1. Lithium batteries: a look into the future.
Bruno Scrosati
Department of Chemistry, University of Rome “Sapienza”

2. To fight the global warming a large diffusion in the road of low emission vehicles (HEVs) or no emission vehicles (EVs) is now mandatory

3. Electrified Vehicle sales forecast for Asia Pacific countries
Source: The Korean Times

4. Source: http://aspoitalia. blogspot

5. 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

6. Courtesy of Dr. Jürgen Deberitz CHEMETALL GmbH
Where lithium is taking us?
Courtesy of Dr. Jürgen Deberitz CHEMETALL GmbH

7. Li-ion battery system: a scheme of operation
Electrochemical Reactions
Cathode
Anode
Overall
Cathode more positive redox potential
Discharge: Li+ intercalates the positive materials -> provide outer electron flow
Charge: Li+ deintercalates from cathode and intercalates the anode.
Li-ion shuttles b/w cathode and anode during cycling -> conversion & storage of electrochemical energy within the
Cells
Energy density: storage of large amount of Li
Power density: fast ionic/electronic transfer
The present Li-ion batteries rely on intercalation chemistry!
(From: K. Xu, Encyclopedia of Power Sources, Elsevier, 2010) 7 7

8. 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

9. Energy Density (Wh/kg)  EV driving range (km)
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!

10. Electric Vehicle Applications- The energy issue
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 kg
Li-ion Batteries
Present
Near future
Modified by courtesy of Dr. Stefano Passerini, Munster University, Germany 10

11. Midterm evolution of the lithium ion battery technology
Some examples of new-concept batteries developed our laboratory.

12. Ente Nazionale Idrocarburi ENI SpA
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.

13. The APPLES SnC/ GPE / LiNi0.5Mn1.5O4 lithium ion polymer battery
anode
GPE
cathode

14. 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

15. 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

16. Li4Ti5O12 / Li[Ni0.45Co0.1Mn1.45]O4 lithium ion battery
H-Gi Jung, M. W. Jang, J. Hassoun, Y-K. Sun, B. Scrosati, Nature Communications, 2 (2011) 516

17. Li4Ti5O12 / Li[Ni0.45Co0.1Mn1.45]O4 lithium ion battery
Li4Ti5O Li[Ni0.45Co0.1Mn1.45]O4  Li4+xTi5O Li (1-x) [Ni0.45Co0.1Mn1.45]O4
Projected energy density: 200 Wh/kg

18. Electric Vehicle Applications- The energy issue
Revolutionary Technology- Change
>500 Wh/kg
Super- Battery < 100kg
140 Wh/kg*
170 Wh/kg*
200 Wh/kg*
Estimated limit of Lithium-Ion Technology
250 kg kg
Li-ion Batteries
Year
Present
2012
2017
Modified by courtesy of Dr. Stefano Passerini, Munster University, Germany 18

19. Cathode side: Li Metal Chemistries
Where should we go ? 1 2 3 4 5 6
250
500
750
1000
1250
1500
1750
4000
3750
Potential vs. Li/Li+
Capacity / Ah kg-1 Li
metal
O2 (Li2O) F2 S
O2 (Li2O2)
Lithium-Element
Battery Cathodes
Li-Ion
Oxide
Cathodes
"4V"
Intercalation
chemistry
Carbon
anodes
Modified by courtesy of Dr. Stefano Passerini, Munster University, Germany

20. < Theoretical capacity of lithium polysulfides >
The lithium-sulfur battery
< Theoretical capacity of lithium polysulfides >
Anodic rxn.: Li → 2Li e-
Cathodic rxn.: S + 2e - → S2-
Overall rxn.: 2Li + S → Li2S, ΔG = kJ/mol
OCV: 2.23V
Theoretical capacity : 1675mAh/g-sulfur
Li2S8 : 209 mAh/g-S, Li2S4 : 418 mAh/g-S
Li2S2 : mAh/g-S, Li2S : mAh/g-S
Cobalt: 42,000 US$/ton Sulfur: 30 US$/ton
Charge process
Discharge process S8
Li2S8
Li2S6
Li2S4
Li2S2
Li2S
Lithium
Sulfur Li
Li+
Li2S
Li+ + S e-
Electrolyte
(polymer or liquid)
Anode
Cathode
B. Scrosati, J. Hassoun, Y-K Sun, Energy & Environmental Science, 2011

21. 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)

22. 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/ /ja206955k
and others
……. however mainly focused on the optimization of the sulfur cathode still keeping Li metal anode

23. 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

24. SnC/ Li2S lithium ion battery
J. Hassoun & B. Scrosati, Angew. Chem. Int. Ed. 2010, 49, 2371

25. THE CATHODE
Potentiodynamic Cycling with Galvanostatic Acceleration, PGCA, response in the CPGE. Li counter and reference electrode. Room temperature.
In situ XRD analysis run on a Li/CGPE/Li2S cell at various stages of the Li2S → S+ 2Li charge process.
Anode peak area = cathode peak area (integration)
Reversibility of the overall electrochemical reaction!
Jusef Hassoun, Yang-Kook Sun and Bruno Scrosati, J. Power Sources, 196 (2011) 343

26. SnC/ Li2S lithium ion polymer battery
SnC+ 2.2Li2S  Li4.4SnC+ 2.2S
Projected energy density: 400 Wh/kg
Safety

27. The kinetics issue 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

28. 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: /jpowsour  

29. Improved sulfur-based cathode morphology
Rate capability
Cycling response room temperature  C
J.Hassoun, J. Kim, D-J. Lee, H.-Gi.Jung,S-M.Lee,Y-K.Sun, B. Scrosati, J.Power Sources, Doi: /jpowsour  

30. LiSiC/ S-C lithium ion battery
J.Hassoun, J. Kim, D-J. Lee, H.-Gi.Jung,S-M.Lee,Y-K.Sun, B. Scrosati, J.Power Sources, Doi: /jpowsour  

31. LiSiC/ S-C lithium ion battery
Projected energy density: 400 Wh/kg

32. 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

33. 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

34. Li / Polymer electrolyte / SP,O2 cell study by PCGA
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. Hamad-Schifferli, Y. Shao-Horn, 2010, JACS, 132,
Y-C. Lu, H.A. Gasteiger, Y. Shao-Horn, Electrochem Solid State Lett , 2011, 14, A70-A74
Lithium superoxide formation
Lithium peroxide formation
Lithium oxide formation
Very low charge -discharge hysteresis with efficiency approaching 90% !
Reaction mechanism
J. Hassoun, F. Croce, M. Armand & B. Scrosati, Angew. Chem. Int. Ed., 2011, 50, 2999

35. Oxygen electrochemistry in the polymer electrolyte lithium cell at RT
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

36. Oxygen electrochemistry in the polymer electrolyte lithium cell at RT
Reduction products
Li / polymer electrolyte / SP,O2 galvanostatic discharge
XRD of the SP electrode

37. The last concern:
are lithium metal reserves sufficient for allowing large electric vehicle production?

38. Main Lithium Deposits

39. B.Scrosati, Nature, 473 (2011) 448

40. LAB-FCT Laboratory structure Principal investigator:
Prof Stefania Panero
Researchers:
Jusef Hassoun
Maria Assunta Navarra
Priscilla Reale
Post Docs:
Sergio Brutti
Inchul Hong
Graduate students: average 3 Visitors : average Master students : average 4
Total : average 15

41. ACKNOWLEDGEMENT
This work was in part performed within the 7th Framework European Project APPLES (Advanced, Performance, Polymer Lithium batteries for Electrochemical Storage )