PGM-free OER Catalysts For PEM Electrolyzer - Energy
PGM-free OER Catalysts forPEM ElectrolyzerDi-Jia Liu (lead), Lina Chong, Hao Wang, Argonne National LaboratoryGang Wu, University of Buffalo (Subcontractor)Hui Xu, Giner Inc. (Subcontractor)pd1572018 DOE Hydrogen and Fuel Cells Program Annual Merit Review andPeer Evaluation Meeting, June 13-15, 2018, Washington, D.C.This presentation does not contain any proprietary, confidential, or otherwise restricted information
Project OverviewLead: Di-Jia Liu, Argonne National LaboratorySub: Gang Wu, U. of Buffalo,Hui Xu, Giner Inc.EE2.2.0.202Start DateYear 1 End DateProject End Date10/1/201709/30/201809/30/2020Total DOE ShareTotal Cost ShareYear 1 DOE Funding 1.0M 0.1M 0.25MProject VisionTo lower the capital cost of PEME bydeveloping platinum group metal-free(PGM-free) OER electro-catalystsMOFCurrent density / mAcm-2TeamAward #40302010OERH2O 2H ½ O2 2 e-01.4Project ImpactTo reduce the anode catalyst cost by 20folds by developing one or more PGMfree OER catalysts with the performanceapproaching to that of Ir catalyst,demonstrated at PEME level.HydroGEN: Advanced Water Splitting MaterialsPNNE1.61.8E (V) / RHEH O2e-H2 O2
Relevance - Proton Exchange MembraneElectrolyzer (PEME) – Opportunities & Challenges‣ Advantages of PEME in hydrogenproduction– High ion conductivity (x5 over alkalinesystem) of small footprint– Quick response for better integrationwith renewable sources (wind, solar)– High purity hydrogen– Non corrosive electrolytes‣ Challenges in PEME technology– Use expensive precious metals (Pt, Ir, Ru,etc.) with high loading– Limited material stability under highvoltage cycling– Limited info available for PGM-free OERcatalyst in acidic mediaOperating principle of PEMECathode (HER)4H 4e- 2H2Anode (OER)2H2O O2 4H 4ee-eH2O2H2H O2H2OO2H2H2OO2 H2OH2H2OH2CathodePEMAnodeWe aim at next-generation, low-cost PGM-free OER catalystsHydroGEN: Advanced Water Splitting Materials3
Relevance & Impact Project Goal – To produce one or more PGM-free OERcatalysts with the performance approaching to the Ircatalyst but at 1/20 of the cost, demonstrated throughthe operating PEM electrolyzer. Project Impact – To reducing the electrolyzer capital costand to facilitate broad implementation of PEME for lowcost hydrogen production ( 2/kg) coupled withrenewable energy sources. Mission Alignment with HydroGen – Accelerating low-costmaterial development to produce clean, sustainablehydrogen through advanced low-temperature electrolyzer(LTE) technologies.HydroGEN: Advanced Water Splitting Materials4
Approach- SummaryProject historyBoth ANL and UB teams are the pioneersin the MOF derived PGM-free catalysts foroxygen redox reactions (ORR). PGM-freecatalyst for oxygen evolution reaction(OER) calls for different approach.Promising results are shown recently atboth institutes. Giner is an industrialleader in PEMWE technology responsiblefor MEA/electrolyzer development.BarriersActivity: although PGM-free catalystshave shown good activity in alkalinemedia, few reported for acidic OERapplication.Durability: instability of most conductivesupports and catalytic center under highpolarization potential limits the lifetimeof supported catalysts.HydroGEN: Advanced Water Splitting MaterialsProposed targetsMetricState of theArtProposedDifference inoverpotentialsagainst Ir blackby RDEOverpotential of 530 mV @10mA/cm2 forPGM-freecatalyst in acidOverpotential 350mV or 15 mV higherthan Ir black @10mA/cm2 in acidicelectrolyteCurrent densityin operatingPEMENon-existing forPGM-freecatalyst inPEMEPEME/MEA withtarget performanceof 200 mA/cm2 @1.80 VPartnerships - HydroGen Computational chemistry andpredictive modeling (LLNL andLBNL) Advanced electron microscopicimaging (SNL) High throughput electrodeoptimization support / catalystsurface characterization (NREL).5
Approach – Innovation @ ANLMetal-Organic Framework (MOF) Derived PGM-free OER CatalystsSolvothermalHighTemperatureor Solid-stateReactionPyrolysis &TreatmentTM ion(SBU) N-containingOrganic LigandMetal-OrganicFramework (MOF)TM CompositeCatalystS. Ma, G. Goenaga, A. Call and D.-J. Liu, Chem: Euro J, 17 (2011) 2063Liu, et. al. US Patent 8,835,343 MOF derived catalysts can significantly reduce the cost by using inexpensiveligand and earthly abundant transition metalFramework structure offers maximal active site density and catalytic active siteexposure through porous structureHydroGEN: Advanced Water Splitting Materials6
Approach – Innovation @ ANLPorous Nano-Network Electrode (PNNE) via Electrospin at ANLElectrospinningCatalyst ConversionElectrode FabricationH O2e-H2 OShui, Chen, Grabstanowicz, Zhao and Liu, PNAS, 2015, vol. 112, no. 34, 10629Liu et. al. US Patent 9,350,026Gas diffusion inside electrodeDeff εD/τ; ε porosityτ (path l/straight l)21/Deff 1/Dmicro 1/Dmeso 1/Dmacro MOF embedded PNNE can improve OER mass/charge transfers via direct macroto-micropore connectionContinuous network offers improved connectivity between the catalytic siteagainst deactivation by oxidative corrosionHydroGEN: Advanced Water Splitting Materials7
Approach – Innovation @ UBZeolitic Imidazolate Framework(ZIF-8) based OER catalystHigh PerformanceZIF-8 catalystsFeMx-ZIF-8/FeMx-ZIF-8GT, Oxides NPSFe-ZIF-8ZIF-8HydroGEN: Advanced Water Splitting Materials8
Approach – MilestonesMilestoneDescriptionCriteriaEnd DateStatusCo-ZIF basedcatalystsynthesesAt least 3 new Co-MOF based OERcatalysts are prepared and tested.Demonstrate at least one catalystwith OER potential 1.74 V at thecurrent density of 10 mA/cm2.100% Completed. A recentMOF-derived catalyst by ANL12/29/2017 team showed OER potentialof 1.667 V at current densityof 10 mA/cm2.Fe-ZIF basedcatalystsynthesisAt least 6 new Fe-ZIF based OERcatalysts are designed, synthesized,heat activated, and tested.100% completed: 16 TMdoped ZIF-8 were3/29/2018synthesized and activated atUB with promising activities.At least 4 MOF embedded PNNEMOF templatedOER catalysts with the second metalPNNE catalystdoping are prepared with at least onesynthesiscatalyst with SSA exceeds 200 m2/g.CatalystPerformanceEvaluation byRDEAt least 14 PGM-free catalysts will betested in acid with 30% loss ofactivity after 5,000 potential cyclesbetween 1.2 and 2.0 V.50% completed. ThreePNNE-MOF catalysts were6/30/2018prepared by ANL with SSA of90 to 150 m2/g obtained.9/28/2018 In processGo/NoGo: Demonstrate one or more PGM-free OER catalysts 15 mV higher than Ir (i 10 mA/cm2and 20 mV loss after 10000 cycles by RDE, or MEA electrolyzer at 200 mA/cm2 @ 1.80 V.HydroGEN: Advanced Water Splitting Materials9
Accomplishments – MOF Based OER CatalystSyntheses @ ANLCo2 SolvothermalControlled heatreactiontreatmentOrganic ligandCo-based Metal-organicFramework (Co-MOF)Activated Co-MOF (Co-MOF-O)OxidizedCo-MOFIntegration withgrapheneGrapheneControlled heattreatmentGraphene-supportedCo-MOF (Co-MOF-G)Graphene-supported activatedCo-MOF (Co-MOF-G-O)New MOF approaches are under development with potential for easierbimetallic and multi-metallic catalyst synthesis through exchange/dopingHydroGEN: Advanced Water Splitting Materials10
Accomplishments – Significant MOF-OERCatalyst Activity Improvement Achieved Several new MOF-derived OERcatalysts were prepared underdifferent compositions/activationswith OER activities measured byrotating disk electrode (RDE) in 0.5M H2SO4. Progressive improvements weremade with the best performingcatalyst showing OER voltage of1.644 V (vs. RHE) at 10 mA/cm2, abenchmark for activity The OER activities of four catalystsamong seven exceeded Q1milestone goal of 1.74 V (vs. RHE)at 10 mA/cm2.ANL MOF-based catalyst demonstrated excellent OERactivity in Acidic ElectrolyteHydroGEN: Advanced Water Splitting Materials11
Accomplishments – ANL MOF-OER CatalystOutperformed PGM-free Benchmarks in ActivityANL’s new catalyst showsthe activity approaching to Irblack measured over coatedsurface HydroGEN: Advanced Water Splitting Materials the activity of ANL’s catalystcompared favorably over severalPGM-free catalysts in the literaturemeasured under similar F-Gra-O354 mVThis workBa[Co-POM]361 mVNat. Chem.,2018Co3O4570 mVChem. Mater.,2017Co3O4@C/CP370 mVNano Energy,201612
Accomplishments – MOF-OER CatalystAchieved Significant Durability ImprovementCVs were measured duringaccelerated aging throughvoltage cycling (1.2 to 2.0 V,scan rate 100mV/s) the current density decayof Ir is significantly fasterthan that of ANL PGM-freecatalystANL’s PGM-free catalyst shows excellent durability compared to Irblack when tested under voltage cycling in acidic electrolyteHydroGEN: Advanced Water Splitting Materials13
Accomplishments – ANL PNNE-OER CatalystAlso Demonstrated Excellent Activity ANL PNNE catalysts were prepared bye-spinning of MOFs in polymer slurry,followed by electrospin, forming andthermal activation New trimetallic MOF-based PNNEcatalyst showed excellent activity of1.58 V (RHE) at current density of 10mA/cm2ANL’s PNNE catalysts also outperformed PGM-free benchmarks in activityby optimizing of composition, e-spin formulation and surface propertyHydroGEN: Advanced Water Splitting Materials14
Accomplishments – PNNE Catalyst ShowedExcellent Durability in Acidic Electrolyte A representative ANL PNNEcatalyst (PNNE-3) showedvery good durability during14 K voltage cycling in 0.1M HClO4 electrolytemeasured by RDE The durability outperformedIr catalyst tested under thesimilar conditionPreliminary RDE investigation shows ANL’s embedded PNNEcatalyst with very good activity and durability; furtherimprovement and validation at MEA level are essential.HydroGEN: Advanced Water Splitting Materials15
Accomplishments – UB’s FeMx ZIF-8 CatalystActivity Made Rapid ImprovementThe OER performance of FeMx-ZIF-8 catalysts in 0.1 M H2SO4 solutionWith metals doping, the activity is gradually improved. Ni and Cocould enhanced the OER electrocatalytic activity, and Mn showsthe positive effect on stability of ZIF-8 in acid media.HydroGEN: Advanced Water Splitting Materials16
Accomplishments – UB’s ZIF-8 Based CatalystDurability Showed Promising ProgressThe stability performance of ZIF-8 based catalysts promoted with TiO2 and CeO2 NPsTiO2 and CeO2 nanoparticles are very stable in acid, showing thepotential to further improve the stability of ZIF-8 based catalystsHydroGEN: Advanced Water Splitting Materials17
Contribution – GinerFrom RDE to MEA (Giner) Electrode design and development using avariety of aqueous and non-aqueous ionomerdispersions Catalyst ink processing and characterization(rheology, dynamic light scattering, zetapotential, and surface energy) Mitigated membranes to lower hydrogencrossover Dimension-stabilized membranes towardsreduced membrane swelling and enhancedmembrane mechanical stability Special anode gas diffusion media and bipolarplates for enhanced corrosion resistanceHydroGEN: Advanced Water Splitting Materials18
Collaboration: Computational ModelingSupports @ LLNL & LBNLNear term: understand factors that improve electronic conductivity of C-doped oxideNext stage: Structure-defect impact to catalyst activity and durabilityApproach: Develop structural models using a combination of DFT simulations andlattice Monte Carlo simulations, to be validated by characterization.LLNL: effect of defects on oxide conductivity(develop structural motifs for LBNL)Oxide crystalLBNL: construct disordered structural modelsusing a lattice Monte Carlo & classical potentialM substituted by CCompleted: modeling of O vacancies, C substitution of M/OOngoing: analysis of electronic structuresNext: C interstitials and N defects simulation being preparedCompleted: L-MC code and potential for simple case (left)Ongoing: analysis of the electronic structure (right)Next: incorporate motifs developed by LLNLRealistic structural models are being developed at LBNL & LLNLHydroGEN: Advanced Water Splitting Materials19
Collaboration: Electron Microscopic Studies @SNLTEM reveals MOF size and graphenewrappingEnergy-Filtered TEMANL-MOANL-MGCarbon coating detected on particle surfaceFolds in grapheneIdentified particles folded by graphene20HydroGEN: Advanced Water Splitting Materials20
Collaboration: Testing of Catalyst Activity &Durability Baselines @NRELCatalyst performance baselinesPredict MEA durabilityis1.55 V [mA cmIr‒2]a) 1.21.00.80.60.4 A mgIr‒10.40.2 A mgIr‒10.20.0JM IrPr Ir/VPr IrAA IrAA IrUm IrUm Ir/Ti0.1 A mgIr‒102040602‒1ECA [m gPGM ]80NREL will also support the catalyst surface characterizationand high throughput electrode optimizationHydroGEN: Advanced Water Splitting Materials21
Proposed Future WorkPhase I Continue to develop Co- and Fe-based monometallic MOF OER catalyststhrough elemental doping and oxide modifications to further improveactivity and durability (ANL/UB) Continue to improve PNNE OER catalyst through e-spin and catalyticadditive optimization (ANL) Initiate PGM-free electrode/MEA fabrication and PEME testing in meetinggo/no-go criteria (ANL/Giner)Phase II Explore multi-metallic MOFs through reticular synthesis and post-synthesismodification to further enhance OER catalyst activity and durability Explore new synthesis methods (graphene wrapping, ALD, etc.) to improvePNNE PGM-free catalyst stability Design, fabricate and demonstrate MEA/PEME with PGM-free OER catalystas viable replacement for Ir, leading to 20x reduction of catalyst costHydroGEN: Advanced Water Splitting Materials22
Project Summary New MOF-derived PGM-free OER catalysts developed by ANLshowed excellent activity and durability in acidic electrolytecompared to PGM-free benchmark catalysts in literature, withperformance approaching to Ir black. Initial study of ANL’s PNNE OER catalysts also demonstrated verypromising activity and excellent durability when measured againstIr black in strong acidic electrolytes. UB team is making excellent progresses in activity and durabilityimprovements for FeMx-ZIF-8 and FeMx-ZIF-8/Oxide basedcatalysts. Collaborations with four nodes of HydroGen yielded insightfulinformation in structural, performance and fundamentalunderstanding of OER catalysts developed by the team.Our initial studies have validated our project approachesdemonstrated by very promising catalytic activity and durabilityHydroGEN: Advanced Water Splitting Materials23
Acknowledgement‣ Argonne National Laboratory– Lina Chong– Hao Wang‣ HydrogGen Consortium––––Lawrence Livermore National Lab (led by Tadashi Ogitsu)Lawrence Berkeley National Lab (led by Lin-Wang Wang)Sandia National Lab (led by Josh Sugar)National Renewable Energy Lab (led by Shaun Alia)‣ US DOE Office of Fuel Cell Technologies– Eric Miller – Program Manager– Dave Peterson – Project ManagerHydroGEN: Advanced Water Splitting Materials24
HydroGEN: Advanced Water Splitting Materials 2 Team Lead: Di-Jia Liu, Argonne National Laboratory Sub: Gang Wu, U. of Buffalo, Hui Xu, Giner Inc. To lower the capital cost of PEME by developing platinum group metal -free (PGM-free) OER electro- catalysts. Project Vision. To reduce the anode catalyst cost by 20 folds by developing one or more PGM-
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the PGM-free and PGM catalysts accounts partly for the substantially lower power density delivered by PGM-free catalysts in practical H 2-air PEMFCs ( 0.57 W·cm2) (4) than that of PGM catalysts ( 1 W·cm2). The most active PGM-free ORR catalysts are pyrolyzed transition metal-nitrogen-carbon (M-N-C, M Fe or Co) catalysts (4-10). This group .
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NH 3 readily generated; varies with PGM - For Pd-only TWC with high PGM: All NO fed converted to NH 3 when very rich - For Pd/Rh Ce (low PGM ) TWC: NH 3 production is still significant but reduced At all conditions, 95% CO conversion - C 3H 6 not observed in effluent N 2O formation observed under lean conditions and varies with PGM content
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