5 Will it be a tank of lithium to drive our next car? Key requisite: availability of suitable energy storage, power sourcesBest 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 ReactionsCathodeAnodeOverallCathode 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 transferThe present Li-ion batteries rely on intercalation chemistry!(From: K. Xu, Encyclopedia of Power Sources, Elsevier, 2010)77
8 Lithium BatteriesAlthough lithium batteries are established commercial productsFurther R&D is still required to improve their performance especially in terms of energy density to meet the HEV, PHEV, EV requirementJumps 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 ISSUEEnergy 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 batteriesEnhancement 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 EVs200kg kgLi-ion BatteriesPresentNear futureModified by courtesy of Dr. Stefano Passerini, Munster University, Germany10
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 coordinatorHydroEco Center at Sapienza including Dept Chemistry(scientific coordinator) , Dept Physics,Universities Camerino and Chieti;Chalmers University of TechnologyEnte Nazionale Idrocarburi ENI SpAChemetallZentrum für Sonnenenergie- und Wasserstoff-Forschung (ZSW)SAES Getters SpAETC Battery and Fuel Cells Sweden ABStena Metall AB.
13 The APPLES SnC/ GPE / LiNi0.5Mn1.5O4 lithium ion polymer battery anodeGPEcathode
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 + LixSnCProjected 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]O4Projected energy density: 200 Wh/kg
18 Electric Vehicle Applications- The energy issue Revolutionary Technology- Change>500 Wh/kgSuper- Battery < 100kg140 Wh/kg*170 Wh/kg*200 Wh/kg*Estimated limit of Lithium-Ion Technology250 kg kgLi-ion BatteriesYearPresent20122017Modified by courtesy of Dr. Stefano Passerini, Munster University, Germany18
19 Cathode side: Li Metal Chemistries Where should we go ?123456250500750100012501500175040003750Potential vs. Li/Li+Capacity / Ah kg-1LimetalO2 (Li2O)F2SO2 (Li2O2)Lithium-ElementBattery CathodesLi-IonOxideCathodes"4V"IntercalationchemistryCarbonanodesModified 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/molOCV: 2.23VTheoretical capacity : 1675mAh/g-sulfurLi2S8 : 209 mAh/g-S, Li2S4 : 418 mAh/g-SLi2S2 : mAh/g-S, Li2S : mAh/g-SCobalt: 42,000 US$/ton Sulfur: 30 US$/tonCharge processDischarge processS8Li2S8Li2S6Li2S4Li2S2Li2SLithiumSulfurLiLi+Li2SLi+ + Se-Electrolyte(polymer or liquid)AnodeCathodeB. 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/ /ja206955kand 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 batteryANODEConventional :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
24 SnC/ Li2S lithium ion battery J. Hassoun & B. Scrosati, Angew. Chem. Int. Ed. 2010, 49, 2371
25 THE CATHODEPotentiodynamic 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+ 2.2SProjected energy density: 400 Wh/kgSafety
27 The kinetics issue Capacity decay upon rate increase. Slow kinetics! Some Li2S particles remain uncoated by carbonOptimization 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 sulfurJ.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 capabilityCycling response room temperature CJ.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 systemsTwo battery versions under investigationLithium-air battery with protected lithium metal anode and/or protected cathode (aqueous electrolyte)2Li + ½ O2 + H2O 2LiOHTheor. energy density : 5,800 Wh/kgLithium-air battery with unprotected lithium metal anode (non aqueous electrolyte)Li + ½ O2 ½ Li2O2Theor. energy density : 11,420 Wh/kgPresent Lithium Ion technology (C-LiCoO2:Theor energy density: 420 Wh/kg
33 The lithium-air battery (organic electrolyte) Unprotected electrode design Organic electrolytesRemaining 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 RTLi / Polymer electrolyte / SP,O2 cell study by PCGAY-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-A74Lithium superoxide formationLithium peroxide formationLithium oxide formationVery low charge -discharge hysteresis with efficiency approaching 90% !Reaction mechanismJ. 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, LiPF6P.G. Bruce et al., IMLB, Montreal, Canada, June 27-July 2, 2010P.G. Bruce et al., ECS, Montreal, Canada, May 01-06, 2011J. 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 productsLi / polymer electrolyte / SP,O2 galvanostatic dischargeXRD of the SP electrode
37 The last concern:are lithium metal reserves sufficient for allowing large electric vehicle production?
40 LAB-FCT Laboratory structure Principal investigator: Prof Stefania PaneroResearchers:Jusef HassounMaria Assunta NavarraPriscilla RealePost Docs:Sergio BruttiInchul HongGraduate students: average 3 Visitors : average Master students : average 4Total : average 15
41 ACKNOWLEDGEMENTThis work was in part performed within the 7th Framework European Project APPLES (Advanced, Performance, Polymer Lithium batteries for Electrochemical Storage )
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