bluuebunny/crossref_metadata_2025_split huggingface dataset:
Ni/Cu/Ag: An Electrochemically Synthesised Trimetallic Stack for CO2 Reduction
Authors: Dickinson Hannah Louise Alexandra , Symes Mark 
Published: September 2023

Climate change, as a result of excess atmospheric CO2 and other greenhouse gases, maintains a position, according to the United Nations as the “defining issue of our time”.1 This has led to research efforts to limit CO2 outputs as well as recycling CO2 which is already present. The electrochemical reduction of CO2 has exponentially gained interest as a possible solution since the late 1990s; if the reduction can be achieved in conjunction with a renewable energy source (e.g solar power), it could be considered carbon negative. Electrochemical CO2 reduction would remove some of the excess CO2 from the atmosphere in conjunction with providing a way for the intermittent energy generated by renewable methods to be stored as chemical bonds, both of which aid the fight against climate change.
Significant focus has been placed on pure metals as electrocatalysts since Hori’s seminal discovery that Cu can uniquely reduce CO2 by more than two electrons to produce hydrocarbons.2 High overpotentials and poor selectivity remain as challenges due to the scaling relations between the simultaneous pathways of CO2 reduction.3 One approach for breaking these is alloying or the use of mixed metal phases. Bimetallic catalysts, particularly those containing Cu have gained considerable interest4, however, limited examples of trimetallic catalysts have been explored.
Herein, a NiCuAg electrocatalyst has been electrochemically synthesised by copper electrodeposition on nickel, followed by galvanic replacement to produce a silver layer. The combination of Ni and Cu was proven to be promising in recent studies5,6 generating desirable non-CO and H2 products such as ethanol. Ag has been shown to promote *CO intermediate production on the Cu surface7 thus its addition to our catalyst should further promote non-CO and H2 products and increase their selectivities.
Linear sweep voltammetry revealed significant activity at potentials more negative than -0.8 V vs. Ag/AgCl, thus CO2 reduction was completed in this region. Reduction products were analysed by gas chromatography and liquid products by NMR. The trimetallic stacks were characterised by XRD, and SEM/EDX before and after reduction to explore their morphology and lifetimes.
References:
[1] https://www.un.org/en/global-issues/climate-change [Accessed 27/11/2022]
[2] Y. Hori, A. Murata and R. Takahashi, J. Chem. Soc., Faraday trans., 1989, 85, 2309—2326
[3] A. A. Peterson and J. K. Nørskov, J. Phys. Chem. Lett., 2012, 3, 251—258
[4] H. L. A. Dickinson and M. D. Symes, Electrochem. Commun., 2022, 135, 107212
[5] X. D. Zhang, K. Liu, J. W. Fu, H. M. Li, H. Pan, J. H. Hu and M. Liu, Front. Phys., 2021, 16, 63500
[6] T. M. Suzuki, T. Ishizaki, S. Kosaka, N. Takahashi, N. Isomura, J. Seki, Y. Matsuoka, K. Oh ishi, A. Oshima, K. Kitazumi, K. Sekizawa and T. Morikawa, ChemComm, 2020, 56, 15008—15011
[7] Y. Zhu, Z. Gao, Z. Zhang, T. Lin, Q. Zhang, H. Liu, L. Gu and W. Hu, Nano Research, 2022, 15, 7861—7867

Figure 1
Electrochemical CO2 Reduction to Ethylene Using Coupled Tandem Electrolyzers
Authors: Strasser Peter 
Published: September 2023

The thermal catalytic “Ethylene to Liquids” (ETL) Process is an emerging alternative to the two classical “Fischer-Tropsch” and “Methanol-to-Liquids” process routes toward production of synthetic/e- hydrocarbon fuels. The ETL process, however, relies on a non-fossil ethylene supply. The electrochemical reduction of CO2 to ethylene can serve as an emerging new ethylene supply route.
In this talk, I will highlight some of our recent advances in the design and characterization of efficient CO2 electrolyzers for the electroreduction of CO2 to ethylene in tandem cell designs. The cell tandem consists of a “CO2 to CO” electrolyzer (cell 1) incorporating NiNC single site, coupled to “CO2/CO mixed feed to ethylene” electrolyzer (cell 2). Carbonate transport processes in cell 1 are diagnosed using the carbon cross over coefficient (CCC). Mechanistic aspects of mixed feed reduction are discussed. Performance and its limitations of tandem operation will be discussed.
Electrochemical Reduction of Amine-Captured CO2 in Aqueous Solutions
Authors: Leverick Graham , Gallant Betar M. 
Published: September 2023

Technologies that can capture CO2 and enable conversion into value-adding chemicals and fuels or stable minerals for sequestration are vital for transitioning towards net zero or even negative greenhouse gas emissions. Conventional approaches for electrochemically converting CO2 have utilized a decoupled approach of first capturing and concentrating CO2, and then using the concentrated CO2 as a feedstock for conventional electrochemical processes. Direct electrochemical reduction of amine-captured CO2
1,2
can potentially offer advantages by removing the need to thermally regenerate the amine capture solution, which can be energy intensive and typically uses thermal energy from nonrenewable sources. In this talk, we share our recent work on the electrochemical reduction of amine-captured CO2 to value-adding products like CO and stable minerals like carbonates. We discuss the influence of the capture environment on the resulting capture solution chemistry, and how to alter the capture solution speciation through electrolyte design. We further consider the detailed CO2 reduction mechanisms in these amine-containing solutions and provide design strategies for increasing the Faradaic efficiency of CO2 reduction vs. the competitive hydrogen evolution reaction (HER), as well as decreasing the overpotential of CO2 reduction.

References:

(1) Chen, L.; Li, F.; Zhang, Y.; Bentley, C. L.; Horne, M.; Bond, A. M.; Zhang, J. Electrochemical Reduction of Carbon Dioxide in a Monoethanolamine Capture Medium. ChemSusChem
2017, 10 (20), 4109–4118.
(2) Lee, G.; Li, Y. C.; Kim, J.-Y.; Peng, T.; Nam, D.-H.; Sedighian Rasouli, A.; Li, F.; Luo, M.; Ip, A. H.; Joo, Y.-C.; Sargent, E. H. Electrochemical Upgrade of CO2 from Amine Capture Solution. Nat. Energy
2021, 6 (1), 46–53.
Electrochemical Reduction of CO2 in Atmospheric Level Using Bimetallic Catalysts on Liquid-Electrolyte Free Cathodic Half Cell
Authors: Choi Youngyu , Govindan Muthuraman , Kim Daekeun 
Published: September 2023

The climate crisis, caused by anthropogenic greenhouse gas (GHG), is one of the most urgent environmental issues. CO2 is one of the GHGs that contributes the most to global warming. Electrochemical CO2 reduction is considered one of the most promising technologies to solve the global warming problem and realize resource recovery. CO2 reduction technology is practically limited because most CO2 reduction techniques are theoretically based on gas-liquid or gas-liquid-solid reactions. Conventional electrochemical CO2 reduction has applied liquid electrolytes, which have the limitation of mass transfer and the problem of liquid product separation. Up to now, most studies have focused on applying high-level CO2 (pure CO2 and % level), which is also practically limited to field application.
This study aimed to establish the gas-solid reaction to enable the electrochemical reduction of CO2 at the atmospheric level (hundreds ppm level). We proposed agar gel solid electrolyte inserted between the bimetallic catalysts and ion exchange membranes system for the gas phase CO2 reduction at liquid electrolyte free state. A bimetallic (Cu-Ni or Cu-Zn) metal-organic frameworks (MOFs) used, as electrocatalyst, after coating on 3D foam base. The electrode surface characteristics were confirmed through x-ray diffraction (XRD) and scanning electron microscope (SEM) analysis, and the presence of bimetals on the electrode was confirmed through energy dispersive X-ray spectrometer (EDS). The redox behaviors of the electrode and it’s catalytic CO2 reaction were confirmed through gas-phase cyclic voltammetry and linear sweep voltammetry. It was observed in the experiment that CO2 removal reached up to 99%, and initial product analysis ended with methane, methanol, and dimethyl ether, which will be analyzed and discussed.
Acknowledgment
This research was supported by Basic Science Research Program through the National Research Foundation of Korea(NRF) funded by the Ministry of Education(NRF-2021R1I1A1A01049901)
Understanding Solid Electrolyte Interphase (SEI) Species at the Electrode-Electrolyte Interface in Liquid Lithium Metal Batteries Via in-Situ Fourier Transform Infrared (FTIR) Spectroscopy
Authors: Wang Daniel , Katayama Yu , Minafra Nicolò , Lopez Jeffrey , Shao-Horn Yang 
Published: September 2023

Lithium metal is the ideal candidate to replace conventional carbonaceous anodes due to its high theoretical specific capacity of 3860 mAh/g and low negative thermodynamic potential of -3.040 V vs. SHE [1]. Fine tuning the solid-electrolyte interphase (SEI) is critical for the practical implementation of liquid lithium metal batteries [2]. The presence of particular SEI species are hypothesized to improve the coulombic efficiency and mitigate dendrite formation for enhanced lifetime and safety, respectively [2]. Recently, Zhang et al. developed a novel in-situ Fourier transform infrared (FTIR) spectroscopy method to reveal electrolyte oxidation via carbonate dehydrogenation on Ni-based oxides in Li-ion batteries [3]. We leverage this technique and apply it to the Cu side in a Li || Cu battery to probe SEI growth and evolution. In this study, we systematically change the salt, solvent and additive components of the electrolyte and monitor the organic and inorganic SEI species that form under different electrochemical conditions. Furthermore, we directly correlate the chemical composition of the SEI to cell-level coulombic efficiency [4]. Complimentary characterization techniques will be used to further resolve the chemical structure of the SEI. Finally, results from this study will help generate descriptors for the rationale design of new electrolytes.
References
1. Cheng, Xin-Bing, et al. "Toward safe lithium metal anode in rechargeable batteries: a review." Chemical reviews 117.15 (2017): 10403-10473.
2. Peled, E., and S. Menkin. "SEI: past, present and future." Journal of The Electrochemical Society 164.7 (2017): A1703.
3. Zhang, Yirui, et al. "Revealing electrolyte oxidation via carbonate dehydrogenation on Ni-based oxides in Li-ion batteries by in situ Fourier transform infrared spectroscopy." Energy & Environmental Science 13.1 (2020): 183-199.
4. Hobold, Gustavo M., et al. "Moving beyond 99.9% Coulombic efficiency for lithium anodes in liquid electrolytes." Nature Energy 6.10 (2021): 951-960.
Improved Electrochemical Properties of Aqueous Lithium-Ion Batteries Via the Optimization of Gel Polymer Electrolytes
Authors: Lee Junghun , Yeo Jae-Seong , Yoo Eunji , Yu Hye-Ryeon , Ahn Tae-Young , Kim Jiyoun , Choi Yusong 
Published: September 2023

Lithium-ion batteries (LIBs) have been developed for their high energy density and long cycle life in military systems. However, the use of non-aqueous electrolytes based on toxic and flammable organic solvents have raised serious safety concerns including fire and explosion in LIBs. Aqueous LIBs with non-flammable and environmental aqueous electrolytes are promising alternative to eliminate the safety issues. Because aqueous batteries use water as a solvent of electrolyte, they are stable with no flammable. However, the narrow electrochemical stability window (ESW) of water in aqueous electrolytes limits operating voltage and energy density of aqueous batteries. Recently, ESW was expanded by applying a high concentration lithium salt electrolyte called “water-in-bisalt” (WIBS). A 4.0 V aqueous LIB was developed by passivating graphite anodes with hydrophobic LiTFSI-HFE gels, which effectively extended electrolyte stability [1].
In this study, we developed a 4.0 V aqueous LIBs using UV-cured gel polymer electrolytes. Highly concentrated UV-cured gel polymer electrolytes were coated to cathodes and UV-cured gel protection layers were applied to anode surfaces for improving stability. Also, gel polymer electrolytes were optimized with various lithium salts and additives. We also evaluated cycle performance and safety such as cutting, penetration test with LiMn2O4∥graphite pouch type cells. There were no fires and explosions.

References

[1] Yang et al., Joule 1, 122-132, September 6, 2017
Establishing an Appropriate Voltage Window for Stable Cycling of Li/Mn-Rich Layered Oxide || Graphite Full Cells
Authors: Arifiadi Anindityo , Schmuch Richard , Kasnatscheew Johannes , Winter Martin 
Published: September 2023

Li/Mn-rich layered oxide cathode active materials (LMR) have gained attention due to their exceptionally high practical specific discharge capacity (>250 mAh g-1) originating from both conventional cationic as well as anionic oxygen redox contributions. To achieve this high capacity, the Li2MnO3-like regions of the material, which give rise to oxygen redox need to be electrochemically activated at high voltage (above 4.6 V versus Li+/Li0). This high voltage activation, however, results in the destabilization of lattice oxygen that creates subsequent adverse phenomena such as first-cycle hysteresis and the evolution of redox couples. The latter happens continuously during cycling and results in the activation of Mn3+/Mn4+ redox couple. This redox couple involving Mn3+ is problematic because, at this oxidation state, Mn disproportionation reaction can occur, resulting in the formation of highly soluble Mn2+ species. In a half-cell setup, the impact of Mn dissolution may be subtle, however, in LMR||Graphite full cells, the impact is consequential.
This work focuses on investigating the degradation mechanism of LMR||Graphite full cells at different voltage windows applied during the activation cycles and the long-term cycling. These different voltage windows alter the redox contributions and thus affect the long-term performance of the cells. We observe that lowering the upper cut-off voltage (UCV) from 4.7 V to 4.5 V during the entire cycling process can increase capacity retention, although rapid degradation can still be observed. Only when the UCV during the long-term cycling is lowered to 4.3 V, can we obtain incremental degradation of the cells. We also show that lowering the activation cycles UCV to 4.5 V is beneficial for long-term cycling due to the lower contribution of Mn3+/Mn4+ redox couple after the activation cycles. Finally, we observe that increasing the lower cut-off voltage from 1.9 V to 2.4 V results in higher discharge voltage. Nevertheless it is followed by a reduction in discharge capacity, resulting in a lower specific energy. This study offers insights into the high-voltage cycling performance of practical LMR||Gr full cells that can be used for the foundation of material design to alleviate the adverse effect of oxygen redox in LMR.
Estimation of Crack Formation By Digital-Twin Structure of a Single Secondary Particle
Authors: Song Jihun , Lee Hyobin , Kim Suhwan , Lim Jaejin , Kim Kyung-Geun , Lee Yong Min 
Published: September 2023

Most of the recently commercialized active materials for lithium-ion batteries (LiB) adopt secondary particles, and most of them are designed by evaluating cell-level electrochemical properties. Therefore, the relationship between particle design and battery performance is not properly understood because it is not possible to grasp the intrinsic properties of the electrode active material. Therefore, a single particle measurement technique has been developed in which a gold or platinum filament having a diameter of several tens of microns is directly contacted with a single particle to evaluate the single particle electrochemical properties. However, since it is a non-sealed battery system, only less-volatile electrolytes can be applied. Also, the experiment is difficult because the contact between particle and filament can easily break down with small vibration. Additionally, there are a lot of particle design parameters such as particle shape, size, and size distribution. Moreover, with operating conditions, the particle design needs to be changed. So, it is challenging to cover all cases by experiment.
In this study, digital-twin structure of a single secondary particle was formed using focused ion beam / scanning electron microscope. Using the digital-twin structure, digital-twin electrochemo-mechanical model was developed and more than 99% of accuracy was secured by comparing the voltage profiles with result of single particle measurement technique. Using the well-matched model. Operando analysis of electrochemical properties (State of Lithiation, overpotential, potential, and concentration) and mechanical properties (von Mises stress and strain energy density) were performed. The strain energy density can be the criteria to determine the crack formation by comparing with the fracture toughness which is the strain energy density when the fracture occurs.
Dilation Study of Si-Rich Anode in the Next Generation Lithium-Ion Batteries
Authors: Banifarsi Sanaz , Abdellatif Abdelaziz , Wohlfahrt-Mehrens Margret 
Published: September 2023

Silicon has attracted a lot of attention as anode material in lithium ion batteries due to its high practical capacity (around 3579 mAh.g-1 at Li15Si4 phase [1]). The main drawback for the use of Silicon is its significant volume expansion around 300% in fully intercalate state which causes particles pulverisation, dynamic formation of the solid electrolyte interface (SEI), losing electrical contact and capacity loss.[2] The solution is hidden in using silicon composite instead of pure silicon, [1,3] applying partial lithiation or delithiation process,[4] and improving the electrical particles contact by applying optimum external pressure.[5] The main aim of the current study is to investigate the electrochemical performance and the dilatometry behaviour of a multilayer pouch cells (0.06 to 1.5 Ah) under the external mechanical pressure. Using 1/3 of the Si capacity in order to stabilized electrochemical performance of a highly content silicon anodes (70 wt% Si), exhibited electrode irreversible expansion around 20% after 3 cycles of formation at 0.1C and 75% electrode thickening after 200 cycles at 0.5C.

References

[1] P. Li, H. Kim, S.-T. Myung, Y.-K. Sun, Energy Stor. Mater. 35 (2021) 550–576. https://doi.org/10.1016/j.ensm.2020.11.028.
[2] L.Y. Beaulieu, K.W. Eberman, R.L. Turner, L.J. Krause, J.R. Dahn, Electrochem. Solid-State Lett. 4 (2001) A137. https://doi.org/10.1149/1.1388178.
[3] P. Kargl, V. Drews, P. Daubinger, O. Schweighofer, M. Marinaro, G.A. Giffin, M. Wohlfahrt-Mehrens, A. Thaler, J. Power Sources 548 (2022) 232042. https://doi.org/10.1016/j.jpowsour.2022.232042.
[4] M.N. Obrovac, L.J. Krause, J. Electrochem. Soc. 154 (2007) A103. https://doi.org/10.1149/1.2402112.
[5] M. Göttlinger, P. Daubinger, W. Stracke, S. Hartmann, G.A. Giffin, Electrochim. Acta 419 (2022) 140354. https://doi.org/10.1016/j.electacta.2022.140354.

Acknowledgment

Funding of the project HysKaDi (03XP0321) by the German Federal Ministry of Education and Research (BMBF) are gratefully acknowledged.

Figure 1
Study of Transport Phenomena in Next Generation Lithium Batteries, Assisted by 3D Printing
Authors: Laventure Audrey , Dolle Mickael , Faral Manon 
Published: September 2023

Lithium-ion batteries (LIB) have a major role in the global energy future as they currently offer the best alternative for energy storage. The increase in energy demand is driving the development and optimization of high-performance batteries. With the specific objective of improving energy densities, studying the limiting phenomena such as the transport of species through the batteries’ components is essential. In this regard, using a new emerging technology such as 3D printing to process some of the batteries’ components could answer some issues. Thanks to its design flexibility compared to conventional manufacturing methods, this technique offers the possibility of creating customizable and complex architectures that could help unravel limiting phenomenon.
More specifically, 3D printing is an interesting way to design solid electrolytes. This study aims at showing how the structure, the composition and the configuration of the solid electrolyte will affect the systems properties and thus its electrochemical performances. A first part of the study consists in evaluating the feasibility of 3D printing a solid composite electrolyte with a complex architecture. Thus, 3D printing techniques will be discussed as well as the formulation of a ceramic ink. Other aspects will be addressed such as the ink printability studies via rheology, the processing of different structures via printing and the print fidelity. Using different compositions and architectures, different structural characterizations and conductivity tests are performed to evaluate the impact of the processing on the system properties. The optimization of this proof of concept involving various polymer/ceramic ratios, geometrical architectures and processing studies is an interdisciplinary project that can lead to significant advances in the field of batteries.
Comprehensive Approach about Time-Relevant Degradation of Ni-Rich Cathode Materials for Electric Vehicles
Authors: Park Nam-Yung , Kim Su-Bin , Lee Han Uk , Sun Yang-Kook 
Published: September 2023

With the prevalence of electric vehicles, Ni-rich layered cathodes have been extensively developed to increase the energy density of Li-ion batteries (LIBs). However, cathodes with a high Ni content suffer from inherent structural and chemical instabilities, which lead to rapid capacity fading and thermal instability.1 In particular, the rapid capacity fading of Ni-rich layered cathodes is largely caused by microcracking and the resultant microstructural instability.2 In addition to microcracking, the time during which highly reactive Ni4+ ions are exposed to the electrolyte when the cathode is in a highly charged state also affects the deterioration of the cathode. Although the exposure time is not significant for cathodes with Ni contents of <60%, the calendar aging test of Ni-rich cathodes reveals that the exposure time, especially at high SoCs, critically affects the degradation of these high-Ni cathodes, as the internal surfaces of the particles are also exposed to the electrolyte via the microcracks.3 The exposure time is particularly pertinent for electric vehicle (EV) LIBs, as they remain stationary for long periods in the highly charged state and are operated intermittently. Consequently, the upper SoC limit of EV LIBs is commonly limited to ≈85%, but this limits the driving range and increases the cost of the batteries. Therefore, a holistic approach considering real-use behavior, as well as the properties of the material itself, is needed to overcome the limitations of Ni-rich cathodes.
Here, 1 mol% B doping of a core–shell concentration gradient (CSG) Li[Ni0.88Co0.10Al0.02]O2 cathode (CSG-NCA88) is shown to dramatically alter the microstructure of the cathode and effectively protect the particle interior from parasitic electrolyte attack. The B-doped CSG-NCA88 cathode, CSG-NCAB87, maintains its original microstructure even after holding for 500 h in the fully charged state, whereas irreversible structural damage occurs in the pristine CSG-NCA88 cathode during the prolonged electrolyte exposure. The long-term cycling results confirm that the capacity retention of the cathodes is determined by the electrolyte exposure time at a high SoC and that microstructural modification can effectively suppress the time-dependent degradation from electrolyte attack. The proposed CSG-NCAB87 cathode can be utilized at full capacity without restricting the SoC, thus realizing the development of economical high-energy-density LIBs.

Reference
s
:

[1] H.-J. Noh, S. Youn, C. S. Yoon, Y.-K. Sun, J. Power Sources, 2013, 233, 121.
[2] H.-H. Ryu, K.-J. Park, C. S. Yoon, Y.-K. Sun, Chem. Mater. 2018, 30, 1155.
[3] H.-H. Ryu, G.-T. Park, C. S. Yoon, Y.-K. Sun, Small, 2018, 14, 1803179.