On the Problem of “Super” Storage of Hydrogen in Graphite Nanofibers
"> Figure 1
<p>Processing (using the technique [<a href="#B20-carbon-08-00023" class="html-bibr">20</a>]) of thermal desorption (TDS) and thermogravimetric (TG) data from [<a href="#B5-carbon-08-00023" class="html-bibr">5</a>] for “super” desorption of “irreversible” hydrogen from GNF samples with a herringbone structure (see Figure 2 in [<a href="#B5-carbon-08-00023" class="html-bibr">5</a>]). (<b>a</b>) Fitting by three Gaussians (peaks ##1–3) of the TDS spectrum (β = 0.17 K s<sup>−1</sup>) for samples subjected to hydrogenation in gaseous H<sub>2</sub> (at 300 K, 11–4 MPa, 24 h); the red curve corresponds to the sum of three peaks. (<b>b</b>) Fitting by three Gaussians (peaks ##1–3) of the temperature derivative of the TG spectrum for samples subjected to hydrogenation in gaseous H<sub>2</sub> (at 300 K, 11–4 MPa, 24 h) and subsequent heating (β = 0.17 K/s) in He; the red curve corresponds to the sum of three peaks.</p> "> Figure 2
<p>Processing (in the first-order reaction approximation) of kinetic data from [<a href="#B4-carbon-08-00023" class="html-bibr">4</a>] on the change in hydrogen pressure in the working chamber during “super” adsorption of “reversible” hydrogen (at a temperature of about 300 K) for three samples of graphite nanofibers with a “herringbone” structure.</p> "> Figure 3
<p>Processing of thermodynamic and kinetic data from [<a href="#B10-carbon-08-00023" class="html-bibr">10</a>] on the “super” sorption of “reversible” hydrogen (~15 wt.%) for GNF samples with a “plate” structure (see <a href="#carbon-08-00023-f004" class="html-fig">Figure 4</a>) subjected to hydrogenation (24 h) in gaseous molecular hydrogen (at a pressure of 12 MPa and a temperature of 300 K) and subsequent dehydrogenation with a decrease in hydrogen pressure to 0.1 MPa: (<b>a</b>) processing of adsorption data in the approximation of the sorption isotherm of the Henry–Langmuir type [<a href="#B17-carbon-08-00023" class="html-bibr">17</a>]; (<b>b</b>) processing of thermal desorption data in the first-order reaction approximation.</p> "> Figure 4
<p>A micrograph of graphite nanofibers [<a href="#B11-carbon-08-00023" class="html-bibr">11</a>] subjected to hydrogenation (24 h) in gaseous molecular hydrogen at a pressure of 12 MPa and a temperature of 300 K to a content of “reversible” hydrogen of ~17 wt.%. The sizes of lenticular nanocavities in one of the nanofibers are shown, which are necessary for estimating (see works [<a href="#B2-carbon-08-00023" class="html-bibr">2</a>,<a href="#B17-carbon-08-00023" class="html-bibr">17</a>,<a href="#B18-carbon-08-00023" class="html-bibr">18</a>,<a href="#B24-carbon-08-00023" class="html-bibr">24</a>]) the volume of such nanocavities and the density of “reversible” hydrogen localized in them.</p> "> Figure 5
<p>Approximation by two Gaussians of the thermal desorption spectrum (kinetic curves 0.08 wt.% and 0.02 wt.% from Figure 18 in [<a href="#B13-carbon-08-00023" class="html-bibr">13</a>]) for sample #3 GNF with a herringbone structure (Table 3 in [<a href="#B13-carbon-08-00023" class="html-bibr">13</a>]), subjected to the action of gaseous molecular hydrogen at a pressure of 13 MPa and subsequent heating from 293 K (β = 0.10 K s<sup>−1</sup>) to a stop and isothermal holding at 1173 K.</p> ">
Abstract
:1. Introduction
2. Methods
3. Results of the Study of a Number of Experimental Data
3.1. Analysis and Interpretation of TDS and TG Spectra of the Rodriguez and Becker Group for “Irreversible” Hydrogen in GNF
3.2. Analysis and Interpretation of the Kinetic Data of the Rodriguez and Becker Group on the “Super” Sorption of “Reversible” Hydrogen (~30 wt.%) in GNF
3.3. Consideration of the Kinetic Data of the Rodriguez and Becker Group on X-ray Diffraction
3.4. Consideration of the Results of the Gupta’s Group on the “Super” Sorption of “Reversible” Hydrogen (~17 wt.%) in GNF
3.5. Physics of “Super” Storage of “Reversible” Hydrogen in GNF
4. Analysis of TDS Data for “Irreversible” Hydrogen in GNF
5. Conclusions
- The study carried out in this work (using the methodology and results of [17,18,19,20,21,22,23,24,25]) of a number of kinetic and thermodynamic aspects (fundamentals) related to solving the problem of “super” storage of hydrogen in graphite nanofibers (GNF) [1,2,3] shows that the results obtained in works [5,6,7,8,9,10,11,12], i.e., the extraordinary experimental results (accumulation of about 20–30 wt.% of “reversible” hydrogen and about 7–10 wt.% of “irreversible” hydrogen), are neither a mistake nor a mystification.
- It is shown that the physics of accumulation of ~20–30 wt.% of “reversible” high-density hydrogen intercalated in nanocavities between the base carbon layers in GNF is connected with the Kurdjumov phenomenon and the spillover effect in terms of thermoelastic phase equilibrium.
- The conducted study shows that there is a real possibility of reproducing the earlier extraordinary experimental results [5,6,7,8,9,10,11,12], but only if the details of the technologies used in these works for activating GNF are revealed, which led to the appearance of a type #1 thermal desorption peak in the material (Figure 1a) corresponding to “irreversible” chemisorbed hydrogen (in an amount of ~8 wt.%) with certain kinetic and thermodynamic characteristics.
- In this regard, further experimental and theoretical studies are needed.
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
Appendix A. Cavity Model
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Peak # | Tmax, K | Reaction Order | Q, kJ mol−1 | K0, s−1 | K(Tmax), s−1 | Q*, kJ mol−1 | γ | CH2, wt.% | (H/C) |
---|---|---|---|---|---|---|---|---|---|
1 | 914 | 1 | 39.0 | 1.5 × 10−1 | 9 × 10−4 | 39 | 0.76 | 8.4 | 1.1 |
2 | 77.5 | 5.1 × 101 | 2 × 10−3 | 77.5 | |||||
2 | 1036 | 1 | 199 | 4.2 × 107 | 4 × 10−3 | 198 | 0.02 | 0.2 | 0.02 |
2 | 398 | 8.8 × 1017 | 7 × 10−3 | 396 | |||||
3 | 1161 | 1 | 126 | 8.5 × 102 | 2 × 10−3 | 125 | 0.22 | 2.4 | 0.30 |
2 | 250 | 7.0 × 108 | 4 × 10−3 | 250 |
Peak # | Tmax, K | Reaction Order | Q, kJ mol−1 | K0, s−1 | K(Tmax), s−1 | Q*, kJ mol−1 | γ | wt. % | (H/C) |
---|---|---|---|---|---|---|---|---|---|
1 | 923 | 1 | 43 | 2.9 × 10−1 | 1 × 10−3 | 43 | 0.23 | 8.5 | 1.1 |
2 | 87 | 1.7 × 102 | 2 × 10−3 | 87 | |||||
2 | 1165 | 1 | 152 | 1.5 × 104 | 2 × 10−3 | 152 | 0.08 | 2.9 | 0.4 |
2 | 304 | 2.0 × 1011 | 4 × 10−3 | 303 | |||||
3 | 1345 | 1 | 149 | 1.0 × 103 | 2 × 10−3 | 148 | 0.69 | 26 | |
2 | 298 | 1.2 × 109 | 1 × 10−3 | 297 |
Peak # | Tmax, K | Reaction Order | Q, kJ mol−1 | K0, s−1 | K(Tmax), s−1 | Q*, kJ mol−1 | γ | wt. % | (H/C) |
---|---|---|---|---|---|---|---|---|---|
1 | 1203 | 1 | 163 | 1.6 × 104 | 1.3 × 10−3 | 162 | 0.96 | 0.08 | 0.010 |
2 | 325 | 3.6 × 1011 | 2.7 × 10−3 | 324 | |||||
2 | 397 | 1 | 68 | 4.5 × 106 | 5.1 × 10−3 | 67 | 0.04 | 0.02 | 0.002 |
2 | 133 | 4.1 × 1015 | 1.0 × 10−3 | 134 |
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Nechaev, Y.S.; Denisov, E.A.; Cheretaeva, A.O.; Shurygina, N.A.; Kostikova, E.K.; Öchsner, A.; Davydov, S.Y. On the Problem of “Super” Storage of Hydrogen in Graphite Nanofibers. C 2022, 8, 23. https://doi.org/10.3390/c8020023
Nechaev YS, Denisov EA, Cheretaeva AO, Shurygina NA, Kostikova EK, Öchsner A, Davydov SY. On the Problem of “Super” Storage of Hydrogen in Graphite Nanofibers. C. 2022; 8(2):23. https://doi.org/10.3390/c8020023
Chicago/Turabian StyleNechaev, Yury S., Evgeny A. Denisov, Alisa O. Cheretaeva, Nadezhda A. Shurygina, Ekaterina K. Kostikova, Andreas Öchsner, and Sergei Yu. Davydov. 2022. "On the Problem of “Super” Storage of Hydrogen in Graphite Nanofibers" C 8, no. 2: 23. https://doi.org/10.3390/c8020023