Presentation on theme: "STATO DI SVILUPPO DELL’ACCUMULO ENERGETICO PER VIA ELETTROCHIMICA"— Presentation transcript:
1STATO DI SVILUPPO DELL’ACCUMULO ENERGETICO PER VIA ELETTROCHIMICA LE BATTERIE AL LITIOBruno ScrosatiLaboratory for Advanced Batteriesand Fuel Cell TechnologyLAB-FCTDipartimento di Chimica Centro Hydro-ECO SAPIENZA Università di Roma
2Courtesy of Dr. Ahiara, Samsung Research, Yokohama, Japan Research backgroundWindGeothermalCost of Oil (WTI)SolarIntermittent alternative energy sources (REPs) , as well as electric transportation, require convenient energy storage systems, e.g., batteriesGlobal warming : suppression of CO2Demand of oil in the world(particularly in BRICs) Energy Storage, VehicleCourtesy of Dr. Ahiara, Samsung Research, Yokohama, JapanKyoto protocol
3Li-ion battery system Electrochemical Reactions Cathode Anode Overall Cathode more positive redox potentialDischarge: Li+ intercalates the positive materials -> provide outer electron flowCharge: Li+ deintercalates from cathode and intercalates the anode.Li-ion shuttles b/w cathode and anode during cycling -> conversion & storage of electrochemical energy within theCellsEnergy density: storage of large amount of LiPower density: fast ionic/electronic transferFigure. Schematic illustration of a rechargeable lithium battery(From: K. Xu, Encyclopedia of Power Sources, Elsevier, 2010)33
6Lithium BatteriesLithium batteries: high energy density (3 times lead-acid) Power sources of choice for the consumer electronics marketThe application of lithium batteries spans beyond the electronics market
7Courtesy of Dr. Ahiara, Samsung Research, Yokohama, Japan HEV, EV and FCV in JapanHybrid (HEV) and electric (EV) vehicles are already on the roadHEV in marketPHEVFCHV?Their diffusion is expected to drammatically increase in the next few yearsEVCourtesy of Dr. Ahiara, Samsung Research, Yokohama, JapanReference: Institute of Information Technology, Japan
8Lithium BatteriesAlthough lithium batteries are established commercial productsfurther R&D is still required to improve their performance to meet the REP andHEV-EV requirementEnhancement in safety, energy density and cost are needed!
11SAFETYActions:Replacement of the oxygen releasing cathode material (LiCoO2) with structurally stable alternative compounds, e.g. LiFePO4Replacement of the flammable liquid organic electrolyte with more stable materials, for examplePolymer ionic conducting membranes
12AVERAGE PRICE PER CELL IN 2005 THE COST ISSUEBattery typeCost (US$/W)Lead- acid0.15Ni-Cd0.95Li-ion (C-LiCoO2)1.35Li-ion (C-LiMn2O4)1.10Ni-MH2.00AVERAGE PRICE PER CELL IN 2005Cost of lithium batteries in comparison with other rechargeable systemsSource : The rechargeable battery market, , June 2006Source :TIAX, based on MEDI data
13COSTActions:Replacement of the expensive cathode material (LiCoO2) with low cost, abundant alternative compounds, ideally iron or sulfur – based cathodes
14Comparison of various raw materials for lithium secondary batteries. CostComparison of various raw materials for lithium secondary batteries.CobaltCoIronFe (ore)NickelNiManganeseMn (ore)CopperCuSulfur(S)CostUS $/ton41,85013512,3505642,77028Materials in use: LiCoO2 (cathode) ; Cu (current collector)Alternative materials: LiFePO4, LiMn2O4, S (cathode) ; Stainless Steel (current collector)
15Energy Density (Wh/kg) driving range (km) THE ENERGY ISSUEEnergy 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 batteriesEnhancement of about 2-3 times in energy density is needed!
16Electric Vehicle Applications- The energy issue 500 km BatteryPb-acid kgNi-MH kgRevolutionary Technology- Change>500 Wh/kgSuper- Battery < 200kg140 Wh/kg*170 Wh/kg*200 Wh/kg*Estimated limit of Lithium-Ion Technology700 Kg kgLi-ion BatteriesYearPresent20122017Courtesy of Dr. Stefano Passerini, Munster University, Germany16
17Actions: ENERGY DENSITY Replacement of the present electrode materials with alternative compounds having much higher values of specific capacity
18X High-Energy Battery Technologies Where should we go? "4V"1234562505007501000125015001750Potential vs. Li/Li+Capacity / Ah kg-1IntercalationmaterialsOxideCathodesCarbonanodesLi-ion500 km BatteryXWhere should we go?High capacitycathodes"0V"Super- Battery <200kg/500kmLi/O2 , Li/SCourtesy of Dr. Stefano Passerini, Munster University
19Future Li-S performance region Why Li/S battery?AnodeCathodee-e-Anodic rxn.: Li → 2Li e-Cathodic rxn.: S + 2e - → S2-Overall rxn.: 2Li + S → Li2S, ΔG = kJ/molOCV: 2.23VTheoretical capacity : 1675mAh/g-sulfurLi+Li+Li+Li+ + SElectrolyte(polymer or liquid)LiLi2SNi/CdNi/MHCylindrical Li-ionPrismatic Li-ionPrismatic Li-PolymerSion Power Corp.Future Li-S performance regionLi-S, 2001Li-S, 2005SION POWER CORPORATIONPBFC-2, Las Vegas, Nevada, USA,June 12-17, 2005Fig. Energy density comparison with commercial secondary batteries.
20------- VIII ------- ------- 8 ------- Why Li and S for electrode active material? (1)LithiumSulfur-. 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/gPeriodGroup** 1 IA 1A18 VIIIA 8A11 H2 IIA 2A13 IIIA 3A14 IVA 4A15 VA 5A16 VIA 6A17 VIIA 7A2 He 4.00323 Li 6.9414 Be 9.0125 B 10.816 C 12.017 N 14.018 O 16.009 F 19.0010 Ne 20.18311 Na 22.9912 Mg 24.313 IIIB 3B4 IVB 4B5 VB 5B6 VIB 6B7 VIIB 7B891011 IB 1B12 IIB 2B13 Al 26.9814 Si 28.0915 P 30.9716 S 32.0717 Cl 35.4518 Ar 39.95VIII419 K 39.1020 Ca 40.0821 Sc 44.9622 Ti 47.8823 V 50.9424 Cr 52.0025 Mn 54.9426 Fe 55.8527 Co 58.4728 Ni 58.6929 Cu 63.5530 Zn 65.3931 Ga 69.7232 Ge 72.5933 As 74.9234 Se 78.9635 Br 79.9036 Kr 83.80537 Rb 85.4738 Sr 87.6239 Y 88.9140 Zr 91.2241 Nb 92.9142 Mo 95.9443 Tc (98)44 Ru 101.145 Rh 102.946 Pd 106.447 Ag 107.948 Cd 112.449 In 114.850 Sn 118.751 Sb 121.852 Te 127.653 I 126.954 Xe 131.3655 Cs 132.956 Ba 137.357 La* 138.972 Hf 178.573 Ta 180.974 W 183.975 Re 186.276 Os 190.277 Ir 190.278 Pt 195.179 Au 197.080 Hg 200.581 Tl 204.482 Pb 207.283 Bi 209.084 Po (210)85 At (210)86 Rn (222)787 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 140.159 Pr 140.960 Nd 144.261 Pm (147)62 Sm 150.463 Eu 152.064 Gd 157.365 Tb 158.966 Dy 162.567 Ho 164.968 Er 167.369 Tm168.970 Yb 173.071 Lu 175.0Actinide Series~90 Th 232.091 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
21Why Li / S battery ? Comparison of various secondary batteries. System NegativeelectrodePositiveVoltage(V)Th. Cap.(mAh/g)Th. En.(Wh/kg)Ni-CdCdNiOOH1.2162219Ni-MHMH alloy~178~240Li-IonLixC6Li1-xCoO23.6137(for x=0.5)360Li-SLiS2.11,6752,600Li-FeS2FeS21.58931,273Comparison 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)12,350564(Mn ore)41,8502,77046,26028Atomic weight(g/mol)55.8558.6954.9458.9363.5595.9432.06Courtesy of Prof. K.Kim, Gyeongsang National University, Korea
22The lithium-sulfur battery The Li/S concept is not new. However, so far limited progress due to a series of practical issuesMajor 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)
23R&D is required to improve the performance of super-batteries, such as Li-S or Li-O2 to meet the HEV-EV requirementLarge investments are in progress worldwide to reach this important goal.
24Our approach:Total renewal of the battery chemistry, including all three components, i.e. anode, electrolyte and cathode.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 compositeConventional : liquid organic (Li-metal-free battery )(Li metal battery)Jusef Hassoun and Bruno Scrosati, Angew. Chem. Int. Ed. 2010, 49, 2371
25Specific 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)
26SnC 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
27Acknowledgement Funds Italian Ministry of Education , University and Resarch, MIUR , PRIN 2007 ProjectandSIID Project “REALIST” (Rechargeable, advanced, nano structured lithium batteries with high energy storage) sponsored by Italian Institute of Technology.