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A valence balanced rule for discovery of 18-electron half-Heuslers with defects

Journal Article · · Energy & Environmental Science
DOI:https://doi.org/10.1039/c8ee00306h· OSTI ID:1775288
 [1];  [2];  [3];  [4];  [3];  [2];  [3];  [3]
  1. Northwestern Univ., Evanston, IL (United States); Northwestern University
  2. Zhejiang Univ., Hangzhou (China)
  3. Northwestern Univ., Evanston, IL (United States)
  4. Northwestern Univ., Evanston, IL (United States); Koc Univ., Istanbul (Turkey)
+ Show Author Affiliations
Using first-principles DFT we systematically investigate the thermodynamic stability and off-stoichiometry in 108 nominal 19-electron half-Heusler (hH) compounds. We demonstrate unambiguously that considering a cation deficiency towards the off-stoichiometric valence balanced, VEC = 18 composition is necessary for explaining the stability of all previously reported nominal VEC = 19 compounds. This is understandable in terms of an energy benefit from valence balance considering the valence of each atom using Zintl chemistry that offsets the energy penalty of forming defects in nearly all cases. Thus, we propose a valence balanced rule to understand the ground state stability of half-Heuslers irrespective of stoichiometry and nominal electron count (8, 18 or 19). Using this generalized rule we (a) predict 16 previously unreported nominal 19-electron XYZ half-Heuslers and (b) rationalize the reports of giant off-stoichiometries in compounds such as Ti(1–x)NiSb which has been known for over 50 years. Of the 16 new compounds predicted here, Ti(1–x)PtSb was synthesized and the half-Heusler phase confirmed through X-ray studies. Here, the flexibility in stoichiometry of the half-Heusler systems to attain a stable valence balanced composition by accommodating large defect concentrations opens up multiple dimensions for discovery of multi-component defective half-Heuslers based on intrinsic and extrinsic defects which compensate for the nominally non-18-electron count of the structure.
Research Organization:
Northwestern Univ., Evanston, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0001299; SC0014520
OSTI ID:
1775288
Alternate ID(s):
OSTI ID: 1434107
OSTI ID: 1470453
Journal Information:
Energy & Environmental Science, Journal Name: Energy & Environmental Science Journal Issue: 6 Vol. 11; ISSN 1754-5692
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (11)

Design of High‐Performance Disordered Half‐Heusler Thermoelectric Materials Using 18‐Electron Rule journal August 2019
Manipulation of Ni Interstitials for Realizing Large Power Factor in TiNiSn‐Based Materials journal May 2019
Temperature Dependent n-Type Self Doping in Nominally 19-Electron Half-Heusler Thermoelectric Materials journal September 2018
Short-range order in defective half-Heusler thermoelectric crystals journal January 2019
Cost effective synthesis of p-type Zn-doped MgAgSb by planetary ball-milling with enhanced thermoelectric properties journal January 2018
Low thermal conductivity and promising thermoelectric performance in A x CoSb (A = V, Nb or Ta) half-Heuslers with inherent vacancies journal January 2019
Thermoelectric transport trends in group 4 half-Heusler alloys journal October 2019
Advances in thermoelectrics journal April 2018
Half Heusler compounds: promising materials for mid-to-high temperature thermoelectric conversion journal September 2019
Band Structures and Transport Properties of High-Performance Half-Heusler Thermoelectric Materials by First Principles journal May 2018
Half-Heusler Compounds: Promising Materials For Mid-To-High Temperature Thermoelectric Conversion text January 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY