bluuebunny/crossref_metadata_2025_split huggingface dataset:
Traveling Solvent Floating Zone Growth and Ionic Conductivity of Li0.1La0.3Nb0.8Ta0.2O3 Single Crystals
Authors: Onimaru Mizuki , Maruyama Yuki , Nagao Masanori , Watauchi Satoshi , Tanaka Isao 
Published: December 2024

Li
x
La(1-x)/3Nb1-y
Ta
y
O3 (LLNT) is a solid electrolyte with a double perovskite-type structure. It was reported that the highest ion conductivity of LLNT was 7.78 × 10-5 S/cm at x = 0.1, y = 0.2 [1,2]. Therefore, in this study, we investigated the preparation conditions of the feed and the growth conditions of Li0.1La0.3Nb0.8Ta0.2O3 single crystals by the traveling solvent floating zone (TSFZ) method.
Li2CO3, La2O3, Nb2O5, and Ta2O5 were used as starting materials, weighed at Li
x
La(1-x)/3Nb1-y
Ta
y
O3 (x = 0.1, y = 0.2) stoichiometric composition, and mixed with ethanol. The mixed powder was calcined at 800 °C for 2 hours in air. The calcined powder was grounded and calcined again at 1200°C for 12 hours in air. The calcined powder was then shaped into a cylindrical shape by rubber pressing and sintered at 1350°C for 5 hours in air. Solvent of 5 mol% of La(Nb,Ta)3O9-poor, La(Nb0.5Ta0.5)O4-poor or La(Nb0.8Ta0.2)O4-poor composition relative to the stoichiometric composition of LLNT feeds was prepared using the same procedure as the feed rod preparation. The optical floating zone machine was used for crystal growth. The growth conditions were the growth rate of 2 or 5 mm/h, the growth atmosphere of Ar or N2. The grown crystals were characterized using X-ray diffraction, electron probe micro-analyzer (EPMA), and impedance measurements.
As a result of crystal growth of LLNT by the floating zone (FZ) method, the La(Nb,Ta)3O9 phase was deposited as an inclusion in the initial growth region, even though Li evaporation from the molten zone was not observed. This result indicates that LLNT is an incongruently melting compound. Next, the TSFZ method, FZ method using solvents, was applied to the growth of LLNT crystals. La(Nb,Ta)O4 inclusion phase deposited in the initial growth part of the grown crystal when using solvent of 5 mol% La(Nb,Ta)3O9-poor composition relative to the stoichiometric LLNT. In the case of using a 5 mol% La(Nb0.8Ta0.2)O4-poor solvent composition, crystals with a length of 12 mm and a diameter of 5 mm were obtained as shown in Fig. 1(a). La(Nb,Ta)O4 inclusion phase was not detected in the grown crystal. The chemical composition of the LLNT phase was determined to be y = 0.14-0.25 by quantitative analysis using EPMA as shown in Fig. 1(b). Therefore, inclusion-free LLNT crystals were obtained using a solvent with 5 mol% La(Nb0.8Ta0.2)O4-poor composition relative to the stoichiometric LLNT composition. Moreover, the molten zone was stable in Ar gas or N2 gas flow at growth rate of 5 mm/h. The ionic conductivity of the grown crystal was σ= 2.0 ×10-5 S/cm . The low conductivity is due to cracks, and inhomogeneous in the grown LLNT crystal. Optimization of the solvent composition is required for LLNT crystals with homogeneous and high ionic conductivity.
References.
[1]Y. Maruyama, et. al., J. Ceram. Soc. Jpn. 128, 761-765 (2020). [2]Y. Maruyama, et. al., J. Ceram. Soc. Jpn. 129, 535-539 (2021).

Figure 1
Studies of Solid State Electrolytes for Li-Type Batteries
Authors: Pan Jian , Tutusaus Oscar , Shu Chan , Mohtadi Rana 
Published: December 2024

Solid state electrolyte has been one of the most promising candidates for advanced batteries due to its higher energy density and higher safety. However, current highly conducting solid state electrolytes (SSEs) still suffer from challenges associated with their intrinsic properties.1 These challenges of interfacial issues related to instabilities to the electrode active materials can lead to cell failure. Herein, we have carefully examined common solid state electrolytes and showcase new type of solid state electrolytes that can overcome the existing challenges.
Reference:

O. Tutusaus, H. Kuwata, M. J. Counihan and R. Mohtadi, Chem. Commun., 59, 4746 (2023).
Charge-Discharge Performance of All-Solid-State Lithium Batteries with Amorphous MoS4 Electrodes Prepared By Thermal Decomposition of (NH4)2[Mo3S(S2)6]·H2o
Authors: Imai Keitaro , Shigedomi Tatsuki , Furukawa Tomohiro , Kowada Hiroe , Motohashi Kota , Sakuda Atsushi , Hayashi Akitoshi 
Published: December 2024

All-solid-state lithium batteries with nonflammable inorganic solid electrolytes have attracted attention in terms of safety. Transition-metal sulfides are promising positive electrode active materials because of their relatively high electronic conductivities and capacities. Generally, higher specific capacities would be achieved by increasing the S content in transition-metal sulfide [1]. We have investigated electrochemical performance of all-solid-state cells using transition-metal sulfide active materials (TiS
x

[1−3], NbS
x

[4], MoS
x

[5,6] etc.). For example, amorphous molybdenum polysulfides exhibited higher capacities than MoS2 active materials by using anion redox reactions of sulfur [5,6].
In this study, amorphous MoS4 (a-MoS4) samples prepared by thermal decomposition of (NH4)2[Mo3S(S2)6]·H2O were applied to the electrode active materials for all-solid-state batteries. By XRD measurement, it was confirmed that amorphous materials were obtained through thermal decomposition of (NH4)2[Mo3S(S2)6]·H2O in an argon atmosphere. The molar ratio of S to Mo was determined to be 4 (MoS4) by CHNS elemental analysis. The Mo3d XPS spectrum of a-MoS4 indicated that the electronic state of Mo in a-MoS4 was close to that in MoS2. In the S2p XPS spectrum, two sets of doublet peaks were observed. Thus, in a-MoS4, sulfur would form the S-S bonds which enhance its capacity. The electronic conductivities of a-MoS4 measured by DC polarization were 5.0 × 10−4 S cm−1 at 25 ºC. Composite working electrodes were fabricated by mixing a-MoS4, Li3PS4 glass, and acetylene black (40 : 60 : 6 wt%). Li3PS4 glass and Li–In alloy were used as a solid electrolyte separator and a counter electrode, respectively. All-solid-state lithium cells using a-MoS4 active materials operated with a cut-off voltage of 0.9–2.2 V (vs. Li–In) at 25 ºC under a current density of 0.13 mA cm−2. The cells exhibited high reversible capacities of about 460 mAh g−1 for 150 cycles.
In conclusion, amorphous MoS4 active materials were successfully prepared by thermal decomposition of (NH4)2[Mo3S(S2)6]·H2O. All-solid-state cells (Li-In / Li3PS4 glass / a-MoS4) showed relatively high capacities and good cyclabilities.

References

[1] A. Sakuda et al., J. Am. Chem. Soc., 139 (2017) 8796–8799.
[2] A. Hayashi et al., Chem. Lett., 41 (2012) 886–888.
[3] A. Sakuda et al., Electrochem. Commun., 31 (2013) 71–75.
[4] A. Sakuda et al., ECS Electrochem. Lett., 3 (2014) A79.
[5] T. Matsuyama et al., J. Mater. Chem. A, 3 (2015) 14142–14147.
[6] G. Shirota et al., J. Ceram. Soc. Jpn., 130 (2022) 308–312.
Probing the Mechanical Properties of Superionic Boron Cluster Solid Electrolytes
Authors: Tutusaus Oscar , Hempel Jacob , Thapa Santosh , Kim Kwangnam , Kweon Kyoung E. , Wood Brandon C. , Hentz Luke , Hill Ryan Christopher , Mohtadi Rana , Cheng Yang-Tse 
Published: December 2024

All-solid-state batteries (ASSB) are a promising alternative to their conventional liquid electrolyte-based counterparts due to their increased safety and their potential to achieve higher energy density. To achieve these goals, a ASSB requires a solid-state electrolyte (SSE) with high ionic conductivity near room temperature and high electrochemical stability. Lithium and sodium salts of boron cluster anions have attracted much attention as SSE candidates due to their high ionic conductivities (>103 S/cm) following a solid-phase transition into a disordered phase at relatively low temperatures (50-130°C) and relatively wide electrochemical window.[1]
In considering their application to ASSB, their mechanical properties also play a critical role due to the stresses the electrolyte material is subjected to during battery operation.[2] First-principle calculations have been instrumental so far to provide an initial assessment of bulk and elastic moduli for some selected boron cluster solid electrolytes,[3-5] but direct measurements are still lacking. Herein, we will report the first determination of elastic moduli and hardnesses of the most representative boron cluster salts using both nanoindentation continuous stiffness method (CSM) and ultrasound under inert atmosphere and compared with DFT calculations.

References

[1] R. Mohtadi et al., Nat.
Rev. Mater., 2, 16091 (2017)
[2] S. Kalnaus et al., Science, 381, eabg5998 (2023)
[3] H. Chen et al., J. Electrochem. Soc., 166, A493 (2019).
[4] Z. Lu et al., Chem. Mat., 29, 9308 (2017)
[5] R. Moury et al., Acta Crystallogr., Sect. B: Struct. Sci., 75, 406 (2019)
Synthesis and Characterization of BH4-Substituted Lithium Argyrodite for Assbs
Authors: Han JiHoon , Lee Young-Su , Yi Kyung-Woo , Cho Young Whan 
Published: December 2024

In the present study, we have successfully synthesized BH4-substituted lithium argyrodites by dry ball milling as well as by wet mechanochemical processing. Simultaneous substitution of BH4 and Cl/Br/I for non-bridging sulfur in the argyrodite structure was also possible by ball milling. The ionic conductivity of these BH4-substituted argyrodite-type electrolytes exhibit a maximum conductivity of up to 16.4 mS/cm at 25°C in their cold-pressed state. We confirmed the composition and distribution of substituted ions in the crystal structure by XRD Rietveld refinement and investigated the movement of lithium ions and the substitution of BH4 by solid-state NMR. The thermal stability and decomposition product at high temperatures have also been analyzed by thermo-gravimetric analysis/mass spectrometry (TGA/MS) and XRD. To characterize the electrochemical properties of BH4-substituted argyrodite-type electrolytes, we have used various analytical tools such as electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). Li symmetric cell, c-rate and long-term cycle tests of full cells with LiNbO3-coated NCM811 as a cathode, have also been done. The test results so far have shown very high ionic conductivity, excellent electrochemical stability and much higher critical current density compared with similar cells with commercial Li6PS5Cl as the electrolyte.
References
1. Y.-J. Jang, H. Seo, Y.-S. Lee, S. Kang, W. Cho, Y. W. Cho, J.-H. Kim, Lithium Superionic Conduction in BH4-Substituted Thiophosphate Solid Electrolytes. Adv. Sci. 2023, 10, 2204942.
2.Ji-Hoon Han, Do Kyung Kim, Young Joo Lee, Young-Su Lee, Kyung-Woo Yi and Young Whan Cho,
Mater. Horiz.
, 2024,11, 251-261. DOI: 10.1039/d3mh01450a
Growth of Solid Electrolyte Li1+X
Al
x
Ti2-X
(PO4)3 Single Crystals
Authors: Maruyama Yuki , Okanda Kohei , Nagao Masanori , Watauchi Satoshi , Tanaka Isao 
Published: December 2024

The bulk single crystals are useful for our understanding of interfacial properties. Single crystals of lithium ion conductor, which can reveal intrinsic electrochemical properties, are an essential material for the development of high-performance all-solid-state lithium-ion secondary batteries. Li1+x
Al
x
Ti2-x
(PO4)3 (LATP) has a high ionic conductivity of ~10-3 S/cm at room temperature and show promise for the application of solid electrolyte for all solid-state batteries1, 2). We have tried to grow LATP crystals by floating zone method. Lithium phosphate such as Li4P2O7 evaporated from the molten zone during the crystal growth. As the result, AlPO4 and TiO2 phases precipitated in the LATP grown crystals. Therefore, excessive addition of lithium phosphate into the feeds to compensate for the evaporation component is necessary for LATP crystal growth. Next, we grew LATP crystals using the feed with a Li4P2O7 excess from the LATP composition by the melt slow cooling method. As the result, we have successfully grown LATP single crystals as shown in Fig 1, when the crystals were grown with a molar ratio of LATP : Li4P2O7 = 1 : 1, a maximum temperature of 1400°C, and a slow cooling rate of 5°C/h. The concentration of Al in the grown crystals was x = 0.16, which is approximately half of the feed concentration (x = 0.3). The crystal orientation was [100], and the ionic conductivity was σ[100] = 9.1 × 10-4 S/cm at room temperature.
Reference
1) H. Aono et al., J. Electrochem. Soc., 137, 4, 1023-1027 (1990).
2) Yihzou Zhu et al., J. Mater. Chem. A 4, 3253 (2016).

Figure 1
Na-Ion Battery Based on Carbon and Phosphate Chemistries
Authors: Krajewski Michał , Grabowski Oskar , Chmielniak Marta , Winkowska-Struzik Magdalena , Czerwinski Andrzej 
Published: December 2024

Lithium-ion batteries are one of the most used power sources in a variety of fields: microelectronics, portable devices, automotive or even stationary energy storage. The huge growth of the Li-ion battery market raises concerns about the limited availability of lithium resources and its rising cost of acquisition. To counteract that effect, scientists again focused on sodium, as a cheaper and easily acquirable element to use in electrochemical power sources [1, 2].
In principle, sodium-ion batteries operate through similar mechanisms as lithium-ion cells, where Na+ ions are charge carriers between negative and positive electrodes. Most of the electrode materials used in the Na-ion technology come from their widely used analogues in Li-ion systems. However, due to differences in ion transport, reaction kinetics and Solid Electrolyte Interphase layer composition, there is a need for extensive studies to be carried out before the wide commercialisation of Na-ion batteries can take place [2].
In this presentation, we show our results from research on Na-ion battery systems, based on carbon and phosphate chemistries. From the negative electrode side, carbonaceous materials prepared in our lab showed good capacities (ca. 200 mAh g-1), outstanding cyclability and high-rate performance (above 95% and 50% capacity retention during cyclability and high-rate tests, respectively). For the positive electrode, transition metal phosphates obtained through various synthetic routes also showed excellent performance (above 95% and 95% capacity retention during cyclability and high-rate tests, respectively) in Na-ion cells. Materials with the best electrochemical performances were used to construct a full Na-ion battery, which showed promising results in full-cell geometry and the feasibility of carbon and phosphate chemistries in the development of post-lithium battery systems.

Acknowledgements: This work was supported by The Polish National Centre of Science through a research grant 2021/43/D/ST5/01220 entitled “High-voltage sodium-ion batteries based on exfoliated graphite electrodes”.
Literature:
[1] Jamesh, M. I. & Prakash, A. S. J. Power Sources
378, 268–300 (2018).
[2] Delmas, C. Adv. Energy Mater.
8, 1–9 (2018).
Enhancing Rate Performance and Stability of Nickel Hexacyanoferrate through K+ Substitution for Na+ Guest Ions
Authors: Kang San Chun , Song Na Young , Chun Sang-Eun 
Published: December 2024

Nickel hexacyanoferrate (NiHCF) is a promising cathode for aqueous Na-ion batteries, exhibiting excellent rate performance and stability due to its stable and 3D open structure. During the coprecipitation for NiHCF synthesis, H2O molecules are inevitably introduced into the structure occupying Fe sites or interstitial sites. The H2O coordinated to the Ni atom induces Fe vacancy, reducing capacity. Additionally, the interstitial H2O can hinder the movement of Na-ions intercalated into the NiHCF structure, impairing the rate capability. Accordingly, suppressing H2O formation during coprecipitation would enhance electrochemical performance by increasing the amount of redox-active Fe and allowing for rapid ion movement. This study aimed to minimize the H2O amount within the structure by employing more chelating agent and introducing guest ions causing less hydration during the synthesis.
The NiHCF samples were synthesized with varying concentrations of chelating agent (0.03 M, 0.1 M citrate ions) and different guest ions (Na+, K+). With more citrate ions, the enlarged cubic particles are formed with less water, inferring a higher crystallinity. The NiHCF sample with K+ guest ion instead of Na+ prepared at higher citrate ion concentration contains fewer Fe vacancies with the lowest H2O contents (Na0.02K1.59Ni[Fe(CN)6]0.96∙0.75H2O) compared to the NiHCF sample with Na+ with guest ion (Na1.59Ni[Fe(CN)6]0.93∙2.75H2O). The reduced H2O contents generated less Fe vacancy, inducing a highly crystalline structure among all samples. The lowest H2O amount is formed due to the high concentration of the chelating agent, which blocks the direct bonding of Ni with H2O during the coprecipitation. Furthermore, the lower hydration of K+ than Na+ leads to decreased H2O amount within the crystal. As a result, the improved capacity of 80 mAh g-1 at 0.1 A g-1 was obtained based on the reduced Fe vacancy. The enhanced stability of 83% capacity retention is achieved by lower H2O contents after 1,000 cycles at 1.0 A g-1. Additionally, the K-inserted NiHCF exhibits a higher rate performance of 82% (10 A g-1 vs. 0.1 A g-1) compared to 69% of the Na-inserted NiHCF (Fig. 1). The highly stable and high-rate NiHCF cathode can be synthesized with appropriate amount of chelating agent and selecting guest ion for aqueous Na-ion batteries.

Figure 1
Enhancing Electrochemical Performance through Anode Modification Strategies in Aqueous Zn Battery System
Authors: Cho Beom-Keun , Yu Seung-Ho 
Published: December 2024

Commercial Li-ion batteries are widely applied in everyday life and industries, but there are some limitations in terms of low energy density/safety issues and unstable supply of resources. As an alternative to Li-ion batteries, aqueous Zn batteries have gained attention due to the abundance of Zn metal, low reduction potential (– 0.76 V vs. standard hydrogen electrode), and high theoretical capacity (820 mAh g–1) of multivalent Zn2+ ion.
However, the growth of Zn dendrites on anode surface and the formation of irreversible surface reaction byproducts poses challenges for ensuring long battery lifespan and commercialization. Common approaches to controlling performance degradation factors at the anode include functional surface coatings, electrolyte optimization, etc. In this presentation, we will discuss the effects of anode surface coating techniques and the effects of electrolyte additive conducted by our research group to enhance the performance of aqueous Zn batteries. We will elucidate the basis of our improvement strategies by conducting simultaneous (electro)chemical analyses. Additionally, we will introduce advanced techniques such as operando imaging/computational method to facilitate a comprehensive understanding of uniform Zn deposition.
The significance of the experimental results lies in the improved performance of aqueous Zn battery system by anode modification. We anticipate that the result will have a significant impact on the future development of aqueous Zn battery systems.

Figure 1
Addition Effect of Crown Ether on Intercalation of Solvated Mg2+ into Graphite Interlayers
Authors: Yamamoto Keito , Shimizu Masahiro 
Published: December 2024

Rechargeable batteries with Mg ions as carrier ions have attracted much attention as one of a next-generation energy storage system.1−7 There have been few reports on the use of graphite as a negative electrode material. We have shown that the reversible capacity based on intercalation/deintercalation of solvated Mg2+ into/from graphite interlayers.8 In the formation of ternary graphite interlayer compounds (t-GICs) containing solvated Mg2+, the sizes of solvents and coordination ability associated with donor numbers and dielectric constant in electrolyte compositions should be significant.
In this study, we focused on the bulkiness of the solvated Mg2+. Crown ethers (12C4, 15C5, 18C6) with equimolar ratio to Mg2+ were added to electrolytes to capsulate and to control the overall sizes of the solvated ions. The solvation environments of the Mg2+ were characterized by using Raman spectroscopy. X-ray diffraction clearly represented the formation of t-GICs with a stage structure by using the electrolyte in which the ligand of Mg2+ was replaced to crown ether from the solvents. It was shown that reducing the bulkiness of the solvated Mg2+ facilitated the formation of t-GICs.
Acknowledgement
This work was supported by a Grant-in-Aid for Scientific Research (B) (20H02840) from the Japan Society for the Promotion of Science (JSPS).
References

J.-M. Tarascon, M. Armand, Nature, 414 (2001) 359.

D. Aurbach, Z. Lu, A. Schechter, Y. Gofe, H. Gizbar, R. Turgeman, Y. Cohen, M. Moshkovich, E. Levi, Nature, 407 (2000) 724.

H. D. Yoo, I. Shterenberg, Y. Gofer, G. Gershinsky, N. Pour, D. Aurbach, Energy Environ. Sci., 6 (2013) 2265.

J. Muldoon, C. B. Bucur and T. Gregory, Chem. Rev., 2014, 114, 11683–11720.

Y. Orikasa, T. Masese, Y. Koyama, T. Mori, M. Hattori, K. Yamamoto, T. Okado, Z. D. Huang, T. Minato, C. Tassel, J. Kim, Y. Kobayashi, T. Abe, H. Kageyama, Y. Uchimoto, Sci. Rep., 4 (2014) 5622.

R. Mohtadi, M. Matsui, T. S. Arthur, S. J. Hwang, Angew.
Chem. Int. Ed., 51 (2012) 9780.

T. Mandai, M. Watanabe, J. Mater. Chem. A, 11 (2023) 9755.

M. Shimizu, A. Nakahigashi, S. Arai, Phys. Chem. Chem. Phys., 23 (2021) 16981.
Electrochemical Solid Polymer Electrolyte Coating of Carbon Fibres for Structural Sodium Micro Batteries
Authors: Lind Elvira , Cattaruzza Martina , Zenkert Dan , Johansson Mats , Lindbergh Goran 
Published: December 2024

Carbon fibre based structural batteries combine energy storage and mechanical load transfer into a single material. Multifunctional materials as such are attractive alternatives to today's state-of-the-art monofunctional batteries, particularly in mobile applications where the battery pack constitutes parasitic weight that decreases range. Structural batteries take advantage of carbon fibres’ ability to store electrochemical energy by insertion of alkali-ions and their outstanding mechanical properties, making them an inherently multifunctional material. A key aspect to structural batteries is an electrolyte that can transfer mechanical load and ions between the electrodes. A solid PEG-based solid polymer electrolyte (SPE) has been synthesised for Li chemistries in previous work, utilising electrochemical grafting to produce thin homogeneous films covering individual carbon fibres [1].
This method remains unexplored for Na based chemistries as an attractive, abundant and cheap alternative to Li. This paper demonstrates this single step, energy efficient electrochemical process to produce a chemisorbed, dense and homogeneous SPE around single carbon fibres for Na chemistries. Propylene glycol methyl ether acrylate is grafted and polymerised onto single fibres using sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) as supporting electrolyte. The synthesised SPE is characterised using various techniques and the electrochemical properties of the coated carbon fibre electrodes were investigated by cycling the electrodes in a battery setup. The results show a dense SPE that covers each individual fibre in a carbon fibre bundle and the electrodes cycle stably against Na metal with capacities that are on par with findings in previous work [2]. In a step towards realising single carbon fibre battery cells, this method holds the potential to produce fully solid state structural batteries, by using sustainable chemicals, that are scalable from micrometer dimensions and allow for novel battery design.
[1] Leijonmarck, S., Carlson, T., Lindbergh, G., Asp, L.E., Maples, H. and Bismarck, A., 2013. Solid polymer electrolyte-coated carbon fibres for structural and novel micro batteries. Composites Science and Technology, 89, pp.149-157.
[2] Harnden, R., Peuvot, K., Zenkert, D. and Lindbergh, G., 2018. Multifunctional performance of sodiated carbon fibers. Journal of The Electrochemical Society, 165(13), p.B616.