Experimental Assessment of the Practical Oxidative Stability of Lithium Thiophosphate Solid Electrolytes

Author(s):  
Georg Dewald ◽  
Saneyuki Ohno ◽  
Marvin Kraft ◽  
Raimund Koerver ◽  
Paul Till ◽  
...  

<p>All-solid-state batteries are often expected to replace conventional lithium-ion batteries in the future. However, the practical electrochemical and cycling stability of the best-conducting solid electrolytes, i.e. lithium thiophosphates, are still critical issues that prevent long-term stable high-energy cells. In this study, we use <i>stepwise</i><i>cyclic voltammetry </i>to obtain information on the practical oxidative stability limit of Li<sub>10</sub>GeP<sub>2</sub>S<sub>12</sub>, a Li<sub>2</sub>S‑P<sub>2</sub>S<sub>5</sub>glass, as well as the argyrodite Li<sub>6</sub>PS<sub>5</sub>Cl solid electrolytes. We employ indium metal and carbon black as the counter and working electrode, respectively, the latter to increase the interfacial contact area to the electrolyte as compared to the commonly used planar steel electrodes. Using a stepwise increase in the reversal potentials, the onset potential at 25 °C of oxidative decomposition at the electrode-electrolyte interface is identified. X‑ray photoelectron spectroscopy is used to investigate the oxidation of sulfur(-II) in the thiophosphate polyanions to sulfur(0) as the dominant redox process in all electrolytes tested. Our results suggest that after the formation of these decomposition products, significant redox behavior is observed. This explains previously reported redox activity of thiophosphate solid electrolytes, which contributes to the overall cell performance in solid-state batteries. The <i>stepwise cyclic voltammetry</i>approach presented here shows that the practical oxidative stability at 25 °C of thiophosphate solid electrolytes against carbon is kinetically higher than predicted by thermodynamic calculations. The method serves as an efficient guideline for the determination of practical, kinetic stability limits of solid electrolytes. </p>

2019 ◽  
Author(s):  
Georg Dewald ◽  
Saneyuki Ohno ◽  
Marvin Kraft ◽  
Raimund Koerver ◽  
Paul Till ◽  
...  

<p>All-solid-state batteries are often expected to replace conventional lithium-ion batteries in the future. However, the practical electrochemical and cycling stability of the best-conducting solid electrolytes, i.e. lithium thiophosphates, are still critical issues that prevent long-term stable high-energy cells. In this study, we use <i>stepwise</i><i>cyclic voltammetry </i>to obtain information on the practical oxidative stability limit of Li<sub>10</sub>GeP<sub>2</sub>S<sub>12</sub>, a Li<sub>2</sub>S‑P<sub>2</sub>S<sub>5</sub>glass, as well as the argyrodite Li<sub>6</sub>PS<sub>5</sub>Cl solid electrolytes. We employ indium metal and carbon black as the counter and working electrode, respectively, the latter to increase the interfacial contact area to the electrolyte as compared to the commonly used planar steel electrodes. Using a stepwise increase in the reversal potentials, the onset potential at 25 °C of oxidative decomposition at the electrode-electrolyte interface is identified. X‑ray photoelectron spectroscopy is used to investigate the oxidation of sulfur(-II) in the thiophosphate polyanions to sulfur(0) as the dominant redox process in all electrolytes tested. Our results suggest that after the formation of these decomposition products, significant redox behavior is observed. This explains previously reported redox activity of thiophosphate solid electrolytes, which contributes to the overall cell performance in solid-state batteries. The <i>stepwise cyclic voltammetry</i>approach presented here shows that the practical oxidative stability at 25 °C of thiophosphate solid electrolytes against carbon is kinetically higher than predicted by thermodynamic calculations. The method serves as an efficient guideline for the determination of practical, kinetic stability limits of solid electrolytes. </p>


2019 ◽  
Author(s):  
Georg Dewald ◽  
Saneyuki Ohno ◽  
Marvin Kraft ◽  
Raimund Koerver ◽  
Paul Till ◽  
...  

<p>All-solid-state batteries are often expected to replace conventional lithium-ion batteries in the future. However, the practical electrochemical and cycling stability of the best-conducting solid electrolytes, i.e. lithium thiophosphates, are still critical issues that prevent long-term stable high-energy cells. In this study, we use <i>stepwise</i><i>cyclic voltammetry </i>to obtain information on the practical oxidative stability limit of Li<sub>10</sub>GeP<sub>2</sub>S<sub>12</sub>, a Li<sub>2</sub>S‑P<sub>2</sub>S<sub>5</sub>glass, as well as the argyrodite Li<sub>6</sub>PS<sub>5</sub>Cl solid electrolytes. We employ indium metal and carbon black as the counter and working electrode, respectively, the latter to increase the interfacial contact area to the electrolyte as compared to the commonly used planar steel electrodes. Using a stepwise increase in the reversal potentials, the onset potential at 25 °C of oxidative decomposition at the electrode-electrolyte interface is identified. X‑ray photoelectron spectroscopy is used to investigate the oxidation of sulfur(-II) in the thiophosphate polyanions to sulfur(0) as the dominant redox process in all electrolytes tested. Our results suggest that after the formation of these decomposition products, significant redox behavior is observed. This explains previously reported redox activity of thiophosphate solid electrolytes, which contributes to the overall cell performance in solid-state batteries. The <i>stepwise cyclic voltammetry</i>approach presented here shows that the practical oxidative stability at 25 °C of thiophosphate solid electrolytes against carbon is kinetically higher than predicted by thermodynamic calculations. The method serves as an efficient guideline for the determination of practical, kinetic stability limits of solid electrolytes. </p>


Author(s):  
Maoyi Yi ◽  
Li Jie ◽  
Xin-ming Fan ◽  
Maohui Bai ◽  
Zhi Zhang ◽  
...  

PEO-based composite electrolytes are one of the most practical electrolytes in all-solid batteries (ASSBs). To achieve the perspective of ASSBs with high energy density, PEO based composite electrolytes should match...


Molecules ◽  
2020 ◽  
Vol 25 (9) ◽  
pp. 2121
Author(s):  
Vinsensia Ade Sugiawati ◽  
Florence Vacandio ◽  
Thierry Djenizian

All-solid-state batteries were fabricated by assembling a layer of self-organized TiO2 nanotubes grown on as anode, a thin-film of polymer as an electrolyte and separator, and a layer of composite LiFePO4 as a cathode. The synthesis of self-organized TiO2 NTs from Ti-6Al-4V alloy was carried out via one-step electrochemical anodization in a fluoride ethylene glycol containing electrolytes. The electrodeposition of the polymer electrolyte onto anatase TiO2 NTs was performed by cyclic voltammetry. The anodized Ti-6Al-4V alloys were characterized by scanning electron microscopy and X-ray diffraction. The electrochemical properties of the anodized Ti-6Al-4V alloys were investigated by cyclic voltammetry and chronopotentiometry techniques. The full-cell shows a high first-cycle Coulombic efficiency of 96.8% with a capacity retention of 97.4% after 50 cycles and delivers a stable discharge capacity of 63 μAh cm−2 μm−1 (119 mAh g−1) at a kinetic rate of C/10.


2020 ◽  
Vol 22 (17) ◽  
pp. 9204-9209 ◽  
Author(s):  
Yigang Yan ◽  
Wilke Dononelli ◽  
Mathias Jørgensen ◽  
Jakob B. Grinderslev ◽  
Young-Su Lee ◽  
...  

Light weight and cheap electrolytes with fast multi-valent ion conductivity can pave the way for future high-energy density solid-state batteries, beyond the lithium-ion battery.


Metals ◽  
2020 ◽  
Vol 10 (11) ◽  
pp. 1523
Author(s):  
Lilian Schwich ◽  
Michael Küpers ◽  
Martin Finsterbusch ◽  
Andrea Schreiber ◽  
Dina Fattakhova-Rohlfing ◽  
...  

In the coming years, the demand for safe electrical energy storage devices with high energy density will increase drastically due to the electrification of the transportation sector and the need for stationary storage for renewable energies. Advanced battery concepts like all-solid-state batteries (ASBs) are considered one of the most promising candidates for future energy storage technologies. They offer several advantages over conventional Lithium-Ion Batteries (LIBs), especially with regard to stability, safety, and energy density. Hardly any recycling studies have been conducted, yet, but such examinations will play an important role when considering raw materials supply, sustainability of battery systems, CO2 footprint, and general strive towards a circular economy. Although different methods for recycling LIBs are already available, the transferability to ASBs is not straightforward due to differences in used materials and fabrication technologies, even if the chemistry does not change (e.g., Li-intercalation cathodes). Challenges in terms of the ceramic nature of the cell components and thus the necessity for specific recycling strategies are investigated here for the first time. As a major result, a recycling route based on inert shredding, a subsequent thermal treatment, and a sorting step is suggested, and transferring the extracted black mass to a dedicated hydrometallurgical recycling process is proposed. The hydrometallurgical approach is split into two scenarios differing in terms of solubility of the ASB-battery components. Hence, developing a full recycling concept is reached by this study, which will be experimentally examined in future research.


2021 ◽  
Vol 2 (1) ◽  
Author(s):  
Atsutaka Kato ◽  
Mari Yamamoto ◽  
Futoshi Utsuno ◽  
Hiroyuki Higuchi ◽  
Masanari Takahashi

AbstractDue to their high conductivity and interface formability, sulfide electrolytes are attractive for use in high energy density all-solid-state batteries. However, electrode volume changes during charge-discharge cycling typically cause mechanical contact losses at the electrode/electrolyte interface, which leads to capacity fading. Here, to suppress this contact loss, isolated PS43- anions are reacted with iodine to prepare a sulfide polymer electrolyte that forms a sticky gel during dispersion in anisole and drying of the resulting supernatant. This polymer, featuring flexible (–P–S–S–)n chains and enhanced solubility in anisole, is applied as a lithium-ion-conductive binder in sheet-type all-solid-state batteries, creating cells with low resistance and high capacity retention.


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