bluuebunny/crossref_metadata_2025_split huggingface dataset:
Impacts of Microstructures on the Ionic Diffusivity of Solid Electrolytes: Mesoscale Modeling Approach
Authors: Heo Tae Wook , Grieder Andrew , Wan Liwen , Adelstein Nicole , Wood Brandon C. 
Published: February 2020

Development of viable solid electrolytes is key for commercial adoption of all-solid-state batteries that can solve critical issues associated with electrochemical stability and safety for wider scale applications of the current battery technology. Recent years have seen the emergence of several solid electrolyte candidates with high ionic conductivity; however, practical processing and synthesis routes often generate internal interfaces that can disrupt conduction channels in these materials. In this talk, we will present our development of an efficient mesoscopic computational method for predicting the effective diffusivity through a solid electrolyte with a complex polycrystalline or polygranular microstructure. Our method considers simultaneous interfacial and bulk conduction modes, going far beyond simplified circuit descriptions to account for factors such as orientational variation of crystallite domains and the effects of interfacial strain. Using the Li7La3Zr2O12 (LLZO) solid electrolyte as a model system, we show how our simulation framework can be parameterized using a multiscale approach that derives digital microstructures from phase-field simulations and diffusivity tensors of reference phases and boundaries from molecular dynamics simulations. Simulations of the effective diffusivity of polycrystalline LLZO are applied to investigate the relationship between relevant microstructural features and ionic conductivity, with a focus on topological features of grains and grain networks. Using several instances, we will discuss a high sensitivity to these features, highlighting the need to account for microstructure when assessing mass transport in LLZO and related solid electrolyte materials.
This work of was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.
Experimental and Theoretical Analysis of Li-Stuffed Garnet-Type Electrolytes
Authors: Palakkathodi Kammampata Sanoop , Yamada Hirotoshi , Ito Tomoko , Paul Reginald , Thangadurai Venkataraman 
Published: February 2020

Rechargeable lithium-ion batteries (LIBs) are one of the dominant technologies for electrochemical energy storage. They are widely used in portable electronics, electrical vehicles, and large-scale energy storage systems. Current LIBs use organic polymer based electrolytes and they have several problems such as dendrite formation, flammability and leakage.1 Therefore, there is much attention on developing a solid-state Li-ion electrolyte that is thermally and chemically stable. Among the various inorganic solid Li-ion conducting electrolytes, garnet structured compounds have shown great promise as potential electrolytes for all-solid-state lithium batteries due to their high ionic conductivities (10-4 S/cm), compatibility with Li metal anode, and wide electrochemical window (~ 6V vs Li/Li+).2 The present study reports a comparison of the experimental and theoretical data of garnet type Li-ion solid electrolytes. The solid electrolytes, Li6.5La2.9A0.1Ta0.6Zr1.4O12 (A = Ca, Sr, Ba) were prepared by conventional solid state sintering and spark plasma sintering method. The formation of the ‘‘single-phase’’ garnet-type structure was analysed by powder X-ray diffraction (PXRD). Li-ion conductivity was determined using electrochemical impedance spectroscopy (EIS) and all the members have exhibited ionic conductivity in the order of 104 S/cm at 25 °C. Interfacial resistance of the garnet samples and Li metal was measured using EIS and the interfacial stability of the same was confirmed by DC galvanostatic cycling experiments. Li-ion conductivity and activation energy of the prepared compounds were also calculated using a statistical mechanical approach and the estimated values are in good agreement with the experimental values.
References
1. S. Chen, K. Wen, J. Fan, Y. Bando and D. Golberg, J. Mater. Chem. A, 2018, 6, 11631–11663.
2. R. Murugan, V. Thangadurai and W. Weppner, Angew. Chem. Int. Ed., 2007, 46, 7778–7781.
Li Garnet Dopant Stability Against Li Metal: A TOF-SIMS Study
Authors: Zhang Lei , Gong Yunhui , Hamann Tanner R. , Wachsman Eric D. 
Published: February 2020

Solid-state lithium batteries (SSLiBs) has been extensively studied in the past five years. The widely studied solid-state electrolytes (SSEs) includes LiSICON [1], NASICON-type Li conductors [2], perovskites [3] and garnets [4]. It is realized that garnet electrolyte is the most promising oxide electrolyte, due to its high Li-ion conductivity, stability with high voltage Li cathodes and Li anode. However, recently there has been reports [5, 6] on metal element reduction in certain garnet composition. Metal element reduction can lead to electronic conductivity, which is detrimental to cell performance. The reduction reaction is mostly likely to occur at grain boundaries. Since grain boundary is very thin and Li element is hard to detect, limited techniques can characterize the reduction reaction. Fudong and co-workers [5] applied neutron depth profiling technique to study Li content variation. Yisi and co-workers [6] conducted advanced XPS technique to study reduction on garnet grain surface.
TOF-SIMS is surface sensitive technique with nano scale resolution. Herein, we will present our TOF-SIMS study on garnet dopant stability against Li metal. It is found that Nb dopant is not stable to Li metal. Nb doped garnet changes color upon contacting Li metal. This color change progress through the whole ceramic sample. EIS results show that resistance continues increase while the reaction progress. TOF-SIMS results indicate Nb element segregates to grain boundary and presents a different coordination at grain boundary than in bulk garnet.
Reference:
[1] Xu, X. et al. Chem. Mater. 23, 3798-3804 (2011).
[2] Feng, J. K. et al. Mater. Technol. 28, 276-279 (2013).
[3] Ihlefeld, J. F. et al. Adv. Mater. 23, 5663-5667 (2011).
[4] Thangadurai, V. et al. Chem. Soc. Rev. 43, 4714-4727 (2014).
[5] Han, F. et al. Nature Energy 4, 187-196 (2019).
[6] Zhu, Y. et al. Adv. Energy Mater. 9, 1803440 (2019).

Figure 1
Tuning the Performance of Conversion Coatings with Various Additives
Authors: Kumar Kuldeep , Bezer Silvia 
Published: February 2020

Traditionally, conversion coatings based on metal phosphates and chromium based species were extensively used in industrial coating processes to provide anti-corrosion properties to metal substrates (e.g. AA6111, steel). Due to increasing environmental constraints, new solutions based on titanium and zirconium species are currently being commercialized around the world.
The growth of conversion coatings on metal alloys exhibits oxidation reactions at the alloy surface (e.g. M → Mn+ + ne‒). These electrons are consumed in the reduction of solution species (e.g. H+ + e‒ → ½ H2) leading to gaseous evolution and deposition of solid species at the alloy surface. At this step, a higher pH in the vicinity of alloy surface causes decomposition of the passivating ion, which in turn leads to initiation and growth of the coating layer. Interfacial properties, such as adhesion and anti-corrosion behavior, are dependent on the chemical bonding, thermodynamic stability, uniformity, and continuity of this coating layer along the metal surface. This presentation will show our recent studies on the effect of various additives in the conversion coating solutions using electrochemical tools, thermodynamic stability measurements, and electron microscopic analysis.
(Invited) Na-Ion Batteries: Challenges and Opportunities
Authors: Rojo Teofilo 
Published: February 2020

With the ever-increasing demands of modern societies, energy generation, storage, and distribution are becoming increasingly important research fields. Currently, one of the most promising areas of research and development is Sodium ion Battery (SIB) technology, which has a range of potential applications but remains particularly suited for use in stationary systems. [1-5].
Here we will discuss SIB systems in terms of what may be considered its three most significant components: anodes, electrolytes, and cathodes. SIB anodes are mainly based on hard carbon materials, due to their attractive combination of low cost and high energy density. However, there has also been interest in other systems, such as intermetallic alloying materials and metal oxides, as well as exploiting specific electrolyte co-solvation effects so as to enable the use of graphite. In general, the SIB research community uses organic electrolytes which are analogous to already existing Lithium ion batteries (LIB). However, recently there has been growing interest in developing new electrolytes which are specifically tailored for use in SIBs, such as optimized liquid and solid electrolytes. At the present time, cathodes are one of the most explored SIB components - with a plethora of options to choose from, including Prussian blue and organic materials. However, the most promising are polyanionic and layered materials, with their good combinations of electrochemical performance, low cost, stability and available constituents. Although interest in SIB technology has only relatively new, when compared to LIBs, it has been already developed at the prototyping level.
A general overview of the most interesting electrode and electrolyte materials for Na-ion batteries paying special attention to those related to the current prototypes will be presented. By examining this topic in detail, it will be shown that there exists a strong drive to exploit this technology and that there are a wide range of opportunities to develop new and improved SIB technologies.
References:
[1] V. Palomares, T.Rojo et al., Energy Environ. Sci., 2012, 5, 5884.
[2] M. Á., Muñoz-Márquez, T.Rojo et al., Adv. Energy Mater., 2017, 1700463.
[3] N. Ortiz-Vitoriano, T.Rojo et al., Energy Environ. Sci., 2017, 10, 1051.
[4] D. Saurel, T.Rojo et al., Adv. Energy Mater., (2018,1703268).
[5] T.Rojo et al., Adv. Energy Mater., (2018,8,1800880).
(IBA Early Career Award) Challenges and Opportunities for Interphased Ca Metal Anode Batteries
Authors: Ponrouch Alexandre 
Published: February 2020

Various metals have been used as battery anodes in electrochemical cells ever since the birth of the batteries with Volta’s pile and in the first commercialized primary (Zn/MnO2, Leclanché 1866) and secondary (Pb/acid, Planté 1859) batteries. Li-MoS2 cells, employing Li metal anodes, with specific energies two to three times higher than both Ni/Cd and Pb/acid cells, were withdrawn from the market due to safety issues related to dendrites growth. Instead, electrodeposition of Mg and Ca appears to be less prone to dendrite formation.[1,2] Pioneering work by Aurbach et al. in the early 1990’s showed a surface-film controlled electrochemical behavior of Ca and Mg metal anodes in electrolytes with conventional organic solvents.[3,4] The lack of metal plating was attributed to the poor divalent cation migration through the passivation layer. Nevertheless, recent demonstration of Ca and Mg plating and stripping in the presence of a passivation layer or an artificial interphase [2,5,6] has paved the way for assessment of new electrolyte formulations with high resilience towards oxidation. However, several challenges remain to be tackled for the development of Ca based batteries.[7] Among these, the need for reliable electrochemical test protocols, mass transport limitations and high desolvation energies (due to strong cation-solvent and cation–anion interactions) are implied.[8] Here, the reliability of electrochemical set-ups involving multivalent chemistries is discussed, and a systematic investigation on the impact of the electrolyte formulation on the cation solvation structure and transport is presented. Finally, a systematic characterization of the SEI formed on the Ca metal anode in various electrolyte formulations using complementary techniques allowed for the identification of the most suitable SEI compounds in terms of divalent cation mobility.

Reference
s
:

[1] M. Matsui, J. Power Sources, 196 (2011) 7048.
[2]. A. Ponrouch, C. Frontera, F. Bardé, M.R. Palacín, Nat. Mater., 15 (2016) 169.
[3] D. Aurbach, R. Skaletsky, Y. Gofer, J. Electrochem. Soc.138 (1991) 3536.
[4] Z. Lu, A. Schechter, M. Moshkovich, D. Aurbach, J. Electroanal. Chem. 466 (1999) 203.
[5] D. Wang, X. Gao, Y. Chen, L. Jin, C. Kuss, P. G. Bruce, Nat. Mater. 17 (2018) 16.
[6] S.-B. Son, T. Gao, S. P. Harvey, K. X. Steirer, A. Stokes, A. Norman, C. Wang, A. Cresce, K. Xu, C. Ban, Nat. Chem. 10 (2018) 532.
[7] A. Ponrouch, M.R. Palacín, Current Opinion in Electrochemistry 2018,doi.org/10.1016/j.coelec.2018.02.001.
[8] D. S. Tchitchekova, D. Monti, P. Johansson, F. Bardé, A. Randon-Vitanova, M. R. Palacı́n, A. Ponrouch, J. Electrochem. Soc., 164 (2017) A1384.

Figure 1: Scheme of a Ca metal anode-based battery
with the main problems/ requirements outlined.[7]

Figure 1
Semi-Solid Li-S Battery Electrolytes
Authors: Navarro-Suárez Adriana , Johansson Patrik 
Published: February 2020

The urge for electrochemical energy storage devices with high gravimetric and volumetric energy density is imminent and the lithium−sulfur (Li-S) battery has been poised as a major next generation battery concept candidate. While it has a (very) high theoretical energy density, low cost and non-toxicity of starting materials,[1] its practical application has been hampered by several obstacles; the active material(s) elemental sulfur (S8) and lithium sulfide (Li2S) are both electronic insulators, polysulfides dissolve into the electrolyte and diffuse between the cathode and anode –generating an active material loss, there are dendrites formed at the lithium metal anode, etc.[2,3]
To address (some of) these problems, the solubility properties of the electrolyte are of utmost importance [4] and here we use semi-solid electrolytes to try to hinder the dissolution of sulfur and possibly also mitigate the creation of lithium dendrites. These systems are composed of a deep eutectic electrolyte (DEE), LiTFSI and/or LiFSI based, confined within a porous silica framework – creating an eutectogel.[5] We here report on the initially assessed physico-chemical properties, basic electrochemical properties such as ion conductivity (Figure 1), before progressing to feasibility tests in Li-S battery cells.
This work was funded by “Batterifondsprogrammet” of the Swedish Energy Agency.
Figure 1. Arrhenius plot of a DEE and a DEE confined in a SiO2 framework.

Reference
s

[1] Q. Pang, X. Liang, C.Y. Kwok, L.F. Nazar, Nat. Energy 1 (2016) 16132.
[2] X. Judez, H. Zhang, C. Li, G.G. Eshetu, J.A. González-Marcos, M. Armand, L.M. Rodriguez-Martinez, J. Electrochem. Soc. 165 (2018) A6008–A6016.
[3] J. Scheers, S. Fantini, P. Johansson, J. Power Sources 255 (2014) 204–218.
[4] S. Drvarič Talian, S. Jeschke, A. Vizintin, K. Pirnat, I. Arčon, G. Aquilanti, P. Johansson, R. Dominko, Chem. Mater. 29 (2017) 10037–10044.
[5] B. Joos, T. Vranken, W. Marchal, M. Safari, M.K. Van Bael, A.T. Hardy, Chem. Mater. 30 (2018) 655–662.

Figure 1
A Stable 3 V All-Solid-State Battery Based on a Closo-Borate Electrolyte
Authors: Duchêne Léo , Kühnel Ruben-Simon , Asakura Ryo , Payandeh Seyedhosein , Remhof Arndt , Battaglia Corsin 
Published: February 2020

Closo-borates represent a promising but yet under-explored alternative class of electrolytes for all-solid-state batteries. We recently reported ionic conductivities of 1 mS/cm and an electrochemical stability window of 3 V at room temperature for Na4(B12H12)(B10H10).[1] The mixed-anion configuration stabilizes the ion-conducting high-temperature phase at room temperature.
We further demonstrated stable cycling for a 3V class all-solid-state battery based on this electrolyte consisting of a sodium metal anode and a NaCrO2 cathode.[2] The cathode composite can be assembled by simple cold pressing, but cycling performance is enhanced through a preliminary solvent-based impregnation step of the cathode particles by a thin electrolyte coating. This coating guarantees intimate contact between cathode particles and electrolyte resulting in reversible and stable cycling with a capacity of 85 mAh/g at C/20 and 80 mAh/g at C/5 with more than 90% capacity retention after 20 cycles at C/20 and 85% after 250 cycles at C/5. We also investigated the effect of cycling outside the electrochemical stability window and observed that electrolyte decomposition leads to faster though not critical capacity fading.
We will further present routes to translate these results to lithium analogues and our efforts to establish low-cost synthesis routes for these non-toxic materials. Our results demonstrate that owing to their physical properties and processability, closo-borate-based electrolytes could play a significant role in the development of a competitive all-solid-state battery technology.
[1] L. Duchêne, R.-S. Kühnel, D. Rentsch, A. Remhof, H. Hagemann, C. Battaglia, Chem. Comm. 53, 4195 (2017)
[2] L. Duchêne, R.-S. Kühnel, E. Stilp, E. Cuervo Reyes, A. Remhof, H. Hagemann, C. Battaglia, Energy & Environmental Science 10, 2609 (2017)

Figure 1
Electrochemical Properties of Nano-Sized MoS2 Positive-Electrodes in Ester-Based Electrolyte Solutions for Magnesium Rechargeable Batteries
Authors: Mishima Kohei , Doi Takayuki , Inaba Minoru 
Published: February 2020

Magnesium rechargeable batteries (MRBs) have attracted attentions as next-generation secondary batteries. Mg metal is a promising negative-electrode material because it has a high volumetric capacity (3830 mAh cm-3) and a low standard potential (-2.37 V vs. NHE). In addition, MRBs ensure a higher safety compared to lithium metal rechargeable batteries, since Mg metal forms no dendrite. We previously reported that g-butyrolactone (GBL)-based electrolyte solutions allowed the electrochemical deposition/dissolution reactions of Mg and the insertion of Mg2+ into Chevrel phase Mo6S8 positive-electrodes. Mo6S8 is a prototypical active material that has a wide path for rapid diffusion of Mg2+. However, it works at extremely low potentials (1.1 V vs. Mg2+/Mg), and has a small theoretical capacity (129 mAh g-1). On the other hand, MoS2, a popular member of metal dichalcogenides, has a larger theoretical capacity (223.2 mAh g-1) at a higher working voltage around 1.8 V 1). In this work, we synthesized MoS2 nanoparticles with a short diffusion path of Mg2+, and investigated the charge and discharge properties of AZ31|MoS2 cells using 0.3 mol dm-3 Mg(CF3COO)2 in GBL as the electrolyte solution.
MoS2 nanoparticles were synthesized by a solvothermal method 2). Mo(CO)6 powder and sulfur powder were mixed into 120 ml 2-propanol as a solvent. The solutions were stirred under heating at 80oC for 10 h, and then the solution was cooled to room temperature naturally. The dark powders were anneled at 800oC for 2h under Ar atmosphere. The resultant powder was characterized by an X-ray diffraction and Raman spectroscopies. The morphology was observed with a scanning electron microscope. Electrochemical measurements were conducted at a constant current of ca. 5-7 mA cm-2 at 100oC using a three-electrode cell. The counter and reference electrode were AZ31 foil (Mg alloy). After the initial discharge and charge, the MoS2 electrode was analyzed by Raman spectroscopy.
The resultant MoS2 was impurity-free, and spherical in shape with a diameter of 80-100 nm. The lattice fringe of 0.623 nm corresponds to the spacing of the MoS2 (002) planes. The Raman bands at 378 cm-1 and 405 cm-1 were clearly observed, corresponding to in-plane vibrational E1
2g mode and out-of-plane vibrational A1g mode, respectively 3
). The initial discharge capacity of AZ31|MoS2 cell was ca. 180 mAh g-1. After the intial discharge, the Raman bands shifted to higher frequencies of 382 cm-1 and 407 cm-1, which is quite similar to those for the insertion of Li+ into MoS2
4). After initial charge, each Raman band returned to its original position. These results indicated that the insertion/extraction reactions of Mg2+ at the MoS2 occur in the GBL-based electrolyte solutions.

Reference
s
:

1) Liang, et al., Adv. Mater., 23, 640-643 (2011).
2) Tao, et al., CrystEngComm, 14, 3027-3032 (2012).
3) Lee, et al., ACN Nano, 4 (5), 2695-2700 (2010).
4) Wang, et al., PNAS, 49, 19701-119706 (2013)
Development of a New UV-Crosslinking Polymer Electrolyte for Extra-Thin Li Metal Batteries
Authors: Piana Giulia , Armel Vanessa , Oukassi Sami , Martin Steve , Amiran Johnny , Franger Sylvain , Porthault Hélène 
Published: February 2020

The increasing miniaturization of electronic devices and the needs for stand-alone systems require adapted power sources in terms of dimensions and energy. With these new demands, new constraints come out like flexibility, limited thickness or tighter security requirements. To achieve these requests, both battery core materials and packaging need to be redesigned.
In this work, we developed simultaneously a new gel polymer electrolyte (GPE) material and a new battery design to reach both security (no leakage concern, no flammability, thermal stability) and application requirements (flexibility, thin system (<400µm)). We worked on a quaternary GPE based on a bi-components UV-curable polymer network giving the mechanical strength combined with a binary liquid phase composed of ionic liquid and Li salt. The GPE was optimized in terms of mechanical and electrochemical properties by varying the nature and the proportion of each components (polymer network, ionic liquid and Li salt) and the UV-curing parameters. The optimized GPE exhibits a good conductivity at room temperature (0.375mS.cm-1) and a Li+ transference number of 0.299 (NMR measurements) which is relatively high for this GPE type (Fig.a).
Our new battery design is composed of LiCoO2 cathode realized by standard coating processes. The liquid solution of GPE precursors is then deposited on the LiCoO2 cathode and directly polymerized by UV-curing (Fig.b). This step allows a good soaking of the electrolyte in the electrode pores. This system was then integrated in our thin battery design with Li metal foil as anode material (Fig.c). By optimizing each component dimension and sealing parameters (sealing conditions and adhesive type), we succeeded in producing a flexible, less than 400µm thick working battery (Fig.d) with interesting electrochemical performances (more than 2mAh.cm-2).

This work was done as part of the project EnSO. EnSO has been accepted for funding within the Electronic Components and Systems For European Leadership Joint Undertaking in collaboration with the European Union's H2020 Framework Programme (H2020/2014-2020) and National Authorities, under grant agreement n° 692482

Figure 1