High density carbon materials for hydrogen...

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