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Net Energy Analysis of Solar Fuel Device

Presented by Pei

The work was supported by LBNL and JCAP

GCEP workshop, Stanford 03/31/15 • Free sunshine • How to harness it directly? – many ways-- water heater, photovoltaics, bio-fuel

A relatively new technology— Solar Fuel Device Other names: Artificial photosynthesis, Artificial leaf, Solar water splitting, and Photo-electro-chemical (PEC) device Principles

Simply speaking, one device combining two steps: 1) converting sunlight to electric energy (electron-hole) 2) converting electric energy to hydrogen (reduction of H+ by electrons)

+ + 4h + 2H2O  4H + O2(g) photoanode

- + 4e + 4H  2H2(g) photocathode Research centers worldwide

Institutes, universities and industries involved

• U.S.A.– MIT ($9.5 million),Caltech, Berkeley ($116 million) Joint Center of Artificial Photosynthesis (JCAP) (2010 DOE energy hub)

• Europe– EU (€ 4 million), Netherlands (€25 million),UK

• Asia—Japan (14 billion), , Singapore Why Net Energy Analysis (NEA)? • Renewable energy technologies: purpose is to harness free energy • Net energy = energy out - energy in • Bottomline requirement: Net energy is positive • Energy in : direct (fabrication) and indirect (embodied in materials)

Input Output Primary energy Energy requirement to PEC content of produce PEC device hydrogen

Net energy = Output - Input Contributions and limitations of NEA

Context– renewable energy technologies • Fundamental requirement for renewable energy technologies • Good ‘Entry Point’ into life cycle thinking • Should not mask the other impact assessments (land use, toxicity release) • Could be one of many metrics to help decision- making

Conceptual structure of PEC device (solar fuel) Pipes and other components (not included) Glass cover Photo-anode Membrane Photo-cathode Chamber

Photo-anode micro-wire Catalyst Membrane Photo-cathode micro-wire Catalyst

Note: figures are not in real scale Defining system boundary and functional units

PEC device LCA boundary Materials

Photoelectrodes

Catalysts LCA method

Membrane Goal: Net primary

Encapsulation Energy

material Scope: materials and Other materials fabrication processes Functional units: Fabrication MJ per m2 PEC

Photoelectrode MJ per kg Hydrogen

fabrication

Catalyst deposition

Membrane fabrication Other processes

Life Cycle Assessment of emerging technologies --Challenges and opportunities

• Opportunities– • Help scientists to have a big picture of their research • Point out some energy intensive components which they may not have realized • Minimize the negative environmental impacts even at very early stage of R&D

• Challenges– • Few available data or literatures • Dynamics and uncertainties (material and experimental procedures always change, making assumptions of future) • Interpretation of the results (never single point, always a range)

Assumptions for Lower, Medium and Higher cases

Category Component Lower case Medium case Higher case Material Photocathode Si Si choices Photoanode WO3 WO3 GaAs Catalysts for Co Pt Pt photocathode Catalysts for No catalyst No catalyst Pt photoanode Encapsulation PVC PVC Polycarbonate Thickness of 3 mm 5 mm 7 mm chamber Thickness of 30 um 50 um 70 um membrane Fabrication Thermodynamic 70% 50% 30% efficiency Details of calculation (medium case)

• Embodied energy in materials • Primary energy use in fabrication PEC device LCA boundary Materials

Photoelectrodes

Catalysts LCA method

Membrane Goal: Net primary

Encapsulation Energy

material Scope: materials and Other materials fabrication processes Functional units: Fabrication MJ per m2 PEC

Photoelectrode MJ per kg Hydrogen

fabrication

Catalyst deposition

Membrane fabrication Other processes

Photo-electrodes and catalysts

Photo-electrodes (Si, WO3); catalyst (Pt)

Materials Thickness Mass Energy Embodied (nm) (g/m2) intensity energy (MJ/g) (MJ/m2) Si 2000A 4.7 0.2 5.2 B WO3 20 0.1 1.1 0.02 Pt 1.5 0.03 279 9.0

A: It is equivalent thickness converting from Si wire array which has 2.8 µm of diameter, 50 µm of length and 7 µm of lattice spacing.

B: It is an equivalent thickness converting from WO3 wire array which has 70 nm of diameter, 4 µm of length and 0.5 µm of lattice spacing. PEC device LCA boundary Materials

Photoelectrodes

Catalysts LCA method

Membrane Goal: Net primary

Encapsulation Energy

material Scope: materials and Other materials fabrication processes Functional units: Fabrication MJ per m2 PEC

Photoelectrode MJ per kg Hydrogen

fabrication

Catalyst deposition

Membrane fabrication Other processes

Membrane

• Nafion®-- Perfluoro-sulfonic acid (PFSA)

• Very few data from any database or literature review • PE (polyethylene) as a proxy • The cost of PSFA is 19 times of PE, we assume the energy intensity of PSFA is 19 times of PE

• Primary energy of PFSA is estimates as 139 MJ/m²

PEC device LCA boundary Materials

Photoelectrodes

Catalysts LCA method

Membrane Goal: Net primary

Encapsulation Energy

material Scope: materials and Other materials fabrication processes Functional units: Fabrication MJ per m2 PEC

Photoelectrode MJ per kg Hydrogen

fabrication

Catalyst deposition

Membrane fabrication Other processes

Chamber and glass cover

• Using the most common plastic and glass which are PVC and coated flat glass • Data for primary energy in materials are from a LCA database -- Ecoinvent 2.2 • Total primary energy is 534 MJ/m² PEC device LCA boundary Materials

Photoelectrodes

Catalysts LCA method

Membrane Goal: Net primary

Encapsulation Energy

material Scope: materials and Other materials fabrication processes Functional units: Fabrication MJ per m2 PEC

Photoelectrode MJ per kg Hydrogen

fabrication

Catalyst deposition

Membrane fabrication Other processes

Photo-cathode--Si wire array growth • Main step: vapor-liquid-solid (VLS) growth • Growth environment: 1000 °C

Figure : p-Si wire array from (Boettcher S.W., et.al. 2011) Photo-anode--WO3 wire array growth

• Main step: vapor-liquid-solid (VLS) growth • Growth environment: 1000 °C

Figure : WO3 wire array from (Cao B., et.al. 2009) Catalysts – Pt depostion

• Electron-beam deposition requires high vacuum environment (8e-04 Pa)

Source: McKone, J. R. et al. (2011). Energy use for Electrodes micro-wire array growth

Thermo-dynamic models

Heating: Eh= mass * specific heat * (T-T0) Vacuum pumping: Ev= P0 *V * Ln (P/P0) PEC device LCA boundary Materials

Photoelectrodes

Catalysts LCA method

Membrane Goal: Net primary

Encapsulation Energy

material Scope: materials and Other materials fabrication processes Functional units: Fabrication MJ per m2 PEC

Photoelectrode MJ per kg Hydrogen

fabrication

Catalyst deposition

Membrane fabrication Other processes

Membrane fabrication

• Main process is heating at 140 °C

Source: Spurgeon, J. M. et al. (2011) PEC device LCA boundary Materials

Photoelectrodes

Catalysts LCA method

Membrane Goal: Net primary

Encapsulation Energy

material Scope: materials and Other materials fabrication processes Functional units: Fabrication MJ per m2 PEC

Photoelectrode MJ per kg Hydrogen

fabrication

Catalyst deposition

Membrane fabrication Other processes

For other ancillary processes, data are adjusted from PV industry • Environmental control 200 MJ/m² • Water pumping 31 MJ/m² • Miscellaneous chemicals 15 MJ/m² Break-down results of primary energy requirement 1200

1000

Materials Fabrication

800

600 MJ/m2

400

200

0

(medium case, error bars showing lower and higher cases) Functional unit is important for LCA study Now the results of ‘energy in’ are in MJ/m² –> Because the ‘energy out’ MJ/kg in hydrogen –> in order to calculate Net energy

• Need to convert MJ/m² to MJ/kg, • That brings more uncertainty • Because need to know performance parameters: efficiency and longevity of PEC • It is in early-stage, we could only assume a range. Equation-- Primary energy requirement in MJ to produce 1 kg of hydrogen

MJ/kg

MJ/m2

Determined by Solar-to-Hydrogen Longevity STH efficiency (years) Results-- MJ to produce 1 kg of hydrogen

Lower left part of the figure below the black line has negative net energy, (e.g. if efficiency is 3% and longevity is 8 years, net energy is zero) Scenarios of future achievement

Different STH efficiency and longevity combination would lead to different net energy

STH Longevity Primary energy Energy content MJ Net energy MJ of 1 Efficiency (year) requirement MJ of 1 kg H2 kg of H2 3% 5 194 120 (-)74 3% 8 120 120 0 5% 10 58 120 62 10% 10 29 120 91 10% 30 10 120 110 Uncertainties could affect results

1. STH efficiency and longevity 2. thermodynamic models efficiency 3. material choice, chamber layer thickness

Which uncertainties have higher effect? Base point -- 29 MJ/kg (medium case, 10% efficiency and 10 years) Discussions • The most energy intensive process is the fabrication of photo- electrodes • Now, the method requires very high temperature 1000 °C • In future, it is possible to adopt other methods like chemical-etching.

• Chamber material costs 20% energy • Point to the direction of designing with less chamber material

• Electrodes and catalyst materials cost < 1% • From energy analysis perspective, no worries

• The key parameters to determine the net energy balance device STH efficiency, longevity and fabrication thermal-efficiency • This study points out the bottom-line requirement (positive net energy) Publication and acknowledgement

• Publication: Net primary energy balance of a solar-driven photoelectrochemical water-splitting device, Energy and Environmental Science, 2013

(For all the citations used in this presentation, please refer to this publication)

• Co-authors: Sophia Haussener, Joel Ager, Roger Sathre, Karl Walczak, Jeffery Greenblatt, Thomas McKone • Funding agency: DOE—LBNL and JCAP

Following up works by my colleagues at LBNL

More information

• Tomorrow 1:15pm, Jeff Greenblatt will talk more about large-scale application and early technology appraisal

• Joint Center of Artificial Photosynthesis http://solarfuelshub.org/

• Lawrence Berkeley National Lab – CarbonCycle 2.0 Initiative http://carboncycle2.lbl.gov/ Thank and would like to take any comment or suggestion

Pei Zhai [email protected]