LLNL-PRES-XXXXXX This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under contract DE-AC52-07NA27344. Lawrence Livermore National Security, LLC
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This presentation does not contain any proprietary, confidential, or otherwise restricted informationProject ID# ST129
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•! Lack of understanding of hydrogen physisorption and chemisorption (Barrier O)
•! System weight and volume (Barrier A) •! Charge/discharge rate (Barrier E)
FY15 DOE Funding: $250K FY16 Planned DOE Funding: $735K Total Funds Received: $985K
Funded Partners: Sandia National Laboratories (lead) Lawrence Berkeley National Laboratory
Project start date: 9/17/2015
Timeline Barriers addressed
Team Budget
Phase I end date: 9/30/2018
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16001590158015701560Photon Energy (eV)
Al K-edge TEY (Surface) TFY (Bulk)
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NaAlH4
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Bond chemistry
Thermodynamics &
Task 1: ThermodynamicsTask 2: TransportTask 3: Gas-surface interactionsTask 4: Solid-solid interfacesTask 5: Additives and dopantsTask 6: Materials informatics
Additives
Approach: HyMARC tasks target thermodynamics and kinetics
3
Approach: Validated multiscale modeling
10-10 10-6 10-210-8 10-4
Length (m)
10-12
10-9
10-3
10-6
100
Tim
e (s
)
MgB2
Mg(BH4)2
H2
Quantum Monte Carlo
DFT/ab initio molecular
dynamics
Classical molecular dynamics
Kinetic Monte Carlo
Phase field modeling
Modeling approach focuses on integrating techniques at multiple scales to tackle complexities of “real” (beyond-ideal) materials
Validation: X-ray spectroscopy,
NMR, FTIR
Validation: TGA, Sieverts,
PCT calorimetry
Validation: TEM & microscopy
4
LLNL contributions to HyMARC
Porous carbon synthesis
X-ray absorption/emission
Jon Lee
Ted BaumannDFT & ab initio molecular dynamics: Brandon Wood
Phase-field mesoscale kinetic modeling: Tae Wook Heo
Kinetic Monte Carlo: Stanimir Bonev
Quantum Monte Carlo: Miguel Morales
Postdocs: ShinYoung Kang, Keith Ray, Roman Nazarov, Patrick Shea
Multiscale modeling
Pat Campell
5
Progress towards milestones with key LLNL FY16 activities
Q1: (S) Synthesize library of bulk-phase model storage systems for T1-T5Task 1: Synthesize and characterize high-surface area carbon frameworks with pore sizes < 2 nm (100%)
Q2: (S) Demonstrate size control method for one prototype complex hydride nanostructureTask 1: Perform sensitivity studies to determine design rules for nanoconfined metal hydrides (50%)
Q3: (C) Demonstrate in-situ soft X-ray AP-XPS, XAS, XES tools, with sample heatingTasks 3 & 5: Performed XAS spectroscopy of hydrides and dopants at LBL/ALS, SLAC, and Canadian Light Source (75%)
Q4: (C+T) Identify hydride mobile species and diffusion pathwaysTask 2: Perform ab initio molecular dynamics of surface and bulk model hydrides (80%)Task 2: Gather defect formation energies and migration barriers for model materials (70%)Task 2: Construct initial KMC framework for interface/amorphous transport (100%)Task 3: Compute H2 dissociation energetics on model surfaces (75%)Task 3: Construct initial microkinetic model for surface reactions (100%)Task 4: Construct initial phase-field modeling code for solid-solid interface kinetics (100%)
Q4: (S+C) Synthesize library of nanoparticles: 1 – 5 nm, 5 – 10 nm, > 10 nm for one prototype hydrideTasks 1-5: Select model materials for facilitating experiment-theory feedback within each Task (100%)
6
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Task 1 Accomplishment: Modeling sorbent charge/field effects
Developed first-principles modeling framework for simulating charge and field effects on H2 physisorption on conductive sorbents for guiding synthesis
±qUses Effective Screening Medium Method* to compute physisorption as function of Fermi level
Bound & polarized H2
Infinite dielectric medium
Can be applied to functionalized materials and any 2D conductive sorbents, and will be used to assess polarization effects in HyMARC experiments
Unbound & unpolarized
H2 (reference)
*Otani & Sugino, Phys. Rev. B 73, 115407 (2006)
Predicted field-induced enhancement of physisorptionV
9
Task 1 Accomplishment: More accurate hydride thermodynamics
Established protocols for more accurate DFT computations of hydride thermodynamics that can improve predictive power beyond established methods by accounting for:
Mg
BH
• Dynamical (anharmonic) contributions to free energy via explicit finite-T simulations• Microstructure, including phase coexistence and interface/surface contributions• Phase morphology & nucleation: dispersed molecular defects vs. amorphous vs. crystalline
Anharmonic molecular modes in I-m42 (MgBH4)2 from ab initio molecular dynamics
Results: Anharmonic modes can contribute as much as
12 kJ/mol in some predicted phases of Mg(BH4)2, which could alter phase stability
10
Task 1&4 Accomplishment: Hydride phase fraction predictions
Demonstrated thermodynamic phase fraction prediction as a function of pressure, temperature, and size, accounting for microstructure, phase coexistence, and nucleation
DFT + Wulff construction Free energy minimization with respect to phase fractions in assumed microstructure
Predicted size-dependent phase fractions for hydrogenation of Li3N/[LiNH2+2LiH] system in core-shell microstructure
Interface-induced Li2NH phase suppression improves kinetics and reversibility
Successfully predicted Sandia-measured reaction pathway in nanoconfined Li-N-H and confirmed relevance of interfaces in determining phase stability
11
Task 1,4&5 Accomplishment: Phase nucleation in hydrides
Computed critical nucleus size for Li-N-H and Mg-B-H systems, including intermediates
Computed critical nucleus sizes for model hydrides to guide nanoscale synthesis as a means of kinetically suppressing undesirable intermediate phases
LiH nucleation during hydrogenation of the Li3N/[LiNH2+2LiH] system
Homogeneous nucleation Heterogeneous nucleation
{pij} configuration index
Interface energy approximation:
Small size: No nucleation
Large size: Nucleation
12
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Task 2 Accomplishment: Ab initio molecular dynamics (AIMD)
AIMD is being used to elucidate transport/reaction pathways and enable finite-temperature calculations of thermodynamic and spectroscopic quantities
Established software framework for automating AIMD, to be integrated within open-source AiiDA task management engine
AIMD of an Mg(BH4)2
surface @800K showing
desorption of H2and BH3
Initialization(DFT electronic structure)
Thermalization(NVT AIMD)
dynamically set number of steps
for each task
internal error-
checking identifies successful
completion of each task
Molecular dynamics manager
Equilibration(NVE AIMD)
Production(NVT AIMD)
Observables
Atomic coordinates (e.g, from ICSD)
14
Task 2&3 Accomplishment: Multiscale surface hydrogen kinetics
Surface redistribution of atomic hydrogen Surface dissociation + diffusion
Demonstrated multiscale modeling of surface dissociation and diffusion of hydrogen by synthesizing DFT and continuum approaches
Combining with low-energy ion scattering (Sandia) to analyze surface diffusion
On model carbon surface from DFT calculations of H on graphene
15
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External collaborations
• NMR and borohydride chemistry: T. Autrey, M. Bowden, B. Ginovska-Pangovska(PNNL; H2 Storage Characterization Group)• Several discussions, plus site visits in November 2015 and April 2016
• HyMARC will focus on solid-state aspects and PNNL on borohydride chemistry
• Neutron diffraction/spectroscopy: T. Udovic (NIST)• DFT computations of H2 physisorption on MOFs: M. Head-Gordon (LBNL;
H2 Storage Characterization Group)• Li-N-H system: N. Poonyayant, N. Angboonpong, and P. Pakawatpanurut
(Mahidol University, Thailand)• Kinetic Monte-Carlo for solid-state diffusion: H. Kreuzer (Dalhousie U.)
Collaborations are crucial for realizing HyMARC goals
Also extensive collaborations within HyMARC
18
Remaining challenges/barriers & mitigation strategies
• Understanding internal microstructure evolution is challenging• Working with HyMARC team and collaborators to develop protocols for imaging low-Z
materials with minimal beam damage• Focusing early efforts on materials (e.g., MgH2) that can be more easily characterized
• Phase transformations of complex hydrides combine composition & phasechanges, yet we are currently treating these separately• Separate treatment allows each to be independently validated, but integration of both will
be explored in collaboration with the Mg(BH4)2 individual FOA project in FY17
• Need better validation of thermodynamics and transport for amorphous materials• Working with HyMARC team to synthesize amorphous materials for testing our amorphous
transport and thermodynamics theory framework
• Improved interface energy estimates are desirable• HyMARC data will be used to benchmark new approaches for dealing with chemical and
elastic contributions to the interface free energy• Statistical approach allows us to quantify robustness of predictions with respect to
interface energy assumptions
• QMC needs reliable input geometries for sorbent energetics• HyMARC will collaborate with M. Head-Gordon (LBNL, part of NREL-led consortium) to use
high-throughput DFT with corrected functionals on clusters to obtain geometries
19
Proposed future work
Milestone Description & LLNL subtask % complete
Q3 FY16 Demonstrate in situ soft X-ray AP-XPS, XAS, XES tools with sample heatingPerform synchrotron XAS/XES of hydrogenation on catalyzed materials
100
Q4 FY16 Identify hydride mobile species and diffusion pathwaysCompute defect formation energies and ab initio dynamics of mobile species in model systems
25
Q4 FY16 SMART
Synthesize library of nanoparticles: 1-5 nm, 5-10 nm, > 10 nm for prototype hydrideDemonstrate porous carbon nanoconfining medium synthesis with controlled pore sizes
50
Q1 FY17 Compute H2 binding curves by QMC 15
Q2 FY17 Perform sensitivity analysis of local binding and second-sphere effects 0
Q2 FY17 G/NG
Rank improvement strategies: open metal sites, acid sites, polarization effects, phase change materialsPerform analysis of potential of open metal sites (via QMC), acid sites/polarization (via DFT), and phase change materials (thermodynamic analysis)
25
20
Summary
• Integrated theory/synthesis/characterization framework of HyMARC aims toprovide foundational understanding and new tools for solid-state hydrogenstorage
• FY16 LLNL modeling tasks focused on establishing framework for multiscaleintegration and approaches for beyond-ideal materials modeling
• FY16 LLNL synthesis tasks focused on establishing key strategies for tailoredporous carbon
• FY16 LLNL characterization tasks focused on spectroscopic changes uponhydrogenation (complements LBNL activities)
• Early feedback between experiments and theory on the Pd-H and Mg-H systemsdemonstrates feasibility of multiscale (de)hydrogenation kinetics simulation
• Will be moving towards testing on complex hydrides and more complicatedsorbents in FY17
• Flexible modeling, synthesis, and characterization protocols are being developedin preparation for application to upcoming FOA projects
21
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