]O4 / SnC lithium ion battery
Projected energy density: 170 Wh/kg
Li[Ni0.45Co0.1Mn1.45]O4 + SnC Li (1-x)[Ni0.45Co0.1Mn1.45]O4 + LixSnC
Li4Ti5O12 / Li[Ni0.45Co0.1Mn1.45]O4 lithium ion battery
500 nm 10 nm
Crystallized carbon
Primary
particles
A B
0 20 40 60 80 100 120 140 160
1.0
1.5
2.0
2.5
3.0
3.5
1.0-3.0 V, 1 C charge
0.5 C, 0.85 A g-1, 1 C, 0.17 A g-1
3 C, 0.51 A g-1, 5 C, 0.85 A g-1
10 C, 1.7 A g-1, 20 C, 3.4 A g-1
Voltage / V
Capacity / mAhg-1
A
0.0 0.2 0.4 0.6 0.8 1.02.8
3.2
3.6
4.0
4.4
4.8
5.2
Pote
ntial V
s. L
i / V
X in Li1-x
[Ni0.45
Co0.1
Mn1.45
]O4
A
H-Gi Jung, M. W. Jang, J. Hassoun, Y-K. Sun, B. Scrosati, Nature Communications, 2 (2011) 516
Li4Ti5O12 / Li[Ni0.45Co0.1Mn1.45]O4 lithium ion battery
0 20 40 60 80 100 120 1401
2
3
4
0.2C 0.5C 1C 3C 5C 7C 10C 2C
Capacity / mAh g-1
Voltage /
V
2.0 - 3.4 VA
0 4 8 12 16 2060
80
100
120
140
83.5%
10C
1C
7C5C
3C2C
0.5C0.2C
2.0 - 3.4 V
Capacity /
mA
h g
-1
Number of Cycle
0.1C
B
0 100 200 300 400 5000
20
40
60
80
100
120
140
1C
Capacity /
mA
h g
-1
Number of Cycle
C
Projected energy density: 200 Wh/kg
Li4Ti5O12 + Li[Ni0.45Co0.1Mn1.45]O4
Li4+xTi5O12 + Li (1-x) [Ni0.45Co0.1Mn1.45]O4
Electric Vehicle Applications- The energy issue
>500 Wh/kg
Super- Battery < 100kg
Li-ion Batteries
Year Present 2012 2017
140 Wh/kg*
170 Wh/kg*
200 Wh/kg*Estimated
limit of Lithium-Ion Technology
250 kg
140 kg
250 kg
140 kg
Revolutionary Technology-
Change
Modified by courtesy of Dr. Stefano Passerini, Munster University, Germany
Cathode side: Li Metal Chemistries
"4V"
Li-IonOxide
Cathodes
1
2
3
4
5
6
250 500 750 1000 1250 1500 1750 40003750
Pote
ntial
vs.
Li
/Li+
00
Capacity / Ah kg-1
Li Li metalmetal
O2 (Li2O)
F2
S
O2 (Li2O2)
Lithium-Element Battery Cathodes
Where should we go ?
Intercalationchemistry
CarbonanodesCarbonanodes
Modified by courtesy of Dr. Stefano Passerini, Munster University, Germany
Li2S8 : 209 mAh/g-S, Li2S4 : 418 mAh/g-S
Li2S2 : 840 mAh/g-S, Li2S : 1675 mAh/g-S
Li2S8 : 209 mAh/g-S, Li2S4 : 418 mAh/g-S
Li2S2 : 840 mAh/g-S, Li2S : 1675 mAh/g-S
< Theoretical capacity of lithium polysulfides >
Ch
arg
e p
roce
ssC
har
ge
pro
cess
Dis
char
ge
pro
cess
Dis
char
ge
pro
cess
S8
Li2S8
Li2S6
Li2S4
Li2S2
Li2S
LithiumSulfur
Li
Li+
Li2S
Li+ + S
e-
Li+Li+
e-
•Electrolyte(polymer or liquid)
Anode Cathode
Anodic rxn.: 2Li → 2Li+ + 2e-
Cathodic rxn.: S + 2e - → S2-
Overall rxn.: 2Li + S → Li2S,
ΔG = - 439.084kJ/mol
OCV: 2.23V
Theoretical capacity : 1675mAh/g-sulfur
The lithium-sulfur battery
B. Scrosati, J. Hassoun, Y-K Sun, Energy & Environmental Science, 2011
Cobalt: 42,000 US$/ton Sulfur: 30 US$/ton
The lithium-sulfur battery
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)
Major Issues:
Ji, X., Lee, K.T., Nazar, L.F., Nat. Mater 8, 500 (2009)
N. Jayprakash,J. Shen, S.S. Morganty, A. Corona, L.A. Archer, Angew. Chemie Intern. Ed. 50, 5904 (2011)
Lai, C. Gao, X.P., Zhang, B., Yan, T.Y., Zhou, Z J. Phys. Chem. C 113, 4712 (2009).
The lithium-sulfur batterySleeping for long time……. booming in the most recent years…………
Ji, X., S. Ever, R. Black, L.F. Nazar, Nat. Comm., 2, 325 (2011)
Ji, X., L.F. Nazar, J. Mat. Chem, ., 20, 9821 (2010)
and others
……. however mainly focused on the optimization of the sulfur cathode still keeping Li metal anode
E.J. Cairns et al, JACS, doi.org/10.1021/ja206955k
Our approach:
Jusef Hassoun and Bruno Scrosati, Angew. Chem. Int. Ed. 2010, 49, 2371
ANODEConventional :Li metal our work : Sn-C nanocomposite
(gain in reliability and in cycle life)
ELECTROLYTEConventional : liquid organic our work : gel-polymer
membrane (gain in safety and cell fabrication)
CATHODEConventional : sulfur-carbon our work : C- Li2S composite Conventional : liquid organic (Li-metal-free battery ) (Li metal battery)
SnC nanocomposite / gel electrolyte/ Li2S-C cathode sulfur lithium-ion polymer battery
SnC/ Li2S lithium ion battery
J. Hassoun & B. Scrosati, Angew. Chem. Int. Ed. 2010, 49, 2371
Potentiodynamic Cycling with Galvanostatic Acceleration, PGCA, response in the CPGE. Li counter and reference
electrode. Room temperature.
THE CATHODE
Anode peak area = cathode peak area (integration)
Reversibility of the overall electrochemical reaction!
30 35 40 45 50 55
Support
JCPDS-772145
Li2S
Inte
nsity
/ cp
s
2 / degree
1 2 3 4 5
In situ XRD analysis run on a Li/CGPE/Li2S cell at various stages of the Li2S → S+ 2Li charge
process.
0 150 300 450 600
1.6
2.4
3.2
4.0
4.8543
2
1
Ce
ll vo
ltag
e /
V
Capacity / mAhg-1
Jusef Hassoun, Yang-Kook Sun and Bruno Scrosati, J. Power Sources, 196 (2011) 343
SnC/ Li2S lithium ion polymer battery
0 20 40 60 80 1000
100
200
300
400
500
600
700
0
200
400
600
800
1000
1200
1400
Cap
acity
(Li
2S-C
mas
s) /
mA
hg-1
Capacity (Li
2 S-C
mass) / m
Ahg
-1
C/10 C/20
C/6
C/5
Cycle number
Projected energy density: 400 Wh/kg
SnC+ 2.2Li2S Li4.4SnC+ 2.2S
Safety
Capacity decay upon rate
increase. Slow kinetics!
Some Li2S particles remain uncoated by carbon
Optimization of the cathode material morphology is needed. Work in progress in our laboratories
The kinetics issue
0 20 40 60 80 1000
100
200
300
400
500
600
700
0
200
400
600
800
1000
1200
1400
Cap
acity
(Li
2S-C
mas
s) /
mA
hg-1
Capacity (Li
2 S-C
mass) / m
Ahg
-1
C/10 C/20
C/6
C/5
Cycle number
SEM
FIB EDX
Scheme
Improved sulfur-based cathode morphology
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
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
Cycling response room temperature 0 C
Rate capability
LiSiC/ S-C lithium ion battery
0 200 400 600 800
0.0
0.5
1.0
1.5
2.0
2.5
3.0
0 3 6 9 12 15 18 210
400
800
1200
0.2 A g-10.5 A g-1
1 A g-1
0.1 A g-12 A g-1
Vol
tage
(V)
Capacity (mAh g-1)
0.1 A g-1
Cycle number
Cap
acity
(mA
h g
-1)
20 40 60 80 100
0
600
1200
1800
2400
0 500 1000 1500 2000
1.0
1.5
2.0
2.5
3.0
Ca
pa
city (
mA
h g-1
(S) )
1 A g-1
(S)
Cycle number
Vo
lta
ge
(V
)
Capacity (mAh g-1
(S) )
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 10 200
500
1000
1500
2000
0 250 500
0.5
1.0
1.5
2.0
2.5
3.00.5 A g-1
Ca
pa
city (
mA
h g
-1
(S) )
Cycle number
1th
2nd
3th
4th
Volta
ge
/ V
Capacity (mAh g-1
(S) )
0 20 40 60 80 100
0
300
600
900
1200
1500
18000.5 A g-1
(S)
Ca
pa
city (
mA
h g
-1
(S) )
Cycle number
Projected energy density: 400 Wh/kg
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 2LiOHTheor. 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
Reaction mechanism
Lithium superoxide formationLithium
peroxide formation
Lithium oxide formation
Y-C. Lu, Z. Xu, H.A. Gasteiger, S. Chen, K. Hamad-Schifferli, Y. Shao-Horn, 2010, JACS, 132, 12170-
12171
Y-C. Lu, H.A. Gasteiger, Y. Shao-Horn, Electrochem Solid State Lett , 2011, 14, A70-A74
Very low charge -discharge hysteresis with efficiency
approaching 90% !
J. Hassoun, F. Croce, M. Armand & B. Scrosati, Angew. Chem. Int. Ed., 2011, 50,
2999
Oxygen electrochemistry in the polymer electrolyte lithium cell at Oxygen electrochemistry in the polymer electrolyte lithium cell at RTRT
Li / Polymer electrolyte / SP,O2 cell study by PCGA
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
Electrolyte decomposition !
Polymer electrolytePolymer electrolyte
EC:DMC, LiPFEC:DMC, LiPF66
J. Hassoun, F. Croce, M. Armand & B. Scrosati, Angew. Chem. Int. Ed., 2011, 50,
2999
Oxygen electrochemistry in the polymer electrolyte lithium cell at Oxygen electrochemistry in the polymer electrolyte lithium cell at RTRT
Reduction products
XRD of the SP electrode
Li / polymer electrolyte / SP,O2 galvanostatic discharge
Oxygen electrochemistry in the polymer electrolyte lithium cell at Oxygen electrochemistry in the polymer electrolyte lithium cell at RTRT
The last concern: are lithium metal reserves sufficient for allowing large electric vehicle production?
Main Lithium Deposits
B.Scrosati, Nature, 473 (2011) 448
Laboratory structurePrincipal investigator:
Prof Stefania Panero
Post Docs:
Priscilla Reale
Maria Assunta Navarra
Graduate students: average 3 Visitors : average 2 Master students : average 4
Total : average 15
Inchul Hong
Researchers:
Jusef Hassoun
Sergio Brutti
ACKNOWLEDGEMENT
This work was in part performed within the 7th Framework European Project APPLES (Advanced, Performance, Polymer Lithium batteries for Electrochemical Storage )