Studies on Hydrogen Storage in Carbon
Materials
Store and generate
B.Viswanathan*, S. Ramaprabhu#, P.Selvam*, Prathap Haridass$, S. Rajalakshmi
&, K.S.Dhathatreyan& and Pani@
*National Centre for Catalysis Research, Department of Chemistry
#Alternative Energy and Nanotechnology Laboratory (AENL),
Nano Functional Materials Technology Centre (NFMTC),
Department of Physics
$Department of Materials and Metallurgical Engineering
Indian Institute of Technology Madras, Chennai 600 036
1
&ARC Centre for Fuel Cell Technology, and @Nanoram
HYDROGEN FUTURE: FACTS
AND FALLACIES: CAUTION
[M. Aulice Scibioh and B. Viswanathan, Bulletin of the Catalysis Society of India, vol.3,
pp.72-81(2004)]
A transition to a ‘hydrogen economy’ is a sea change in our energy infrastructure and is
not to be taken lightly.
As an energy carrier, hydrogen is to be compared to electricity, the only wide spread and
viable alternative.
When hydrogen is employed to transmit renewable electricity, only 50% can reach the
end user due to losses in electrolysis, hydrogen compression and the fuel cell.
The rush into a hydrogen economy is neither supported by energy efficiency arguments
nor justified with respect to economy or ecology.
In fact, it appears that hydrogen will not play an important role in a sustainable energy
economy because the synthetic energy carrier cannot be more efficient than the energy
from which it is made.
Renewable electricity is better distributed by electrons than by hydrogen. Consequently, the
hasty introduction of hydrogen as an energy carrier cannot be a stepping stone into a
sustainable energy future. The opposite may be true.
Because of the wastefulness of a hydrogen economy, the promotion of hydrogen may
counteract all reasonable measures of energy conservation. Even worse, the forced transition
to a hydrogen economy may prevent the establishment of a sustainable energy economy based
on an intelligent use of precious renewable resources.
Transition to Hydrogen Economy
 Production
Storage
Metal Hydride
MOF
Choice limited
Distribution
Petrol dispensing station
Transition to a “Hydrogen Economy”
• Broad-based use of hydrogen as a
fuel
– Energy carrier analogous to
electricity
– Produced from variety of primary
energy sources
– Can serve all sectors of the
economy: transportation, power,
industry,
buildings and residential
– Replaces oil and natural gas as the
preferred end-use fuel – Makes
renewable and nuclear energy
“portable” (e.g. transportation needs)
• Advantages:
– Inexhaustible
– Clean
– Universally available to all countries
Before and Now
Hydrogen Storage some Directions
Situation and Questions
 Production, storage and application - challenges of hydrogen
economy
 Solid state storage – remarkable but not reproducible
 6.5 wt% - desired level (according to original DOE standards)
 Demands consistent and innovative practice
(i)
Are the carbon materials appropriate for solid state hydrogen
storage?
(ii) If this were to be true, what type of carbon materials or what
type of treatments for the existing carbon materials are suitable
to achieve desirable levels of solid state hydrogen storage?
(iii) What are the stumbling blocks in achieving the desirable solid
state hydrogen storage?
(iv) Where does the lacuna lie? Is it in our theoretical foundation of
the postulate or is it in our inability to experimentally realize
the desired levels of storage?
Why carbon materials for solid state
hydrogen storage?
 Coordination number is variable/expandable
 Promote new morphologies
 Covalent character retention
 Variable hybridization possible
 Geometrical possibilities/size considerations
 Meta-stable state
 Similar to biological architectures “Haeckelites”
 Boron and nitrogen doped graphitic
arrangements promise important applications.
Hydrogen storage capacity reported in carbon nanostructures
Temp
(K)
Pressure
(bar)
Wt%
GNF (Herring bone)
RT
113.5
67.6
Graphitic Nano Fibers
RT
101
10
Fan et al ., (1999)
Graphitic Nano Fibers
RT
80-120
10
Gupta et al., (2000)
SWNTs (low purity)
273
0.4
5-10
Dillon et al., (1997)
SWNTs (high purity)
80
70-180
8.25
Ye et al., (1999)
SWNTs (50% purity)
RT
101
4.2
Liu et al ., (1999)
SWNTs (high purity + Ti alloy)
300-600
0.7
3.5-4.5
Dillon et al., (1999)
Li-MWNTs
473-673
1
20
Chen et al., (1999)
Li-MWNTs (K-MWNTs)
473-673
1
2.5 (1.8)
Yang et al., (2000)
MWNTs
RT
Ele.chem
<1
Beguin et al., (2000)
CNF
RT
1-100
0.1-0.7
Poirier et al., (2001)
300-520
1
0.1
Hirscher et al., (2000)
Various CNM
RT
35
<0.1
Tibbets et al., (2001)
SWNTs (+ Ti alloy)
RT
0.8
0
Hirscher et al., (2001)
Material
SWNTs
Group
Chambers et al., (1998)
9
A plot of the reported hydrogen storage capacities of CNTs from the literature versus their year of publication.
Reprinted with . Seung Jae Yang , Haesol Jung , Taehoon Kim , Chong Rae Park, Recent advances in hydrogen
storage technologies based on nanoporous carbon materials, Progress in Natural Science: Materials International,
Volume 22, Issue 6, 2012, 631 – 638, http://dx.doi.org/10.1016/j.pnsc.2012.11.006
Research objectives
1. Processing of carbon based nanostructured materials
2. Doping of Nitrogen/Boron on carbon based nanostructured materials
3. Dispersion of Pd metal nanoparticles on Boron/Nitrogen doped carbon
based nanostructured materials
4. Characterization of these materials by XRD, SEM, HRTEM, XPS
6. Measurement of the hydrogen absorption/adsorption and kinetics of
sorption using pressure reduction facility
7. Development of novel low cost Carbon based materials with a hydrogen
storage capacity of 4-5 wt% hydrogen at room temperature and
moderate pressure
11
Hydrogen exfoliated Graphene
20 nm
5 nm
12
Materials investigated for hydrogen storage
Pristine carbon nanostructures
Few layer graphene (G)
Chemical modifications
Acid functionalization
Acid functionalized
Few layer graphene (f-G)
Nitrogen/Boron doping
Nitrogen / Boron doped
Few layer graphene (N-G)
Pd transition metal doping
Pd metal nanoparticles decorated
acid functionalized few layer
graphene (Pd/f-G)
Pd metal nanoparticles decorated
Nitrogen doped few layer graphene
(Pd/N-G)
13
NITROGEN DOPING
Acid functionalization leads to the
agglomeration of graphene sheets
Nitrogen Plasma
 Treating Graphene with nitrogen plasma
for 30 min using RF sputtering
 Chamber pressure ~ 0.05 mbar
 RF power ~ 120 W
 Aluminum disc was used as target
14
Characterizations of Pd/acid functionalized graphene
FTIR
Graphene
Pd/f-Graphene
Pd/f-Graphene
G
f-Graphene
Graphene
Graphene
Pd/f-Graphene
XRD
Pd/f-G
Pd nanoparticle size ~ 6.6 nm
Graphene
Pd metal loading is 20 wt%
C
GO
Pd
Graphite
O
15
Characterizations of Pd/nitrogen doped graphene
Raman spectra
XPS spectra
Pd/N-G
N-G
Graphene(G)
High resolution XPS spectra of (a) C 1s
(b) N 1s (c) Pd 3d and (d) O 1s orbital of
Pd/N-G
C
Pd
O
Nitrogen content in Pd/N-G :7 atomic %
Pd metal loading is 20 wt%
16
Microscopes images of Pd/nitrogen doped graphene
N-Graphene
Pd/N-Graphene
N-Graphene
Pd/N-Graphene
Pd nanoparticle size ~ 3.1 nm
17
Hydrogen adsorption isotherms of graphene composites
N-Graphene
H (wt%)
Graphene
Note the comparison between Graphene and heteroatom containing
graphene
18
Hydrogen adsorption isotherms of graphene composites
Pd/f-Graphene
Pd/N-Graphene
Pd/B-Graphene
19
Comparison of hydrogen adsorption isotherm values for
different carbon nanocomposites
wt% of hydrogen
Sample
stored at 25 °C
and 20 bar
Graphene
0.53
N-Graphene
0.90
Pd bulk
0.61
Pd NPs
0.72
Pd/f-Graphene
1.75
Pd/N-Graphene
2.10
Pd/B-Graphene
3.60
wt% of hydrogen
stored at 25 °C
and 32 bar
0.65
1.30
0.65
0.74
2.50
3.80
5.00
(Patent to be filed
20
(2014)
MECHANISM
Increase in hydrogen storage capacity of Pd/chemically modified
graphene samples are due to
1) Nitrogen/Boron doping effect on graphene support and Pd
nanoparticles
Nitrogen/Boron doping can induce atomic
charge density over graphene surface that
enhances the interaction between carbon
atoms and hydrogen molecules.
Nitrogen/Boron doping of graphene
surface leads to high dispersion, small
particle size and strengthened interaction
of catalyst metal nanoparticles over the
support.
21
SUMMARY
 Graphene and GNP were chemically modified by acid functionalization
and nitrogen doping for the dispersion of 3d transition metal nanoparticles.
 Nitrogen doping provides high dispersion, small particle size and
strengthened interaction of catalyst metal nanoparticles over the support.
 Pd nanoparticles decorated Boron doped graphene gives an hydrogen
storage capacity of 5.0 wt% at room temperature and 3.2 MPa pressure.
 Enhancement in hydrogen storage capacity of Pd-Graphene nanocomposite
is due to heteroatom doping and spillover mechanism.
Future plan
Work is in progress to achieve 5.0 wt% at room temperature
and 2.0 MPa pressure.
22
Studies on Hydrogen storage in carbon
materials( No.103/140/2008-NT)
PI
Prof.B.Viswanathan, Head, NCCR, Department of Chemistry, IIT Madras, Chennai
Co-PI:
• Dr.K.S.Dhathathreyan, CFCT,ARCI,
• Prof. A.R.Phani, NanoRam
08-04-2015
MNRE 5th Aug 2014 (CFCT ARCI)
23
Major Equipments procured
TGA with MS, Sieverts apparatus and ASAP
08-04-2015
MNRE 5th Aug 2014 (CFCT ARCI)
24
Activated carbons from different precursors
After Carbonization
08-04-2015
Before Carbonization
Lemon Outer
MNRE 5th Aug 2014 (CFCT ARCI)
25
Characterisation and hydrogen absorption studies
08-04-2015
MNRE 5th Aug 2014 (CFCT ARCI)
26
Schematic of Hydrogen storage Apparatus
Part -2
Part - 1
1
7
6
2
5
1. Manifold Pressure
Gauge (0-150 bar)
2. H2 gas inlet
3. Vacuum pump
4. Connecting channel
5. Reaction Chamber
6. Vent
7. RC pressure Gauge (0-25
bar)
3
4
The total amount of hydrogen adsorbed by the sample can be :
∆nH2
=
P Man. V Man
P RC. (V RC + Vman+ Vtub- Vsam )
Z (PMan,T) R. TMan
08-04-2015
Z (PRC,T) R. TRC
MNRE 5th Aug 2014 (CFCT ARCI)
27
Hydrogen storage capacity for corn cob , Jute , TSC, Cotton
P (bar)
40
30
20
100
75
50
25
10
0
0.0
0.5
1.0
1.5
2.0
2.5
H (wt%)
08-04-2015
MNRE 5th Aug 2014 (CFCT ARCI)
28
Hydrogen storage datalog of Cotton-800-2hr
08-04-2015
MNRE 5th Aug 2014 (CFCT ARCI)
29
Consolidated data of all the samples at RT and at 40 bar
Sample
TSC-1
TSC-2
TSC-3
TSC-P
2%Pd-TSC-1
PSC-1-600
PSC-3-600
PSC-P
MWTSC-50
MWTSC-75
MWTSC-100
TSC-3-700
Jute-700-1hr
Jute-700-1hr(1:1)
Jute-700-1hr(1:3)
Jute-700-1hr (1:5)
Cotton-600-2hr
Cotton-700-2hr
Cotton-800-2hr
08-04-2015
SA (m2/g)
353
672
785
775
280
672
1356
750
MPV (cm3/g)
0.14
0.27
0.31
0.08
0.1
0.28
0.56
0.04
1770
382
894
1224
1141
444
526
1279
0.59
0.16
0.35
0.43
0.42
0.19
0.21
0.46
MNRE 5th Aug 2014 (CFCT ARCI)
H capacity wt %
0.27
TBD
TBD
TBD
TBD
1.47
1.67
1.43
0.67
1.19
1.36
4.12
0.53
0.82
1.2
0.97
1.2
1.5
4.2
30
PUBLICATIONS
Publications
•Vinayan B P., Rupali Nagar, K. Sethupathi and S. Ramaprabhu, The
Journal of Physical Chemistry C, 115, 15679, (2011).
•Vinayan B P, K. Sethupathi and S. Ramaprabhu, Transactions of the
Indian Institute of Metals, 64, 169, (2011).
•Vinayan B P, K.Sethupathi and S.Ramaprabhu, Journal of
Nanoscience and Nanotechnology, 12, 1, (2012)
•Vinayan B P, Rupali Nagar, and S. Ramaprabhu, Langmuir, 28,7826,
(2012).
•Transition metal - graphene based hydrogen storage nanomaterial
(Indian patent) filed (2012).
•Chemically modified- carbon based hydrogen storage material
(patent) to be filed (2014).
31
Publications/ Paper
1.
Activated carbons derived from Tamarind seeds- T.Ramesh kumar,
N.Rajalakshmi and K.S.Dhathathreyan, Communicated (2013)
2.
Pt loaded on carbon derived from corn cobs for hydrogen storage R.Karthikeyan, N.Rajalakshmi and K.S.Dhathathreyan Communicated (2013)
3. .
Jute fibres based activated carbons for Hydrogen storage , M.
Vivekanandan, T.Ramesh kumar, N.Rajalakshmi and K.S.Dhathathreyan Communicated (2013)
4. Carbon from Cotton as hydrogen storage medium– T.Ramesh kumar,
N.Rajalakshmi and K.S.Dhathathreyan In preparation (2014)
5.
Hydrogen storage from composites based on Mg and activated carbon
derived from tamarind seeds(2014).
Conferences:
6.
T.Ramesh, G.Subashini, N.Rajalakshmi and K .S.Dhathathreyan ,
Activated Carbon from Tamarind Seeds- Promising Hydrogen storage material
, Paper presented at the National conference on Advanced materials ,
NCAMA-2013 at NIT, Trichy during 4th and 5th April 2013
32
a)
3.5
Room temperature
b)
Liquid N2 temperature
0.5
Hydrogen adsorbed (wt%)
Hydrogen adsorbed (wt%)
3.0
2.5
2.0
1.5
1.0
0.5
0.0
0.4
0.3
0.2
0.1
0.0
-0.5
0
20
40
60
Pressure (bar)
80
100
0
20
40
60
80
Pressure (bar)
Boron substituted carbon materials and hydrogen absorption capacity for
comparison purpose ( by another independent group)
33
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THANK YOU FOR
YOUR
KIND ATTENTION
NCCR
IIT Research Park
7th April 2008
NCCR
34