high density carbon materials for hydrogen...
TRANSCRIPT
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
A. A. LinaresLinares--SolanoSolano, M. , M. JordJordáá--BeneytoBeneyto, , D. LozanoD. Lozano--CastellCastellóó, F. , F. SuSuáárezrez--GarcGarcííaa, ,
D. D. CazorlaCazorla--AmorAmoróóss
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
University
UNIVERSITY OF ALICANTE(http://www.ua.es)
UA museum
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Content
H2 storage results at RT & 77K
Experimental and equipments
Introduction
Conclusions
Reporting H2 data; weight/volume ?
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)University of Alicante Carbon Materials and Environment Research Group
(http:/www.ua.es/grupo/mcma)
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Introduction
Still a challenge !HYDROGEN FOR AUTOMOTIVESis an interesting objective but...
500-600 km driving needs 5-7 kg H2
Compressed Hydrogen (10-70 MPa)Liquid Hydrogen (20K)Metal Hydrides,..Metal Organic FrameworksCarbon Materials
Absorption
Adsorption
Compressed Hydrogen (10-70 MPa)Liquid Hydrogen (20K) Metal Hydrides,..Metal Organic FrameworksCarbon Materials
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Introduction
Carbon precursors (many)
Carbon monoliths
Carbon nanotubes
Carbon nanofibers
Carbon microfibers
Carbon fibers
OUR STUDY ON CARBON OUR STUDY ON CARBON COVERS DIFFERENT COVERS DIFFERENT
ACTIVATED MATERIALS:ACTIVATED MATERIALS:
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Introduction
All theseproperties are important forH2 storage !
ACsACs PERFORMANCES CAN BE PERFORMANCES CAN BE TAILORED DURING ACTIVATION TAILORED DURING ACTIVATION
Porosity (volume & and PDS)
Surface area
Density
Thermal and electrical conductividad
Surface chemistry (oxygen groups)
Shapes & forms (powder, pellet, monolith...)
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Introduction
EXAMPLE SHOWING CONTROL OF EXAMPLE SHOWING CONTROL OF THE THE PSDsPSDs AND OF BET SURFACEAND OF BET SURFACE
L (nm)A. Linares-Solano, D. Lozano-Castelló, M. A. Lillo-Ródenas, and D. Cazorla-AmorósCarbon Activation by Alkaline Hydroxides, in Chemistry and Physics of Carbon, Volume 30 (2008)
MPSD
dV/d
L (c
c/nm
/g)
Pore Width (nm)
0
1
2
3
4
5
0 1 2 3
4:1
3:1
5:1
2:1
All same BET (~ 2500 m2/g)
EXAMPLE SHOWING CONTROL OF EXAMPLE SHOWING CONTROL OF THE THE PSDsPSDs AND OF BET SURFACEAND OF BET SURFACE
Runs numbersBE
T su
rfac
e ar
ea (m
2 /g)
01 2 3 4 5 6 7 8 9 10 11 12 13 14
500
1000
1500
2000
2500
3000
3500
4000
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Introduction
ADDITIONAL ADDITIONAL ACsACs ADVANTAGESADVANTAGES
Low cost & well known process
Easiness to machine
Good chemical stability
Good thermal & mechanical stability
1,5 cm
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Equipments
LABORATORY SCALE LABORATORY SCALE ACTIVATIONACTIVATION
Fixed bed
PHYSICAL & CHEMICAL
ACTIVATION
Fixed bed
Fluidized bedreactor
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Equipments
CHARACTERIZATION: SUBCHARACTERIZATION: SUB--ATMOSPHERIC ADSORPTION ATMOSPHERIC ADSORPTION
Porous texture(surface, pore volume)
and PSD
2 Autosorbs-6 (Quantachrome) ASAP 2020 (Micromeritics)
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Equipments
CHARACTERIZATION: HIGHCHARACTERIZATION: HIGH--PRESSURE ADSORPTIONPRESSURE ADSORPTION
Volumetricunit
20 MPa H2
77 – 750 K1-20 MPa
H2storage
Gravimetric units
77 – 298 K<1- 4 MPa
Cyclic unit
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Results
KUA5AX21KUA6
A20ACF
KUA1
a.NF
a.CNTNF
0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 5 10 15 20 25Pressure (MPa)
Exce
ssH
2(w
t.%) 0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
0 0.5 1 1.5
Total mpV (DR N2) (cc/g)
H2(w
t. %
)
KUA5
KUA6
Vnmp (DR CO2) (cc/g)
0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 0.2 0.4 0.6 0.8
H2(w
t. %
)
KUA6
HYDROGEN STORAGE AT ROOM HYDROGEN STORAGE AT ROOM TEMPERATURE (20 MPa) TEMPERATURE (20 MPa)
M. Jordá-Beneyto, D. Lozano-Castelló, F. Suárez-García, D. Cazorla-Amorós and A. Linares-Solano. Hydrogen storage on chemically activated carbon nanomaterials at high pressures, Carbon 45, 293–303 (2007)
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Results
BALANCE
High micropore volume
High packing density
Control of pore size distribution
H2 STORAGE (1-20 MPa)
HYDROGEN STORAGE AT ROOM HYDROGEN STORAGE AT ROOM TEMPERATURE (20 MPa): TEMPERATURE (20 MPa):
CONCLUSIONS CONCLUSIONS
0.6-0.7 nm
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Results
HYDROGEN STORAGE AT ROOM HYDROGEN STORAGE AT ROOM TEMPERATURE (70 MPa): TEMPERATURE (70 MPa):
CONCLUSIONS CONCLUSIONS
H2 (w
t % )
Micropore volume (cc/g)
BET (m2/g)
KUA6
1
2
3
0.5 1.0 1.5
20000 4000
Hydrogen storage in activated carbons and activated carbon fibers, J. Phys.
Chem. B 106, 10932, (2002)
M. de la Casa-Lillo, F. Lamari-Darkrim, D. Cazorla-Amoros, A. Linares-Solano
BALANCE
High micropore volume
High packing density
H2 STORAGE (30-70 MPa)
>> 0.7 nmH2 (w
t % )
KUA61
2
3
Micropore volume (cc/g)0.5 1.0 1.5
BET (m2/g)20000 4000
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Adsorption concepts
Low P/PoMedium P/Po
n = f (P) T, gas, solid
High P/Po
n (a
.u)
0 0.2 0.4 0.6 0.8 1P/Po (or Pcs)Gas (T&P)
Adsorption isotherm
Porous Solid
ADSORPTION ADSORPTION ON MICROPORESON MICROPORES
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Adsorption concepts
Pr = P/PCS
0 0.2 0.4 0.6 10.8
n (a
.u)
77 K 4MPa
0.1MPa
10 MPa20MPa
Pr = P/PCS
0 0.2 0.4 0.6 10.8
n (a
.u)
298 K
FUNDAMENTS OF H2 HIGH FUNDAMENTS OF H2 HIGH PRESSURE ADSORPTIONPRESSURE ADSORPTION
Supercritical conditions both at 298K & 77K
PCS = PC(T/TC)2Dubinin approach
20.39 KNormal Boiling PointCritical Density (DC)
13.150 barCritical Pressure (PC)
33.19 KCritical Temperature (TC)
0.0301 g/ml
7MPa
70MPa 1060MPa
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Results
HYDROGEN STORAGE AT 77K HYDROGEN STORAGE AT 77K (4 MPa): (4 MPa): CONCLUSIONS
HYDROGEN STORAGE AT 77K HYDROGEN STORAGE AT 77K (4 MPa): CONCLUSIONS (4 MPa): CONCLUSIONS
Pressure (MPa)
Exce
ssH
2(w
t.%)
0.0
1.0
2.0
3.0
4.0
5.0
6.0
0 1 2 3 4 5
H1
KUA6KUA5AX21
KUA4
KUA3
KUA1
a.NT
a.NF
H2
(wt.
%)
Micropore volume (cc/g)
0
0 0.5 10
BET surface area (m2/g)
1000 2000 3000
1
2
3
4
5
6ACsa.CNF & a. CNT
1.5
4000
KUA6
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
HYDROGEN STORAGE HYDROGEN STORAGE (ACs (ACs and MOFs,and MOFs, 77 K) 77 K)
Per gram
Per gramBET (m2/g)
Exce
ssH
2(w
t %)
0
1
2
3
4
5
6
7
8
0 1000 2000 3000 4000 5000
ACs
MOFs
MOFs
Adapted from Wong – Foy A.G. et al. J.Am. Chem Soc. 2006, 128, 3494-3495, including additional data ( )
HYDROGEN STORAGE HYDROGEN STORAGE (ACs and MOFs, 77 K) (ACs and MOFs, 77 K)
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Reporting results
Adsorption in gravimetric basis
Adsorption involumetric basis
??
• H2 uptakes much better when reported per unit of volume
• Density has to be measured !
FOR HYDROGEN VEHICULE APPLICATIONS: FOR HYDROGEN VEHICULE APPLICATIONS: SAMPLE WEIGHT OR SAMPLE VOLUME ? SAMPLE WEIGHT OR SAMPLE VOLUME ?
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Results
Importance of: POROSITY +DENSITY
Gravimetric basis
0
2
4
6
8
102000 30001000 4000
BET (m2/g)
Monoliths (full symbols)
Exce
ssH
2(w
t %
)
VDR (N2 (cc/g)0.6 0.8 1 1.2 1.40.4 1.6
0
5
10
15
20
25
30
35
Exce
ssH
2 (g
/l)
Volumetric basis
POROSITY +DENSITY
Importance of:HYDROGEN STORAGE HYDROGEN STORAGE (77K & 4 MPa)(77K & 4 MPa)
M. Jordá-Beneyto, D. Lozano-Castelló, F. Suárez-García, D. Cazorla-Amorós and A. Linares-Solano. Advanced Activated Carbon monolith for Hydrogen storage, Microporous and Mesopoporous Materials (in press, 2008)
Same situation occurs for MOFs !
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Results
DENSITY CHANGES DENSITY CHANGES WITH POROSITY WITH POROSITY
DR 2V (N ) (cm3/g)
3Den
sity
(g/c
m)
0.5 0.7 0.9 1.1 1.3 1.50
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8Packing densityTap density
40001000 2000 3000
BET surface area (m2/g)
Height
1 Ton
15 mm
Importance of preparing high density monoliths having good
mechanical (ease handling) and chemical behaviors
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Results
AC MONOLITH AC MONOLITH PREPARATIONPREPARATION
ACTIVATED CARBON + BINDER
140 ºC
3.5 TON
Pressing1) Carbonization2)
N2
750 ºC
ACTIVATED CARBON MONOLITHS (ACM)
SBET (m2/g) ~ 1000 2000 3000 Density (g/cm3) ~ 1.0 0.7 0.5
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Results
HIGH PRESSURE ADSORPTION AT DIFFERENT TEMPERATURES &
PRESSURES ON CARBON MONOLITH
250 5 10 15 200
20
40
60
x ad
s(m
g/g)
Pressure (bar)
AC1M
AC1 (powder)
(50 K)
(120 K)
(50 K)
(120 K)
Sample Packing density
AC1 0.4AC1M 0.7
(cc/g)
Compression strenght > 22 MPa
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Results
TOTAL H2 STORAGE CAPACITY CONCEPT
298 K 20MPa
Total
Adsorbed
Compressed
Stor
edH
2 (g
H2/
l)
Porous Solid
Compressed gas
+
Adsorbed gas
=
Total stored H2
Presión (MPa)
Stor
edH
2 (g
H2/
l)
Presión (MPa)
Total
Adsorbed
Compressed
77 K 4 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
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Results
TOTAL H2 STORAGE AT 298 K & 70MPa Best Best samplessamples: KUA6 & KUA 5: KUA6 & KUA 5
Pressure (MPa)
H2/g
/l)
37.2 g H2 (g/l)
0 10 20 30 40 50 600
10
20
30
40TotalTotal
AdsorbedAdsorbed
KUA 5KUA 5
CompressedCompressed
= 6.8 wt %
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Results
TOTAL H2 STORAGE AT 77 K & 4MPa Best Best samplesample: KUA 6: KUA 6
TotalTotal
CompressedCompressed
AdsorbedAdsorbed
38.8 g H2 (g/l)
H2/g
/l)
Pressure (MPa)
ACM1ACM1
= 8.0 wt %
05
1015202530
354045
0 1 2 3 4 5
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Results
TOTAL H2 STORAGE AT 77 K & 4MPa
Best Best monolith sample monolith sample ACM1ACM1
= 8.1 wt %TotalTotal
CompressedCompressed
AdsorbedAdsorbed
39.3 g H2 (g/l)
H2/g
/l)
Pressure (MPa)05
1015202530
354045
0 1 2 3 4 5
+ = + +ACM1ACM1
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Results
SUMMARY OF HYDROGEN STORED IN CURRENTLY AUTOMOTIVE DEVICES
200 barsteel cylinders
700 bar compositecylinders
LT- MH
HT- MHanalates
ACs RT (20-70 MPa) & ACs 77K (1-4 MPa)
Importance of preparing dense AC monoliths !
100
10
1 10 wt. % H2
g/l
USA target (DOE 2010, 45g/l)
European target (33g/l)
Our best results
High density carbon materials for hydrogen storage
University of Alicante Carbon Materials and Environment Research Group(http:/www.ua.es/grupo/mcma)
Conclusions
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 H2 storage (20MPa) needs:1. High MPV 2. Narrow micro PSD 3. High density
For 77 K (4MPa) needs:1. High MPV2. High density
Carbon Materials and Environment Research Group (http:/www.ua.es/grupo/mcma)
Department of Inorganic Chemistry University of Alicante, Spain
Thanks for your attention !
High density carbon materials for hydrogen storage
A. A. LinaresLinares--SolanoSolano, M. , M. JordJordáá--BeneytoBeneyto, , D. LozanoD. Lozano--CastellCastellóó, F. , F. SuSuáárezrez--GarcGarcííaa, ,
D. D. CazorlaCazorla--AmorAmoróóss