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Polycrystalline C12A7 electrides were successfully synthesized via spark plasma sintering (SPS) process. C2 2 ions, generated from
graphite by the spark plasma, presumably serve as a template for the formation of the C12A7 phase during the re-crystallization
process and are spontaneously released from the cage of C12A7 during the SPS process, remaining mobile electrons in the cage.
The polycrystalline C12A7 electride processed at 1100 C exhibits an electrical resistivity of 1.7 101 cm1 , an electron
concentration of 5.3 1019 /cm3 and optical absorptions of 0.4 eV and 2.7 eV at room temperature.
2011 The Electrochemical Society. [DOI: 10.1149/2.021112esl] All rights reserved.
Manuscript submitted July 29, 2011; revised manuscript received September 8, 2011. Published October 25, 2011.
E-mail: kbshim@hanyang.ac.kr
Experimental
The starting C12A7 powder was prepared using a conventional
citrate-gel method. Synthesized C12A7 powders (1 g) were loaded
into a cylindrical graphite die with a diameter of 15 mm and heated
R
using the SPS (Dr. Sinter model
, SPS-2080, Japan) process within a
temperature range of 900 to 1100 C, with a heating rate of 100 C/min
and an uni-axial pressure of 40 MPa in vacuum (106 Torr). The
samples were held for 10 min at each temperature. The direct current
was 1500 A with a pulsed duration of 12 ms and a pulse interval of
2 ms. After SPS process, the samples are grinded and polished for
removed carbon lms on the surface using SiC abrasive paper. The
thickness samples were about 2 mm.
Phase analysis was performed using an X-ray diffractometer
(Rigaku D/MAX2C, Japan, Cu- ( = 1.5046 )). Optical absorption
spectra were measured by UV-Vis spectroscopy (UV 3600, Shimadzu,
Japan) in a range of 0.4 - 4.0 eV, and Raman spectra were measured
(NRS-3000, laser ( = 532nm)) in a range of 4002000 cm1 at
room temperature. The electron concentration and electrical resistivity
were measured using four-probe type Hall measurement (RESISTEST
8300, DongYang Tech, Japan).
Results and Discussion
Photographs of the C12A7 samples at different processing temperatures are presented in Figure 1. The colors of the samples changed
depending on the temperature; white at 900 C, gray at 1000 C and
dark green color at 1100 C. This change was suggested to be induced
by the optical absorption level (2.7 eV) generated by the electrons that
replaced the free oxygen ions.20
Figure 2 shows optical absorption results of the C12A7 samples
depending on the processing temperature. The sample processed at
900 C showed no specic absorption peak; however, the samples
processed at 1000 C and 1100 C showed absorption peaks near the
0.4 and 2.7 eV regions, indicating electron trapping in the C12A7
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E42
2.7 eV
0.4 eV
Absorption(Kubelaka-Munk)
5
4
3
1100oC
1000oC
900oC
1
0
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
Phothon Energy(eV)
Figure 2. UV-Vis spectra of the C12A7 specimens processed via SPS at
different processing temperatures.
13
10
10
3.2 x 1011 cm
10
10
10
2.6 x 102 cm
10
10
21
10
17
10
13
10
10
-3
10
Electron concentration(cm )
cage structure.20 The energy level of the 2.7 eV peak reects the color
change from white to dark green, as shown in Figure 1. The optical
absorption levels of 0.4 eV and 2.7 eV can be caused by an inter-cage
transition (0.4 eV) and intra-cage transition (2.7 eV), respectively.2022
Figure 3 shows the electric resistivities and electron concentrations of the C12A7 samples at different processing temperatures.
The electric resistivity of the C12A7 sample processed at 900 C was
3.2 1011 cm, indicating a perfect insulator. The electric resistivities of the samples processed at 1000 C and 1100 C dramatically
decreased to 2.6 102 and 1.7 101 cm1 , respectively. While
the electron concentrations of the samples processed at 900 C were
6.1 108 /cm3 , those of the C12A7 samples processed at 1000 C and
1100 C were 3.2 1017 and 5.3 1019 /cm3 , respectively. The results
of the sample processed at 1100 C were comparable with previous
results19 and conrmed that the SPS process can successfully convert
C12A7 to C12A7 electrides.
Figure 4a represents the XRD results of the C12A7 samples depending on the processing temperature. Compared with the powder
sample, the SPS processed sample at 900 C showed mixed phases
composed of 3CaO Al2 O3 (C3A) and CaO Al2 O3 (CA) with the
C12A7 phase. Increasing processing temperature to 1000 C decreased
the peak intensities of the C3A+CA phases, which are completely disappeared at 1100 C, indicating that the C12A7 phase decomposed to
-2
900
1000
1100
o
Sintering Temp( C)
Figure 3. Electric resistivity and electron concentration of the C12A7 specimens at room temperature (300 K).
Figure 4. (a) X-ray diffraction patterns and (b) raman spectroscopy of the
C12A7 specimens produced via SPS at different processing temperatures.
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E43
Figure 5. Schematics of a one-step fabrication route for C12A7 electride using the PECS process. (a) The C12A7:O2 powders were placed between two graphite
rams in a cylindrical graphite die, (b) decomposition from C12A7 phase to C3A+CA phases due to spark plasma-induced electric current, (c) diffusion of carbon
ions (C2 2 ) into decomposed C3A+CA phases and re-crystallization from C3A+CA to C12A7:C2 2 by C2 2 ions and (d) transition from C12A7:C2 2 to
C12A7:e and emission of carbon ions as 2C or 2CO into the atmosphere.
shown in Figure 5b. The decomposed C3A+CA phases were combined with C2 2 ions diffused into samples by the electric eld and
re-crystallized to the C12A7 phase by C2 2 ions, as shown in Figures
5c5d according to the following reaction,
C3A + CA + C2 2 C12A7 : C2 2
[1]
As shown in Figures 4a, processed below 1000 C, the decomposed C3A+CA phases were not perfectly re-crystallized to C12A7
because of insufcient temperatures for re-crystallization. However,
above 1100 C, only a single C12A7 phase existed, indicating that the
decomposed C3A+CA phases were perfectly re-crystallized to the
C12A7 phase, as shown Figure 5d. During the SPS process, C2 2 ions
are diffused into the C3A+CA phases by the electric eld, and then
the decomposed C3A+CA phases can be re-crystallized to the C12A7
phase by C2 2 ions. Therefore, the C2 2 ions instead of O2 ions serve
as a template for compensating positive charges of [Ca24 Al28 O64 ]4+
because the ionic radius of the C2 2 ion (1.2 ) is similar to that
of O2 (1.4 ).19 The C2 2 ions trapped in the cages of the C12A7
were only stable in the initial stage of re-crystallization and were then
released from the cages during the re-crystallization procedure. In this
process, the electrons were generated in cages of the C12A7 via the
following reactions,
C2 2 (graphite) C2 2 (cage) 2C (solid) + 2e (cage)
[2]
and/or
C2 2 (cage) + 2O2 2 (cage) 2CO (atmosphere) + 6e (cage)
[3]
Through above process, C2 2 ions generate electrons to the cages
and release 2C or 2CO into the atmosphere.19
Conclusions
Polycrystalline C12A7 electride was successfully fabricated via
the SPS process. The optical absorption bands at 0.4 eV and 2.7 eV and
electric properties such as electric resistivity and electron concentration conrmed that C12A7:O2 was successfully converted to C12A7
electride. The C12A7 electride synthesized via the one-step SPS process is attributable to the carbon-related anion, C2 2 , generated by
spark plasma induced by the charging-discharging process. The C2 2
ion serves as the template anion, instead of the O2 anions, to stabilize the C12A7 phase and then is removed from the cage, remaining
electrons in the cages of C12A7 during the re-crystallization process.
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