High density carbon materials for hydrogen storage A. Linares-Solano, M. Jordá-Beneyto, D. Lozano-Castelló, F. Suárez-García, D. Cazorla-Amorós
Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma) Department of Inorganic Chemistry University of Alicante, Spain
High density carbon materials for hydrogen storage
UNIVERSITY OF ALICANTE (http://www.ua.es)
University
UA museum
University of Alicante
Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma)
Content
High density carbon materials for hydrogen storage
Introduction Experimental and equipments H2 storage results at RT & 77K Reporting H2 data; weight/volume ? Conclusions
University University ofof Alicante Alicante
Carbon Materials and Environment Research Group Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma) (http:/www.ua.es/grupo/mcma)
Introduction
High density carbon materials for hydrogen storage
HYDROGEN FOR AUTOMOTIVES
Still a challenge !
is an interesting objective but...
¾ 500-600 km driving needs
5-7 kg H2
Compressed Hydrogen (10-70 MPa) Liquid Hydrogen (20K) Metal Hydrides,.. Metal Organic Frameworks Carbon Materials University of Alicante
Absorption Adsorption
Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma)
Introduction
High density carbon materials for hydrogen storage
OUR STUDY ON CARBON COVERS DIFFERENT ACTIVATED MATERIALS: Carbon nanotubes Carbon nanofibers Carbon microfibers Carbon fibers Carbon precursors (many) Carbon monoliths University of Alicante
Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma)
Introduction
High density carbon materials for hydrogen storage
ACs PERFORMANCES CAN BE TAILORED DURING ACTIVATION Surface area Porosity (volume & and PDS) Density Thermal and electrical conductividad
All these properties are important for H2 storage !
Surface chemistry (oxygen groups) Shapes & forms (powder, pellet, monolith...)
University of Alicante
Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma)
Introduction
High density carbon materials for hydrogen storage
EXAMPLE SHOWING CONTROL OF THE PSDs AND OF BET SURFACE 4000
All same BET (~ 2500 m2/g)
dV/dL (cc/nm/g)
4 3
MPSD
3:1
2:1
3500
BET surface area (m2/g)
5
4:1
2 5:1
1
3000 2500 2000 1500 1000 500
0 0
1
Pore Width (nm)
2
3
0 1
2
3
4
5
6
7
8
9
10
11 12 13
Runs numbers
L (nm)
A. Linares-Solano, D. Lozano-Castelló, M. A. Lillo-Ródenas, and D. Cazorla-Amorós Carbon Activation by Alkaline Hydroxides, in Chemistry and Physics of Carbon, Volume 30 (2008) University of Alicante
Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma)
14
Introduction
High density carbon materials for hydrogen storage
ADDITIONAL ACs ADVANTAGES Low cost & well known process Easiness to machine 1,5 cm
Good chemical stability Good thermal & mechanical stability
University of Alicante
Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma)
Equipments
High density carbon materials for hydrogen storage
LABORATORY SCALE ACTIVATION PHYSICAL & CHEMICAL ACTIVATION
Fixed bed
Fluidized bed reactor
Fixed bed University of Alicante
Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma)
Equipments
High density carbon materials for hydrogen storage
CHARACTERIZATION: SUBATMOSPHERIC ADSORPTION
2 Autosorbs-6 (Quantachrome)
University of Alicante
Porous texture (surface, pore volume) and PSD
ASAP 2020 (Micromeritics)
Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma)
Equipments
High density carbon materials for hydrogen storage H2 storage
CHARACTERIZATION: HIGHPRESSURE ADSORPTION Cyclic unit
Gravimetric units 77 – 298 K > 0.7 nm Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma)
High density carbon materials for hydrogen storage
ADSORPTION ON MICROPORES
Adsorption isotherm n (a.u)
Adsorption concepts
Gas (T&P) 0
0.2
P/Po (or Pcs) 0.4
0.6
0.8
1
High P/Po Medium Low P/Po P/Po
n = f (P) T, gas, solid Porous Solid University of Alicante
Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma)
Adsorption concepts
High density carbon materials for hydrogen storage Critical Temperature (TC)
FUNDAMENTS OF H2 HIGH PRESSURE ADSORPTION
13.150 bar
Critical Density (DC)
0.0301 g/ml
Normal Boiling Point
20.39 K
20MPa 10 MPa
0
0.2
0.4
0.6
0.8
Pr = P/PCS Supercritical conditions both at 298K & 77K Dubinin approach PCS = PC(T/TC)2 University of Alicante
1
7MPa
4MPa
77 K n (a.u)
n (a.u)
1060MPa
70MPa
298 K
Critical Pressure (PC)
33.19 K
0.1MPa
0
0.2
0.4
0.6
0.8
1
Pr = P/PCS Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma)
High density carbon materials for hydrogen storage
Results
HYDROGEN STORAGE AT 77K (4 MPa): CONCLUSIONS BET surface area (m2/g) 6.0
KUA6 KUA5 AX21 H1 KUA4
4.0
KUA3
3.0
KUA1 2.0
a.NT
1.0
a.NF
2
3
Pressure (MPa)
University of Alicante
4
3000
4000
a.CNF & a. CNT
4
KUA6
3 2
0 1
2000
1
0.0 0
1000
ACs
5
H2 (wt.%)
Excess H2 (wt.%)
5.0
6
0
5
0
0.5
1
Micropore volume (cc/g)
Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma)
1.5
High density carbon materials for hydrogen storage HYDROGEN STORAGE (ACs and MOFs, 77 K) 8
Excess H2 (wt %)
Per gram
7
MOFs
6
ACs
5 MOFs
4 3 2 1 0
0
1000
2000
3000
BET (m2/g)
4000
5000
Per gram
Adapted from Wong – Foy A.G. et al. J.Am. Chem Soc. 2006, 128, 3494-3495, including additional data ( Carbon Materials and Environment Research Group University of Alicante (http:/www.ua.es/grupo/mcma)
)
Reporting results
High density carbon materials for hydrogen storage
FOR HYDROGEN VEHICULE APPLICATIONS: SAMPLE WEIGHT OR SAMPLE VOLUME ? Adsorption in gravimetric basis
?
Adsorption in volumetric basis
• H2 uptakes much better when reported per unit of volume • Density has to be measured ! University of Alicante
Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma)
High density carbon materials for hydrogen storage
HYDROGEN STORAGE (77K & 4 MPa) 1000
Excess H2 (wt %)
DENSITY
BET (m2/g) 2000
10
POROSITY +
Importance of: 3000
4000
35
Volumetric basis
30
8
25
6
20
4
15
2 0
Gravimetric basis
0.4
0.6
0.8
10 5
Monoliths (full symbols)
1 1.2 VDR (N2 (cc/g)
1.4
Excess H2 (g/l)
Results
1.6
0 Same situation occurs for MOFs !
M. Jordá-Beneyto, D. Lozano-Castelló, F. Suárez-García,Carbon D. Cazorla-Amorós A. Linares-Solano. Materials and and Environment Research Group University of Alicante Advanced Activated Carbon monolith for Hydrogen storage, Microporous and Mesopoporous Materials (in press, 2008) (http:/www.ua.es/grupo/mcma)
High density carbon materials for hydrogen storage
Results
DENSITY CHANGES WITH POROSITY 0.8
BET surface area (m2/g) 2000
1000
3000
Packing density
0.7 Density (g/cm3)
4000 Tap density
0.6 0.5 0.4 0.3 0.2 0.1 0
1 Ton
Importance of preparing high density monoliths having good mechanical (ease handling) and chemical behaviors
0.5
0.7
0.9
1.1
1.3
Height
1.5
15 mm
VDR(N2) (cm3/g) University of Alicante
Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma)
High density carbon materials for hydrogen storage
Results
AC MONOLITH PREPARATION 1)
ACTIVATED CARBON + BINDER
Pressing
2)
Carbonization
3.5 TON
750 ºC
N2
ACTIVATED CARBON MONOLITHS (ACM)
140 ºC
University of Alicante
SBET (m2/g) ~ Density (g/cm3) ~
1000 1.0
2000 0.7
3000 0.5
Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma)
High density carbon materials for hydrogen storage
Results
HIGH PRESSURE ADSORPTION AT DIFFERENT TEMPERATURES & PRESSURES ON CARBON MONOLITH
Compression strenght > 22 MPa
60
x ads (mg/g)
(50 K)
40
AC1 (powder) AC1M
(50 K)
Sample
20
AC1 AC1M
(120 K)
0
(120 K)
0
5
University of Alicante
10
15
Pressure (bar)
20
Packing density (cc/g)
0.4 0.7
25
Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma)
Results
High density carbon materials for hydrogen storage Stored H2 (gH2/l)
TOTAL H2 STORAGE CAPACITY CONCEPT
= Porous Solid
Total stored H2
Stored H2 (gH2/l)
Adsorbed gas
Total Compressed Adsorbed
Presión (MPa)
Compressed gas +
298 K 20MPa
77 K 4 MPa
Total
Adsorbed Compressed Presión (MPa)
M. Jordá-Beneyto, M. Kunowsky, D. Lozano-Castelló, F. Suárez-García, D. Cazorla-Amorós and A. Linares-Solano. Hydrogen storage in carbon materials in “Carbon Materials: Theory and Practice” (2008). Editor, Artur P. Terzyk
University of Alicante
Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma)
High density carbon materials for hydrogen storage
Results
TOTAL H2 STORAGE AT 298 K & 70MPa
Best samples: KUA6 & KUA 5
40
37.2 g H2 (g/l)
Total Compressed
30
H2 /g/l)
= 6.8 wt %
KUA 5
20
Adsorbed
10 0 0
10
20
30
40
50
60
Pressure (MPa) University of Alicante
Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma)
High density carbon materials for hydrogen storage
Results
TOTAL H2 STORAGE AT 77 K & 4MPa
Best sample: KUA 6
45
38.8 g H2 (g/l)
40
H2 /g/l)
35
ACM1
30 25
= 8.0 wt %
Total Adsorbed
20 15
Compressed
10 5 0
0
University of Alicante
1
2
3
Pressure (MPa)
4
5
Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma)
High density carbon materials for hydrogen storage
Results
TOTAL H2 STORAGE AT 77 K & 4MPa
ACM1
+
=
+
Total
= 8.1 wt %
+
Best monolith sample ACM1 45
39.3 g H2 (g/l)
40
H2 /g/l)
35
Adsorbed
30 25 20 15
Compressed
10 5 0
0
University of Alicante
1
2
3
Pressure (MPa)
4
5
Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma)
High density carbon materials for hydrogen storage
Results
SUMMARY OF HYDROGEN STORED IN CURRENTLY AUTOMOTIVE DEVICES ACs RT (20-70 MPa) & ACs 77K (1-4 MPa)
g/l
European target (33g/l)
LT- MH
USA target (DOE 2010, 45g/l)
100
HT- MH analates
Our best results
200 bar steel cylinders 10
1 University of Alicante
700 bar composite cylinders
10
Importance of preparing dense AC monoliths ! wt. % H2
Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma)
Conclusions
High density carbon materials for hydrogen storage
Advanced SAC can be prepared in many forms (powder,
m monolith,...) having good chemical,thermal & mechanical b b behaviors and high H2 storage capacity The density of the adsorbents has to be reported and H2 to r
agstorage be expressed in a volumetric basis (attention to MOFs) Carbon Monolith seems very suitable for H2 carrier allowing
o to reach high value of total H2 storage value (40g H2/l) RT 1. 2. 3.
H2 storage (20MPa) needs: High MPV Narrow micro PSD High density
University of Alicante
For 77 K (4MPa) needs: 1. High MPV 2. High density
Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma)
Thanks for your attention ! High density carbon materials for hydrogen storage A. Linares-Solano, M. Jordá-Beneyto, D. Lozano-Castelló, F. Suárez-García, D. Cazorla-Amorós
Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma) Department of Inorganic Chemistry University of Alicante, Spain