Hydrogen Storage and Fuel Cells

Di-Jia Liu

Argonne National Laboratory

Short Course – Physics of Sustainable Energy

Energy Policy Institute at The University of Chicago

June 18, 2016

2

Global Primary Energy Supplies

Source: International Energy Agency - energy statistics, Sept 2006, Data compiled up to 2004

Coal, 25.1%

Nuclear, 6.5%Renewable,

13.3%

Oil, 34.3%Gas, 20.9%

Outlook of Globe Energy Demand & its Impact to

Environment

3

Fossil fuels will lead world energy consumption in decades to come

Energy Information Administration: www.eia.doe.gov/iea

IPCC Fifth Assessment 2013: http://www.ipcc.ch/index.htm

Quadrillion BTU

GHG emission causes rise of global temperature and threatens ecosystem

U.S. National Energy Strategy

4

“We’ve got to invest in

a serious, sustained,

all-of-the-above energy

strategy that develops

every resource

available for the 21st

century.”- President Barack Obama

“As part of an all-of-the-above energy

approach, fuel cell technologies are

paving the way to competitiveness in

the global clean energy market and to

new jobs and business creation

across the country.”

- Secretary Moniz,

U.S. Department of EnergySecretary Moniz at 2015 DC Auto Show

Transportation electrification depends critically on

next-generation power train development

Cost

Durability

Performance

Convenience

Tesla Model S – Li ion battery Toyota Mirai – hydrogen fuel cell

Factors Important to Consumer

Source: US Department of Energy, Office of Energy Efficiency and Renewable Energy

6

Current Status of Polymer Electrolyte Fuel Cells

and Future Direction for Development

Different Types of Fuel Cells

7

200-kW PAFC

Fuel Cell TypeTemperature

ApplicationsElectrolyte / Ion

Polymer Electrolyte

Membrane (PEM)

60 - 100° C Electric utility

Portable power

TransportationNafion/H+

Alkaline

(AFC)

90 – 100° C Military

SpaceKOH / OH-

Phosphoric Acid

(PAFC)

175 – 200° C Electric utility

Distributed power

TransportationH3PO4 / H+

Molten Carbonate

(MCFC)

600 – 1000° C Electric utility

Distributed power(Li,K,Na)2CO3 / CO2-

Solid Oxide

(SOFC)

600 – 1000° C Electric utility

Distributed power

APUs(Zr,Y) O2 / O-

SOFC kW Stack 2MW MCFC Plant

85-kW PEMFC

1.5-kW AFC

8

Polymer Electrolyte Membrane Fuel Cell (PEMFC)

Anode H2 2 H+ + 2 e-

Cathode O2 + 4 e- + 4 H+ 2 H2O

Membrane

Catalyst

GDLBipolar

Plate

e- e-

H2O

H2

O2

PEMFC Stack

Power density: 650 W/L

Efficiency: 50 to 60%

H+

U S DOE Fuel Cells Strategy

Reducing platinum usage to < 0.125 g/kW (or 10 g/vehicle at 80 kW rated power)

Increasing MEA durability to 5000 hours under cycling

Increasing stack power density to 0.85kW/L (or stack volume of 94L for 80kW unit)

Reducing costs of accessories, bipolar plates, air compressor, humidification, etc.

9

High

Medium

Low to Medium

Level of

Difficulty

BARRIERS NEAR TO MID-TERM LONG-TERM

700 bar tanks, composites, cryo-

compressedHydrogen Production and Delivery

Materials R&D for low pressure

storage

Non-PGM Catalysts

AEMs

Fuel Cell Cost and Durability

Hydrogen Storage

R&

D

Low-PGM catalysts , MEAs, performance

durability, components

H2 from NG/electrolysis; delivered H2, compression

H2 from renewables (PEC, biological, etc.),

pipelines, low P option

Near and mid-term research focuses

Replacing the platinum group metal (PGM) catalysts with earthly abundant materials

Improving ion conductivity and stability of alkaline electrolyte membranes

Long-term research focuses

10

The Electrode Catalyst Challenges – Demand for

Reducing or Replacing Pt Usage

Platinum and platinum group metals (PGMs) are catalysts of choice for polymer electrolyte fuel cell, posing a significant barrier for FCEV commercialization

More Pt (x3~4) is needed for cathodic oxygen reduction reaction(ORR)

New design/synthesis and/or alternative materials are underdevelopment to reduce Pt dependence

Manufactured Stack Cost Analysis

Data obtained from the presentation by TIAX on 80 kW direct H2 PEMFC at DOE 2010 Annual Merit Review

$0

$40

$80

$120

$160

2006 2008 2010 2012 2020

FC

Sys

tem

s C

os

t ($

/kW

ne

t)

Projected Transportation Fuel Cell System Cost -- (500,000 units/year)

MEA Innovation - 3M’s Nanostructured Thin Film (NSTF)

11

Conventional MEA 3M NSTF MEA

Electrolyte AnodeCathode

H2 e-

e-

H+

H2

e-

e-

O2

H2O

H2

3M’s NSTF altered conventional membrane electrode assembly morphology and significantly improved Pt usage and fuel cell performance. More need to be done in improving fuel cell robustness -

Pt Catalyst Innovation: Nanoframe Pt Alloy with

Improved Activity

12

• PtNi nanoframe catalysts synthesized through spontaneous corrosion and annealing

• Catalysts have specific and mass activities 15 and 20x those of Pt/C

• Low-loaded MEA testing shows 3x specific activity and 2x mass activity relative to DOE targets

• Further work is needed to increase performance at high current density

V. Stamenkovic, P. Yang, et. al. . Science, 343,

(2014) 1339-1343

http://www.anl.gov/

Next Generation PGM-free Catalyst – Two Innovative ANL

Approaches

13

Improving activity through rationally designed precursors – MOFs/POPs

Improving mass/charge transports through nanofibrous network

Volumetric Activity Turn-Over-Freq. x Site Density

• Argonne’s nano-fibrous network provides higher surface area and nearly exclusive micropores

• New electrode offers enhanced mass transport and charge transfer via a unique micro-macro-porous nano-network

Conventional New ANL design Conventional ANL nano-network

New nano-network architecture not only increases surface area but also site density

New 3-D precursors breaks away from 50-years of square-planar molecular approach

• Argonne introduced Metal-organic-framework & porous organic polymer as next-generation catalyst precursors

• “Support-free” and pore-former free • Uniform distribution & high active site

density

“One-Pot” Synthesis of MOF-based TM/N/C Catalysts

14

(a)

(c)

(b)

(d)

Mixing Solid State Reaction Thermolysis

ZnO

Fe complexIm mIm

eIm abIm

Different MOFsOrganic Ligands

+

TM/N/C Catalysts

0 500 1000 1500 2000 2500 3000 3500 4000

0.2

0.4

0.6

0.8

1.0

Current Density (mA cm-2)

Ce

ll P

ote

nti

al (V

)

0

200

400

600

800

1000

Po

wer

Den

sit

y (

mW

cm

-2)P = 924 mW/cm2 @ 0.38V

P = 855 mW/cm2

@ 0.47V

One-bar Oxygen

D. Zhao, J.-L. Shui, L. R. Grabstanowicz, C. Chen, S.M. Commet, T. Xu, J. Lu, and D.-J. Liu, Advanced Materials, 2014, 26, 1093–1097 (Frontpiece article)

Catalytic Mass/Charge Transport Improvement through

Nanonetwork Architecture

15

Conventional Support Nanofibrous SupportO2

H+

O2

H+

Impeded O2 transport through porous carbon, macro → meso → micro

Hindered charge transfer through particle percolation

Exposed active site at carbon surface

Improved O2 transport through voids b/w fibers, macro → micro

Enhanced charge transfer via fiber nano-network

Embedded catalytic site inside nanofibers

MOF Catalyst

Nano-network

Electrospinning Conversion to catalyst Fuel cell fabrication

e-

H+

O2

H2O

ANL’s PGM-free Catalyst with Nano-network Architecture

J. Shui, C. Chen, L. R. Grabstanowicz, D. Zhao and D.-J. Liu, Proceedings of National Academy of Sciences, 2015,112, 34, 10629

Fabrication of PGM-free catalyst with nano-network architecture

Comparison of PGM-free nano-network catalyst (Fe/N/CF) with Pt/C

17

Current Status of On-board Hydrogen Storage

and Future Direction for Development

18

Opportunities & Challenges in Hydrogen Storage for

Transportation Application

Onboard H2 production Onboard H2 storage

• Catalytic reforming of hydrocarbon fuels

• Existing fuel distribution network

• Start up time

• System efficiency (fuel utilization &CO2

reduction)

• Compressed hydrogen

• Different storage media (chemical, metallic, carbon-based, etc)

• Needs H2 distribution infrastructure

• Storage capacity issues

GasStation Fuel

StorageFuel Reformer

Fuel Cell

HydrogenChargingStation

H2

StorageFuel Cell

DOE System Targets for On-Board Hydrogen Storage for Light-Duty Vehicles

Storage Parameter Units 2017 Ultimate

System Gravimetric

Capacity

kWh/kg

(kg H2/kg system)

1.8

(0.055)

2.5

(0.075)

System Volumetric

Capacity

kWh/L

(kg H2/L system)

1.3

(0.040)

2.3

(0.070)

DOE Technology Portfolio of On-board H2 Storage

19

Hydrogen Storage

Near-Term Approach

700 bar Compressed

•Lower Cost Carbon Fiber•Improved Composites•Conformable designs•Lower Cost BOP

•System Engineering•Advanced Insulation•Improved Dormancy•Composite Development

Longer-Term Approach

Chemical H2 Storage

Sorbents

Metal Hydrides

Cold / Cryo-Compressed

Ex. NaAlH4

Ex. MOF-5

Ex. NH3BH3

•Higher Material Capacity•System Cost•Fill Time•Onboard Efficiency

•Higher Material Capacity•System Cost•Dormancy•WTP Efficiency

•Lower Cost Off-board Regen•System Cost•Gravimetric Density

Dual approach Technology Focus Barriers and R&D Focus

The long term objective is a vehicle with a range of at least 300 miles

20

Current Status of Hydrogen Storage Technology

0

10

20

30

40

50

60

70

0 1 2 3 4 5 6 7 8

Gravimetric Capacity (wt%)

Vo

lum

etr

ic C

ap

acit

y (

g/L

)

complex

hydride

chemical

hydride

liquid hydrogen

cryocompressed

compressed hydrogen

"Learning Demos"

Revised

DOE

system

targets

700 bar

350 barC-sorbent

2015

Ultimate

Alane Slurry

MOF-177 (250 bar)

KEY CHALLENGE: > 300-mile driving range in all vehicle platforms, without compromising passenger/cargo space, performance, or cost

Source: US DoE, Fuel Cell Technologies Program

Low Pressure H2 Storage Material Challenges

Material Type Examples Advantages Challenges

Metal Hydride

LiBH4, NaBH4, Mg(BH4)2 , etc.

High volumetric & gravimetric capacities,Highly stable at ambient temperature

Discharge-charge kinetics & time,Reversibility,Parasitic energy consumption

Chemical Hydride

NH3-BH3, C6H5-CH3, etc.

Good gravimetric & volumetric capacities, Stable at ambient temperature

Poor on-board/off-board regen,Parasitic energy consumption

Sorbent

MOF, POP, Porouscarbon, etc.

Good gravimetric capacity,Fast discharge-charge time and lower energy consumption

Cryo-compressionneeded,Unstable at ambient temperature (dormancy concern)

21

• Low pressure storage is essential in improving overall system efficiency

• Fundamental understanding and molecular manipulation are critical in

advancing next-generation storage materials

N B

H

H

H

H

H

HHB

NH

BH

NH

HB

HN

22

Sorption-based Material Challenges: Some Examples

of Next-generation Adsorbent Approaches

Design of high surface area & narrow/adjustable pore size

Incorporating “metallic” feature

Develop fundamental understanding through modeling and advanced characterization

vdW

Inte

ract

ion

Enh

ance

d v

dW

Inte

ract

ion

Re

con

form

atio

nP

ote

nti

al

H2

Kin

etic

En

erg

y

Improving storage capacity and H2 binding energy through molecular design

Metal Ion

Metal-Organic Framework (MOF) Sorbents

SolvothermalReaction

Organic Ligand

+

Porous Organic Polymer (POP) Sorbents

Contorted Core

Molecular Strut

+Crosslinking & metal doping

Improving H2 Discharge-Charge Reversibility using

Graphene Encapsulated Hydride

23

Graphene Hydrides

Nanoencapsulated hydrides

Rehydrogenation

Dehydrogenation

L. Chong, X. Zeng, W. Ding, D.-J. Liu and J. Zou, Advanced Materials, 2015, 27, 5070–5074J. Zou, L. Chong, D.-J. Liu, et. al. Science, 2016, 351 (6278), 1223

“Graphene wrapping” prevents the escape of dehydrogenation products and catalyzes the rehydrogenation during H2 charging

More innovative approaches combined with improved fundamental

understanding could ultimately resolve the current issues in H2 storage!

NaBH4 ↔ Na + B + H2, (B2H6, etc.)

24

Hydrogen Production and Distribution

Infrastructure Development

25

Borrow a Page from Gasoline Distribution?

26

DOE’s H2 Production & Delivery RD&D Portfolio

US DOE – Fuel Cell Technologies Office

H2 Infrastructure Development and Status

27

• 1,500 mi. of H2 pipeline

• >9M metric tons produced/yr

• ~50 stations (~10 public)

Nationwide California

• >~$70M awarded

• ~$100M planned through 2023

• Goal - 100 stations

H2 stations in CA

Other States

• 8-State MOU Members: CA, CT,

NY, MA, MD, OR, RI and VT

• MA, NY, CT: Preliminary plans for H2

infrastructure and FCEVs deployment

in metro centers in NE states.

• Hawai’i: Public access refueling

infrastructure on Oahu by 2020

NE states, California, and Hawaii have H2 infrastructure efforts underway

Representative Hydrogen Refueling Stations

28

LAX refueling station

Hydrogen and gasoline station, WA DCChino, CA

DTE/BP Power Park,

Southfield, MI

Courtesy K. Wipke, National Renewable Energy Laboratory and the California Fuel Cell Partnership

29

H2 at Scale – A “Big Idea”

Major Administration Energy Goals

30

1.

2.

3.

4.

5.

H2 at Scale primary impact on 1 and 4 (above), also impacts 2.

Energy System Challenges

31

• Multi-sector requirements

o Transportation

o Industrial

o Grid

• Renewable challenges

o Variable

o Concurrent generation

Over half of U.S. CO2

emissions come from the industrial and

transportation sectors

-5,000

0

5,000

10,000

15,000

20,000

25,000

30,000

35,000

PV Penetration and Hour

Ge

ne

rati

on

(M

W)

PV

Gas

TurbinePumped

StorageHydro

Combined

CycleImports

Coal

Nuclear

Wind

Geo

Exports

Base 2% 6% 10%

(no PV)

Denholm et al. 2008

Carbon-free Electricity Prices Continually Drop with

Increase in Capacity

32

2

4

6

8

10

12

2008 2010 2012 2014 ‘15

$.02/kWh

Contract

Price

cents/kWh

Capacity

(GW)

Source

(Arun Majumdar)

1. DOE EERE

Sunshot Q1’15

Report

2. DOE EERE

Wind Report,

2015

Conceptual H2 at Scale Energy System

33

*Illustrative example, not comprehensive

BAU(Business As Usual) vs. High H2 – CO2 Difference

34

45% reduction in CO2 emissionsGrid 75%, Transportation 25%, Industrial 25%

Emissions difference between 2050 high-H2 and AEO 2040 scenarios (million MT)

Red flows represent a reduction (between scenarios)

H2

11Reduction in Carbon Emissions

-2538

Remaining Carbon

Emissions3237

solar0

nuclear0

hydro0

wind0

geother.1

NG902

coal456

biomass0

Petro.1879

Comm.239

Indus.949

Transp.1226

Resid.263

-1709Elec.550

-327

-405

-97

-96

-405

-97

-231

-462

-1240

1226

949

550

Acknowledgement

35

Fuel Cell Research - Shengqian Ma, Dan Zhao, Shengwen Yuan, Jianglan Shui, Gabriel Goenaga, Chen Chen, Heather Barkholtz, Lina Chong, Lauran Grabstanowicz, Alex Mason, Brianna Reprogle, Sean Comment, Zachary Kaiser, Junbing Yang, Debbie Myers

Technology & Implementation Analyses - John Kopasz, Tom Benjamin, Nancy Garland

H2 at Scale – Amgad Elgowainy

DOE Program Managers – Nancy Garland, Dimitrios Papageorgopoulos

US DOE, US DOE Office of Fuel Cell Technologies and Office of Science. The use of Advanced Photon Source and Electron Microscopy Center are supported by Office of Science, U. S. Department of Energy under Contract DE–AC02–06CH11357.