bluuebunny/crossref_metadata_2025_split huggingface dataset:
Phase Transformation of YSZ Electrolyte in Anode-Supported SOFCs
Authors: Bai Qingchuan , Bagarinao Katherine Develos , Ishiyama Tomohiro , Yamaguchi Toshiaki , Kishimoto Haruo 
Published: February 2024

Cubic-stabilized zirconia doped with 8 mol% Y2O3 (8YSZ) is a highly popular electrolyte material for solid oxide fuel cells (SOFCs) due to its exceptional oxide ionic conductivity, which remains consistent across a broad range of oxygen partial pressures. However, previous studies [1,2] have shown that the addition of nickel oxide (NiO) to 8YSZ can expedite the phase transformation process (from cubic to tetragonal) when exposed to a reducing atmosphere at relatively high temperature as 900℃. This phase transformation is closely related to the degradation of 8YSZ's conductivity. Therefore, it is crucial to investigate whether NiO, which should dissolve into the YSZ electrolyte during the co-sintering process with the NiO-YSZ anode at high temperatures, can lead to a similar phenomenon in anode-supported cells (ASCs). Hence, investigating the NiO solid solution phenomenon and its effect on the phase transformation in the YSZ electrolyte of ASCs can offer insights into its degradation behavior.
In this study, NiO-YSZ anode support and YSZ electrolyte were co-sintered at 1370℃, 1450℃, and 1550℃, respectively, for 2 hours to fabricate the half-cell samples. Subsequently, these samples were reduced at 900℃ and 700℃, respectively, with a flow of 50ccm dry H2. High-resolution secondary ion mass spectrometry (SIMS) was used to detect the presence of NiO in YSZ, and Raman spectroscopy was used to detect the phase transformation (cubic to tetragonal) occurring in the YSZ.
The SIMS results showed that the amount of NiO in the YSZ electrolyte increased with higher sintering temperatures. Moreover, after reducing the cells at 900℃, phase transformation was detected in all samples. However, there was no significant difference among those cells in terms of the degree of phase transformation, which indicated that phase transformation was not accelerated by the increase of dissolved NiO in YSZ. On the other hand, no phase transformation was observed for the cells reduced at 700℃. The mechanism of phase transformation of YSZ in anode-supported SOFCs and its related conductivity degradation will be discussed in the presentation.
References
[1] T. Shimonosono, H. Kishimoto, M.E. Brito, K. Yamaji, T. Horita, H. Yokokawa, Phase transformation related electrical conductivity degradation of NiO doped YSZ, Solid State Ionics 225 (2012) 69.
[2] H. Kishimoto, K. Yashiro, T. Shimonosono, M.E. Brito, K. Yamaji, T. Horita, H. Yokokawa, J. Mizusaki, In situ analysis on the electrical conductivity degradation of NiO doped yttria stabilized zirconia electrolyte by micro-Raman spectroscopy, Electrochimica Acta 82 (2012) 263.
K
x
Mn[Mn(CN)6] as a High Capacity Positive Electrode Material for Potassium Batteries
Authors: Hoshi Yuki , Hosaka Tomooki , Tatara Ryoichi , Komaba Shinichi 
Published: February 2024

Recently, Na-ion and K-ion batteries have attracted attention as next-generation secondary batteries.1 Prussian blue analogues (PBAs) are promising cathode materials for these batteries. In 2014, it was reported that Na
x
Mn[Mn(CN)6] exhibited higher capacity in Na cells than the theoretical capacity based on Mn2+/3+ redox, which could be attributed to the reduction of Mn in [Mn(CN)6] to monovalence.2 Thus, PBA with Mn at the C-coordination site exhibits unique properties, but there is no report of high capacity in K cells. In this study, K
x
Mn[Mn(CN)6] (KMnHCM) was synthesized, and K+ ion extraction/insertion properties were evaluated.
KMnHCM was synthesized by the solution precipitation method.3 The solution was sufficiently deoxygenated by bubbling nitrogen gas, and synthesis was performed under N2 atmosphere. The obtained samples were washed three times with deionized water under N2 atmosphere, and then dried at 150 °C under vacuum. The active material was mixed with conductive carbon (KB) and binder (PVdF) at a weight ratio of 7:2:1 in a glove box under an Ar atmosphere. Galvanostatic charge-discharge tests were conducted in a two-compartment three-electrode cell using a composite electrode coated on an Al foil as the working electrode, an activated carbon counter electrode, and an Ag+/Ag reference electrode.
Figure 1(a) shows the X-ray diffraction (SXRD) patterns and Rietveld refinement results of the synthesized sample. The diffraction patterns of KMnHCM can be attributed to the monoclinic structure with space group P21/n and are almost identical to that previously reported. SXRD patterns were successfully fitted with the satisfied R values, and the composition of KMnHCM was estimated to be K1.87Mn[Mn(CN)6]0.96·0.29H2O.
Figure 1(b) shows the charge-discharge curves of KMnHCM. The electrode showed an initial charge capacity of 163 mAh g-1 and an initial discharge capacity of 220 mAh g-1, corresponding to respective ~2.0 and 2.76 potassium extraction and insertion, respectively, from/into K
x
Mn[Mn(CN)6]. The discharge capacity exceeds the theoretical capacity of 160 mAh g-1 based on the Mn2+/3+ redox of K1.87Mn[Mn(CN)6]0.96·0.29H2O. Furthermore, the additional plateau was observed at the low voltage of around 1.5 and 1.7 V in the discharge and charge curves, respectively. The extremely high capacity and the third plateau at low voltage are similar to Na
x
Mn[Mn(CN)6] in Na cells.2 Thus, the third plateau would be attributed to the reversible redox of [MnII(CN)6]4-⇄[MnI(CN)6]5-. In the talk, we will further discuss the charge-discharge mechanisms, including redox behavior and structural changes of KMnHCM during charge/discharge.
References
[1] T. Hosaka, S. Komaba, et al.,
Chem. Rev., 120 6358 (2020).
[2] Y. Cui et al., Nat. Commun.,
5, 5280 (2014).
[3] V. Renman, M. Valvo, et al.,
J. Phys. Chem. C, 123, 22041 (2019)

Figure 1
(Invited) Ion-Exchange Route for the Cathode Development of Na-Ion Batteries
Authors: Kim Haegyum 
Published: February 2024

Ion-exchange reactions are frequently used to develop novel metastable electrode materials for alkali-ion batteries that cannot be synthesized (or difficult to synthesize) using direct chemical reactions. We have recently demonstrated that potassium (K)-containing compounds can be good Na+-hosting cathode materials that exhibit good electrochemical performance.[1-2] In this presentation, we will discuss, with layered oxide and polyanionic compounds as model systems, how K+-to-Na+ ion exchange occurs and how the K-containing structure benefits the electrochemical Na+ intercalation and deintercalation properties.

References

[1] H. Kim et al. Energy Storage Materials.
2022, 47, 105
[2] H. Kim et al. Advanced Functional Materials
2019, 29, 1902392
Ni and Fe Doped (La,Sr)TiO3 Fuel Electrodes for Solid Oxide Cells – Electrical and Electrochemical Properties
Authors: Wang Shu , Hendriksen Peter Vang , Sudireddy Bhaskar Reddy 
Published: February 2024

Development of robust and impurity tolerant solid oxide cells (SOCs) has attracted a significant R&D-effort in recent years. The shortcomings of Ni-YSZ fuel electrodes in terms of redox stability, carbon and sulfur tolerance and long-term durability under strong polarization has spurred the search for alternative fuel electrode materials. Among them, doped strontium titanate materials has shown promising performance due to their good electrical transport properties, chemical and redox stability and tolerance towards impurities.
In the present study, the electrical properties of the La0.477Sr0.33Ni0.03Fe0.03Ti0.94O3-
δ (LSFNT) material, which is designed with the potential for exsoluting Ni and Fe nanoparticles, is investigated in detail. In addition, the performance of LSFNT based fuel electrodes is characterized in a symmetrical cell configuration. The electrical conductivity measurements are performed on both dense and porous LSFNT layers, as a function of temperature and pO2. The pre-reduced (1100oC, 24 hours, dry 5%H2/N2) dense LSFNT sample showed an electrical conductivity of ca. 10 S/cm at 850 oC in dry 5%H2/N2. The “in-situ reduced” (850oC, 700 hours) porous LSFNT layer showed a conductivity 10 times smaller. The conductivity was tracked as a function of pO2 showing an approximate pO2
-1/6 dependence. Also the ionic conductivity of the material was determined using an electron blocking method. At 850oC at a pO2 of 10-20 bar the ionic conductivity is ca. 0.05 S/cm at which is similar to that of Y2O3 doped ZrO2 electrolytes demonstrating that LSFNT is indeed a very good mixed ion- and electron-conducting material.
Motivated by the observed conductivities SOC fuel electrodes of LSFNT were prepared by incorporating Gd-doped CeO2 electrocatalyst into LSFNT porous backbones and their electrochemical performance was measured in 50% H2 / 50% H2O at OCV. An electrode polarization resistance of 0.05 Ω cm2 at 850oC and 0.26 Ω cm2 at 650 oC is measured for these electrodes. The polarization resistance at 850 oC is comparable to that of Ni-YSZ fuel electrodes; while at 650oC it is significantly lower in similar atmospheres. This promising electrochemical performance shows the potential of the LSFNT fuel electrodes, as an alternative to Ni-YSZ fuel electrodes, in solid oxide cell applications.
Intolerance of Ruddlesden-Popper La2NiO4±δ Structure to a-Site Cation Deficiency
Authors: Bamburov Aleksandr , Naumovich Yevgeniy , Khalyavin Dmitry , Yaremchenko Aleksey 
Published: February 2024

Mixed ionic-electronic conductors derived from Ruddlesden-Popper Ln2NiO4+δ (Ln = La, Pr, Nd) attract significant attention as oxygen electrode materials for solid oxide fuel and electrolysis cells. However, literature data on the impact of A-site deficiency on the phase relationships and functional properties of Ln2NiO4+δ-based phases are contradictory. While some works report an accommodation of A-site vacancies up to x = 0.15 in La2-x
NiO4±δ, others indicate difficulties in the synthesis of single-phase La2-x
NiO4+δ even for low x values. The present work explores the impact of the nominal A-site deficiency on the phase composition and electrical transport properties of La2-x
NiO4±δ ceramics.
Ceramics with the nominal composition La2-x
NiO4±δ (x = 0, 0.02, 0.05, 0.10) were synthesized by the glycine-nitrate technique and sintered at 1350-1450°C. While XRD analysis suggested the formation of single-phase materials with orthorhombic K2NiF4-type structure, the lattice parameters remained independent of composition within the experimental uncertainty. Neutron diffraction studies of x = 0 and 0.05 samples revealed that the lattice parameters, La:Ni atomic ratio (2:1) and oxygen sites occupancy remain identical for both samples, while the presence of impurity NiO phase (0.4 wt.%) was detected for La1.95NiO4±δ. SEM/EDS inspection of ceramic samples confirmed the presence of nickel-rich inclusions for x ≥ 0.02, which could not be eliminated by increasing the temperature and time of sintering. The volume fraction of inclusions increased with x. The experimental observations are supported by the atomistic simulations showing that the coexistence of cation-stoichiometric La2NiO4+δ with nickel-rich La4Ni3O10 or NiO is more favorable compared to cation-deficient La1.95NiO4±δ. Molecular dynamics simulations of La1.95NiO4±δ lattice demonstrated that the introduction of La vacancies leads formation of instability zone in the rock-salt-type layer and destabilization of the crystal lattice. The intolerance of La2NiO4+δ lattice to A-site vacancies and coexistence of La2NiO4+δ with traces of Ni-rich secondary phase in the samples with the nominal composition La2-x
NiO4±δ results in an insignificant variation of electrical transport properties with x.

Acknowledgements

This work was developed within the scope of the project CARBOSTEAM (POCI-01-0145-FEDER-032295) funded by FEDER through COMPETE2020 - Programa Operacional Competitividade e Internacionalização (POCI) and by national funds through FCT/MCTES, and the project CICECO-Aveiro Institute of Materials (UIDB/50011/2020, UIDP/50011/2020 & LA/P/0006/2020) financed by national funds through the FCT/MCTES (PIDDAC). A.B. acknowledges the PhD scholarship by the FCT (grant SFRH/BD/150704/2020). This work was partially supported by the National Science Centre, Poland, grant UMO-2020/37/B/ST8/02097.
Degradation Issues in Solid Oxide Electrolysers
Authors: Laguna-Bercero Miguel A 
Published: February 2024

One of the crucial aspects to achieving long lifetime and high-efficient SOCs (Solid oxide cells) is to enhance durability of the current devices.
Degradation issues are typically associated with problems in both electrodes. For example, nickel-yttria stabilized zirconia (Ni-YSZ) hydrogen electrodes present under extreme conditions of high steam partial pressures, a low durability due to Ni oxidation resulting in lowered electronic conductivity and catalytic activity of the electrode. Ni agglomeration, depleting and micro crack in Ni-containing hydrogen electrode can also occur leading to a lower activity of the Ni-based electrodes as an SOEC fuel electrode. Furthermore, carbon deposition and sulfur poisoning on the Ni surface are also lead to cell performance degradation and poor durability.
In addition, the performance of the oxygen electrode is also particularly more important in electrolysis mode than in fuel cell mode, as it is well established that electrochemically induced oxygen pressure increase at the electrolyte-oxygen electrode interface and subsequent membrane failure have been theoretically predicted and experimentally observed in SOEC mode. For example, several examples in the literature reported the presence on voids at the YSZ electrolyte, leading to delamination of the oxygen electrode. In this sense, lanthanide nickelates (Ln = La, Nd, Pr) have received considerable interest as materials for IT-SOFC electrodes and oxygen separation membranes, and they seem to be very attractive for electrolysis applications. The hyperstoichiometry of some oxygen electrode materials such as these Ruddlesden-Popper phases is believed to be favourable for effective oxygen evolution, as performance of these electrodes is enhanced in SOEC mode.
Different strategies to develop optimized electrode structures as well as controlled operating conditions will be discussed in order to improve the durability of SOCs.
Effects of Doping on Conduction/Densification of BaCe0.5fZr0.3Y0.2O3-Δ Electrolyte for Green Hydrogen Applications
Authors: Fung Kuan-Zong , Tsai Shu-Yi , Tsai Yuan Jie 
Published: February 2024

For reaching the goal of 2050 net-zero carbon emission, the production of green H2 needs a very efficient and cost-effective approach. A proton-solid oxide electrolyzer cell (P-SOEC) based on BaCe0.5Zr0.3Y0.2O3-δ (BCZY) proton conducting electrolyte may show some advantages such as (1) Use of lower cost metals, alloys and coatings, (3) Ease of gas sealing, (4) Reduced cost of hydrogen production. BaCe0.5Zr0.3Y0.2O3-δ (BCZY) is known for its unique stability and high proton conduction properties due to the doping effect from the substitution of Zr and Y for Ce ions. For better performance of P-SOEC, a solid electrolyte with good densification to prevent the direct mixing of fuel and oxidant is essential.
Thus, the objective of this study is to develop a cost-effective process with proper dopant in order to obtain well-densified BCZY at a temperature as low as 1200°C. For undoped BCZY, much less densification was observed. With the addition of proper dopant, BCZY may reach 97% relative density at the same temperature. It is believed that the presence of liquid phase is the reason for densification enhancement of doped BCZY. The affected electrical and structural properties will be analyzed and discussed based on sintering theory and kinetics. The crystal structure and microstructure of sintered BCZY was also characterized using XRD, field-emission SEM, and STEM.
(Invited) Zn Batteries: Stable Anode and High Energy Cathodes
Authors: Zhi Chunyi 
Published: February 2024

Our research focuses on a stable aqueous Zn-based battery with long cycling stability, decent energy density, and ultimate safety performance for large-scale energy storage. To achieve this purpose, we did systematic studies on the Zn metal anode, electrolytes, and new cathode development.
For the anode side, we developed a few strategies, including pH value manipulation, ion redistribution coating, gradient coating, etc to induce stable stripping and plating of Zn. Moreover, we also found that a Zn initially plated can be much more stable than the one initially stripped during the subsequent deposition. We further utilize this observation to develop a pre-deposited Zn for Zn batteries with improved stability.
For the electrolyte, we develop a reverse micelle electrolyte, with it, the Zn anode exhibits balanced merits including strong H2 coevolution suppression, prevention of dendritic and dead Zn, inhibition of corrosion, as well as relatively fast reaction kinetics. In a more extensive context, the new reverse micelle structure of electrolytes is expected to benefit other emerging battery chemistries, where a balance between fast ion transport and sufficient stabilization against side reactions is required.
For the cathode with high energy density, we studied the critical research concerns and further potential developments of chalcogen/halogen-based batteries, primarily focusing on the electrochemically active chalcogen/halogen sources, reaction modes, soluble products, and electrolyte adaptability.
For the cathode, we use iodine as the fixing agents working in highly concentrated electrolytes to successfully enable reversible Cl-based redox electrode. The interhalogen coordinating chemistry fixes Cl in a configuration of ICl3
-. Furthermore, we simultaneously exploit two redox centers of Cl and I to realize a novel three-electrons transfer electrode, in which the Cl-I electrode can deliver remarkably high capacity up to 612.5 mAh gI
-1 and energy density as 905 Wh kgI
-1. The as-obtained energy density is 387% higher compared to the traditional one-electrons transfer of ZnǁI2 battery system and superior cycling stability with capacity retention as 95.7% after 2,000 cycles.
A Novel Aqueous Zinc-Ion Batteries with a Magnetron Sputtered SnxNy Layer with Suppressed Dendrite Formation
Authors: Kurmangaliyeva Dana , Konarov Aishuak , Bakenov Zhumabay 
Published: February 2024

Thе аquеоus zіnc-іоn bаttеry іs а prоmіsіng оptіоn fоr lаrgе-scаlе еnеrgy stоrаgе systеms duе tо іts sаfеty, cоst-еffеctіvеnеss аnd еlеctrоchеmіcаl prоpеrtіеs. Hоwеvеr, thе grоwth оf dеndrіtеs оn mеtаllіc zіnc аnоdеs prеvеnts іts wіdеsprеаd prаctіcаl аpplіcаtіоn, аnd thеrе іs stіll uncеrtаіnty аbоut thе undеrlyіng mеchаnіsm оf dеndrіtе еvоlutіоn. Tо prеvеnt thіs grоwth, а prоtеctіvе lаyеr cаn bе аddеd tо thе аnоdе іntеrfаcе [1].
Thе cоmmоn prоtеctіvе lаyеrs usеd іn аquеоus zіnc-іоn bаttеrіеs (АZІBs) аrе bоrоn nіtrіdе BN [2], zinc оxіdе ZnО [3] аnd zіnc-аlumіnum аllоy Zn0.73Аl0.27 [4]. Thіs wоrk prеsеnts а Zn аnоdе dеcоrаtеd wіth а nоvеl SnxNy lаyеr thаt wаs fаbrіcаtеd by mаgnеtrоn sputtеrіng mеthоd fоr pаssіvаtіоn оf zіnc dеndrіtеs fоrmаtіоn.
А cоnductіvе tіn nіtrіdе prоtеctіvе lаyеr hаs bееn crеаtеd usіng а sіmplе аnd scаlаblе mаgnеtrоn sputtеrіng mеthоd. Thіs lаyеr hаs а hіgh zіnc аffіnіty аnd dіffusіоn bаrrіеr fоr zіnc mіgrаtіоn, lеаdіng tо mоrе еvеn zіnc dеpоsіtіоn аnd іmprоvеd еlеctrоchеmіcаl stаbіlіty. Thіs study оffеrs а nеw pеrspеctіvе fоr futurе rеsеаrch оn dеndrіtе-frее zіnc mеtаl аnоdеs thrоugh іntеrfаcіаl mоdіfіcаtіоn.
Cоmpаrеd tо bаrе Zn, zіnc thаt hаs bееn sputtеrеd wіth SnxNy prоvіdеs strоngеr Zn nuclеаtіоn sіtеs аnd lоwеr Zn оvеrpоtеntіаl, rеsultіng іn іmprоvеd Zn plаtіng/strіppіng wіth hіgh cоulоmbіc еffіcіеncy аnd lоwеr pоtеntіаl fоr hydrоgеn еvоlutіоn rеаctіоn. Thе usе оf SnxNy іn bоth symmеtrіcаl аnd zіnc-lіthіum hаlf cеlls lеаds tо lоngеr cyclе lіfе, іn cоntrаst tо uncоаtеd Zn. Thіs tеchnіquе іs а dіrеct, crеаtіvе, аnd еffеctіvе mеаns оf prеvеntіng Zn dеndrіtеs аnd оptіmіzіng thе pеrfоrmаncе оf АZІBs. Thе dеtаіls оf thе study wіll bе prеsеntеd durіng thе mееtіng.
1. Shenglin Xiong et al. Recent Progress, Mechanisms, and Perspectives for Crystal and Interface Chemistry Applying to the Zn Metal Anodes in Aqueous Zinc-Ion Batteries // Advanced Energy Materials. - 2022.- Vol. 2. -P. 114-141.
2. Xiangwu Znang et al. Nano-scale BN interface for ultra-stable and wide temperature range tolerable Zn anode // Functional Materials for Green Energy and Environment. - 2022. - Vol. 4. - P. 12190.
3. M. Masłyka et. al. Influence of absolute argon and oxygen flow values at a constant ratio on the growth of Zn/ZnO nanostructures obtained by DC reactive magnetron sputtering// Applied Surface Science. - 2016.- Vol. 389. - P. 287-293.
4. Hanfeng Liang et. al. Electrostatic Shielding Regulation of Magnetron Sputtered Al-Based Alloy Protective Coatings Enables Highly Reversible Zinc Anodes // Nano Letters.- 2022.-Vol. 3. - P. 1017-1023.
Acknowledgement
This research was supported by the research grant IRN51763/ ПЦФ- МЦРОАП РК -19 from the Ministry of Digital Development, Innovations and Aerospace Industry of the Republic of Kazakhstan “New materials and devices for defense and aerospace applications”.
LIOVIX® Printable Lithium Technology for Lithium Anode Manufacturing at Scale
Authors: Xia Jian , Fitch Brian , Yakovleva Marina 
Published: February 2024

The commercialization of lithium metal batteries requires the mass production of cost-effective thin lithium metal foil with thickness less than 30 µm. However, today’s known technologies are not yet commercially available. For example, thin lithium metal foil can be produced by hydraulic extrusion followed by a rolling process. This process usually requires a delicate balance between the pressure and tension created by both extruder and winder, so that the resulting foil is not torn or stretched, retaining all the dimensional characteristics required. This process can be extremely challenging when making lithium metal films with thickness less 20 µm due to the poor mechanical properties of lithium metal. Lithium metal foil can also be produced by physical vapor deposition (PVD). Lithium metal foil produced by PVD process are generally homogenous and have good control in thickness. However, PVD technology requires high vacuum chamber and is slow in the deposition rate, typically in the range of 0.1 to 100 nm s−1, making industrial scale of 20 µm lithium foil very challenging1.
Livent has developed LIOVIX®printable lithium technology, a proprietary formulation that combines Stabilized Lithium Metal Powder (SLMP®), rheology modifiers and solvent to produce a stable suspension that can be printed on most common substrates. LIOVIX®printable lithium technology is an enabling technology that can produce thin lithium foil with thickness of 5 µm to 50 µm with no limitation in width, length and at high deposition speed. LIOVIX®enables pattern printing and can be applied to any substrate, for example a prefabricated anode, cathode, current collector, separator, and solid or polymer electrolyte. This technology enables 3D battery printing in a custom form factor shape.
In this presentation, we will cover thin lithium foil manufacturing processes using standard industrial equipment and electrochemical performance results.
References

Acebedo, Begoña, et al. "Current Status and Future Perspective on Lithium Metal Anode Production Methods." Advanced Energy Materials (2023): 2203744.