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Bruno Scrosati Laboratory for Advanced Batteries and Fuel Cell Technology Dipartimento di Chimica Centro Hydro-ECO SAPIENZA Università di Roma STATO DI.

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Presentation on theme: "Bruno Scrosati Laboratory for Advanced Batteries and Fuel Cell Technology Dipartimento di Chimica Centro Hydro-ECO SAPIENZA Università di Roma STATO DI."— Presentation transcript:

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

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

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

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

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

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

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

8 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! Although lithium batteries are established commercial products Lithium Batteries

9

10 THE SAFETY ISSUE

11 Actions: SAFETY Replacement of the flammable liquid organic electrolyte with more stable materials, for example Polymer ionic conducting membranes Replacement of the oxygen releasing cathode material (LiCoO 2 ) with structurally stable alternative compounds, e.g. LiFePO 4

12 Cost of lithium batteries in comparison with other rechargeable systems AVERAGE PRICE PER CELL IN 2005 Source : The rechargeable battery market, , June 2006 Source :TIAX, based on MEDI data Battery typeCost (US$/W) Lead- acid0.15 Ni-Cd0.95 Li-ion (C- LiCoO 2 ) 1.35 Li-ion (C- LiMn 2 O 4 ) 1.10 Ni-MH2.00 THE COST ISSUE

13 Actions: COST Replacement of the expensive cathode material (LiCoO 2 ) with low cost, abundant alternative compounds, ideally iron or sulfur – based cathodes

14 Cost Cobalt Co Iron Fe (ore) Nickel Ni Manga nese Mn (ore) Copper Cu Sulfur (S) Cost US $/ton 41, , ,77028 Comparison of various raw materials for lithium secondary batteries. Materials in use: LiCoO 2 (cathode) ; Cu (current collector) Alternative materials: LiFePO 4, LiMn 2 O 4, S (cathode) ; Stainless Steel (current collector)

15 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! THE ENERGY ISSUE

16 Electric Vehicle Applications- The energy issue 500 km Battery Pb-acid 3000 kg Ni-MH 1200 kg >500 Wh/kg Super- Battery< 200kg Li-ion Batteries Year Present Wh/kg * 170 Wh/kg * 200 Wh/kg * Estimated limit of Lithium-Ion Technology 700 Kg 500 kg Revolutionary Technology- Change Courtesy of Dr. Stefano Passerini, Munster University, Germany

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

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

19 Anodic rxn.: 2Li → 2Li + + 2e - Cathodic rxn.: S + 2e - → S 2- Overall rxn.: 2Li + S → Li 2 S, ΔG = kJ/mol OCV: 2.23V Theoretical capacity : 1675mAh/g-sulfur SION POWER CORPORATION PBFC-2, Las Vegas, Nevada, USA, June 12-17, 2005 Why Li/S battery? Li Li + Li 2 S Li + + S e-e- Li + e-e- Electrolyte (polymer or liquid) 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 Fig. Energy density comparison with commercial secondary batteries. AnodeCathode

20 Why Li and S for electrode active material? (1) Period Group** 1 IA 1A 18 V IIIA 8A 1 1 H IIA 2A 13 IIIA 3A 14 IVA 4A 15 VA 5A 16 VIA 6A 17 VIIA 7A 2 He Li Li 4 Be B C N O F Ne Na Mg IIIB 3B 4 IVB 4B 5 VB 5B 6 VIB 6B 7 VIIB 7B IB 1B 12 IIB 2B 13 Al Si P S Cl Ar VIII K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr Rb Sr Y Zr Nb Mo Tc (98) 44 Ru Rh Pd Ag Cd In Sn Sb Te I Xe Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi 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 Pr Nd Pm (147) 62 Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Actinide Series~ 90 Th 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) Lithium Sulfur -. Atomic weight: 32.06g/mol -. Light yellow solid (2.07g/cm 3 ) -. Non-toxic, “green” material -. Abundant and cheap (28 US$/ton) -. Theoretical capacity: Ah/g -. Atomic weight: 6.94g/mol -. Lightest alkali metal (0.54g/cm 3 ) -. Silvery, metallic solid -. Theoretical capacity: 3.86Ah/g -. E = V SHE Gyeongsang National University, Korea Courtesy of Prof. K.Kim, Gyeongsang National University, Korea

21 Why Li / S battery ? System Negative electrode Positive electrode Voltage (V) Th. Cap. (mAh/g) Th. En. (Wh/kg) Ni-CdCdNiOOH Ni-MHMH alloyNiOOH1.2~178~240 Li-IonLi x C 6 Li 1-x CoO (for x=0.5) 360 Li-SLiS2.11,6752,600 Li-FeS 2 LiFeS ,273 Comparison of various secondary batteries. Iron (Fe) Nickel (Ni) Manganese (Mn) Cobalt (Co) Copper (Cu) Molybdenum (Mo) Sulfur (S) Cost (US$/ton) 135 (Fe ore) 12, (Mn ore) 41,8502,77046,26028 Atomic weight (g/mol) Comparison of various raw materials for lithium secondary batteries. Gyeongsang National University, Korea Courtesy of Prof. K.Kim, Gyeongsang National University, Korea

22 The lithium-sulfur battery  solubility of the polysulphides Li x S y in the electrolyte (loss of active mass  low utilization of the sulphur cathode and in severe capacity decay upon cycling) The Li/S concept is not new. However, so far limited progress due to a series of practical issues  low electronic conductivity of S, Li 2 S and intermediate Li-S products (low rate capability, isolated active material)  Reactivity of the lithium metal anode (dendrite deposition, cell shorting, safety) Major Issues:

23 . R&D is required to improve the performance of super-batteries, such as Li-S or Li-O 2 to meet the HEV-EV requirement Large investments are in progress worldwide to reach this important goal

24 Our approach: Jusef Hassoun and Bruno Scrosati, Angew. Chem. Int. Ed. 2010, 49, 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- Li 2 S composite Conventional : liquid organic (Li-metal-free battery ) (Li metal battery)

25 Low cost ( abundant materials; simple preparation) Control of lithium sulphide solubility (specifically designed polymer electrolyte) Easiness of fabrication (polymer configuration; match between anode and cathode specific capacity) THE BATTERY Specific advantages Safety ( no lithium metal anode; no LiPF 6 in the electrolyte; chemical stability of electrodes)

26 SnC nanocomposite / gel electrolyte/ Li 2 S-C cathode sulfur lithium-ion polymer battery High energy density (about 3 times that offered by common lithium ion batteries) and plastic design. 26 Jusef Hassoun and Bruno Scrosati, Angew. Chem. Int. Ed. 2010, 49, 2371

27 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. Acknowledgement Funds


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