Binary Alkali-Metal Silicon Clathrates by Spark Plasma Sintering: Preparation and Characterization
"> Figure 1
<p>Crystal structures of (<b>a</b>) Na<sub>4</sub>Si<sub>4</sub>; (<b>b</b>) <span class="html-italic">M</span><sub>4</sub>Si<sub>4</sub> (<span class="html-italic">M</span> = K, Rb, or Cs); (<b>c</b>) <span class="html-italic">M</span><sub>8-<span class="html-italic">x</span></sub>Si<sub>46</sub>; and (<b>d</b>) <span class="html-italic">M</span><sub>24-<span class="html-italic">x</span></sub>Si<sub>136</sub>.</p> "> Figure 2
<p>(<b>a</b>) SPS setup for the preparation of clathrates; (<b>b</b>–<b>e</b>) Location and relative amounts of the reaction products for different polarities and different die and punch materials; (<b>f</b>–<b>h</b>) Optical micrographs of the cross-sections from fractured post-reaction pellets illustrating the directional growth of clathrates at the anode.</p> "> Figure 3
<p>Powder X-ray diffraction (PXRD) patterns of the SPS-prepared clathrates-I K<sub>7.6</sub>Si<sub>46</sub> (550 °C) and K<sub>6.8</sub>Si<sub>46</sub> (600 °C). Red asterisks mark the reflections of <span class="html-italic">α</span>-Si (<0.2 mass % in K<sub>7.6</sub>Si<sub>46</sub> and 1.5 mass % in K<sub>6.8</sub>Si<sub>46</sub>). The experimental intensities are shown as a solid line. The difference between the experimental and calculated intensities is shown below the experimental data; the tick marks represent the positions of the diffraction reflections of the clathrate-I phase.</p> "> Figure 4
<p>Powder X-ray diffraction (PXRD) patterns of the Rb<sub>6.2</sub>Si<sub>46</sub> and Rb<sub>11.1</sub>Si<sub>136</sub> mixed product and clathrate-II Cs<sub>7.8</sub>Si<sub>136</sub>. The experimental intensities are shown as a solid line. The differences between the experimental and calculated intensities are shown below the experimental data. The tick marks represent the positions of the diffraction reflections. Red asterisks mark the reflections from <span class="html-italic">α</span>-Si (<0.2 mass % in Rb<sub>6.2</sub>Si<sub>46</sub> and Rb<sub>11.1</sub>Si<sub>136</sub> and 2.5 mass % in Cs<sub>7.8</sub>Si<sub>136</sub>).</p> "> Figure 5
<p>Lattice parameters versus <span class="html-italic">M</span> content, <span class="html-italic">x</span> for clathrate-I Na<span class="html-italic"><sub>x</sub></span>Si<sub>136</sub> (0 < <span class="html-italic">x</span> < 24) [<a href="#B28-materials-09-00593" class="html-bibr">28</a>], Na<sub>24</sub>Si<sub>136</sub> [<a href="#B16-materials-09-00593" class="html-bibr">16</a>], K<sub>17.2</sub>Si<sub>136</sub> [<a href="#B19-materials-09-00593" class="html-bibr">19</a>], Rb<sub>11.5</sub>Si<sub>136</sub> (this work), and Cs<sub>7.8</sub>Si<sub>136</sub> (this work), as well as ternary Rb<sub>8</sub>Na<sub>16</sub>Si<sub>136</sub> and Cs<sub>8</sub>Na<sub>16</sub>Si<sub>136</sub> [<a href="#B27-materials-09-00593" class="html-bibr">27</a>].</p> "> Figure 6
<p>Transport properties of polycrystalline K<sub>7.6</sub>Si<sub>46</sub> and K<sub>6.8</sub>Si<sub>46</sub>. The low temperature, 2 to 300 K, and high temperature, 300 to 700 K, are described in the text. (<b>Top</b>) electrical resistivity <span class="html-italic">ρ</span>; (<b>Middle</b>) Seebeck coefficient <span class="html-italic">S</span>; (<b>Bottom</b>) thermal conductivity <span class="html-italic">κ</span>.</p> "> Figure 6 Cont.
<p>Transport properties of polycrystalline K<sub>7.6</sub>Si<sub>46</sub> and K<sub>6.8</sub>Si<sub>46</sub>. The low temperature, 2 to 300 K, and high temperature, 300 to 700 K, are described in the text. (<b>Top</b>) electrical resistivity <span class="html-italic">ρ</span>; (<b>Middle</b>) Seebeck coefficient <span class="html-italic">S</span>; (<b>Bottom</b>) thermal conductivity <span class="html-italic">κ</span>.</p> ">
Abstract
:1. Introduction
2. Results and Discussion
112 M+ + 112 e− → 112 M0 (cathode)
76 M+ + 76 e− → 76 M0 (cathode)
3. Materials and Methods
3.1. Synthesis of Precursors
3.2. Spark Plasma Synthesis
3.3. Sample Characterization
4. Conclusions
Acknowledgments
Author Contributions
Conflicts of Interest
References
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Precursor | TR (°C) a | tR (min) b | Die/Punches c | Products d |
---|---|---|---|---|
Na4Si4 | 550 | 180 | C/C | Na24Si136 (M) + Na8Si46 (m) |
600 | 180 | C/C | Na24Si136 (M) | |
700 | 180 | C/C | Na24Si136 (M) + Si (m) | |
K4Si4 | 500 | 60 | BN/SS | K8-xSi46 (tr) |
550 | 60 | BN/SS | K8-xSi46 (M) | |
600 | 60 | BN/SS | K8-xSi46 (M) + Si (m) | |
650 | 60 | BN/SS | Si (M) + K8-xSi46 (m) | |
Rb4Si4 | 450 | 60 | BN/SS | Rb8-xSi46 (M) + Rb24-xSi136 (m) + Si (tr) |
500 | 60 | BN/SS | Si (M) + Rb8-xSi46 (m) + Rb24-xSi136 (m) | |
Cs4Si4 | 350 | 60 | BN/SS | Cs8-xSi136 (M) + Si (tr) |
Phase | K7.6(1)Si46 | K6.8(1)Si46 | Rb6.2(1)Si46 |
---|---|---|---|
Lattice parameter a, Å | 10.2776 (1) | 10.2747 (1) | 10.2848 (1) |
Radiation, wavelength λ, Å | Cu Kα1, 1.54056 | ||
Maximal diffraction angle 2θ, ° | 100.30 | ||
Residuals RI/RP | 0.04/0.10 | 0.04/0.09 | 0.02/0.10 |
M1 2a (0 0 0) | Occ * = 0.783 (1) | Occ = 0.695 (4) | Occ = 0.244 (3) |
M2 6d (¼ ½ 0) | Occ = 1.013 (3) ** | Occ = 0.918 (3) | Occ = 0.961 (2) |
Si1 6c (¼ 0 ½) | – | – | – |
Si2 16i (x x x) | x = 0.1845 (1) | x = 0.1846 (1) | x = 0.1840 (1) |
Si3 24k (0 y z) | y = 0.3068 (1) | y = 0.3060 (1) | y = 0.3043 (1) |
z = 0.1183 (1) | z = 0.1185 (1) | z = 0.1190 (1) |
Phase | Rb11.1(1)Si136 | Cs7.8(1)Si136 |
---|---|---|
Lattice parameter a, Å | 14.7142 (9) | 14.6733 (3) |
Radiation, wavelength λ, Å | Cu Kα1, 1.54056 | |
Maximal diffraction angle 2θ, ° | 100.30 | |
Residuals RI/RP | 0.10/0.10 | 0.05/0.13 |
M1 8b (⅜ ⅜ ⅜) | Occ * = 0.85 (2) | Occ = 0.968 (2) |
M2 16c (0 0 0) | Occ = 0.272 (1) | Occ = 0.0 |
Si1 8a (⅛ ⅛ ⅛) | – | – |
Si2 32e (x x x) | x = 0.2198 (6) | x = 0.2168 (2) |
Si3 96g (x x z) | x = 0.1839 (2) | x = 0.1822 (1) |
z = 0.3698 (6) | z = 0.3699 (2) |
Precursor | Preparation Technique a | Clathrate Phases Obtained | References |
---|---|---|---|
Na4Si4 | CTC | Na8Si46 and Na24-xSi136 | [6,33] |
KCTD | Na8Si46 and Na24-xSi136 | [18] | |
CO | Na8Si46 and Na24-xSi136 | [7,25] | |
SPS | Na8Si46 and Na24-xSi136 | [16,24], this work | |
K4Si4 | CTC | K8-xSi46 | [6,26] |
KCTD | K8-xSi46 and K24-xSi136 | [19] | |
CO | K8-xSi46 | [7] | |
SPS | K8-xSi46 | this work | |
Rb4Si4 | CTC | Rb8-xSi46 | [6,26] |
SPS | Rb8-xSi46 and Rb24-xSi136 | this work | |
Cs4Si4 | CTC | Cs24-xSi136 | [6] |
SPS | Cs24-xSi136 | this work |
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Veremchuk, I.; Beekman, M.; Antonyshyn, I.; Schnelle, W.; Baitinger, M.; Nolas, G.S.; Grin, Y. Binary Alkali-Metal Silicon Clathrates by Spark Plasma Sintering: Preparation and Characterization. Materials 2016, 9, 593. https://doi.org/10.3390/ma9070593
Veremchuk I, Beekman M, Antonyshyn I, Schnelle W, Baitinger M, Nolas GS, Grin Y. Binary Alkali-Metal Silicon Clathrates by Spark Plasma Sintering: Preparation and Characterization. Materials. 2016; 9(7):593. https://doi.org/10.3390/ma9070593
Chicago/Turabian StyleVeremchuk, Igor, Matt Beekman, Iryna Antonyshyn, Walter Schnelle, Michael Baitinger, George S. Nolas, and Yuri Grin. 2016. "Binary Alkali-Metal Silicon Clathrates by Spark Plasma Sintering: Preparation and Characterization" Materials 9, no. 7: 593. https://doi.org/10.3390/ma9070593