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Polymer-Based Activated Carbon Nanostructures for H2 Storage by ubb16013

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									Project ID # STP_03_CABASSO



  Polymer-Based Activated Carbon
   Nanostructures for H2 Storage

                                 Israel Cabasso and Youxin Yuan
                              State University of New York
                  Polymer Research Institute at Syracuse N.Y.
                               May 20, 2009

                                                                                                         1
This presentation does not contain any proprietary, confidential, or otherwise restricted information.
The Michael Szwarc Polymer Research Institute of the State
University of New York-esf (Syracuse) and PoroGen LLC have
collaborated in an effort to develop polymer-based nano
structured carbons:

     High BET surface area > 2600 m2/g;
     High microporosity > 95%;
     Average pore size ~ 10 Å;
     Hydrogen uptake: ~ 7 wt% and 45 g H2/L at elevated
     Temperature;
     Increasing hydrogen storage temperature by introduction of
     active sites in the carbons with polycyclic triazine rings (poly-
     melem).
                                                                         2
DE-FG36-05GO15009
                             Overview
     Timeline                                   Barriers
  Start - May 2005                          Improved Gravimetric and
                                            volumetric density of H2 uptake
  End - April 2010
  65% Completed (due to DOE’s               Controlled matrix doping and
                                            polymers compatibility
  budget shortage)
                                             Improved heat H2 of adsorption


      Budget
  Total project funding                        Partners
  – DOE - $1,543,420                    PoroGen (Boston MA)
  – Cost Share: $391,767 (20%)
  Total funding received in FY 2008     collaborations:
  – $300K                                -GTI (Chicago)
                                        -{several national labs and research
  Funding for FY 2009                   institutions for high pressure testing}
  – $250K
                                                                                  3
                Project Objectives/Relevance
 Overall
 Develop and demonstrate reversible nanostructured polymer-based carbon on
 hydrogen storage materials with materials-based volumetric capacity of 50 g
 H2/L, with potential to meet DOE 2010 system-level targets.
      Performance Measure              June, 2008 – May, 2009 performance
                                                     Target
  Carbon Surface Area and Pore                   S BET > 3000 m 2/g
            Volume                                V mp > 1.4 cc/g
                                      Gravimetric Capacity (Material Based)
    Hydrogen Storage Capacity                       >6 wt%
                                      Volumetric Capacity (Material Based)
                                                   >40 g/L
 Durability of Hydrogen Storage on                  > 30 cycle
               Carbon
   Incorporation of Unsaturated
Functionalized Polycyclic Complexes            > 20 wt% on Carbon
   (Melem, F-Melem, Ni-Melem)
Improve Hydrogen Binding Energy                    >>12 kJ/mole                4
                                                Technical Approach
Task 1: Processing Precursors                                  Task 3:Hydrogen Storage (Physisorption
                                                                      &Chemisorptions)
                        - Material Development
.                       - Modification                                         Incorporating reactive sites into
    80% complete




                                                                60% complete
                                                                               the carbon nanostructures.
                        - Characterization                                     Incorporation and polymerization of unsaturated
                                                                               functionalized polycyclic complexes (Melem, F-
                       Processing polymer precursors                           Melem, Ni-Melem) rich in double bonds with a
                       (MPPO,MPEEK and PEI) and high melt                      reduction factor of 10-50 kJ/mol (chemical interaction
                       shear rate Controlling morphology and                   binding energy is a function of pressure, temp. and trace
                       crystalline orientations                                of co-catalyst Fe,or Ni).


Task 2: Nanostructured Carbon                                  Task 4: Hydrogen Storage Testing
        Preparation                                                             - Testing hydrogen adsorption
                       - Prepare high surface area                               the temp. range:77K-300K and
        70% complete




                                                                50% complete
                          activated polymer based                                pressure of: 0.1 to 60 bar
                          carbon                                                 -Testing durability of material in
                        - Analysis morphology                                    repeated runs.
                          (surface area, porosity,
                          pore volume and size                  Note: Tasks 1 and 2 have been designed
                          distribution)                         to modify high performance polymer-based
                                                                                                         5
                        - Production scale up                   nanostructure carbon material to fit Task 3.
       Nanostructured Activated Polymer Carbon
              Preparation Methodology
Polymer Precursor
                                                          Carbonized Polymer

                    Modification:    Carbonization:
                    stabilization    temperature
                    crosslinking     heating rate, time




      Melem/Carbon                                        Activated Carbon
                           Alloyed/ and Polymerizing:
                                  Poly-Melem
                                    F-Melem
                                    Ni-Melem
                                                                               Activation:
                                                                               activation agent
                                                                               temperature
                                                                               homogeneity


                                                                                       6
 Correlation of Surface Area with Pore Size
      of Activated Polymer Carbons
                      35


                      30
Avg. Pore Width (Å)
                      25
                                 Pore
                                 Creation
                      20
                                             Pore
                                             Widening
                      15                                                                Achieved

                      10

                                                                                    Target
                       5
                                                               Achieved

                       0
                           0    500         1000        1500      2000       2500   3000     3500   4000
                                                               SBET (m2/g)

                           Target:     SBET > 2600 m2/g with average pore width ~ 8 Å

                           Achieved: SBET ~ 1850 m2/g with average pore width ~ 8 Å
                                     SBET ~ 3000 m2/g with average pore width ~ 18Å
                                                                                                           7
                               Pore Size Distribution as Function of Temperature
                                                                                             0.03
                                                                                                                                         0 .0 3
0.03                                          0.03
                                                                                                                                                                      750oC
                         550oC                                      850oC                    0.02
                                                                                                             Non activated               0 .0 2
0.02                                          0.02
                                                                                             0.01                                         0 .0 1
0.01                                          0.01
                                                                                                                                         0 .0 0
                                                                                             0.00
0.00                                          0.00                                                  5   10    15   20   25    30   35
                                                                                                                                                       5   10     15    20    25   30    35


           5   10 15 20 25 30 35                      5       10 15 20 25 30 35              0.03
                                                                                                                                        0.03



0.03
                                                                                                                                                                      800oC
                                               0.03                                          0.02
                                                                                                                   650oC                0.02

                         600oC                                      1000oC
0.02
                                               0.02
                                                                                             0.01                                       0.01

0.01                                           0.01
                                                                                             0.00                                       0.00
                                                                                                                                                   5       10    15     20    25   30    35
0.00                                           0.00                                                 5   10    15   20   25   30    35

       5       10   15    20   25   30   35               5   10    15   20   25   30   35                                               0.03
                                                                                             0.03


0.03
                                              0.03                                                                 700oC                 0.02
                                                                                                                                                                       850oC
                    700oC                                          1100oC                    0.02

0.02                                          0.02
                                                                                                                                         0.01
                                                                                             0.01
0.01                                          0.01
                                                                                                                                         0.00
                                                                                             0.00
0.00                                          0.00                                                  5   10    15   20   25    30   35
                                                                                                                                                       5    10    15    20    25    30    35

       5       10   15    20   25   30   35           5       10   15    20   25   30   35

                                    Pore Width (Å)                                                                           Pore Width (Å)
                          (A)                                          (B)
       (A). The structure and ordering can be controlled with agumentation of carbonization
            temperature. The structure ordering also narrows the pore size distribution.
       (B). Increase activation temperature(up to 800OC) leads to broadened pore size
           distribution, increases surface area and larger average pore diameter.
                                                                                                                                                                                               8
                                               Correlation of Hydrogen Uptake with Carbon Morphology


                                                                                                                                  0.055 g/cm 3                   0.013 g/cm 3
                                    3.0                                                                               3.0




                                                                                  W ad.H2 ., g/100g (77 K, 0.1 Mpa)
W ad.H2 ., g/100g (77 K, 0.1 Mpa)




                                    2.0                                                                               2.0




                                    1.0                                                                               1.0
                                                q ~16 μ g H 2/m 2




                                    0.0                                                                               0.0
                                          0   500 1000 1500 2000 2500 3000 3500                                             0.0     0.5          1.0      1.5    2.0       2.5
                                                                    2                                                                                     3
                                                            S BET , m /g                                                                          V tp , cm /g



                                    For carbon with SBET ≤ 1300 m2/g, the gravimetric capacity increases linearly with SBET
                                    at average surface coverage ~16μg H2.
                                    For carbon with SBET ≥ 1300 m2/g shows a modest increase in hydrogen uptake up to
                                    WH2 ~ 3.0 wt%
                                    The hydrogen density in pores varies from 0.013 g/cm3 to 0.055 g/cm3.

                                                                                                                                                                                 9
                                                    Theoretic
                                                    coverage




                                a                                       c


                     0.06
                     0.07                                Liq
                                                       Liq H2 H2

                     0.05


                     0.04
       3
        ρ H2, g/cm




                     0.03


                     0.02




                                b
                     0.01


                       0
                                                                        d
                            5       10   15          20            25
                                         d DR , Å


a. Unite surface area hydrogen uptake at 77K and 1 bar achieved average surface
  coverage 21.9 μg/m2 at pore size ~8Å.
b. The hydrogen density in pores at 77 K and 1bar achieved ~0.055 g/cm3 (80% coverage).
                                                                                     10
d. Isosteric heat of adsorption, Q(H2)is ~ 5 – 6 kJ/mol, and 10 kJ/mol at lower pressure.
Correlation of Hydrogen Capacity with Surface Area at
               High Pressure and 77K




                                      Hydrogen uptake at 77K
                                     on polymeric carbon
                                     follows Langmuir
                                     adsorption.
                                     The correlation between
                                     hydrogen uptake and
                                     surface area Sbet (with at
                                     various H2 pressure)
                                     increases linearly.




                                                                  11
          Hydrogen Storage Capacity of Polymer Derived Carbon Nanostructures
                                                           H2Uptake at 77K
 Sample       S BET        V tp       0.1 MPa            1MPa          2MPa                  6MPa
              (m2/g)     (cm3/g)     g/100g g/L       g/100g g/L    g/100g g/L            g/100g g/L
 MPK-1          1800      0.84      2.0       14       3.5     26       4.5       34      5.8   43-46
 MPK-2          1760      0.74      2.1       17       3.0     24       3.3       26      4.4    35
 MPK-3          2000      0.90      2.4       17       3.5     25       3.7       26      4.5    32
 MPK-4          2300      0.97      2.6       18       3.9     26       4.3       29      5.1    35
 MPK-5          2720      1.15      2.7       16       4.4     26       4.9       29      5.8    35
MPK/PI-1        2110      1.03      2.8       18       4.5     29       4.8       31      5.0    33
MPK/PI-2        2430      1.03      2.8       18       4.4     29       4.8       31      4.7    31
MPK/PI-3        2775      1.28      2.7       15       4.7     26       5.3       30      5.4    30
MPK/PI-4        2890      1.29      2.6       14       4.7     26       5.3       30      6.4    36
MPK/PI-5        2935      1.36      2.6       13       4.5     24       5.1       27      5.9    31
MPK/PI-6        3035      1.81      2.5       11       5.1     22       5.9       26      7.4    32
MPK/PI-7        3095      1.60      2.7       12       4.8     22       5.5       26      6.4    30
MPK/PI-8        3160      1.98      2.8       11       5.0     20       5.9       24      7.0    28
MPPO-1          3920      2.20      2.7       10       4.8     18       5.3       20      6.4    24


          The gravimetric hydrogen storage capacity achieved ~7.0 wt% at 77K 60 bar.
          The volumetric hydrogen storage capacity achieved ~ 40-45 g/L at 77 K 60 bar.
                                                                                                 12
Hydrogen Storage Capacity of Polymer Derived Carbon Nanostructures




a. Gravimetric hydrogen uptake increases linearly with surface area, at a rate of ~ 20
   μg H2/(m2/g), which indicates ~ 6 H2 molecules occupy 20 graphene hexagon units.

b-c. High volumetric hydrogen uptake (up to 46 g H2/L) is achieved at Vmp ~ 0.8-0.9 mL/g.
                                                                                         13
            Reproducibility of Carbon Nanostructures
Synthesized from Two Different Batches of MPK/PI Blend precursor

                         1400                                                                        8                                                        8

                         1200                                                                        7                                                        7
                                                                  Batch 1
Ad. N2 Vol (mL/g, STP)




                                                                                                     6                                          Batch 2       6
                         1000
                                                                  Batch 2
                                                                                                     5                                          Batch 1       5




                                                                                      W(H 2 ), wt%
                         800
                                                                                                     4                                                        4
                         600
                                                                                                     3                                                        3
                         400                                                                         2                                                        2

                         200                                                                         1                                                        1

                           0                                                                         0                                                        0
                                0.0   0.2   0.4   0.6       0.8   1.0       1.2                          0          2         4             6             8
                                                                                                                        H2 Pressure (MPa)
                                                  P/P0




                                             Batch of        SBET        Vmp         Vp                      dDR           W(H2),               V(H2), g
                                             Material       (m2/g)      (mL/g)     (mL/g)                    (Å)            wt%                  H2/L
                                                                                                                           77 K                  77 K
                                                        1    3070           1.23    1.82                     20.1            6.7                   30

                                                        2    3365           1.29    1.99                     19.0            6.7                   28

                                                                                                                                                              14
        Poly - Melem Alloyed With Polymer Carbons
                  δ ~ + 0.75


                      δ ~ + 0.40
         δ ~ – 0.28        δ ~ – 0.28
                                                  Fluorination
                    δ~     δ ~ + 0.51
    δ ~ – 0.28    - 0.27
                                 δ ~ – 0.28




 δ ~ + 0.75                        δ ~ + 0.75
                 Melem

                                                                                                                                Ni- poly Melem-F
                                                                                                                                ((tri-triazine rings)
                                                                                                           Ni(111)
Activated Carbons unit-cell
                                                                                                Graphite
                                                                                                 (002)        Ni(200)
                                                   alloyed




                                                                     In ten sity (a.u .)
                                                                                                                      19.5


                                                (Trace quantity
                                                of co-catalyst Ni,                                                        3.3

                                                Fe)
  Melem                                                                                                                     0

  F-Melem
  Ni-Melem                                                                                 0   16     32   48        64         80
                                                                                                    2θ (Degree)                                         15
                  Formation and Characterization of Melem/Carbon

                                                                                           a’
                                                                                       167.71 pm
         120

         100                                      Carbon
Weight (%)




             80                         Melem/ Carbon                                                   Melamine
             60
                                                                                           a
             40                                                                        164.52 pm
                                     melamine
             20

             0                                                                                  b
                  0         200       400        600       800                              155.10 pm

                              Temperature (°C)
                                                                       Melem



                      TGA Monitoring of Melem and [CNH]n         300      250    200        150     100       50        0
                          formation within the Carbon
                                                                                CP-MAS 13C-NMR



                                                                                                                   16
                                                        Performance
                                               25Ma8-01483                              of Melem-Carbon Blend Alloy
                          10000



                           1000
P re s s u re ( K p a )




                            100



                             10
                                                                                                                      b
                                                                            a
                              1
                              0.000   1.000   2.000     3.000       4.000       5.000   6.000
                                                      H.C. (w t%)

                                              R.T.        -78°C        -196°C



                                  (a) The Melem/carbon registered gravimetric capacity of ~ 5.2 wt%, 1.12 wt% and
                                  0.32% at 77 K, 195 K, and 298 K, respectively. The equivalent volumetric capacities
                                  were ~39 g/L, 8.3 g/L, and 2.4 g/L.
                                  (b) Alloyed carbon with Melem or fluorinated Melem raises the hydrogen binding
                                  energy up to 14 kJ/mol at low pressure.                                             17
         Hydrogen Storage By Solvated – Carbon Alloy




Hydrogen storage by Solvated – Carbon alloyed method greatly
increases the storage capacity at elevated temperatures.


                                                               18
         Hydrogen Storage of Solvent - Nanostructured Carbon
                  Alloy of Various Porous Textures
                           Porous Texture                              Hydrogen Storage
Carbon
                     SBET   Vmp      Vtp             dDR            Tde     WH2      VH2
                       2
                    (m /g) (mL/g) (mL/g)             (Å)           (°C)    (wt%) (g H2/L)
BP2000               1560   0.70    2.07              -              -       -        -
MPK-5                2720   1.10    1.15             17.2           -36     6.3      31.4
MPK/PI-9             2040   0.94    1.05             16.2           -50     4.7      23.4
MPK/PI-1             2120   0.98    1.06             16.3           -50     5.4      26.9
MPK/PI-10            2710   1.20    1.29             18.6           -36     5.6      27.9
MPK/PI-11            3300   1.46    1.85             19.0          -135     7.2      35.9
                                                                    -35     6.7      33.4
MPK/PI-12           3530        1.55      1.93       19.7           -36     8.0      39.9
                                                                    -65     5.6      27.9
MPK/PI-13           4020        1.75      2.29       21.7           -40     7.8      38.9
                                                                    -25     5.9      29.4

A gravimetric storage capacity of up to 8.0 wt%, and a volumetric storage capacity of up to ~ 40 g
H2/L have been accomplished at above dry ice temperature by highly porous carbon, e.g.,
PEEK/PEI-12 alloy.                                                                          19
                             Project Summary
Approach: Formulated synthetic strategies toward polymer-based nanostructured carbons
          of controllable porosity and surface area from polymer precursors that would
          be alloyed with organo-active sites
            Established correlation of hydrogen storage with surface area, pore size and
            porosity with can be alloyed with active sites.
Technical Accomplishments and Progress:
            Demonstrated synthesis of a modified polymer based carbons with high
            surface area (up to 4000 m2/g) and low average pore width (down to 8.5
            Å); Accomplished gravimetric storage capacity of ~ 6.7-7.4 wt%, and
            volumetric capacity of ~ 45 g/L at 77 K, 5 - 6 MPa
            Introduction of a carbon alloy with organocyclic-CNHn macromolecules
            rich with unsaturated bonds, that exhibit rigid planar configuration and are
            rich in electronegative nitrogen atoms, that may enable application for RT
            and moderate pressure H2 storage systems at high temperature. (note, the
            interaction with cyclic bonds may reach 100 kJ/mol, that too much,
            controlling and monitoring the interaction binding energy is being work on.).
            A solvent/polymer-carbon alloy method has been developed for enhanced
            hydrogen storage at ambient temperatures (-25 °C). A total H2 gravimetric
            storage > 7.0 wt% (based on carbon) and volumetric storage capacity ~ 40 g
            H2/L has been achieved in preliminary experiments on nanostructured
                                                                                      20
            carbons, at -25 °C.
                             Future work
We concur that the carbon matrix by itself has a slim chance (if at all) to
produce a heat of interaction, of about 20-25 kJ/mol, that is needed for an
effective sorption of hydrogen at ambient temperature. Keeping this in mind
our future work includes:
            Improving the binding of hydrogen (adsorption)
            • Alloying activated carbon with Unsaturated Functionalized
              Polycyclic Complexes (e.g., Melem, Fluorinated-Melem, and
             Ni-Melem). Finding the proper composition for the
             ratio of carbon/alloy and other components needed.
           • Surface modification of the nanostructures of polymer based
             carbon by blending different polymer precursors. Control
             of the binding energy of hydrogen with carbon/alloy.
             Explore nanostructures
           • Continue to develop, modify, and characterize polymer materials.
           • Continue to develop Nanoporous carbons.

            Hydrogen adsorption tests at elevated temperature
            of organo PEEK carbons.                                             21

								
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