1. STATO DI SVILUPPO DELL’ACCUMULO ENERGETICO PER VIA ELETTROCHIMICA
LE BATTERIE AL LITIO
Bruno Scrosati
Laboratory for Advanced Batteries
and Fuel Cell Technology
LAB-FCT
Dipartimento di Chimica Centro Hydro-ECO SAPIENZA Università di Roma

2. Courtesy of Dr. Ahiara, Samsung Research, Yokohama, Japan
Research background
Wind
Geothermal
Cost of Oil (WTI)
Solar
Intermittent alternative energy sources (REPs) , as well as electric transportation, require convenient energy storage systems, e.g., batteries
Global warming : suppression of CO2
Demand of oil in the world
(particularly in BRICs)
 Energy Storage, Vehicle
Courtesy of Dr. Ahiara, Samsung Research, Yokohama, Japan
Kyoto protocol

3. Li-ion battery system 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
Figure. Schematic illustration of a rechargeable lithium battery
(From: K. Xu, Encyclopedia of Power Sources, Elsevier, 2010) 3 3

4. Lithium-Ion Battery Charge
Electrolyte
Cu Current
Collector
AL Current
Collector
Graphite
LiMO2
SEI
SEI

5. Lithium-Ion Battery Discharge
Electrolyte
Cu Current
Collector
AL Current
Collector
Graphite
LiMO2
SEI
SEI

6. Lithium Batteries
Lithium batteries: high energy density (3 times lead-acid) Power sources of choice for the consumer electronics market
The application of lithium batteries spans beyond the electronics market

7. Courtesy of Dr. Ahiara, Samsung Research, Yokohama, Japan
HEV, EV and FCV in Japan
Hybrid (HEV) and electric (EV) vehicles are already on the road
HEV in market
PHEV
FCHV ?
Their diffusion is expected to drammatically increase in the next few years EV
Courtesy of Dr. Ahiara, Samsung Research, Yokohama, Japan
Reference: Institute of Information Technology, Japan

8. Lithium Batteries
Although lithium batteries are established commercial products
further R&D is still required to improve their performance to meet the REP andHEV-EV requirement
Enhancement in safety, energy density and cost are needed!

10. THE SAFETY ISSUE

11. SAFETY
Actions:
Replacement of the oxygen releasing cathode material (LiCoO2) with structurally stable alternative compounds, e.g. LiFePO4
Replacement of the flammable liquid organic electrolyte with more stable materials, for example
Polymer ionic conducting membranes

12. AVERAGE PRICE PER CELL IN 2005
THE COST ISSUE
Battery type
Cost (US$/W)
Lead- acid
0.15
Ni-Cd
0.95
Li-ion (C-LiCoO2)
1.35
Li-ion (C-LiMn2O4)
1.10
Ni-MH
2.00
AVERAGE PRICE PER CELL IN 2005
Cost of lithium batteries in comparison with other rechargeable systems
Source : The rechargeable battery market, , June 2006
Source :TIAX, based on MEDI data

13. COST
Actions:
Replacement of the expensive cathode material (LiCoO2) with low cost, abundant alternative compounds, ideally iron or sulfur – based cathodes

14. Comparison of various raw materials for lithium secondary batteries.
Cost
Comparison of various raw materials for lithium secondary batteries.
Cobalt Co
Iron
Fe (ore)
Nickel Ni
Manganese
Mn (ore)
Copper Cu
Sulfur
(S)
Cost
US $/ton
41,850
135
12,350
564
2,770 28
Materials in use: LiCoO2 (cathode) ; Cu (current collector)
Alternative materials: LiFePO4, LiMn2O4, S (cathode) ; Stainless Steel (current collector)

15. Energy Density (Wh/kg)  driving range (km)
THE ENERGY ISSUE
Energy Density (Wh/kg)  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!

16. Electric Vehicle Applications- The energy issue
500 km Battery
Pb-acid kg
Ni-MH kg
Revolutionary Technology- Change
>500 Wh/kg
Super- Battery < 200kg
140 Wh/kg*
170 Wh/kg*
200 Wh/kg*
Estimated limit of Lithium-Ion Technology
700 Kg kg
Li-ion Batteries
Year
Present
2012
2017
Courtesy of Dr. Stefano Passerini, Munster University, Germany 16

17. Actions: ENERGY DENSITY
Replacement of the present electrode materials with alternative compounds having much higher values of specific capacity

18. X High-Energy Battery Technologies Where should we go?
"4V" 1 2 3 4 5 6
250
500
750
1000
1250
1500
1750
Potential vs. Li/Li+
Capacity / Ah kg-1
Intercalation
materials
Oxide
Cathodes
Carbon
anodes
Li-ion
500 km Battery X
Where should we go?
High capacity
cathodes
"0V"
Super- Battery <200kg/500km
Li/O2 , Li/S
Courtesy of Dr. Stefano Passerini, Munster University

19. Future Li-S performance region
 Why Li/S battery?
Anode
Cathode e- e-
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
Li+
Li+
Li+
Li+ + S
Electrolyte
(polymer or liquid) Li
Li2S
Ni/Cd
Ni/MH
Cylindrical Li-ion
Prismatic Li-ion
Prismatic Li-Polymer
Sion Power Corp.
Future Li-S performance region
Li-S, 2001
Li-S, 2005
SION POWER CORPORATION
PBFC-2, Las Vegas, Nevada, USA,
June 12-17, 2005
Fig. Energy density comparison with commercial secondary batteries.

20. ------- VIII ------- ------- 8 -------
 Why Li and S for electrode active material? (1)
Lithium
Sulfur
-. Atomic weight: 6.94g/mol
-. Lightest alkali metal
(0.54g/cm3)
-. Silvery, metallic solid
-. Theoretical capacity:
3.86Ah/g
-. E = VSHE
-. Atomic weight: 32.06g/mol
-. Light yellow solid
(2.07g/cm3)
-. Non-toxic, “green” material
-. Abundant and cheap
(28 US$/ton)
-. Theoretical capacity:
1.675 Ah/g
Period
Group**        
1 IA 1A
18 VIIIA 8A 1
1 H
2 IIA 2A
13 IIIA 3A
14 IVA 4A
15 VA 5A
16 VIA 6A
17 VIIA 7A
2 He 4.003 2
3 Li 6.941
4 Be 9.012
5 B 10.81
6 C 12.01
7 N 14.01
8 O 16.00
9 F 19.00
10 Ne 20.18 3
11 Na 22.99
12 Mg 24.31
3 IIIB 3B
4 IVB 4B
5 VB 5B
6 VIB 6B
7 VIIB 7B 8 9 10
11 IB 1B
12 IIB 2B
13 Al 26.98
14 Si 28.09
15 P 30.97
16 S 32.07
17 Cl 35.45
18 Ar 39.95
VIII 4
19 K 39.10
20 Ca 40.08
21 Sc 44.96
22 Ti 47.88
23 V 50.94
24 Cr 52.00
25 Mn 54.94
26 Fe 55.85
27 Co 58.47
28 Ni 58.69
29 Cu 63.55
30 Zn 65.39
31 Ga 69.72
32 Ge 72.59
33 As 74.92
34 Se 78.96
35 Br 79.90
36 Kr 83.80 5
37 Rb 85.47
38 Sr 87.62
39 Y 88.91
40 Zr 91.22
41 Nb 92.91
42 Mo 95.94
43 Tc (98)
44 Ru 101.1
45 Rh 102.9
46 Pd 106.4
47 Ag 107.9
48 Cd 112.4
49 In 114.8
50 Sn 118.7
51 Sb 121.8
52 Te 127.6
53 I 126.9
54 Xe 131.3 6
55 Cs 132.9
56 Ba 137.3
57 La* 138.9
72 Hf 178.5
73 Ta 180.9
74 W 183.9
75 Re 186.2
76 Os 190.2
77 Ir 190.2
78 Pt 195.1
79 Au 197.0
80 Hg 200.5
81 Tl 204.4
82 Pb 207.2
83 Bi 209.0
84 Po (210)
85 At (210)
86 Rn (222) 7
87 Fr (223)
88 Ra (226)
89 Ac~ (227)
104 Rf (257)
105 Db (260)
106 Sg (263)
107 Bh (262)
108 Hs (265)
109 Mt (266) () () () () () ()
Lanthanide Series*
58 Ce 140.1
59 Pr 140.9
60 Nd 144.2
61 Pm (147)
62 Sm 150.4
63 Eu 152.0
64 Gd 157.3
65 Tb 158.9
66 Dy 162.5
67 Ho 164.9
68 Er 167.3
69 Tm
168.9
70 Yb 173.0
71 Lu 175.0
Actinide Series~
90 Th 232.0
91 Pa (231)
92 U (238)
93 Np (237)
94 Pu (242)
95 Am (243)
96 Cm (247)
97 Bk (247)
98 Cf (249)
99 Es (254)
100 Fm (253)
101 Md (256)
102 No (254)
103 Lr (257)
Courtesy of Prof. K.Kim, Gyeongsang National University, Korea

21. Why Li / S battery ? Comparison of various secondary batteries. System
Negative
electrode
Positive
Voltage
(V)
Th. Cap.
(mAh/g)
Th. En.
(Wh/kg)
Ni-Cd Cd
NiOOH
1.2
162
219
Ni-MH
MH alloy
~178
~240
Li-Ion
LixC6
Li1-xCoO2
3.6
137
(for x=0.5)
360
Li-S Li S
2.1
1,675
2,600
Li-FeS2
FeS2
1.5
893
1,273
Comparison of various raw materials for lithium secondary batteries.
Iron
(Fe)
Nickel
(Ni)
Manganese
(Mn)
Cobalt
(Co)
Copper
(Cu)
Molybdenum
(Mo)
Sulfur
(S)
Cost
(US$/ton)
135
(Fe ore)
12,350
564
(Mn ore)
41,850
2,770
46,260 28
Atomic weight
(g/mol)
55.85
58.69
54.94
58.93
63.55
95.94
32.06
Courtesy of Prof. K.Kim, Gyeongsang National University, Korea

22. The lithium-sulfur battery
The Li/S concept is not new. However, so far limited progress due to a series of practical issues
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)

23. R&D is required to improve the performance of super-batteries, such as Li-S or Li-O2 to meet the HEV-EV requirement
Large investments are in progress worldwide to reach this important goal .

24. Our approach:
Total renewal of the battery chemistry, including all three components, i.e. anode, electrolyte and cathode.
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

25. Specific advantages THE BATTERY
 Control of lithium sulphide solubility (specifically designed polymer electrolyte)
Easiness of fabrication (polymer configuration; match between anode and cathode specific capacity)
 Safety ( no lithium metal anode; no LiPF6 in the electrolyte; chemical stability of electrodes)
 Low cost ( abundant materials; simple preparation)

26. SnC nanocomposite / gel electrolyte/ Li2S-C cathode sulfur lithium-ion polymer battery
 High energy density (about 3 times that offered by common lithium ion batteries) and plastic design.
Jusef Hassoun and Bruno Scrosati, Angew. Chem. Int. Ed. 2010, 49, 2371

27. Acknowledgement Funds
Italian Ministry of Education , University and Resarch, MIUR , PRIN 2007 Project
and
SIID Project “REALIST” (Rechargeable, advanced, nano structured lithium batteries with high energy storage) sponsored by Italian Institute of Technology.