Halide perovskites
are anticipated to impact next generation high
performance solar cells because of their extraordinary charge transport
and optoelectronic properties. However, their thermal transport behavior
has received limited attention. In this work, we studied the thermal
transport and thermoelectric properties of the CsSnBr3‑xI
x
perovskites. We find a strong correlation
between lattice dynamics and an ultralow thermal conductivity for
series CsSnBr3‑xI
x
reaching
0.32 Wm–1K–1 at 550 K. The CsSnBr3‑xI
x
also possess a decent
Seebeck coefficient and controllable electrical transport properties.
The crystallography data and theoretical calculations suggest the
Cs atom deviates from its ideal cuboctahedral geometry imposed by
the perovskite cage and behaves as a heavy atom rattling oscillator.
This off-center tendency of Cs, together with the distortion of SnX6 (X = Br or I) octahedra, produces a highly dynamic and disordered
structure in CsSnBr3‑xI
x
, which gives rise to a very low Debye temperature and phonon velocity.
Moreover, the low temperature heat capacity data suggests strong coupling
between the low frequency optical phonons and heat carrying acoustical
phonons. This induces strong phonon resonance scattering that induces
the ultralow lattice thermal conductivity of CsSnBr3‑xI
x
.
The recent advances and new insights resulting thereof in applying defect engineering to improving the thermoelectric performance and mechanical properties of inorganic materials are reviewed.
We investigate the structural and physical properties of the AgSnmSbSem+2 system with m=1-20 (i.e. SnSe matrix and ~5-50 % AgSbSe2) from length scales ranging from atomic, nano and macro. We find the 50:50 composition, with m=1 (i.e. AgSnSbSe3), forms a stable cation disordered cubic rock-salt p-type semiconductor with a special multipeak electronic valence band structure. AgSnSbSe3 has an intrinsically low lattice thermal conductivity of ~0.47 Wm -1 K -1 at 673 K owing to the synergy of cation disorder, phonon anharmonicity, low phonon velocity, and low-frequency optical modes. Furthermore, Te alloying on the Se sites creates a quinary high entropy NaCl-type solid solution AgSnSbSe3-xTex with randomly disordered cations and anions. The extra point defects and lattice dislocations lead to glass-like lattice thermal conductivities of ~0.32 Wm -1 K -1 at 723 K and higher hole carrier concentration than AgSnSbSe3. Concurrently, the Te alloying promotes greater convergence of the multiple valence band maxima in AgSnSbSe1.5Te1.5, the composition with the highest configurational entropy. Facilitated by these favorable modifications, we achieve a high average power factor of ~9.54 μWcm -1 K -2 (400-773 K), a peak thermoelectric figure of merit ZT of 1.14 at 723 K and a high average ZT of ~1.0 over a wide temperature range of 400-773 K in AgSnSbSe1.5Te1.5.
Defect
chemistry is critical to designing high performance thermoelectric
materials. In SnTe, the naturally large density of cation vacancies
results in excessive hole doping and frustrates the ability to control
the thermoelectric properties. Yet, recent work also associates the
vacancies with suppressed sound velocities and low lattice thermal
conductivity, underscoring the need to understand the interplay between
alloying, vacancies, and the transport properties of SnTe. Here, we
report solid solutions of SnTe with NaSbTe2 and NaBiTe2 (NaSn
m
SbTe
m+2 and NaSn
m
BiTe
m+2, respectively) and focus on the impact of the ternary alloys
on the cation vacancies and thermoelectric properties. We find introduction
of NaSbTe2, but not NaBiTe2, into SnTe nearly
doubles the natural concentration of Sn vacancies. Furthermore, DFT
calculations suggest that both NaSbTe2 and NaBiTe2 facilitate valence band convergence and simultaneously narrow the
band gap. These effects improve the power factors but also make the
alloys more prone to detrimental bipolar diffusion. Indeed, the performance
of NaSn
m
BiTe
m+2 is limited by strong bipolar transport and only exhibits modest
maximum ZTs ≈ 0.85 at 900 K. In NaSn
m
SbTe
m+2 however, the doubled vacancy
concentration raises the charge carrier density and suppresses bipolar
diffusion, resulting in superior power factors than those of the Bi-containing
analogues. Lastly, NaSbTe2 incorporation lowers the sound
velocity of SnTe to give glasslike lattice thermal conductivities.
Facilitated by the favorable impacts of band convergence, vacancy-augmented
hole concentration, and lattice softening, NaSn
m
SbTe
m+2 reaches high ZT ≈
1.2 at 800–900 K and a competitive average ZTavg of 0.7 over 300–873 K. The difference in ZT between two chemically
similar compounds underscores the importance of intrinsic defects
in engineering high-performance thermoelectrics.
Energy filtering has been a long-sought strategy to enhance a thermoelectric material’s Figure of Merit zT through improving its power factor. Here we show a composite of multi-layer graphene nanoplatelets...
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