scholarly journals Molar Volume Mismatch: A Malefactor for Irregular Metallic Electrodeposition in Solid Electrolytes

Author(s):  
Aashutosh Mistry ◽  
Parth Mukherjee

Regularizing metallic electrodeposition has been a long-standing challenge in energy storage. Leveraging mechanical stresses, solid ion conductors have been proposed to stabilize the evolving interface. Paradoxically softer electrodepositing metals are often found to form penetration fronts under the hypothesized stable conditions. We find that mechanical contributions to energy of the interacting species (i.e., metal and cation) relate to respective molar volumes. The stresses at the electrodepositing interface are correlated, and consequently, localized deposition is energetically favored for larger cationic molar volumes. Electrolyte stresses cause a stress-driven ionic flux away from compressed locations, which proves to be a stabilizing influence. Stability is found to be nonlinearly related to electrolyte stiffness. Material complexities such as interphases, interlayer, and grain boundaries are also examined to proffer guidelines for a stabilized growth.

Author(s):  
Aashutosh Mistry ◽  
Parth Mukherjee

Regularizing metallic electrodeposition has been a long-standing challenge in energy storage. Leveraging mechanical stresses, solid ion conductors have been proposed to stabilize the evolving interface. Paradoxically softer electrodepositing metals are often found to form penetration fronts under the hypothesized stable conditions. We find that mechanical contributions to energy of the interacting species (i.e., metal and cation) relate to respective molar volumes. The stresses at the electrodepositing interface are correlated, and consequently, localized deposition is energetically favored for larger cationic molar volumes. Electrolyte stresses cause a stress-driven ionic flux away from compressed locations, which proves to be a stabilizing influence. Stability is found to be nonlinearly related to electrolyte stiffness. Material complexities such as interphases, interlayer, and grain boundaries are also examined to proffer guidelines for a stabilized growth.


1988 ◽  
Vol 135 ◽  
Author(s):  
Werner Weppner

Solid State ion conductors are sucessfully employed in chemical sensors for gases such as oxygen for process control and environmental protection. The application requires elevated temperatures for sufficiently high ionic conductivity and is restricted to a few gases for which suitable solid electrolytes are available.


2021 ◽  
pp. 2130005
Author(s):  
Qing Huang ◽  
Gongxuan Chen ◽  
Ping Zheng ◽  
Wei Li ◽  
Tian Wu

The demand for electrical energy storage (EES) is ever increasing in order to develop better batteries. NASICON-structured Na ion conductor represents a class of solid electrolytes, which is of great interest due to its superior ionic conductivity and stable structures. They are widely employed in all-solid-state ion batteries, all-solid-state air batteries, and hybrid batteries. In this review, their structure, composition, properties, and applications for next generation energy storage are reviewed.


2016 ◽  
Vol 4 (18) ◽  
pp. 6972-6979 ◽  
Author(s):  
Beatriz Lopez-Bermudez ◽  
Wolfgang G. Zeier ◽  
Shiliang Zhou ◽  
Anna J. Lehner ◽  
Jerry Hu ◽  
...  

The development of new frameworks for solid electrolytes exhibiting fast Li-ion diffusion is critical for enabling new energy storage technologies.


1983 ◽  
Vol 48 (8) ◽  
pp. 2327-2334
Author(s):  
Otakar Söhnel ◽  
Petr Novotný ◽  
Zdeněk Šolc

Two methods are given for assessment of density of binary aqueous solutions of electrolytes; one is based on partial molar volume of the dissolved electrolyte at infinite dilution, and the other is based on additivity of apparent molar volumes at a given concentration. The density estimates of aqueous solutions by means of the two methods are compared with experimental values for some electrolytes of the type 1-1 to 4 and 2-2. In all cases the estimates agree with experimental densities up to concentrations of the saturated solutions.


1985 ◽  
Vol 40 (5) ◽  
pp. 520-524 ◽  
Author(s):  
K. Igarashi ◽  
Y. Iwadate ◽  
H. Ohno ◽  
J. Mochinaga

Molar volumes of molten CaCl2-NaCl, LaCl3-NaCl, LaCl3-CaCl2 and the quasi-binary systems LaCl3-nNaCl · mCaCl2 (mole ratio n : m = 1:3.2, 1:1, and 2.6:1) have been measured by the dilatometric method, and expressed as functions of both temperature and mole fraction by means of least squares regression. The molar volumes of molten LaCl3-NaCl and LaCl3-CaCl2 showed positive and negative deviations, respectively, from additivity, while CaCl2-NaCl and the three quasi-binary systems satisfied approximately the additivity. The isotherm of molar volume for ternary LaCl3-CaCl2-NaCl system at 900 °C was represented according to the isotherms of three binary and three quasi-binary systems.


2020 ◽  
Vol 2020 ◽  
pp. 1-7
Author(s):  
Hongfang Hou ◽  
Wanjing Cui ◽  
Jiaojiao Chen ◽  
Lingzong Meng ◽  
Yafei Guo ◽  
...  

Densities of sodium arsenite (NaAsO2) aqueous solution with the molality varied from 0.19570 to 1.94236 mol·kg−1 at temperature intervals of 5 K from 283.15 to 363.15 K and 101 ± 5 kPa were measured by a precise Anton Paar Digital vibrating-tube densimeter. Apparent molar volumes (VΦ) and thermal expansion coefficient (α) were obtained on the basis of experimental data. The 3D diagram of apparent molar volume against temperature and molality and the diagram of thermal expansion coefficient against molality were generated. According to the Pitzer ion-interaction equation of the apparent molar volume model, the Pitzer single-salt parameters (βM,X0υ, βM,X1υ, βM,X2υ, and CM,Xυ, MX = NaAsO2) and their temperature-dependent correlation F(i, p, T) = a1 + a2ln (T/298.15) + a3(T − 298.15) + a4/(620 − T) + a5/(T − 227) (where T is temperature in Kelvin and ai are the correlation coefficients) for NaAsO2 were obtained for the first time. The predictive apparent molar volumes agree well with the experimental values, and those results indicated that the single-salt parameters and the temperature-dependent formula are reliable.


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