bluuebunny/crossref_metadata_2025_split huggingface dataset:
New Low Cost Sulfide Electrolytes for All Solid State Batteries
Authors: Raj Hari , Neveu Audric , Pralong Valerie 
Published: February 2024

The low cost, safe and high energy storage technology is needed to ensure a continuous energy supply from renewal energy sources. However, current Li-ion batteries (LiBs) are facing challenges to fulfil the safety and high energy and power demands of fast-growing market of electric vehicles (EVs). In particular, liquid organic electrolytes used in conventional LIBs have raised the safety issues due to serious fire risk. Solid state batteries (SSBs) are considered to provide better safety as compared to LIBs because of solid electrolytes (SEs) are used in SSBs instead of flammable organic liquid based electrolytes [1-4].
The various types of solid electrolytes have already been reported for SSBs which can be divided into oxides, sulfides, halides and polymers based on their properties, advantages and disadvantages [5]. Among these solid electrolytes, sulfide solid electrolytes have advantages over other due to high conductivity and ductile nature of sulfides [6]. The discovery of Li10GeP2S12 solid electrolyte called LGPS structured sulfide electrolyte have shown great potential to replace liquid electrolyte as ionic conductivity of LGPS was found 1.2×10-2 S cm-1 at room temperature comparable to the conductivity of organic liquid electrolyte [7]. However, Li10GeP2S12 electrolyte suffers with poor cyclability in solid state batteries due to reduction of Ge+4 ions to Ge0, and instable against lithium metal anode. Moreover, germanium (Ge) is a rare and expensive element, which limits the industrial application of Li10GeP2S12 [8, 9].
Therefore, in the present work, we have developed LGPS structured based new Ge free solid electrolytes with high conductivity and better electrochemical stability. The phase identification of newly synthesized solid electrolytes is done by X-ray diffractometer technique along with Rietveld refinement analysis. The conductivity of prepared solid electrolytes is determined by electrochemical impedance spectroscopy. The ionic conductivity of newly synthesised electrolytes has reached upto 0.67 mS cm-1 at room temperature. The electrochemical analysis of prepared solid electrolytes is done using Li-metal in both side (in symmetric cell) as well as using standard cathode and anode materials (full cell).
References:

Janek et al., Energy 1, 2016, 16141.

Xu et al., Joule 2, 2018, 1991.

Li et al., RSC Adv. 5, 2015, 52382.

Scrosati et al., Power Sources 195, 2010, 2419.

Zhang et al., Energy Storage Mater. 10, 2018, 139-159.

Jiang et al., ACS Appl Mater Interfaces 12, 2020, 54662-70.

Kamaya et al., Mater., 10, 2011, 682–686.

Neveu et al., Power Sources 467, 2020, 228250.

Wan et al., ACS Energy Lett., 6, 2021, 862–868.
Dithiolate-Based Scorpion Arm Ligand Synthesis and Characterization
Authors: Mazumder MD Motiur Rahaman , Islam Rejaul , Islam Rezoanul 
Published: February 2024

Redox flow batteries (RFBs) play a vital role in the efficient and reliable utilization of renewable energy sources by providing a means to capture and store excess energy for later use.1–6 The synthesis and characterization of a novel scorpionate arm ligand, i-mntPy- (2,2-dicyano-1-pyridin-2-ylmethyl-1,1-dithiolate), are presented in this study. The ligand i-mntPy- was synthesized through a multistep synthetic route, starting from commercially available precursors. The chemical structure of the ligand was confirmed using various spectroscopic techniques, including NMR spectroscopy, ESI-MS, and Elemental analysis. Furthermore, the coordination ability of i-mntPy- to facilitate 2e- transfer in M(II/IV) coordination environment was investigated by the computational study and addition of Ni(II) and Pd(II) ions in the i-mntPy- solution. The results demonstrate the successful synthesis and characterization of the novel scorpionate arm ligand i-mntPy-, which coordinates with d8 metal centers and holds promise for future applications in coordination chemistry and energy storage.

References

(1) Mazumder, Md. M. R.; Jadhav, R. G.; Minteer, S. D. Phenyl Acrylate-Based Cross-Linked Anion Exchange Membranes for Non-Aqueous Redox Flow Batteries. ACS Mater. Au
2023. https://doi.org/10.1021/acsmaterialsau.3c00044.
(2) Rahaman Mazumder, M. M.; Islam, R.; Khan, M. A. R.; Anis‐Ul‐Haque, K. M.; Rahman, M. M. Efficient AcFc‐[Fe III (Acac) 3 ] Redox Couple for Non‐aqueous Redox Flow Battery at Low Temperature. Chem. – Asian J.
2023, 18 (1). https://doi.org/10.1002/asia.202201025.
(3) Mazumder, Md. M. R.; Dalpati, N.; Pokkuluri, P. R.; Farnum, B. H. Zinc-Catalyzed Two-Electron Nickel(IV/II) Redox Couple for Multi-Electron Storage in Redox Flow Batteries. Inorg. Chem.
2022, 61 (48), 19039–19048. https://doi.org/10.1021/acs.inorgchem.2c03124.
(4) Mazumder, Md. M. R.; Burton, A.; Richburg, C. S.; Saha, S.; Cronin, B.; Duin, E.; Farnum, B. H. Controlling One-Electron vs Two-Electron Pathways in the Multi-Electron Redox Cycle of Nickel Diethyldithiocarbamate. Inorg. Chem.
2021, acs.inorgchem.1c01699. https://doi.org/10.1021/acs.inorgchem.1c01699.
(5) MAZUMDER MDMOTIURRAHAMAN, Islam R. Temperature-dependent study of AcFc-FeIII(acac)3 redox couple for non-aqueous redox flow battery. ChemRxiv. Cambridge: Cambridge Open Engage; 2022; https://doi.org/10.26434/chemrxiv-2022-3177p
(6) Islam, R.; Mazumder, M. M. R.; Farnum, B. H. Solvent Dependent Spectroscopic and Electrochemical Studies of Nickel (II) Diethyldithiocarbamate for Energy Storage. ECS Meet. Abstr.
2021, MA2021-01 (1), 54–54. https://doi.org/10.1149/ma2021-01154mtgabs.

Figure 1
Laser-Induced Printing of Next Generation Silicon-Graphite Anodes for the Development of Advanced Lithium-Ion Batteries
Authors: Rist Ulrich , Sterzl Yannic , Falkowski Viktoria , Pfleging Wilhelm 
Published: February 2024

The expansion of renewable causing a rising demand for affordable and improved energy storage systems. Lithium-ion batteries (LIB) are one of the most promising technologies for this achievement, with further improvements to be made in terms of new materials and an advanced electrode architecture. As a new generation electrode material to be included in LIB, silicon is in the focus of the today’s investigations. Silicon offers one order of magnitude higher theoretical specific capacity (3579 mAh/g) compared to the state-of-the-art material graphite (372 mAh/g). However, during lithiation of silicon a volume expansion of up to 300 % takes place. Due to the huge volume expansion tremendous mechanical degradation of the anode occurs, resulting in a drop in capacity and a shorten lifetime.
Laser induced forward transfer (LIFT) is applied in this study as printing technology to develop enhanced silicon-graphite electrode compositions and electrode architectures. LIFT was performed using a pulsed nanosecond UV-laser with a maximum power of 10 W and repetitions rate of up to 30 kHz. For the LIFT process of anodes, polyacrylic acid (PAA) is used as binder, in contrast to the polyvinylidene fluoride (PVDF) binder commonly used for LIFT assisted printing of electrodes. PAA is a more appropriate binder for silicon-containing anodes than PVDF. In addition, also a customized architecture using subtractive and additive laser process techniques is introduced for an increase in lifetime of batteries containing silicon-based electrodes. For this purpose, graphite electrodes were structured with an ultrashort pulse laser with pattern widths of 100 µm. Subsequently, silicon rich slurry was printed into the patterns to increase the areal capacity. The as-prepared electrodes have spatially separated graphite and silicon regions. The respective electrodes were electrochemically cycled in half-cells and charged at different C-rates up to 5C to investigate their lithiation capability. After the rate capability analysis, the cells were cycled at C/2 to investigate the long-term degradation. The cells with the printed electrodes were cycled for more than 450 cycles with a capacity fade of 5 %. At their end-of-life, the cells were analyzed post-mortem. Finally, full-cells were assembled with cathodes containing NMC 622 as the active cathode material. Subsequently to the cell priming a lifetime analysis was performed at a C-rate of C/2 and cycle stability as well as lithium loss during cycling were evaluated.
Stability of Alizarin for Aqueous Organic Redox Flow Batteries
Authors: Maleki Meysam , Imhanria Sarah , Duguet Lisa , Goulet Marc-Antoni 
Published: February 2024

The intermittent nature of renewable energy sources like solar and wind requires suitable large-scale energy storage technologies to properly respond supply and demand of energy. Aqueous organic redox flow batteries (AORFBs) have demonstrated great potential to revolutionize grid-scale energy storage as a result of their low-cost, safety and ability to separate energy and power1. However, most of the organic compounds suffer from lack of sufficient long-term stability.
Alizarin (1,2-dihydroxyanthraquinone) is a low-cost, nontoxic, and industrially accessible dye which could potentially be used as an affordable redox-active negative electrolye (negolyte)2. Here, we present an in-depth investigation on the long-term cycling stability of Alizarin. Furthermore, we implement an aggressive cycling conditions to investigate the degradation of the cycled negolyte within just a single day, achieving an equivalent capacity fade percentage as electrolyte cycled for over two weeks3. The capacity fade of alizarin was partially mitigated by the employment of a SOC restriction strategy which was able to decrease the capacity fade rate by more than 60 %.4 Capacity fade measured via cycling is corroborated by ex situ chemical analysis methods.
References:
(1) Kwabi, D. G.; Ji, Y.; Aziz, M. J. Electrolyte Lifetime in Aqueous Organic Redox Flow Batteries: A Critical Review. Chem. Rev.
2020, 120 (14), 6467–6489.
(2) Liu, Y.; Lu, S.; Chen, S.; Wang, H.; Zhang, J.; Xiang, Y. A Sustainable Redox Flow Battery with Alizarin-Based Aqueous Organic Electrolyte. ACS Appl. Energy Mater.
2019, 2 (4),
(3) Goulet, M.-A.; Aziz, M. J. Flow Battery Molecular Reactant Stability Determined by Symmetric Cell Cycling Methods. J. Electrochem. Soc.
2018, 165 (7), A1466–A1477.
(4) Goulet, M.-A.; Tong, L.; Pollack, D. A.; Tabor, D. P.; Odom, S. A.; Aspuru-Guzik, A.; Kwan, E. E.; Gordon, R. G.; Aziz, M. J. Extending the Lifetime of Organic Flow Batteries via Redox State Management. J. Am. Chem. Soc.
2019, 141 (20), 8014–8019.
Space Charges in Solid State Batteries: Friend, Foe or Fantasy?
Authors: Al-Kutubi Hanan , Ganapathy Swapna , Wagemaker Marnix 
Published: February 2024

Thermodynamics tells us that all materials have an internal energy that determines how they act and react with all matter in the universe. Furthermore, it forces all matter to strive towards equilibrium with its surroundings. For solid-state lithium-ion conductors, the chemical potential of lithium is an important parameter that determines stability and influences conductivity. However, it also implies something deeper. The chemical potential of an element in a solid is determined by the bonds that surround it as well as its concentration. Whereas the former is an intrinsic property of the material, the latter can be altered. When two solids with different chemical potentials are placed in contact, a driving force is created for atoms to migrate across the surface and establish thermodynamic equilibrium by altering their concentration. For semiconductors, in which either only a hole or electron can migrate, something interesting occurs. The migrating entity moves across but the counter-charge cannot, resulting in excess charge at the interface. The migrating partner, unable to return to its original material due to thermodynamics, is now unable to dissipate into the new material due to electrostatics. The result is a thin, charged layer across the interface. Because solid electrolytes conduct lithium cations but no anions or electrons, this ‘space-charge layer’ is also thought to occur in solid-state batteries between electrolyte and electrode. Whereas its size is thought to only be a few nanometres, its (negative) influence could be very large as it can act as barrier for lithium transport across the surface. Yet experimental evidence of its existence is rare and investigation of its behaviour even more so. The space charge between two materials is very thin and chemically almost identical to the bulk. But just like how water can carve the stone, we employ liquids to crack a solid-state problem.
We find that when mixing an argyrodite solid electrolyte (Li6PS5Cl) with an ionic liquid (1-Ethyl-3-methylimidazolium bis(trifluoromethyls ulfonyl) imide or EMIN TFSI) , we observe a new chemical environment with NMR (see figure) that cannot be attributed to dissolved precursors. We see an increase in the mobility of lithium ions in the solid electrolyte itself with NMR and an increase in conductivity of the mixture with EIS. Furthermore, exchange of lithium has been confirmed between argyrodite and the mystery environment. What does this all mean? Are we observing the illusive space charge layer? Or are we just staring at an empty promise in the well-known shape of a mysterious peak in a spectrum?

Figure 1
Next-Generation Polymeric Organic Semiconductors for Electrochemical Transistors with Applications in Bioelectronics
Authors: LeCroy Garrett , Cendra Camila , Salleo Alberto , Giovannitti Alexander 
Published: February 2024

Over the last decade, significant progress has been made in developing efficient mixed-organic-ionic-electronic conductors (OMIECs) for electrochemical transistors. Improvements in device performance for both transconductance and operational stability paved the way for applications of electrochemical transistors for health monitoring, neuromorphic computing, or electrochemical sensors. While the tuning of the energy levels (via backbone engineering) and the local environment of the polymers (via side-chain engineering) is reported to be a successful strategy for improving the electronic and ionic charge transport properties, little is known about how the short- and long-range order of polymers impacts the device performance.
In my talk, I will discuss the importance of microstructure and dynamic microstructural rearrangements of OMIECs which greatly influence the electronic charge transport properties in electrochemical transistors [1]. By combining electrochemical and spectroelectrochemical measurements alongside electrochemical X-ray diffraction measurements, we observe that holes and anions are placed in ordered aggregates and crystallites at relatively low charge carrier densities (< 2x1020 cm-3) for selected OMIECs, explaining the large increase in transconductance at low operational voltages. Moreover, we find that the electrochemical charging of p-type polymeric OMIECs induces structural order along the polymer backbones. We interpret this structural ordering as the key factor for achieving high transconductance since percolating networks can form more easily when polymer chains are planarizing. Surprisingly, these dynamic microstructural rearrangements are highly reversible, however only when high charge carrier densities are avoided where bipolarons are forming. Based on these findings, I will discuss chemical design strategies for next-generation OMIECs with improved transconductance and operation stability in electrochemical transistors.
[1] Garrett LeCroy, Camila Cendra, Tyler J. Quill, et.al., Role of aggregates and microstructure of mixed-ionicelectronic-conductors on charge transport in electrochemical transistors, Mater. Horiz., 2023, accepted.
Γ-Graphyne: A Promising Electron Acceptor for Organic Photovoltaics
Authors: Stasyuk Anton , Stasyuk Olga A. , Solà Miquel 
Published: February 2024

The most significant discovery of recent years is graphene, which consists of a single layer of sp2-hybrid carbon atoms arranged in a two-dimensional (2D) honeycomb lattice nanostructure.Graphynes – a two-dimensional materials similar to graphene, but composed of sp-hybridized carbons periodically integrated into a sp2-hybridized carbon network. Structure of graphynes were first theoretically proposed in 1987 by Baughman et al.[1] More than 20 years later, in 2010, Li et al. developed the first successful methodology for creating γ-graphdiyne films [2]. Despite the significant attention from the scientific community, only recently Hu et al. reported the synthesis of γ
-graphyne with unified long-range crystalline structure [3].
We demonstrate that γ
-graphyne is an efficient electron acceptor due to its low LUMO and its ability to delocalize an excess charge. Moreover, in contrast to other 2D sheets like graphene its electronic properties are not sensitive to vacancy defects. Investigation of photoinduced electron transfer processes in complexes of γ
-graphyne with typical electron-accepting and electron-donating partners shows that the lowest excited states with donors are charge separated states formed by the electron transfer from partner to γ
-graphyne. This electron transfer is thermodynamically favorable and occurs on nano-to-picosecond time scale. In contrast, electron transfer from γ
-graphyne to strong electron acceptors such as fullerenes or arylenediimides is unlikely [4].
References:
[1] R.H. Baughman, H. Eckhardt, M. Kertesz, J. Chem. Phys. 1987, 87, 6687
[2] G. Li, Y. Li, H. Liu, Y. Guo, Y. Li, D. Zhu, Chem. Commun. 2010, 46, 3256.
[3] Y. Hu, C. Wu, Q. Pan, Y. Jin, R. Lyu, V. Martinez, S. Huang, J. Wu, L.J. Wayment, N.A. Clark, M.B. Raschke, Y. Zhao, W. Zhang, Nat. Synth. 2022, 1, 449.
[4] O. A. Stasyuk, A. J. Stasyuk, M. Solà, A. A. Voityuk, Mater. Des. 2023, 225, 111526.
Step Potential Electrochemical Spectroscopy (SPECS) Technique to Investigate the Ageing of Carbon Electrodes in Organic-Based Electrochemical Capacitors
Authors: Sroka Sylwia , Galek Przemyslaw , Fic Krzysztof , Menzel Jakub 
Published: February 2024

Current research on electrode degradation in electrochemical capacitors (ECs) mainly focuses on the application of new materials and the establishment of their stability on the basis of various standards and qualitative tests. However, there exists limited research that focuses on the elucidation and determination of the degradation mechanisms and pathways of carbon electrodes. The proposed study uses an innovative approach with the use of the Step Potential Electrochemical Spectroscopy (SPECS) technique, which allows one to quantify the contribution of different charge-storing mechanisms, and successfully track any changes that take place after accelerated ageing, including structural changes of the electrode in the organic medium. Additionally, the role of oxygen content on the degradation of ECs was explored.
In this report carbon material, namely binder-free Activated Carbon Cloth (ACC) Kynol® 507-20 was prepared in a furnace under a nitrogen atmosphere at different temperatures, namely 120, 500, and 1000ᵒC. This is so that the effect of the presence of different oxygen functional groups on the surface of carbon could be investigated. The material was selected as a self-standing electrode to eliminate any influence the binder would have on the electrode porosity. Subsequently, these materials were prepared as electrode materials and assembled in a symmetric two-electrode setup with 1M TEABF4/AN (tetraethylammonium tetrafluoroborate in Acetonitrile solvent). In each cell, the potential range of both electrodes was first determined in a 2-electrode Swagelok® cell with RE using galvanostatic charge/discharge (1 A g-1). The further procedure involved 3 CV cycles (1 mV s-1) at a predetermined potential for each electrode in a 3-electrode set-up, followed by SPECS measurement where 5-minute potentiostatic hold with 10 mV potential steps was applied. The obtained current vs. time plots were used to calculate the corresponding capacitance, diffusion and residual parameters. Floating tests at 2.7 V were then carried out for each system. According to the international standard (IEC 62391-1), system failure is reported when the initial capacitance drops below 80% of its initial value; thus floating experiments were halted after that value was reached for each system or when the resistance of the cell doubled in value. The electrochemical investigation of the individual aged electrodes was then repeated in the same manner.
Our study allowed for a thorough examination of individual electrodes prior to and after floating experiments, which helped to elucidate the degradation causes and pathways in organic medium.
A Sustainable Li-Ion Capacitor Using Sawdust-Derived Activated Carbon Cathode Paired with Prelithiated Al Foil Anode
Authors: Guo Xiaoyang , Zheng Tianye , Zhang Jia , Wahl Markus Solberg , Burheim Odne , Boles Steven T 
Published: February 2024

Activated carbon (AC) has long been recognized as a promising electrode material for energy storage/harvesting devices. The extraordinarily high specific area (e.g., ~2000 m2/g) makes AC almost irreplaceable in some applications, such as electrical double-layer capacitors (EDLCs) and capacitive deionization (CDI). [1] Yet the production of AC is often a concern due to the release of unwanted contaminants, such as waste acids and gaseous CO/CO2, resulting from a series of processes involving heating, burning, and the use of strong acids.
In this work, we present an activated carbon cathode that is fabricated following a more sustainable approach, namely by using sawdust waste as the carbon precursor via a physical activation process to modify its surface area and porosity. With the electrochemical performances being characterized by designated cyclic voltammetry (CV), galvanostatic charge-discharge cycling (GCD), and electrochemical impedance spectroscopy (EIS), the activation parameters, such as temperature, activation time and activation gas composition, are expected to be optimized for various application purposes.
To quickly demonstrate the technical feasibility, a high-performance Li-ion capacitor (LIC) is assembled using the sawdust-derived AC cathode to pair with a piece of prelithiated Al foil anode (β-LiAl). [2] Such an LIC is considered a hybrid energy storage device that can potentially combine the high energy density of a Li-ion battery with the high power density of a supercapacitor. Despite decent electrochemical performances, the proposed LIC device using a waste-derived cathode and a simple metallic foil anode can indeed help to better realize sustainability. [3] It is believed that such a unique LIC architecture can be a promising alternative to conventional energy storage devices for various applications, such as renewable energy storage, electric vehicles, and portable electronic devices.