Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive...

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Hydrogen Storage for Mobile Applications Jeff Van Humbeck MacMillan Group Meeting April 14 th , 2010

Transcript of Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive...

Page 1: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review

Hydrogen Storage for Mobile Applications

Jeff Van Humbeck

MacMillan Group Meeting

April 14th, 2010

Page 2: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review

“The Stone Age did not end for lack of stone, and the Oil Age

will end long before the world runs out of oil.”

– Sheikh Zaki Yamani

(warning?) as Saudi OPEC Representative

Page 3: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review

Presentation Overview

! 5 dominant absorptive materials that have been investigated widely

! Not by any means comprehensive review of literature (1000s of papers since 2000)

CHEMIABSORPTIVE MATERIALS PHYSIABSORPTIVE MATERIALS

Conventional hydrides

Complex hydrides

Chemicals hydrides (ammonia borane)

Metal-organic frameworks (MOFs)

Nanostructured carbon (SWCNTs)

! For each material, attempt to highlight two main features:

What are the comparative advantages/disavantages of particular technologies?

What approach is current research taking to improve material characteristics?

Page 4: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review

Why Focus on Mobile Applications?

! Stationary power storage can use technology where the volume and mass of storage don't matter

Page 5: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review

DOE Hydrogen Storage Guidlines

! In 2003 Department of Energy sets hydrogen storage goals

Gravimetric Capacity Volumetric Capacity Operating Temperature/Pressure

2005

2010

2015

4.5 wt%

6.0 wt%

9.0 wt%

36 g/L

45 g/L

81 g/L

–30 to 50 ºC

<100 bar

http://www.eere.energy.gov/

! An onboard reversible system must have an endothermic hydrogen release

Determined

by !G

!S > 60 J/K (T!S strongly favors release) Must be favored by !H

Page 6: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review
Page 7: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review
Page 8: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review

Conventional Hydride Materials: Predictable Properties

! Crystalline starting material and products make calculating properties simple

Principi, G.; Agresti, F.; Maddalena, A.; Lo Russo, S. Energy 2009, 34, 2087.

Metal Alloy Conventional Hydride Gravimetric Uptake (wt%)

LaNi5

FeTi

Mg2Ni

ZrMn2

Mg

LaNi5H6

FeTiH2

Mg2NiH4

ZrMn2H2

MgH2

1.37

1.89

3.59

1.77

7.60

! Nearly demands the use of Mg (also, most cost effective)

! What is limiting application of MgH2 in hydrogen storage?

Page 9: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review
Page 10: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review

Conventional Hydride Materials: Uptake Kinetics

! Unmodified MgH2 requires high temperature for absorption/desorption

Engineering solutions

Ball milling: Reduce particle size, increase S.A.

Nanoscale scaffold synthesis:

HO OH H

O

H

Mg2

H2

Zhang, S., et. al. Nanotechnology, 2009, 20, 204027.

Porous

Polymer

Formation

Form

MgH2

Page 11: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review
Page 12: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review

Conventional Hydride Materials: Current State

! Most important features: Operating parameters, storage capacity, refilling kinetics

MgH2 + 5 wt% Ni MgH2 + 5 at% Mn MgH2 + 0.2 mol% Cr2O3 MgH2 + 0.5 wt% Nb2O5

Temp (ºC)

Kinetics (min)

Wt% H2

# cycles

230-370

90

6.00

800

200-300

8.3-13.3

6.00

N/A

300

2-6

6.70

N/A

300

1-1.5

7.00

N/A

Reiser, A.; Bogdanovic, B.; Schlichte, K. Int. J. Hydrogen Energy, 2000, 25, 425.

Liang, G.; Huot, J.; Boily, S.; Nestea, A. V.; Schulz, R. J. Alloys Compds. 1999, 292, 247.

Dehouche, Z.; Klassen, T.; Oelerich, W.; Goyette, J.; Bose, T. K.; Schulz, R. J. Alloys Compds. 2002, 347, 319.

Barkhordarian, G.; Klassten, T.; Bormann, R. J. Alloys Compds. 2004, 364, 242.

Page 13: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review
Page 14: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review

Reversible Hydrogen Uptake in Complex Metal Hydrides

! Similar strategy for improvement - transition metal dopant

! Different advantages/disadvantages compared to conventional hydrides

3NaAlH4 Na3AlH6 + 2Al + 3H2 Na3AlH6 3NaH + Al + 1.5H2

Dopants: Ti(OnBu)4, TiCl3, Zr(OiPr)4, Ti(s)

Advantages Disadvantages

Lower operating temperature (150-180) Kinetic charging/discharging (>60 min)

Stability (<17 cycles)

Sakintuna, B.; Lamari-Darkrim, F.; Hirscher, M. Int. J. Hydrogen Energy 2007, 32, 1121.

Page 15: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review

Chemiabsorptive Hydrogen Storage in Ammonia Borane

! B/N Coordination compounds fall into 3 main classes

! Inherently more hydrogen rich than simplest complex hydride (19.6wt%)

Hamilton, C. W.; Baker, T. R.; Staubitz, A.; Manners, I. Chem. Soc. Rev. 2009, 38, 279.

N-N and B-N

bonds

B-B and B-N

bonds

B-N bonds

only

H2N BH3

NH2H3B

B

B BH

H

H

H

H H

NH3

B N

HH

HH

HH

Likely to be explosive/shock-sensitive

B

H

H H

H

B

H

H NH3

NH3

Stephens, F. H.; Pons, V.; Baker, T. R. Dalton Trans. 2007, 2613.

! Isoelectronic with alkanes, but far more reactive (protic and hydridic bonds)

Page 16: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review

Solvolytic Hydrogen Release from Ammonia-Borane

! Solvolytic hydrogen release is more viable than for NaBH4

Hamilton, C. W.; Baker, T. R.; Staubitz, A.; Manners, I. Chem. Soc. Rev. 2009, 38, 279.

B N

H

H

H

H

H

H+4 ROH

–3 H2

[NH4][B(OR)4] Catalyzed by: acid, heat, precious metals, base metals

[NH4][B(OR)4]LiAlH4

NH4ClAl(OR3), NH3BH3, ROH, NH3, H2, LiCl

Ramachandran, P. V.; Gagare, P. D. Inorg. Chem. 2007, 46, 7810.

! Requires an efficient conversion of Al(OMe)3 to LiAlH4

Page 17: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review

Direct Dehydrogenation of Ammonia-Borane

! Formation of B–O bonds is energetic sink to be avoided

Hamilton, C. W.; Baker, T. R.; Staubitz, A.; Manners, I. Chem. Soc. Rev. 2009, 38, 279.

B N

H

H

H

H

H

H Catalyzed by: acid, base, precious metals, ligated base metals

! Mechanism for [Cp2Ti], (NHC)2Ni and (POCOP)IrH2 are representative

B N

H

H

H

H

–H2

Ti

Luo, Y.; Ohno, K. Organometallics 2007, 26, 3597.

Ni NPh

NPhNNPhN

NPh

Ph

Ph

COD

Keaton, R. J.; Blacquiere, J. M.; Baker, T. R. J. Am. Chem. Soc. 2007, 129, 1844.

O

O PtBu2

PtBu2

IrH

H

Denney, M. C.; Pons, V.; Hebden, T. J.; Heinekey, D. M.; Goldberg, K. I. J. Am. Chem. Soc. 2006, 128, 12048.

Initial N–Hcleavage

Initial B–Hcleavage

Concerted hydrogentransfer

Page 18: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review

Ti-Catalyzed Dehydrogenation of Ammonia-Borane

! Representative of initial N–H bond cleavage

Ti

Luo, Y.; Ohno, K. Organometallics 2007, 26, 3597.

TiN

H

BH3

Me

Me

TiH

B NH

H

Me

Me

HTiH

H

B N

H

H

H

Me

Me

H

B N

H

H Me

Me

H H

Initial

N–H

bond

cleavage

Catalyst generated

from TiCp2Cl2 and

nBuLi in situ

Iminoborane byproduct

slowly dimerizes under

reaction conditions

N

B N

B

Me

Me

Me

Me

H

H

H

H

Page 19: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review

Ni-Catalyzed Dehydrogenation of Ammonia-Borane

! Representative of initial B–H bond cleavage

Keaton, R. J.; Blacqueire, J. M.; Baker, T. R. J. Am. Chem. Soc. 2007, 129, 1844.

B N

H

H

H

H

H

H

B N

H

H Me

Me

H H

Initial

B–H

bond

cleavage

Nickel-NHC Catalyst

Iminoborane byproduct

form borazine and

higher polymers

Ni

Solv

N

N

N

N

N

N NPhPh

Ph

B

NB

N

BN

H

H

H

H

H

H

Ni

N

N

N

N

H BH2NH3

Ni

N

N

N

N

H BH2

NH3

Ni

N

N

N

N

H H

B N

H

H H

H

Page 20: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review

Ir-Catalyzed Dehydrogenation of Ammonia-Borane

! Representative of concerted hydrogen generation

Ankan, P.; Musgrave, C. B. Angew. Chem. Int. Ed. 2007, 46, 8153.

B N

H

H

H

H

H

H

B N

H

H H

H

H H

ConcertedN–H/B–Hbond

cleavage

Iridium-pincer complex

based on alkane

dehydrogenation catalyst

Iminoborane byproduct

slowly forms [H2NBH2]5

O

O PtBu2

Ir

PtBu2

H

H

O

O PtBu2

Ir

PtBu2

H

H

H

BH2NH3

O

O PtBu2

Ir

PtBu2

H

H

H

BH2

H NH2

O

O PtBu2

Ir

PtBu2

H

H

H

H

H2B

H2NBH2

H2N

B

H2N

BH2

NH2

BH2

H2N

Denney, M. C.; Pons, V.; Hebden, T. J.; Heinekey, D. M.; Goldberg, K. I. J. Am. Chem. Soc. 2006, 128, 12048.

Page 21: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review
Page 22: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review

Electronic Substitution of Ammonia-Borane

! Stabilizing dative bond creates endothermic reaction

Staubitz, A.; Besora, M.; Harvey, J. N.; Manners, I. Inorg. Chem. 2008, 47, 5910.

H3B NH3 H2B NH2 N

F3C

H B

F3C

H N

F3C

B

F3C

H

Electronic substitution does not stabilize true !-bond and dative "-bond as much as dative !-bond

! Clear tradeoff with gravimetric capacity (< 1wt%)

Page 23: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review
Page 24: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review
Page 25: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review
Page 26: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review
Page 27: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review
Page 28: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review
Page 29: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review
Page 30: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review
Page 31: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review

Improving Hydrogen Absorption Beyond Surface Area

! Optimal binding energy can be calculated from first principles (thermodynamic strategy)

Bhatia, S. K.; Myers, A. L. Langmuir 2006, 22, 1688.

!Hopt = T!Sopt + RT•ln P1P2

2P0

2

For a system operating at RT, between

1.5 and 30 bar: 15.1 kJ/mol

For a typical MOF with !Hadb = 6 kJ/mol

Operating temperature: 131K

For a system operating at RT, between

1.5 and 100 bar: 13.6 kJ/mol

! Is there any way to kinetically improve the hydrogen storage properties?

Hysteresis

(May be underestimated)

Page 32: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review
Page 33: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review
Page 34: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review

Thermodynamic Strategies to Increase Binding Enthalpy

! Increase interaction can be based on orbital or Coloumbic features

! These techniques have been applied (at least theoretically) to both MOFs and nanocarbons

WPiPr3OC

iPr3P CO

CO

HH

Kubas' Complex

Orbital overlap

M

H

H

Filled d/Empty !*

M

H

H

Empty p/Filled !

Up to 90 kJ/mol

Li+H

H

Metal ion

Coloumbic interaction

Up to ~24 kJ/mol

Li+ H H

"– "+

Dipole/Induced dipole

Kubas, G. J.; Ryan, R. R.; Swanson, B. I.; Vergamini, P. J.; Wasserman, H. J. J. Am. Chem. Soc. 1984, 106, 451.

Wu, C. H. J. Chem. Phys. 1979, 71, 783.

Page 35: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review
Page 36: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review
Page 37: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review
Page 38: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review
Page 39: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review

MOFs With Exposed Metal Sites

! Metal impregnation on organic linkers provides another avenue

O O

OO

Kaye, S. S.; Long, J. R. J. Am. Chem. Soc. 2008, 130, 806.

MOF-5

Cr(CO)6, THF

nBuO2, 140 ºC

O O

OO

Cr

CO

CO

CO

h!

H2 (atm)

N2 (atm)

O O

OO

Cr

CO

H2

CO

O O

OO

Cr

CO

N2

CO

Page 40: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review
Page 41: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review
Page 42: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review
Page 43: Jeff Van Humbeck MacMillan Group Meeting April 14 · Presentation Overview! 5 dominant absorptive materials that have been investigated widely! Not by any means comprehensive review