An example of high-throughput materials research Ronald Griessen, Nov., Hydrogenography works also for metallic hydrides Bulk, nanocrystals and thin films The electrical cycle How to find new hydrogen storage materials The idea behind hydrogenography The ---H system Measuring isotherms, enthalpies and entropies Finding a destabilized -based hydride Hydrogenography works also for metallic hydrides Sun ENERGY ENERGY The hydrogen cycle Electrons Hydrogen now Sun H Transport Storage Dissociation of water H O O H Battery Toyota Prius. MJ/kg ENERGY O H O Combustion Fuel cells ENERGY Li-ion battery. MJ/kg
Electrons Hydrogen now Electrons Hydrogen tomorrow H. MJ/kg Battery Toyota Prius. MJ/kg Battery Toyota Prius. MJ/kg Li-ion battery. MJ/kg H in modified Prius La H.9 MJ/kg Li-ion battery. MJ/kg NaAlH (AlH ) LiAlH LiBH Al(BH ) 9 MJ/kg MJ/kg MJ/kg MJ/kg MJ/kg Hydrogen pressure ( Pa) Pressure-composition isotherms of PdH x.. 9 K 9 K K K 9 K......... Hydrogen concentration H/Pd Hydrogen pressure ( Pa).. ΔH ΔS ln p = RT R E-....... /T 9 Pressure [ Pa] - - -....... /T [K] The idea behind hydrogenography The ---H system Measuring isotherms, enthalpies and entropies Finding a destabilized -based hydride Hydrogenography works also for metallic hydrides Group 9 Period H Li Na 9 K Rb Cs Fr Be Ca Sr Ba Ra B Al C Si N P 9 Sc V Cr Mn Fe Co Cu Zn Ga Ge As 9 Y O S 9 F Cl Se Br 9 Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I * 9 Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi ** Lr Periodic System Rf *Lanthanoids * 9 La Ce Pr Nd Pm Sm **Actinoids ** 9 9 9 9 9 9 9 Ac Th Pa U Np Pu Am Po At He Ne Ar Kr Xe Rn 9 Db Sg Bh Hs Mt Ds Rg Uub Uut Uuq Uup Uuh Uus Uuo Eu Gd Tb Dy Ho Er 9 Cm 9 9 99 Bk Cf Es Fm 9 Tm Yb Md No
Group 9 Period H Li Na 9 K Rb Cs Fr Be Ca Sr Ba Ra Light ternary compounds B Al C Si N P 9 Sc V Cr Mn Fe Co Cu Zn Ga Ge As 9 Y O S 9 F Cl Se Br 9 Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I * 9 Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi AB x 9 = Po At He Ne Ar Kr Xe Rn 9 ** Lr Rf Db Sg Bh Hs Mt Ds Rg Uub Uut Uuq Uup Uuh Uus Uuo ABC x x 9 = *Lanthanoids * 9 La Ce Pr Nd Pm Sm Eu Gd Tb Dy ABC x x 9 = Ho Er 9 Tm Yb **Actinoids ** 9 9 9 9 9 9 9 9 9 9 99 Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No ABCD x x 9 x 9 = 9 Discharge capacity of y -y films Low rate High rate MH mah/g ~ MJ/kg y in y -y Vermeulen, essen and Notten, Electrochem. Comm. () Light -- ternary alloys Group 9 Period H Li Na 9 K Rb Cs Fr Be Ca Sr Ba Ra B Al C Si N P 9 Sc V Cr Mn Fe Co Cu Zn Ga Ge As 9 Y O S 9 F Cl Se Br 9 Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I * 9 Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi ** Lr *Lanthanoids * La Rf Ce Po At He Ne Ar Kr Xe Rn 9 Db Sg Bh Hs Mt Ds Rg Uub Uut Uuq Uup Uuh Uus Uuo -x-y x y =9 9 Pr Nd Pm Sm Eu **Actinoids ** 9 9 9 9 9 9 9 Ac Th Pa U Np Pu Am Gd 9 Cm Tb Dy Ho 9 9 99 Bk Cf Es Er Fm 9 Tm Yb Md No Looking efficiently for a needle in a huge haystack Yttrium Switchable mirrors The ---H system Measuring isotherms, enthalpies and entropies Finding a destabilized -based hydride Hydrogenography works also for metallic hydrides Y: Metal YH : Metal YH : Insulator
Switchable mirrors: seeing hydrogen Yttrium - in air in H Hydrogenography works also for metallic hydrides Bernard Dam Pd Sputtering system for new H storage materials Pd Pd
Optical transmission of -- during hydrogenation T= K Pa Pressure Robin Gremaud Pa Optical transmission in ternary diagram...... R. Gremaud et al. Advanced Materials 9 () -......9 at. fraction y.9..............9 at. fraction y R. Gremaud et al. Advanced Materials 9 () - Isotherms for each pixel p H (mbar).9.. K K K K K..... ~Hydrogen log(t/tconcentration ) Van t Hoff plot for each pixel Map of hydride formation enthalpies ΔH ΔS ln p = RT R Temperature (K).9.. ΔH = - kj/molh...... p eq (mbar)............9 at. fraction y......9 at. fraction y...9... R. Gremaud et al. Advanced Materials 9 () - /Temperature (K - ) 9 R. Gremaud et al. Advanced Materials 9 () -
p eq [bar] Van t Hoff plots for -based hydrides Temperature [K] - - - - - () nano H () nano H ().. H. () G. Liang et al., J. Alloys Compd. (999) () G. Liang et al., J. Alloys Compd. (99) () A. Krozer and B. Kasemo, J. Less-Common Met. (99).9.. H. H..... /T [K - ] bulk PdH..9... wt% TF H () - - - - - Hydrogenography works also for metallic hydrides Pressure-optical transmission-isotherm Optical determined Van t Hoff plots for PdH x Pressure [mbar] Pd on Quartz cycle 9 K Pd on Plastic cycle Pressure [Bar] Temperature T [K] - - Desorption Absorption ΔH ΔS ln p = RT R ΔH β α ΔS β α [kj/molh ] [J/K/molH ] -.±. -9.± -.±. -9.±. -9.±. -9.±. α -.......... ln(t/to) -......... /Temperature [/K] E. Wicke and H. Brodowsky, Hydrogen in Metals II, G. Alefeld an J. Völkl ed. (9) R. Lässer, K.-H. Klatt, PRB, Hydrogenography works also for metallic hydrides Bulk, nanocrystals and thin films Phase boundaries of Cu-Fe prepared differently Cu the equilibrium phase boundary at room temperature liquid quenching thermal evaporation sputtering sputtering on cryogenic substrates mechanical alloying (nanocrystalline) Cu FCC FCC+BCC BCC Fe Fe E. Ma, Progress in Materials Science () 9
Comparison: films - nanocrystals Enthalpy of formation (kj/mol) 9 Concentration of Ag (at%) sputter-deposited fcc solution terminal fcc solutions from literature ball milled fcc solution Hydrogenography works also for metallic hydrides Bulk, nanocrystals and thin films Optical screening for hydrogen storage properties metallic Y nm yttrium insulating film YH substrate CCD Camera Catalyst, e.g. Pd nm yttrium film substrate Yttrium or any switchable mirror material Light source A. Borgschulte et al J. Catalysis 9 () - Critical Pd thickness metallic Y nm yttrium insulating film YH substrate transmission (arb. u.).... nm nm nm nm nm nm is universal is quantitative for hydride formation and kinetics. can be used for: batteries catalytic caplayers adaptive solar collectors optical fiber H sensors. At least nm Pd are needed for H absorption A. Borgschulte et al J. Catalysis 9 () -. time (s) Thin films are not exotic! Theory feedback is essential
Chase Broedersz Jan Rector Dana Borsa Herman Schreuders Andreas Borgschulte T H ank you W Lo Marta Gonzalez Robin Gremaud Andrea Baldi Bernard Dam Philippe Mauron