scholarly journals Lithium-based vertically aligned nanocomposites for three-dimensional solid-state batteries

MRS Bulletin ◽  
2021 ◽  
Vol 46 (2) ◽  
pp. 152-158 ◽  
Author(s):  
Daniel M. Cunha ◽  
Mark Huijben

AbstractPlanar two-dimensional (2D) solid-state lithium-ion batteries exhibit an undesirable energy versus power balance, which can be dramatically improved by the application of three-dimensional (3D) geometries. Current ceramics-based nanocomposites exhibit limited control of the distribution and orientation of the nanoparticles within the matrix material. However, the tailoring of functionalities by the strong coupling between the two phases and their interfaces, present in epitaxial 3D vertically aligned nanocomposites (VANs), show promising advantages over the conventional 2D planar multilayers. Although a range of epitaxial VANs have been studied in the last decade, lithium-based VANs toward battery applications have remained mostly unexplored. Interestingly, two recent studies by Qi et al. and Cunha et al. demonstrate the unique potential of lithium-based VANs toward the realization of 3D solid-state batteries with enhanced energy storage performance. In this article, we will discuss these promising results as an enhanced current collector within the cathode or as an integrated solid-state cathode-electrolyte composite. Furthermore, we will describe different design configurations that can be applied to realize self-assembled VAN-based complete 3D battery devices.

Batteries ◽  
2021 ◽  
Vol 7 (4) ◽  
pp. 65
Author(s):  
Sergei Kurbatov ◽  
Alexander Mironenko ◽  
Victor Naumov ◽  
Alexander Skundin ◽  
Alexander Rudy

Along with the soaring demands for all-solid-state thin-film lithium-ion batteries, the problem of their energy density rise becomes very acute. The solution to this problem can be found in development of 3D batteries. The present work deals with the development of a technology for a 3D solid-state lithium-ion battery (3D SSLIB) manufacturing by plasma-chemical etching and magnetron sputtering technique. The results on testing of experimental samples of 3D SSLIB are presented. It was found that submicron-scale steps appearing on the surface of a 3D structure formed on Si substrate by the Bosch process radically change the crystal structure of the upper functional layers. Such changes can lead to disruption of the layers’ continuity, especially that of the down conductors. It is shown that surface polishing by liquid etching of the SiO2 layer and silicon reoxidation leads to surface smoothing, the replacement of the dendrite structure of functional layers by a block structure, and a significant improvement in the capacitive characteristics of the battery.


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>


Ceramics ◽  
2021 ◽  
Vol 4 (3) ◽  
pp. 421-436
Author(s):  
Aamir Iqbal Waidha ◽  
Vanita Vanita ◽  
Oliver Clemens

Composite electrolytes containing lithium ion conducting polymer matrix and ceramic filler are promising solid-state electrolytes for all solid-state lithium ion batteries due to their wide electrochemical stability window, high lithium ion conductivity and low electrode/electrolyte interfacial resistance. In this study, we report on the polymer infiltration of porous thin films of aluminum-doped cubic garnet fabricated via a combination of nebulized spray pyrolysis and spin coating with subsequent post annealing at 1173 K. This method offers a simple and easy route for the fabrication of a three-dimensional porous garnet network with a thickness in the range of 50 to 100 µm, which could be used as the ceramic backbone providing a continuous pathway for lithium ion transport in composite electrolytes. The porous microstructure of the fabricated thin films is confirmed via scanning electron microscopy. Ionic conductivity of the pristine films is determined via electrochemical impedance spectroscopy. We show that annealing times have a significant impact on the ionic conductivity of the films. The subsequent polymer infiltration of the porous garnet films shows a maximum ionic conductivity of 5.3 × 10−7 S cm−1 at 298 K, which is six orders of magnitude higher than the pristine porous garnet film.


2020 ◽  
Vol 11 (1) ◽  
Author(s):  
Shuaifeng Lou ◽  
Qianwen Liu ◽  
Fang Zhang ◽  
Qingsong Liu ◽  
Zhenjiang Yu ◽  
...  

Abstract Interfacial issues commonly exist in solid-state batteries, and the microstructural complexity combines with the chemical heterogeneity to govern the local interfacial chemistry. The conventional wisdom suggests that “point-to-point” ion diffusion at the interface determines the ion transport kinetics. Here, we show that solid-solid ion transport kinetics are not only impacted by the physical interfacial contact but are also closely associated with the interior local environments within polycrystalline particles. In spite of the initial discrete interfacial contact, solid-state batteries may still display homogeneous lithium-ion transportation owing to the chemical potential force to achieve an ionic-electronic equilibrium. Nevertheless, once the interior local environment within secondary particle is disrupted upon cycling, it triggers charge distribution from homogeneity to heterogeneity and leads to fast capacity fading. Our work highlights the importance of interior local environment within polycrystalline particles for electrochemical reactions in solid-state batteries and provides crucial insights into underlying mechanism in interfacial transport.


2013 ◽  
Vol 753 ◽  
pp. 307-310
Author(s):  
Kyung Jun Ko ◽  
Jong Tae Park ◽  
Chan Hee Han

During abnormal grain growth, a few Goss grains grow exclusively fast and consume the matrix grains. The Goss abnormally-growing grain (AGG) has peculiar features which are irregular grain boundaries and very high frequency of peninsular grains nearby the growth front of AGG and island grains trapped inside AGG. These features might provide a clue for clarifying the mechanism of Goss AGG. The experimentally-observed microstructural feature and grain boundary characterization of Goss were approached by the solid-state wetting mechanism. In this study, observing the three-dimensional wetting morphology in serial section images of Goss AGG by EBSD, we report some direct microstrucrual evidence supporting solid-state wetting mechanism for Goss AGG. The solid-state wetting mechanism for the evolution of the Goss AGG in Fe-3%Si steel explains the microstructural features evolved during secondary recrystallization, which cannot be approached by the conventional theories based on the grain boundary mobility.


2018 ◽  
Vol 4 (10) ◽  
pp. eaat7629 ◽  
Author(s):  
Hiroaki Gotoh ◽  
Chang Liu ◽  
Abu Bin Imran ◽  
Mitsuo Hara ◽  
Takahiro Seki ◽  
...  

An elastomer is a three-dimensional network with a cross-linked polymer chain that undergoes large deformation with a small external force and returns to its original state when the external force is removed. Because of this hyperelasticity, elastomers are regarded as one of the best candidates for the matrix material of soft robots. However, the comprehensive performance required of matrix materials is a special challenge because improvement of some matrix properties often causes the deterioration of others. For example, an improvement in toughness can be realized by adding a large amount of filler to an elastomer, but to the impairment of optical transparency. Therefore, to produce an elastomer exhibiting optimum properties suitable for the desired purpose, very elaborate, complicated materials are often devised. Here, we have succeeded in creating an optically transparent, easily fabricated elastomer with good extensibility and high toughness by using a polyrotaxane (PR) composed of cyclic molecules and a linear polymer as a cross-linking agent. In general, elastomers having conventional cross-linked structures are susceptible to breakage as a result of loss of extensibility at high cross-linking density. We found that the toughness of the transparent elastomer prepared using the PR cross-linking agent is enhanced along with its Young’s modulus as cross-linking density is increased.


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