High density carbon materials for hydrogen storage

High density carbon materials for hydrogen storage A. Linares-Solano, M. Jordá-Beneyto, D. Lozano-Castelló, F. Suárez-García, D. Cazorla-Amorós Carbo...
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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

ƒ Introduction ƒ Experimental and equipments ƒ H2 storage results at RT & 77K ƒ Reporting H2 data; weight/volume ? ƒ 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

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