Zn
anodes of aqueous Zn metal batteries face challenges
from dendrite
growth and side reactions. Building Zn(002) texture mitigates the
issues but does not eradicate them. Zn(002) still faces severe challenges
from corrosive electrolytes and dendrite growth, especially after
hundreds of cycles. Therefore, it is necessary to have a passivation
layer covering Zn(002). Here, Zn(002) texture and surface coating
are achieved on Zn foils by an one-step annealing process, as demonstrated
by ZnS, ZnSe, ZnF2, Zn3(PO4)2 (ZPO), etc. Using ZPO as a model, the coupling between surface
coating and Zn(002) is illustrated in terms of dendrite-suppressing
ability and diffusion energy barrier of Zn2+. The modified
Zn foils (Zn(002)@ZPO) exhibit the excellent electrochemical performance,
far superior to Zn(002) or ZPO alone. In the full cells, the performance
is greatly improved even under harsh conditions, i.e., high areal
capacity and limited Zn resource. This work achieves crystal engineering
and surface coating on Zn anodes simultaneously and discloses the
in-depth insights about the synergy of crystal orientation and passivation
layers.
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Increasing the crystal resistivity is critically important for enhancing the signal-to-noise ratio and improving the sensing capability of high-temperature piezoelectric sensors based on langasite-type crystals. The resistivity of structural ordered langasite-type crystals is much higher compared to that of the disordered crystals. Here, we selected structural ordered Ca 3 TaGa 3 Si 2 O 14 (CTGS) and disordered La 3 Ga 5 SiO 14 (LGS) as representatives to investigate the microscopic conduction mechanism and further reveal the origin of the different resistivities of the ordered and disordered langasite-type crystals at elevated temperatures. By combining first-principles calculations and experimental investigations, we found that the different conductivity behaviors of the ordered and disordered crystals originate from different types of point defects formed in the crystal and their different contributions to the conductivity. For the disordered LGS crystal, the oxygen vacancies are apt to be formed at high temperatures, promoting the transition of valence electrons and yielding high conductivity. For the ordered CTGS crystal, the dominant Ta Ga antisite defects can introduce an electron−hole recombination center in the electronic band gap, significantly shortening the carrier lifetime and thus reducing the conductivity. This provides effective guidance to improve the resistivity performance of langasite-type crystals at high temperatures by optimizing the experimental conditions, such as oxygen atmosphere treatment, antisite defect modification, etc.
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