Solar Fuels From Light & Heat
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1 Solar Fuels From Light & Heat Xiaofei Ye, Liming Zhang, Madhur Boloor, Nick Melosh Will Chueh Materials Science & Engineering, Precourt Institute for Energy Stanford University
2 Sunita Williams, NASA 2
3 D. Diliff London R. Laddish Tokyo C.-Y. Yu Chicago 3
4 Enhance solar utilization 5 % Ultraviolet 43 % Visible 52 % Infrared Dionne Photo-electrochemical cell Power (W m -2 nm -1 ) eV Wavelength (nm) 4
5 Combining heat & light: what s possible? Solar-to-Fuel Efficiency Unreachable Temp. 10% X. Ye, J. Melas-Kyriazi, A. Feng, N. A. Melosh, W. C. Chueh. PCCP 15 (2013)
6 Can thermal energy make existing materials better? Low mobility Morin, F. J. Phys. Rev. 1954, 93,
7 Low mobility, high stability semiconductor: Fe 2 O 3 Ti doped α-fe 2 O 3 Pt Al 2 O 3 (0001) 30 nm 200 nm TEM SEM AFM Pulsed-Laser Deposition 7
![cm -2 ] 4 2 0 0.2 0.1 72 o C 48 o C 25 o C 7 o C T I Δη~ 70 mv 1.19 V 1.](/docs-images/85/91890303/images/8-1.jpg "24 V 9 suns T 1 sun 0.1 M NaOH ph = 13 Stirrer 0.0 0.8 1.0 1.2 1.4 1.6 1.")
8 Enhancement with temperature & light intensity 5%Ti-Fe 2 O 3 TOP VIEW RHE Thermocouple CE W E Solar simulator Nitrogen Water bath J [ma cm -2 ] J [ma cm -2 ] o C 48 o C 25 o C 7 o C T I Δη~ 70 mv 1.19 V 1.24 V 9 suns T 1 sun 0.1 M NaOH ph = 13 Stirrer E vs RHE [V] 8
9 Enhancement with temperature & light intensity 9
10 Thermally-enhanced fill factor > 4.5 ma cm % Ti-doped Fe 2 O 3 E [V] mv
11 Another low-mobility semiconductor: BiVO 4 5 μm 200 nm Current density (ma/cm 2 ) Effect of doping dark current pure BiVO 4 0.3% Mo doped BiVO 4 1% Mo doped BiVO 4 3% Mo doped BiVO E (V) vs. RHE E (V) vs. RHE 0.5 M K 3 PO 4 buffered ph = 7 Electrolyte 11 Current density (ma/cm 2 ) Effect of catalysts dark current dark current with SO 3 2- without CoPi with CoPi without CoPi with SO 3 2-
12 Thermally-enhanced saturation current Current density (ma/cm 2 ) sun dark 9 C 25 C 42 C T T E (V) vs. RHE Significant enhancement in photocurrent without significant decrease with photovoltage E (V) vs. RHE Open Circuit Voltage (mv) light on 1 sun light off light on 3 suns BiVO 4 Pt Time (s) 1mM [IrCl 6 ] 4- /0.1 mm [IrCl 6 ] Temperature ( C) ( ) 12
13 Stability E (V vs. RHE) E [V vs RHE] % Ti-doped 9 suns, 70 o C 2 ma cm -2 Fe 2 O 3 9 suns, I = 2 ma cm C Time [hour] Time (h) Current density (ma/cm 2 ) C 25 C 9 C BiVO 4 1 sun E = 0.6V vs. RHE Time (h) 13
14 Thermally-enhanced PEC PEC / Solar cells cooling 14
15 Going > 100 C: an all-oxide approach Air Gas Bubbles Light Absorber Liquid Electrolyte Light Absorber Proton-conducting Oxide < 100 C C esolar 15
16 16
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19 Semiconductor/Mixed Conductor Heterojunction A new class of solid state PEC for concentrated sunlight Compatible with elevated temperature Single device, isothermal 19
20 Semiconductor/Mixed Conductor Heterojunction Photon absorption Electron/hole pairs excitation Carrier diffusion Paper submitted 20
21 Semiconductor/Mixed Conductor Heterojunction Light absorber/miec interface: Electrons: thermionic emission Holes: mostly reflected Paper submitted 21
22 Semiconductor/Mixed Conductor Heterojunction MIEC/gas interface Electron transfer, HER Paper submitted 22
23 Semiconductor/Mixed Conductor Heterojunction Gas diffusion (stagnation layer) H 2 O: continuously supplied, diffuse to the surface H 2 : diffuse away from surface, then removed Paper submitted 23
24 Semiconductor/Mixed Conductor Heterojunction Oxygen ions transport to the air side and react with holes Paper submitted 24
25 Efficiency Simulation Efficiency T (K) o C Potential (V) o C µ abs abs /q µ MIEC MIEC /q T (K) E rxn E 0 rxn Broad maximum at ~750 K, 17 % Below 700 K: slow thermionic emission Above 700 K: insufficient photovoltage Paper submitted 25
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27 Figure 1 b Intensity (a.u.) (101) * (011) (-121) * * (004) (200) (002) * (211) (015) (240) (042) * * * * * ** ** ** * (161) (321) (123) * c theta (degree) 5 µm 200 nm
28 Figure 2 Raman intensity (a.u.) pure BiVO 4 0.3% Mo doped BiVO 4 1% Mo doped BiVO 4 3% Mo doped BiVO Raman shift (cm -1 ) Current density (ma/cm 2 ) dark current pure BiVO 4 0.3% Mo doped BiVO 4 1% Mo doped BiVO 4 3% Mo doped BiVO E (V) vs. RHE Current density (ma/cm 2 ) front illumination back illumination Deposition time (min) c
29 Figure 5 a b 2 µm 200 nm c Current density (ma/cm 2 ) dark current macroporous BiVO 4 nanoporous BiVO E (V) vs. RHE
30 Figure 6 a Current density (ma/cm 2 ) b E (V) vs. RHE c Current density (ma/cm 2 ) Current density (ma/cm 2 ) at 0.80 V vs. RHE E (V) vs. RHE Small BiVO 4 NPs Large BiVO 4 NPs
31 Figure 8 Current density (ma/cm 2 ) E (V) vs. RHE log ( j (ma/cm 2 ) ) E (V) vs. RHE
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