Understanding metal propagation in solid electrolytes due to mixed ionic-electronic conduction

In this paper, a method of electronic conductivity measurement is presented. It combines two well known methods of electrochemistry: cyclic voltammetry and chronoamperometry. This DC technique uses the Hebb–Wagner approach to block ionic conduction (when steady state conditions are reached) and allows electronic conduction of solid electrolytes to be determined. In order to get short diffusion times, a micro contact is used as an ion blocking electrode. However, as the electronic conduction in electrolytes is and should be very low, the current is also very low, typically some tens of nanoamps. Thus, the heating system inevitably generates noise problems that are solved using a median filter. As opposed to other related work, our system allows the determination of the conductivities without any preliminary smoothing or fitting of the curves (since the noise is strongly reduced). Some results with oxygen ion conductors are also given.

Download Full-text

Understanding Metal Propagation in Solid Electrolytes Due to Mixed Ionic–Electronic Conduction

SSRN Electronic Journal ◽

10.2139/ssrn.3834690 ◽

2021 ◽

Author(s):

Qingsong Tu ◽

Tan Shi ◽

Srinath Chakravarthy ◽

Gerbrand Ceder

Keyword(s):

Solid Electrolytes ◽

Electronic Conduction

Download Full-text

Electronic conduction and stability of solid electrolytes based on lanthanum gallates

Solid State Ionics ◽

10.1016/s0167-2738(02)00502-7 ◽

2002 ◽

Vol 154-155 ◽

pp. 597-604 ◽

Cited By ~ 4

Author(s):

J Weitkamp

Keyword(s):

Solid Electrolytes ◽

Electronic Conduction

Download Full-text

Electronic Conduction in Oxides

10.1007/978-3-662-02668-7 ◽

1991 ◽

Cited By ~ 113

Author(s):

Nobuo Tsuda ◽

Keiichiro Nasu ◽

Akira Yanase ◽

Kiiti Siratori

Keyword(s):

Electronic Conduction

Download Full-text

Development of Solid Electrolytes for All-Solid-State Batteries

NIPPON GOMU KYOKAISHI ◽

10.2324/gomu.92.430 ◽

2019 ◽

Vol 92 (11) ◽

pp. 430-434

Author(s):

Akitoshi HAYASHI ◽

Atsushi SAKUDA ◽

Masahiro TATSUMISAGO

Keyword(s):

Solid State ◽

Solid Electrolytes ◽

Solid State Batteries ◽

All Solid State Batteries

Download Full-text

How Certain Are the Reported Ionic Conductivities of Thiophosphate-Based Solid Electrolytes? an Interlaboratory Study

10.26434/chemrxiv.11316497.v2 ◽

2020 ◽

Author(s):

Saneyuki Ohno ◽

Tim Bernges ◽

Johannes Buchheim ◽

Marc Duchardt ◽

Anna-Katharina Hatz ◽

...

Keyword(s):

Standard Deviation ◽

Ionic Conductivity ◽

Relative Standard Deviation ◽

Solid Electrolytes ◽

Ionic Conductivities ◽

Ionic Conductors ◽

Energy Storage Devices ◽

Activation Barriers ◽

Storage Devices ◽

Relative Standard

<p>Owing to highly conductive solid ionic conductors, all-solid-state batteries attract significant attention as promising next-generation energy storage devices. A lot of research is invested in the search and optimization of solid electrolytes with higher ionic conductivity. However, a systematic study of an <i>interlaboratory reproducibility</i> of measured ionic conductivities and activation energies is missing, making the comparison of absolute values in literature challenging. In this study, we perform an uncertainty evaluation via a Round Robin approach using different Li-argyrodites exhibiting orders of magnitude different ionic conductivities as reference materials. Identical samples are distributed to different research laboratories and the conductivities and activation barriers are measured by impedance spectroscopy. The results show large ranges of up to 4.5 mScm<sup>-1</sup> in the measured total ionic conductivity (1.3 – 5.8 mScm<sup>-1</sup> for the highest conducting sample, relative standard deviation 35 – 50% across all samples) and up to 128 meV for the activation barriers (198 – 326 meV, relative standard deviation 5 – 15%, across all samples), presenting the necessity of a more rigorous methodology including further collaborations within the community and multiplicate measurements.</p>

Download Full-text

A New Phase of the Na+ Ion Conductor Na3PS4

10.26434/chemrxiv.8003717.v1 ◽

2019 ◽

Author(s):

Theodosios Famprikis ◽

James Dawson ◽

François Fauth ◽

Emmanuelle Suard ◽

Benoit Fleutot ◽

...

Keyword(s):

Solid Electrolytes ◽

Density Functional ◽

Density Functional Theory Calculations ◽

Orthorhombic Crystal ◽

Orthorhombic Crystal Structure ◽

Ion Conductor ◽

Solid State Batteries ◽

Density Analysis ◽

Two Phases ◽

Dynamics Simulations

<div> <p>Solid electrolytes are crucial for next‑generation solid‑state batteries and Na<sub>3</sub>PS<sub>4</sub> is one of the most promising Na<sup>+</sup> conductors for such applications. At present, two phases of Na<sub>3</sub>PS<sub>4</sub> have been identified and it had been thought to melt above 500 °C. In contrast, we show that it remains solid above this temperature and transforms into a third polymorph, γ, exhibiting superionic behavior. We propose an orthorhombic crystal structure for γ‑Na<sub>3</sub>PS<sub>4</sub> based on scattering density analysis of diffraction data and density functional theory calculations. We show that the Na<sup>+</sup> superionic behavior is associated with rotational motion of the thiophosphate polyanions pointing to a rotor phase, based on <i>ab initio</i> molecular dynamics simulations and supported by high‑temperature synchrotron and neutron diffraction, thermal analysis and impedance spectroscopy. These findings are of importance for the development of new polyanion‑based solid electrolytes.</p> </div>

Download Full-text

Operando Visualization of Morphological Dynamics in All-Solid-State Batteries

10.26434/chemrxiv.8299406 ◽

2019 ◽

Author(s):

Xiaohan Wu ◽

Juliette Billaud ◽

Iwan Jerjen ◽

Federica Marone ◽

Yuya Ishihara ◽

...

Keyword(s):

Solid State ◽

Solid Electrolytes ◽

Rational Design ◽

Morphological Evolution ◽

Active Material ◽

Composite Layer ◽

Transference Number ◽

Thermal Stabilities ◽

Solid State Batteries ◽

All Solid State Batteries

<div> <div> <div> <p>All-solid-state batteries are considered as attractive options for next-generation energy storage owing to the favourable properties (unit transference number and thermal stabilities) of solid electrolytes. However, there are also serious concerns about mechanical deformation of solid electrolytes leading to the degradation of the battery performance. Therefore, understanding the mechanism underlying the electro-mechanical properties in SSBs are essentially important. Here, we show three-dimensional and time-resolved measurements of an all-solid-state cell using synchrotron radiation x-ray tomographic microscopy. We could clearly observe the gradient of the electrochemical reaction and the morphological evolution in the composite layer. Volume expansion/compression of the active material (Sn) was strongly oriented along the thickness of the electrode. While this results in significant deformation (cracking) in the solid electrolyte region, we also find organized cracking patterns depending on the particle size and their arrangements. This study based on operando visualization therefore opens the door towards rational design of particles and electrode morphology for all-solid-state batteries. </p> </div> </div> </div>

Download Full-text