bluuebunny/crossref_metadata_2025_split huggingface dataset:
Stabilizing Metallic Zn Electrode Using Organic Acid Additives in Aqueous Zinc-Ion Batteries
Authors: Na Moony , Byon Hye Ryung 
Published: July 2022

Aqueous zinc (Zn)-ion batteries (AZIBs) have been paid attention to as safe, economical, and high-energy-density storages through multiple electron transfer. Although conventional alkaline solution-based AZIBs are primary batteries, recent studies demonstrated the reversible Zn2+ deposition and stripping processes enabled in mildly acidic solutions. It promises the development of rechargeable AZIBs and viable applications for energy storage systems (ESSs). However, metallic Zn employed as the negative electrode has suffered from severe corrosion and precipitation of electrolyte salts in this low pH condition. The Zn electrode undergoes a hydrogen evolution reaction (HER) as Zn2+ is dissolved from the Zn surface. The corrosion leads to a pH rise, precipitating electrolyte salt as zinc hydroxide forms. For example, hexagonal plates of zinc hydroxide sulfate hydrate (Zn4SO4(OH)6∙xH2O, indicated as ZHS) grew on the Zn electrode in 1 M ZnSO4 solution when pH approached ~5.4. The insulating and randomly oriented ZHS increased the surface resistance and caused the non-uniform Zn deposition.
These challenges are mitigated by adding organic acid to the 1 M ZnSO4 solution. As the HER raised pH, the acid was promptly deprotonated, then coordinated with Zn2+. This process caused the thin film formation consisting of three-dimensional zinc glutarate. The zinc glutarate protected the Zn electrode and impeded the electrode corrosion and the ZHS precipitation. We demonstrated a uniform Zn plating and stripping process with 10 mM of organic acid in contrast with dendritic and dead Zn growth in the absence of the additive. Galvanostatic tests of symmetric Zn cells revealed over 1000 h cycles with the additives at a current density of 1 mA cm-2 and a limited capacity of 1 mAh cm-2. In contrast, the Zn cells with the additive-free electrolyte solution exhibited 15 times lower cyclability as micron-scale ZHS plates covered the electrode surface. Our strategy using the cheap additives is feasible to use grid-scale ESSs and shows significantly improved cycling performances. I will present details of Zn surface reactions using organic acid additive and corresponding electrochemical performances in this presentation.
Lithium Iron Phosphate Reconstruction Facilitates Kinetics in High-Areal-Capacity Sulfur Composite Cathodes
Authors: Gao Xiaosi , Zheng Changyang , Shao Yiqi , Jin Shuo , Suntivich Jin , Joo Yong Lak 
Published: July 2022

Lithium-sulfur (Li-S) batteries have been recognized as one of the most promising choices beyond lithium-ion batteries (LIB), because of its low cost and high theoretical specific energy (~2510 Wh/kg or ~10 times of LIB). However, Li-S batteries still face a few challenges, including large volume expansion, poor conductivity, low active material loading, inert end products, and polysulfide crossover called the “shuttle effect”, etc.
To address these challenges, we have incorporated lithium iron phosphate (LFP) into our sulfur composite cathode. The addition of LFP enabled a more uniform slurry rheology, which allowed mass loading to double the amount of typical sulfur cathodes. Meanwhile, LFP can effectively adsorb polysulfides, which restricted the shuttle effects common in high-sulfur-loading batteries. Our LFP-hybrid Li-S batteries showed high areal capacity for 300 cycles under both low- and high-current charge-discharge cycles. More importantly, our characterizations demonstrated that LFP in Li-S batteries can reconstruct into Fe2P during cycling. We propose that Fe2P is an effective electrocatalyst for anchoring polysulfides.
To unveil the role of Fe2P, we have directly incorporated these materials into the sulfur composite cathode. Using a hydrothermal synthesis, we showed that Fe2P nanoparticles can be directly anchored on the sulfur-carbon composite. This approach caused minimal phase separation and enabled a uniform morphology. We presented the analysis of the cathodes by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA). These results allow us to develop a mechanistic hypothesis and a comparison between Fe2P and LFP in terms of the electrochemical performances.
(Invited) Development of Highly Luminescent Radical Core Carbazole Dendrimer
Authors: Albrecht Ken 
Published: July 2022

The development of emitting materials for OLEDs has started with fluorescence, moved to phosphorescence, and reached TADF. These materials have singlet ground state, but recently some ground state doublet (radical) emitting materials have been reported.1,2 The excited state of doublet emitters also has a doublet character, and theoretically, can achieve 100% exciton utilization efficiency in an OLED device. Triphenylmethyl radicals such as PTM (perchlorotriphenylmethyl) radical were recognized as emitters from the 1980s. The photostability of these radicals are extremely low, but in 2006 the introduction of donor (carbazole) unit was reported to improve the photostability and opened the door to utilize them as a luminescent materials.3

Carbazole dendrimers are widely used as solution-processable OLED material including TADF emitters.4 The dendron has a highly polarized unique electronic structure due to the summation of the inductive electron-withdrawing effect of carbazole units.5 The attachment of carbazole dendrons to luminescent radical is expected to increase the stability through the steric and electronic effects.
A carbazole dendron (G2 to G4) attached TTM (tris(2,4,6-trichlorophenyl)-methyl) radicals were successfully synthesized and photophysical parameters were determined. All dendrimers showed red emission. PLQY (photoluminescence quantum yield) increased when the generation increased and reached 80%. The major reason was the decrease in the internal conversion rate (non-radiative decay). The photostability (PL intensity half-life measured under continuous laser irradiation) in solution has increased 100 to 1000 times compared to simple TTM radicals. These results indicate that the carbazole dendron attached TTM radicals are potential material for efficient OLEDs.
References
[1] Q. Peng, A. Obolda, M. Zhang, F. Li, Angew. Chem. Int. Ed.
2015, 54, 7091.
[2] X. Ai, E. W. Evans, S. Dong, A. J. Gillett, H. Guo, Y. Chen, T. J. Hele, R. H. Friend, F. Li, Nature
2018, 563, 536.
[3] V. Gamero, D. Velasco, S. Latorre, F. Lopez-Calahorra, E. Brillas, L. Julia, Tetrahedron Lett.
2006, 47, 2305.
[4] K. Albrecht, K. Matsuoka, K. Fujita, K. Yamamoto, Angew. Chem. Int. Ed.
2015, 54, 5677.
[5] K. Albrecht, K. Yamamoto J. Am. Chem. Soc.
2009, 131, 2244.
(Invited) Simulating Dynamic Excitons Via Quantum Molecular Dynamics: A Case Study in Lead Halide Perovskites
Authors: Uratani Hiroki 
Published: July 2022

The ultrafast electronic and structural dynamics invoked by photoexcitation, i.e., “dynamic exciton” phenomena, not only are important in the context of practical applications such as solar cells, but also raise many questions from the viewpoint of fundamental science. Experimental measurement, computational simulations, and theoretical interpretation will be the three pillars for deciphering the dynamic exciton phenomena.
From the viewpoint of computational simulations, molecular dynamics (MD) techniques combined with quantum chemical calculations, i.e., quantum molecular dynamics (QMD), has been the popular tool to simulate the dynamic exciton phenomena. The quantum chemical calculations, which are typically conducted on the basis of the density-functional theory (DFT), require the large computational resources and time. These have been the limiting factors for the accessible spatial and time scales by the QMD simulations.
To extend the coverage of simulations to more complex, large-scale systems, we have developed efficient excited-state QMD methods that can include nonadiabatic effects. Our method combines the density-functional tight binding (DFTB) method, which is an approximate DFT, and the surface hopping method, which is a theoretical framework to incorporate the nonadiabatic effects into the QMD simulations. The method was further improved to be suitable for condensed-phase simulations explicitly including the environment, i.e., solvent, by using a “divide-and-conquer” style quantum chemical calculation technique. These theoretical framework enables us to simulate the coupled electronic–structural dynamics in excited states of systems consisting of 102–103 atoms[1,2,3].
In addition, using the developed method, we conducted the real-time simulations of the ultrafast processes invoked by photoexcitation of lead iodide perovskites, which are known as the key materials for perovskite solar cells. The dissociation of the exciton into the positive and negative charge carriers was observed. Moreover, the hot carrier cooling, where the charge carriers dissipate excess energy via the electron–phonon coupling and relax to the band edges, was also tracked. Finally, the direct evidence of the polaron formation, where the structural deformation is induced by the presence of charge carriers, was observed. These results highlight the importance of the coupling between electronic and structural degrees of freedom.
In the talk, recent improvements in the methodology and future perspectives will also be presented[5].
References
[1] H. Uratani and H. Nakai, J. Chem. Phys.
152, 224109 (2020).
[2] H. Uratani, T. Morioka, T. Yoshikawa, and H. Nakai, J. Chem. Theory Comput.
16, 7299 (2020).
[3] H. Uratani, T. Yoshikawa, and H. Nakai, J. Chem. Theory Comput.
17, 1290 (2021).
[4] H. Uratani and H. Nakai, J. Phys. Chem. Lett.
11, 4448 (2020).
[5] H. Uratani and H. Nakai, J. Chem. Theory Comput. in press.

Figure 1
Chromophore Nanohybrids for Sensing and Singlet Oxygen Generation
Authors: Hill Jonathan P. 
Published: July 2022

Nanohybrid materials can exhibit the physical properties of their components and be used in various applications. Also, novel chromophores involving synthetically flexible molecules such as pyrazinacenes1 and porphyrins2 can be incorporated into these structures by different means in particular as MOFs or COFs, while other components include simple transition metal salts or oligonuclear metal-oxo clusters. In this work, we discuss nanohybrids materials containing oxoporphyrinogen (OxP), tetrapyrroles or fullerene as the organic component, with hybridization using respectively Ag(I) salt or oxo-Zr(IV) cluster. This yields nanohybrid materials having structures and properties due to their individual components. Highly-colored OxP is a tetrapyrrole macrocycle which can be stimulated to generate reactive singlet oxygen (1O2) under appropriate conditions (1O2 can be used for applications such as photodynamic therapy and environmental remediation). 1O2 generation by OxP undergoes significant enhancement over its unhybridized state when incorporated in nanohybrid structures, either MOFs or COFs, containing respectively oxo-Zr(IV) nodes or electron deficient linkers in porous coordination polymer nanoarchitectures. OxP-oxoZr(IV) nanohybrid can then be applied for oxidation of small molecule substrates to selected products.3 Also, C60 fullerene can be co-crystallized with silver(I) nitrate at the molecular level4 leading to a material that exhibits unique properties during its decomposition so that silver nitrate is released with concurrent deposition of highly nanostructured C60-only crystalline networks. The resulting nanohybrid material has been studied for application as slow-release antibacterial material.4 Other work includes porous materials for sensing applications. The utility of the nanohybrid approaches is demonstrated by using these examples.
References: 1) G. J. Richards, J. P. Hill, Acc. Chem. Res., 2021, 54, 3228–3240. 2) M. K. Chahal, A. Liyanage, A. Z. Alsaleh, P. A. Karr, J. P. Hill, F. D'Souza, Chem. Sci., 2021, 12, 4925–4930. 3) J. Hynek, D.T. Payne, M.K. Chahal, F. Sciortino, Y. Matsushita, L.K. Shrestha, K. Ariga, J. Labuta, Y. Yamauchi, J.P. Hill, Mater. Today Chem., 2021, 21, 100534. 4) J. P. Hill, R. G. Shrestha, J. Song, Q. Ji, K. Ariga, L. K. Shrestha, Bull. Chem. Soc. Jpn., 2021, 94, 1347–1354.
Molecular Lego for Functional 2D Materials: Self-Assembly and Ordering of Bi-Molecular 2D Spinlattices of M(II,III) Phthalocyanines and of Highly Crystalline Free Standing Networks
Authors: Baljozovic Milos , Liu X. , Moradi Mina , Pasti Igor A. , Dreiser Jan , Decurtins Silvio , Shahgaldian Patrick , Liu Shi Xia , Jung Thomas A. 
Published: July 2022

Single layer low-dimensional materials are presently of emerging interest, also in the context of magnetism. We further developed on-surface supra-molecular architecturing to create two-dimensional spin arrays. By chemical programming of the modules, different checkerboards were produced containing metals of different oxidation and spin states, diamagnetic zinc, and a metal-free ‘spacer’. [1] In an in-depth, spectro-microscopy and theoretical account, we correlate the structure and the magnetic properties of these tunable systems and discuss the emergence of 2D Kondo magnetism [2] from the spin-bearing components and via the physico-chemical bonding to the underlying substrate. The contributions of the individual elements, as well as the role of the electronic surface state in the bottom substrate, are discussed. Also we show the the first free-standing single layer networks of calixarenes stabilized via functional groups enabling vdW, coordination and dipole-dipole, interaction. [3]
Fig. 1) Graphical animation of the 2D spin arrays built by C--H - F--C bonding of two different magnetic atom bearing phthalocyanines that have been exploited to investigate the assembly and properties of Kondo lattices.
[1] M. Baljozovic et al. Magnetochemistry 2021, 7, 119.
[2] J. Girovsky et al. Nature Communications 2017 8:15388
[3] M. Moradi, N. Opara, L.G. Tulli, C. Wäckerlin, S.J. Dalgarno, S.J. Teat, M. Baljozovic, O. Popova, E. van Genderen, A. Kleibert, H. Stahlberg, J.P. Abrahams, C. Padeste, T.A. Jung, P. Shahgaldian, Sci. Adv. 2019; 5: eaav4489

Figure 1
Agricultural Waste-Derived Nanoporous Carbon As Electrode Material for High-Power Plant Microbial Fuel Cell
Authors: Lin Yao-Yu , Li Hsin-Tien , Chen Han-Yi , Liu Tzu-Yin 
Published: July 2022

Developing environment-friendly and sustainable energy is urgent these days, as it can solve energy shortages and the pollution that come from fossil fuel. Therefore, Plant microbial fuel cells (PMFCs) start to get attention recently. PMFC is a novel technology that can convert chemical energy into electricity by using microbial in the rhizosphere of plants without producing harmful byproducts during the process. However, PMFCs suffer from some practical issues such as low power output and high costs of electrode materials. This gives rise to the progress of electrode material which can improve the power output and reduce the cost.
To break through the limits of PMFCs, the agricultural waste-derived carbons were prepared and optimized as the anode material in our self-designed Canna-indica PMFCs in this study. Green carbon materials utilizing agricultural waste as precursors are not only environment-friendly but also a part of circular economy which helps to mitigate bio-waste and improve society sustainability. The biowaste-derived activated carbon materials were characterized by Brunauer-Emmett-Teller (BET) surface area analyzer, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The high surface area, porosity morphology, and good conductivity of the biowaste-derived activated carbon are the promising characteristics of high-performance anode materials of PMFCs. The maximum power density of our self-made PMFC device can reach 61 mW m−2. The average power density was maintained at 23 mW m−2 during the long-term measurement. All of the results in this study demonstrate the potential of using agricultural waste as electrode material for improving the electricity production of PMFCs.
Teesmat an Open Innovation Test Bed for Electrochemical Devices: Example of X-Ray Nano-Tomography As Characterization Tool for Battery Analysis
Authors: Vanpeene Victor , Drnec Jakub , Schulli Tobias , Capria Ennio , Villanova Julie 
Published: July 2022

The recent rapid increase of the demand of higher energy density along with higher power density lithium-ion batteries (LiBs) requires the development of advanced cathode/anode materials with higher capacity. These challenges can be addressed providing that powerful characterization tools are able to probe the degradation phenomena occurring at multiple scale. In this context, the TEESMAT platform aims to widen the access to a large panel of characterization techniques among different partners across Europe for solving industrial problematics in energy related field. Among these, X-ray tomography has been used as non-invasive 3D investigation tool that spread along a wide range of applications in order to probe at different length scale their microstructure. Moreover, phase contrast imaging has brought to light a practical way to enhance visibility between weak absorbing materials and/or small details of differing refractive index within structure, and thus accessing a sharpen overview of the 3D morphology of complex material, which is of particular interest in the frame of energy-related materials.
This presentation will focus on various industrial case studies such as NMC-based and LFP-based all solid-state batteries, hybrid Li-ion supercapacitor and current collector manufacturing.
The results presented are part of the TEESMAT project, which received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 814106.
Evaluation of Counter and Reference Electrodes for the Investigation of Ca Battery Materials
Authors: Liu Xu , Elia Giuseppe , Passerini Stefano 
Published: July 2022

The massive demand for batteries required by electromobility and stationary storage is pushing the research activity to evaluate electrochemical storage chemistries based on highly abundant elements, as alternatives to state-of-the-art Li-ion ones.[1] The use of more abundant and sustainable elements is expected to reduce the cost and the environmental impact of the energy storage devices. In particular, calcium, the fifth most abundant element in the Earth’s crust also offering non-toxicity, low standard reduction potential (-2.87 vs. SHE), is an appealing candidate for the realization of electrochemical storage devices.[1] However, the conditions to achieve efficient Ca stripping and deposition have not been found yet, due to the formation of passivation products at the Ca/electrolyte interphase, blocking any electrochemical reaction.[2] Although a limited number of electrolytes enabling the stripping deposition have been found, [3–6] they are characterized by a rather limited efficiency, thus making the Ca metal unsuitable for counter and reference electrodes. The resulting lack of a reliable cell configuration limits the possibility to test candidate electrode materials suitable for Ca2+-based electrochemical storage devices, impeding the progress and research on the topic. Here, we propose an alternative cell configuration, employing activated carbon (AC) as counter electrode and quasi reference electrode (QRE), as a reliable system for the electrochemical characterization of electrode materials for Ca-ion batteries.[7] As a prove-of-the-concept, a few electrode materials, i.e., CaV6O16 cathode and graphite anode exploiting co-intercalation mechanism, have been demonstrated electrochemically active in Ca2+-based electrolytes.

References:

[1] M.E. Arroyo-De Dompablo, A. Ponrouch, P. Johansson, M.R. Palacín, Achievements, Challenges, and Prospects of Calcium Batteries, Chem. Rev. 120 (2020) 6331–6357.
[2] D. Aurbach, R. Skaletsky, Y. Gofer, The Electrochemical Behavior of Calcium Electrodes in a Few Organic Electrolytes, J. Electrochem. Soc. 138 (1991) 3536–3545.
[3] A. Ponrouch, C. Frontera, F. Bardé, M.R. Palacín, Towards a calcium-based rechargeable battery, Nat. Mater. 15 (2016) 169–172.
[4] D. Wang, X. Gao, Y. Chen, L. Jin, C. Kuss, P.G. Bruce, Plating and stripping calcium in an organic electrolyte, Nat. Mater. 17 (2018) 16–20.
[5] A. Shyamsunder, L.E. Blanc, A. Assoud, L.F. Nazar, Reversible Calcium Plating and Stripping at Room Temperature Using a Borate Salt, ACS Energy Lett. 4 (2019) 2271–2276.
[6] Z. Li, O. Fuhr, M. Fichtner, Z. Zhao-Karger, Towards stable and efficient electrolytes for room-temperature rechargeable calcium batteries, Energy Environ. Sci. 12 (2019) 3496–3501.
[7] X. Liu, G.A. Elia, S. Passerini, Evaluation of counter and reference electrodes for the investigation of Ca battery materials, J. Power Sources Adv. 2 (2020) 100008.
Interface Engineering Via Fluorinated Solid Electrolytes for All-Solid-State Li Batteries
Authors: Zhang Shumin , Zhao Feipeng , Sun Xueliang Andy 
Published: July 2022

Solid electrolytes (SEs) are vital for all-solid-state batteries (ASSBs) since they replace the flammable liquid electrolytes to make the ASSBs safer and compacter.1 In order to boost the energy density of ASSBs, a practical SE is not only expected possessing high ionic conductivity, but also good compatibility with both cathode and anode to allow the use of high-voltage cathode and Li metal.2, 3 However, most of the developed SEs show limitations on directly contact with either high-voltage cathode materials or Li metal. As such, SE modification is required to address the interfacial issues between SE and electrodes.
In this work, fluorinated sulfide- and halide-based SEs are proposed to stabilize the SE/Li metal and SE/high-voltage cathode interfaces, respectively. Our results firstly show that fluorinated argyrodite Li6PS5Cl (LPSCl) can enhance the interfacial stability toward the Li metal anode.4 The in-situ formed interface between Li and LPSCl1−xFx are of highly fluorinated and condense, which enables ultrastable Li plating/stripping behavior over 250 hrs at a high current density of 6.37 mA cm−2 and a cutoff capacity of 5 mAh cm−2. The Li metal treated by the LPSCl1−xFx SE is then demonstrated to deliver good durability and rate capability in full cells. Other than anode side improvement, F is introduced into a superionic conductor Li3InCl6 to widen the oxidation limit to over 6 V (vs. Li/Li+).5 Both experimental and computational results identify that F-containing passivating interphases are generated to contribute to the enhanced oxidation stability of Li3InCl6-xFx and stabilization the surface of cathodes at high cut-off voltages. The optimized composition Li3InCl4.8F1.2 is directly matched with bare high-voltage LiCoO2, enabling ASSBs to stably operate at room temperature at a cut-off voltage of 4.8 V (vs Li/Li+). Our studies provide a new strategy of interface engineering by introducing F in SEs, realizing the good compatibility between SE and electrodes and opening up the applications of ASSBs.

Re
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Wang, C. H., Liang, J. W., Zhao, Y., Zheng, M. T., Li, X. N., Sun, X. L. All-solid-state lithium batteries enabled by sulfide electrolytes: from fundamental research to practical engineering design. Energy Environ. Sci.
14, 2577-2619 (2021).

Li, J. C., Ma, C., Chi, M. F., Liang, C. D., Dudney, N. J. Solid Electrolyte: the Key for High-Voltage Lithium Batteries. Adv. Energy Mater.
5, 1401408 (2015).

Zhao, F. P., et al. Ultrastable Anode Interface Achieved by Fluorinating Electrolytes for All-Solid-State Li Metal Batteries. ACS Energy Lett.
5, 1035-1043 (2020).

Zhang, S. M., et al. Advanced High-Voltage All-Solid-State Li-Ion Batteries Enabled by a Dual-Halogen Solid Electrolyte. Adv. Energy Mater.
11, 2100836 (2021).