bluuebunny/crossref_metadata_2025_split huggingface dataset:
Lithium-Ion Batteries Enhancing Cycling Performance of Silicon Graphite Anodes Using Carbon Nanotubes
Authors: Kinyanjui Francis , Hakim Charifa 
Published: February 2024

Silicon graphite anodes have emerged as promising candidates to replace conventional graphite anodes due to their higher theoretical capacity and ability to store more lithium ions. However, the significant volume expansion of silicon during lithiation and delithiation cycles results in severe mechanical degradation and rapid capacity fade, limiting their practical application. Additionally, the realisation of electrodes with high Si content are further limited by poor diffusion kinetics, resulting in an insufficient rate capability performance and lithium trapping.
In this study carbon nanotubes (CNTs) are incorporated into the silicon graphite anode matrix as a strategy to mitigate these issues and enhance the cycling performance of LIBs. The CNTs, with their unique mechanical, electrical, and chemical properties, offer numerous benefits, including enhanced structural integrity, improved electrical conductivity, and increased lithium-ion diffusion kinetics. We investigated the effect of different ratios of CNTs on the cycling performance of silicon graphite anodes. The electrochemical performance of the composite electrodes were systematically evaluated using galvanostatic cycling, cyclic voltammetry, and electrochemical impedance spectroscopy. Preliminary results show that the addition of CNTs to silicon graphite anodes significantly improves their cycling stability and rate capability. The composites exhibit reduced capacity fade, improved coulombic efficiency, and enhanced rate performance compared to silicon graphite anodes absent of the CNTs, facilitated by faster lithium-ion diffusion kinetics, leading to improved electrochemical performance.
A Step Towards the Impossible – the Combination of High Ionic Conductivity and Mechanical Stability in Highly Crystalline Solid Polyketone Electrolytes
Authors: Andersson Rassmus , Johansson Isabell Lee , Hernández Guiomar , Mindemark Jonas 
Published: February 2024

Implementation of solid polymer electrolytes (SPEs) is believed to be one pathway forward in the development of lithium-metal batteries (LMBs) that are both safe and possesses high capacities. This combination is possible since the free-standing SPE maintains its mechanical integrity during electrochemical and thermal exposure while utilizing lithium metal as the negative electrode, thus accessing the extremely high theoretical capacity of lithium metal. The main drawback for SPEs are however the poor ionic conductivity compared to the liquid electrolytes used in lithium-ion batteries today.[1] The low ionic conductivity for SPEs stems from the conduction mechanism of the ions, which is a slower process in SPEs compared to in liquid electrolytes. In general, the conductivity in SPEs are confined to the amorphous regions, where segmental motion of the polymer chains facilitates the ion transport; while the crystalline regions restrict the movements of the polymer chains and impairs the ion transport.[2]

The highly crystalline polyketone poly(1-oxoheptamethylene) (POHM) is a material that has shown interesting characteristics for implementation as a SPE in batteries. In earlier studies, the polyketone revealed an extensive improvement of the ionic conductivity upon increasing the salt concentration, although the crystallinity remained with a high melting point.[3]

Herein this study, the effect of the crystallinity on the characteristics and the performance was investigated further. To understand its effect, a second less hydrogenated version of POHM was synthesized, POHM-75, which is fully amorphous at high salt concentrations. The characteristics of the polyketones were in addition also compared with the more well-studied SPEs, that is polyethylene oxide (PEO) and poly(trimethylene carbonate) (PTMC). Focus of the presentation is on the interplay between the ionic conductivity and mechanical stability for the polyketones, for which something different to the normally observed tradeoff between the two properties is observed. The electrochemical performance of the polyketones are furthermore evaluated when implemented as SPEs in LMBs at extreme temperature environments, a possible application area for mechanically stable SPEs.
[1] D. Zhou, D. Shanmukaraj, A. Tkacheva, M. Armand, G. Wang, Chem
2019, 5, 2326-2352.
[2] M. A. Ratner, P. Johansson, D. F. Shriver, MRS Bulletin
2011, 25, 31-37.
[3] T. Eriksson, H. Gudla, Y. Manabe, T. Yoneda, D. Friesen, C. Zhang, Y. Inokuma, D. Brandell, J. Mindemark, Macromolecules
2022, 55, 10940-10949.

Figure 1
Revisiting the Anodic Stability of Aluminum Current Collectors in High-Voltage Li-Ion Batteries
Authors: Etman Ahmed S. , Nyholm Leif 
Published: February 2024

High-voltage Li-ion batteries are anticipated to play a crucial role in the present transition towards electric vehicles, owing to their high energy density. However, a big challenge is the anodic stability (often referred to as corrosion) of the positive electrodes current collector, aluminum (Al), at potentials > 3.0 V vs. Li+/Li). In this work, we present a systematic study on the corrosion of 12 µm-thick Al foil (©Gränges, Sweden) up to 5.0 V vs. Li+/Li in a series of carbonate electrolytes containing lithium hexafluorophosphate (LiPF6), lithium bis(fluorosulfonyl) imide (LiFSI) or lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) salts. The selection of the 12 µm foil was motivated by the need to decrease the mass or volume of the dead weight components (i.e., current collector) to increase the energy density of the battery.
The electrochemical behavior was investigated using voltammetric techniques, and the results indicated that the anodic oxidation of the 12 µm Al foil was similar to that of the conventionally used 20 µm-thick Al foil. Notably, the first anodic oxidation scan exhibited a two-step oxidation after 3.5 V vs. Li+/Li, suggesting carbonate solvent oxidation and a liberation of H+ ions attacking the native surface Al2O3 layer followed by oxidation of metallic Al. A passivation was observed on the subsequent scans in 1.0 M LiPF6 solutions due to formation of surface layer of AlF3, as confirmed by X-ray photoelectron spectroscopy (XPS) analyses. [1,2]
However, in 1.0 M solutions of the imide salts (i.e., LiFSI or LiTFSI) a continuous anodic oxidation of aluminum was seen between 3.5 and 5.0 V vs. Li+/Li on the first few scans. After this the magnitude of the anodic current decreased significantly. The latter observations can be attributed to formation of soluble Al(TFSI)
x
or Al(FSI)
x
complexes [3] and a gradual saturation of the electrolyte. The voltammetric experiments showed that the magnitude of the anodic current increased when increasing the volume of the used imide electrolyte, supporting the saturation hypothesis.
Results and analyses regarding the anodic oxidation of Al in a series of carbonate solvents and using different salt concentration, as well as effect of the use of carbon coated Al will also be presented.
References:
[1] S. T. Myung, Y. Sasaki, S. Sakurada, Y. K. Sun, H. Yashiro, Electrochim. Acta
2009, 55, 288.
[2] C. Bizot, M.-A. Blin, P. Guichard, J. Hamon, V. Fernandez, P. Soudan, J. Gaubicher, P. Poizot, Electrochem. commun.
2021, 126, 107013.
[3] M. Morita, T. Shibata, N. Yoshimoto, M. Ishikawa, J. Power Sources
2003, 119–121, 784.
Understanding Lithium-Ion Battery Degradation through P2D Model Parameters Evolution
Authors: Sordi Gabriele , Rabissi Claudio , Casalegno Andrea 
Published: February 2024

Despite its commercial level, lithium-ion battery ageing is still a hot topic in the research community. Indeed, the relation between ageing and the operating conditions and loads in a real-life operation is under investigation and the corresponding residual life prediction is still a challenging task.
In this work, a combined approach with experiments and modeling is applied. A wide driving cycle campaign is carried out, involving 12 different profiles to test different combinations of temperature, C-rate, SoC and DoD, whose values were defined after a literature review about the most common values in a real application, and highlight their effect on battery ageing. Two calendar ageing campaigns at the same temperatures are also conducted to quantify the acceleration of the degradation rate due to cycling and analyse if the degradation path is different.
For the interpretation of the results, the P2D model is employed. No explicit description of the main degradation mechanisms is applied. Indeed, the degradation is described through the variation of the physical parameters of the usual model implementation, like a reduction of lithium inventory or active electrode material or a variation of reaction rates and diffusion constants. A specific sequence of tests has been developed as check-up procedure. As detailed in 1, it is a trade-off between testing time and the operating conditions that maximise the identifiability of the parameters of the model.
Therefore, the parameter identification problem is performed periodically upon check-ups and parameters trend over time/cycles is derived. Since it is a physical model, every parameter has a physical meaning and its evolution can be associated to a certain range of degradation phenomena. In this way, the model can support the identification of the most likely phenomena that are ongoing in the battery and the value of the parameters constitutes a new concept of state of health, more comprehensive than the residual capacity value.
Finally, the model interpretation is proved in two ways. First, a validation dataset is provided, to evaluate the capabilities of the calibrated model in reproducing the behaviour of an aged cell under different operating conditions with respect to the check-up procedure. Then, some cells undergo post-mortem analyses to verify the origin of degradation and measure the values of the physical parameters, like optical and chemical analyses, q-OCP discharges of harvested electrodes in coin cell setup for thermodynamic parameters or EIS for kinetic parameters.
This approach, though not suitable on-board, provides a novel physics-based method for a reliable analysis of lithium-ion batteries degradation.

1
G. Sordi, C. Rabissi, A. Casalegno, Reliable thermal-physical modeling of lithium-ion batteries: consistency between high-frequency impedance and ion transport. Under Review
Organic Faradaic Desalination Cell Based on Polyimide Symmetric Electrodes
Authors: Fombona Pascual Alba , Patil Nagaraj , Garcia - Quismondo Enrique , Goujon Nicolas , Mecerreyes David , Marcilla Rebeca , Palma Jesus , Lado Julio J. 
Published: February 2024

Capacitive deionization (CDI) is an energy-efficient and environmentally friendly deionization technology. However, the maximum desalination capacity of conventional carbon-based CDI systems is in the range of 5–25 mg g-1, which compromises the use of this technology in practical applications [1]. Faradaic deionization (FDI) is a promising electrochemical technique, based on storing the ions within the particles/layers of the electrode materials either by intercalation and/or faradic reactions. By this mechanism, FDI has expanded the deionization values above 50 mg g-1. In the last ten years, research on FDI has primarily focused on battery electrode materials, especially in inorganic intercalation compounds, typically used for energy storage [2]. However, inorganic materials have several drawbacks, such as decomposition and dissolution issues, which affect long-term performance along with safety and sustainability aspects and consequently might limit their practical deployment.
As an alternative, we introduce in this work for the first time an all-polymer deionization cell in combination with a rocking-chair desalination (RCD) mechanism with the aim of boosting the deionization performance [3]. A proof-of-concept next generation technology is accomplished by using a redox-active naphthalene-polyimide (poly[N,N′-(ethane-1,2-diyl)-1,4,5,8-naphthalenetetracarboxiimide], named as PNDIE), which is a well conductive and free-standing electrode material, as anode and cathode in a symmetric FDI system. Our approach relies on the synergistic combination of smart redox polymer selection i.e. PNDIE, and the advance configuration of this material into a buckypaper electrode architecture. A detailed electrochemical characterization under various operational conditions in three electrodes standard half-cell and in two electrode coin-cell configurations was performed. The results of those experiments provide critical information to build an all-polymer rocking chair system with practical PNDIE electrodes (92.2 mgPNDIE; 9.6 cm2). This novel FDI lab-cell demonstrated a remarkable desalination capacity (155.4 mg g-1 at 0.01 A g-1) together with a high salt-removal rate and productivity (3.42 mg g-1 min-1 at 0.01 A g-1 and 62 L h-1 m-2, respectively). In addition, long-term stability experiments provided salt adsorption capacity retention values over 95 % after 100 cycles (23 days). Compared to the state-of-the-art deionization technologies (CDI, Hybrid CDI and FDI) the reported technique exhibits superior electrochemical and deionization performance. These results support the idea of using organic materials as a viable alternative for robust and sustainable “water-energy” electrochemical applications.

References:

[1] Y. Lui, ACS Nano, 2021, 15, 13924-13942
[2] Q. Li, Adv. Sci., 2020, 7, 2002213
[3] A. Fombona-Pascual, Chemical Engineering Journal, 2023, 461, 142001

Figure 1
Electrocoagulation Technique for Treating Swine Slaughterhouse Wastewater from Batch to Semicontinuous Operation Mode
Authors: Sandoval Miguel A , Coreño Oscar , García Verónica , Salazar Ricardo 
Published: February 2024

In this study, industrial swine slaughterhouse wastewater was treated by electrocoagulation process using batch and semicontinuous operation systems. Electrochemical technique was carried out in batch operation mode during 2.5 h applying different current densities in sulfate and chloride media. After finding the best operating parameters in batch mode (lab-scale), the process was transferred to a semicontinuous pre-pilot scale process using a filter-press FM01-LC type electrochemical reactor fitted with flat plate aluminum electrodes. In this stage, distinct current densities and mean linear flow rates were assessed.
Total organic carbon, chemical oxygen demand, total phosphorus, total nitrogen, and potassium among other parameters were analyzed during both treatments. The industrial swine slaughterhouse wastewater contained TOC 333 mg L–1, COD 1765 mg L–1, TP 13.55 mg L–1, TN 327 mg L–1, K 45 mg L–1, turbidity 102 NTU, color –absorbance 0.90 A.U. at 415 nm–, conductivity 1.9 mS cm–1, and pH 6.9. The highest TOC removal efficiency (72.7%), in semicontinuous process, was found at j = 25 mA cm-2 and ur
= 0.64 cm s-1 with an energy consumption of 19.80 kW h m-3. Residual COD and TP concentrations met the international standard limits. Moreover, complete discoloration and disinfection were achieved. EDXRF, SEM, EDAX, XRD, and FTIR analyzes indicate pollutants were removed by adsorption on aluminum/iron hydroxides/oxyhydroxides.
Electrochemically Induced CO2 Capture Enabled By Aqueous Organic Redox Chemistry
Authors: Jing Yan , Amini Kiana , Xi Dawei , Jin Martin , Alfaraidi Abdulrahman , Gordon Roy G. , Aziz Michael J. 
Published: February 2024

Investigations are ongoing to determine whether electrochemically-driven CO2 capture with inexpensive redox-active molecules in aqueous electrolyte in a scalable flow cell system has the potential to cost-effectively reach impactful scale.
Water-soluble redox organic molecules “Q” can potentially capture CO2 from diffuse and point sources in an electrochemical flow cell. For example, proton-coupled electron transfer of these molecules (Q+2H++2e- → QH2) can raise the electrolyte pH, leading to the capture of CO2 from air; subsequent electrochemical oxidation of the reduced molecules (QH2 → Q+2H++2e-) acidifies the electrolyte, resulting in the release of pure CO2
[1-2]. The thermodynamic analysis indicates that an idealized cycle requires the minimum work input varying from 16 to 75 kJ/molCO
2 as throughput per cycle increases, with the potential to go substantially lower if CO2 capture or release is performed simultaneously with electrochemical reduction or oxidation. The method appears safe and scalable, as it utilizes non-toxic, non-corrosive, non-volatile and potentially low-cost organic molecules.
An alternative CO2 capture mechanism, which appears to operate in parallel to this pH swing mechanism, is a nucleophilicity swing in which the electrochemically reduced species spontaneously forms a CO2 adduct, Q(CO2)2
2
-, which releases its CO2 upon electrochemical oxidation.
In spite of the advantages in thermodynamic minimum and sustainable electrochemical processes, oxygen intolerance of the reduced molecules (QH2) has limited its application to direct air capture (DAC) due to reversible chemical oxidation of QH2 back to Q by atmospheric oxygen. Here, we report reduced Q species with improved resistance to oxidation by air. The air tolerance of the reduced Q with captured CO2 was evaluated under air exposure and tracked by 1H NMR. From day-1 to day-9, an NMR sample was loosely capped and stored in lab air. There was no sign of chemical changes in the NMR spectra for the first 5 days, and the peaks of Q in the oxidized state did not appear before the ninth day. The air stability of Q(CO2)2
2
- within the first five days suggests the feasibility of utilizing Q for a CO2capture/release cycle in the presence of oxygen that takes << 5 days.
We will report the results of molecular engineering efforts to further improve molecular stability of the reduced form under oxygen.
[1] Jin, S.; Wu, M.; Gordon, R. G.; Aziz, M. J.; Kwabi, D. G. pH swing cycle for CO2 capture electrochemically driven through proton-coupled electron transfer, Energy Environ. Sci., 2020, 13, 3706-3722.
[2] Jin, S.; Wu, M.; Jing, Y.; Gordon, R. G.; Aziz, M. J. Low energy carbon capture via electrochemically induced pH swing with electrochemical rebalancing, Nature Communications, 2022, 13, 2140.
Coating Applications By Pulse/Pulse Reverse Electrolysis
Authors: Hall Timothy , Garich Holly , Wang Dan , Vijapur Santosh Hanamant , Radhakrishnan Rajeswaran , Le Huong , Snyder Stephen , Inman Maria , Taylor Earl Jennings 
Published: February 2024

Faraday Technology Inc. is a research, development and electrochemical engineering firm developing electrochemical innovations based has pulse/pulse reverse electrolytic principles. [1,2] With that founding basis Faraday has been able to bridge the gap between academic understanding and small-scale demonstrations to commercialization of practical components for over 32 years of operation.
This presentation will discuss a broad range of electrodeposition studies including single metal, alloy, composite and electrophoretic. We will highlight some of the key factors that determine the usefulness and successfulness of using pulse/pulse reverse principles to apply materials to a broad range of structures. For instances, we will discuss additive free Cu deposition into a microvia, functionally graded NiMo coatings from a single electrolyte, graphene incorporation into a Cu film, and electrophoretic deposition of CNTs. Each process utilized pulse/pulse reverse plating to overcome key challenges with diffusion, stress, composition, adhesion, and functional properties.

References:

J. Taylor “Adventures in Pulse/Pulse Reverse Electrolytic Processes: Explorations and Applications in Surface Finishing” J. Applied Surface Finishing,
3(4), 178-189 (2008).

J. Taylor, et al., (2019; Chapter 7) “Breaking the Chemical Paradigm in Electrochemical Engineering: Case Studies and Lessons Learned from Plating to Polishing” R.C. Alkire (Volume 18). Electrochemical Engineering: The Path from Discovery to Product.Wiley-VCH.
Reverse Pulse Plating of Thick and Crack-Free Magnetic Layers for MEMS Manufacturing
Authors: Bernasconi Roberto , Cesaro Riccardo , Rinaldi Christian , Magagnin Luca 
Published: February 2024

The integration of hard magnetic alloys in the form of thick films is one of the most interesting challenges for the manufacturing of energy efficient magnetic microelectromechanical systems (MEMS) [1]. With respect to current state of the art devices, whose working principle mostly relies on the exploitation of Lorentzian forces, MEMS based on permanent magnets can potentially present lower power consumption, larger displacements and stronger actuation forces. However, despite these attractive advantages, it is generally difficult to integrate thick hard magnetic layers with currently employed MEMS fabrication techniques.
Electrodeposition is a technique that is compatible with MEMS fabrication and is characterized by many significant advantages: high deposition rates, no necessity of a vacuum system, low cost, possibility to deposit alloys and composites. Despite of these advantages, electrodeposition methods capable to yield the thick hard magnetic films suitable for MEMS sensors/actuators have not been successfully developed yet. The reason resides in the problems typically encountered in the deposition of hard magnetic alloys: high residual stress, presence of cracks and inadequate surface finishing.
In this context, Reverse Pulse Plating (RPP) may constitute a possible solution to address the challenges of hard magnetic alloys electrodeposition [2]. This technique can significantly reduce internal stresses and hydrogen embrittlement, inhibiting thus cracks formation. In addition, it can simplify electrolyte formulation, eliminating the need of excessive amounts of additives. Finally, it can enhance magnetic properties and refine the grain structure of the deposits, resulting in better mechanical properties.
In the present work, RPP of thick and crack-free layers of CoNiP and CoPtP is investigated. These two materials are between the most studied for potential MEMS applications [3, 4]. Indeed, whereas CoPtP offers high coercivities (> 3000 Oe) and excellent remanences, CoNiP represents a low cost alternative characterized by good magnetic properties (with HC up to 2000 Oe). Co-rich CoNiP and CoPtP are deposited from a chloride based acidic electrolyte [3] and from a tartrate based bath, respectively, using ultra-fast RPP. The resulting coatings, characterized by thickness up to 20 µm, are characterized to assess their morphology, phase composition and magnetic behavior.
[1] N. M. Dempsey, “Hard Magnetic Materials for MEMS Applications” in: Nanoscale Magnetic Materials and Applications, Springer, Boston, MA (2009)
[2] S. Pané et al., Electrochim. Acta 56, 8979-8988 (2011)
[3] D. Y. Park et al., Electrochim. Acta 47, 2893-2900 (2002)
[4] D. Mallick et al., J. Appl. Phys. 125, 023902 (2019)