bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Challenges for Accelerating Life Testing of Commercial Lithium-Ion Batteries
Authors: Gasper Paul , Sunderlin Nathaniel , Dunlap Nathan A. , Finegan Donal P. , Smith Kandler , Thakkar Foram 
Published: February 2024

Life testing of commercial lithium-ion batteries is critical for predicting lifetime, anticipating failure, and guaranteeing safe operation of real-world battery energy storage systems. The traditional method for conducting life testing is to use accelerated aging experiments, where stress factors such as temperature, charge/discharge rate, or daily charge-throughput are pushed to extremes to drive cell failure, while taking care not to induce degradation mechanisms that do not reflect real-world use. But even ‘accelerated’ aging tests generally require 6 months to several years of testing to reach end-of-life for the current generation of mass-produced lithium-ion batteries. So, many efforts have been made to accelerate ‘accelerated aging’ of commercial cells throughout the battery community. But it is critical to ensure that the results of invasive or novel accelerated life testing experiments match well with not only changes to the electrochemical performance of traditionally aged cells, but also that the impacts of physical or chemical degradation mechanisms are also well characterized.
This work compares the results of a 2-year accelerated aging test conducted on 23 commercial large-format NMC-Gr cells with a variety of other accelerated life testing experiments. Coin-cell experiments using both full-cell and symmetric-cell configurations were used to study the microstructural changes and electrochemical behavior of both NMC and graphite electrodes, with the small format allowing for destructive characterization of many test replicates throughout cell lifetime; these experiments can be conducted more quickly than their large-format counterparts, and enable more detailed understanding of the degradation trajectory than the large-format test. However, difficulties in transferring electrochemical trends from the coin-cell format to the large-format cell will be discussed. In addition, cascading failure mechanisms observed in the large-format cells may not occur in coin-cells due to differences in the mechanical and thermal environment of each system. Implications for the design of small-format accelerated life testing using electrodes harvested from commercial batteries will be discussed. Calendar aging was accelerated by monitoring daily self-discharge and quantifying both reversible and irreversible capacity losses; challenges for making quantitative predictions from short-term calendar aging tests will be presented.
Can One Project Cell Lifetime Using Wide Temperature Range Ultra-High Precision Coulometry?
Authors: Tuul Kenneth , Taskovic Tina , Harlow Jessie , Johnson Michel B. , Dahn Jeff R. 
Published: February 2024

Using low charge voltage with Li-ion cells significantly extends their lifetime. This makes them advantageous in enabling the implementation of Li-ion batteries for widespread renewable energy storage1. Li[Ni0.83Mn0.06Co0.11]O2/graphite (Ni83/graphite) cells combined with dimethyl-2,5-dioxahexane carboxylate (DMOHC) as electrolyte solvent and lithium bis(fluorosulfonyl)imide (LiFSI) as salt, operating to upper cutoff voltages of 3.8 or 3.9 V, can achieve incredible capacity retention and reduce gassing while cycling at 85°C2. Since these cells have exceptional lifetime projected to be decades when cycling at room temperature, there is keen interest in using high temperatures to screen cell performance in an accelerated manner3. However, how to project a high-temperature lifetime to room temperature remains to be determined.
Ultra-high precision coulometry (UHPC) can give valuable insight into cell degradation within weeks of cycling4. This has been applied to Ni83/graphite cells using a blend of DMOHC and diethyl carbonate (DEC) as electrolyte solvent, LiFSI as salt, and vinylene carbonate (VC) and ethylene sulfate (DTD) as additives. Figure 1 shows the results of UHPC measurements on a series of cells over a wide temperature range between 20-100°C to help determine pathways to project cell lifetime under normal use conditions. The results present exceptional performance at high temperatures and indicate a clear relation between degradation mechanisms and temperature. Remarkably, they also demonstrate similar capacity fade rates when the cycling temperature is increased from 55°C to 100°C. The potential causes of this are further elucidated by post-mortem electrolyte analysis of the measured cells.

REFERENCES

C. P. Aiken, T. Taskovic, and J. R. Dahn, J. Electrochem. Soc., 169, 090523 (2022).

T. Taskovic, A. Eldesoky, C. P. Aiken, and J. R. Dahn, J. Electrochem. Soc., 169, 100547 (2022).

T. Taskovic, A. Eldesoky, W. Song, M. Bauer, and J. R. Dahn, J. Electrochem. Soc., 169, 040538 (2022).

A. J. Smith, J. C. Burns, D. Xiong, and J. R. Dahn, J. Electrochem. Soc., 158, A1136–A1142 (2011).

Figure
1
. Fractional capacity fade per hour (a), fractional charge endpoint slippage per hour (b), and coulombic inefficiency (CIE) per hour (c) of Ni83/graphite cells with 1 M LiFSI in DMOHC:DEC (20:80 w/w) with 2 wt% VC and 1 wt% DTD calculated at cycle 19 of UHPC cycling at different temperatures. Notice that the y-axis is logarithmic.

Figure 1
Effect of Water Vapor on Hydrogen Isotopes Separation by Polymer Electrolyte Fuel Cell
Authors: Furusawa Koichiro , Nago Toranosuke , Ueda Mikito , Matsushima Hisayoshi 
Published: February 2024

Introduction
Hydrogen isotopes are protium (H), deuterium (D) and tritium (T). D and T are important materials not only for fission and fusion reactors, but also for semiconductors since the strong hydrogen termination improves the durability. Various techniques for hydrogen isotope separation have been known for long time, but they have some drawbacks such as low separation efficiency and poor energy consumption. Therefore, new separation and purification methods are required.
In polymer electrolyte fuel cell (PEFC), wettability is optimized well and small amount of Pt catalyst is used. The configuration is also key issue for the conventional method of water-hydrogen chemical exchange. Therefore, we investigated the effect of water in hydrogen isotope separation by PEFC [1].
Experimental
A mixture hydrogen gas of H2 and D2 was supplied to the PFEC. The separation factor for dry and wet gas flow was measured, respectively. Hydrogen gas and water vapor from PEFC were analyzed by quadrupole mass spectrometry (Q-mass) and Fourier infrared spectrometer (FTIR), respectively. The separation factor and mass balance were calculated.
Results and discussion
When no electricity was generated, FTIR results showed that D was enriched in water vapor. This is explained by a gas-phase chemical exchange reaction occurring on a platinum catalyst. When the PEFC was operated, the electrochemical reaction promoted the D separation. A large amount of D (about 45%) was transferred to water vapor during power generation. The separation factor was approximately 1.7, while it was approximately 1.3 for no generation. The present results suggested that gas-phase chemical exchange and the cell reaction had a synergistic effect on D separation.
References
[1] K. Furusawa et al., Int. J. Hydrog. Energy, 47, 36248-36253 (2022).
Deuterium Isotope Separation By Polymer Electrolyte Fuel Cell with Gas Circulation System
Authors: Nago Toranosuke , Furusawa Koichiro , Ueda Mikito , Matsushima Hisayoshi 
Published: February 2024

Introduction
Hydrogen isotopes such as deuterium (D) and tritium (T) are in increasing demand in the fields of materials, energy, and medicine. A international fusion reactor in France will be equipped with water electrolysis for T separation. New methods are required, since the conventional processes perform low separation and consume large amount of energy. We have been studying D separation by polymer electrolyte fuel cell (PEFC) [1-3]. Here, the relationship between the gas consumption rate and separation efficiency is investigated. Therefore, the present PEFC can recirculate the unreacted hydrogen gas discharged from the anode, which proceeds high gas utilization. In our poster presentation, we will show the separation factor, D concentration and production volume depending on the gas circulation ratio.
Experimental
A JARI cell (electrode area: 25 cm2) was used for PEFC, and platinum was used as catalyst for both electrodes. For the anode, protium (H) concentration was set to 90 at% as a mixed gas. Oxygen gas was supplied to the cathode. Power generation was performed at room temperature, and a constant output current was obtained using a variable resistor. The H concentration in the anode gas was analyzed with a quadrupole mass spectrometer, and the gas volume discharged from the PEFC circulation system was calculated.
Results and discussion
The ratio of the hydrogen gas circulation rate to the supply rate is defined as λ. The relationship with the H concentration is shown (Fig. 1). The H concentration was enriched during PEFC operation, while D was condensed in produced water. The gas circulation improved the separation efficiency because the outlet gas was repeatedly processed in PEFC. Figure 2 shows the relationship between λ and the volume rate of exhaust gas from anode. As λ increased, the gas rate decreased linearly from 8 mL min-1 to 2 mL min-1. That is, the circulation system let the gas residential time in PEFC be longer. When the gas was circulated more, the gas could react for long time. This was attributed to the high H concentration seen in Fig. 1. The present results demonstrated the importance of circulation parameter, λ, for the enrichment production.
References
[1] K. Furusawa et al., Int. J. Hydrog. Energy, 47, 36248 (2022).
[2] R. Tanii et al., Int. J. Hydrog. Energy, 44, 1851 (2019).
[3] R. Ogawa et al., Energy, 149, 98 (2018).

Figure 1
(Invited) Electro-Separation Combined with Electro-Conversion for Wastewater Treatment and Recovery: Case Study of Electro-Precipitation or Electro-Sorption Combined with Advanced Electro-Oxidation
Authors: Mousset Emmanuel 
Published: February 2024

The water stress combined with an increase of water demand lead to a worldwide water crisis that is urgent to solve. The United Nation has established sustainable development goals to deal with this challenge. In the meantime, raw materials resources are decreasing, drastically for some of them. Thus, 30 critical raw materials (e.g., rare earth elements, phosphorus, magnesium) have been listed by the European Union in 2020. The reuse of treated wastewater remains one of the most effective solution, while the concomitant recovery of value-added compounds is gaining increasing interest.
To answer this issue, advanced physico-chemical treatments need to be developed in order to separate the value-added compounds from the solution, while the non-valuable biorecalcitrant pollutants must be eliminated. Electrochemical systems are arising importance. Their heterogeneous nature can involve electro-catalysis through the development of innovative multi-functional materials, which is a further step towards the rise of greener processes by avoiding chemicals addition. Electro-separation technologies are able to selectively isolate compounds according particularly to their electrophoretic mobility, the applied current & electrode potential, the electrode materials properties and the electrolyte characteristics. They can be competitive by increasing the selectivity of separation. In the meantime, electro-conversion systems are able to mineralize recalcitrant organic pollutants from wastewater, while value-added organic compounds can be obtained by electro-synthesis. Therefore, the coupling between electro-separation and electro-conversion systems seems promising to solve water issues.
In this talk, two case studies will be presented, one about the electro-precipitation in combination with advanced electro-oxidation and the second case about electro-sorption coupled with advanced electro-oxidation. In the first study, the possibility to recover phosphate, while eliminating tylosin as representative pharmaceutical pollutant will be presented. In the second work, the recovery of phenolic compounds from olive mill wastewater will be exposed, considering the subsequent elimination of residual organic pollutants from the effluent. Emphasis will be given on engineering (e.g., reactor design) and modeling aspects.
Electrochemical Ion Separations By Recyclable Electrode Cell
Authors: Lado Julio J. , Fombona-Pascual Alba , Pérez-Antolín Daniel , Garcia - Quismondo Enrique , Palma Jesus , Ventosa Edgar 
Published: February 2024

Electrochemical separations using Faradaic electrodes are able to exceed the ion adsorption values as well as selectivity when compared to capacitive electrodes, which is due to the bulk reactions for the former vs. surface confined for the latter. However, the cyclability of battery/faradaic electrodes is constrained to hundreds or a few thousands of cycles. This work proposes an electrochemical ion pumping design with the unique feature of using injectable electrodes to overcome the ciclability issue and easily control the areal capacity. The idea consists on using injectable electrodes with the intention of recycling the active material once the end-of-life of the device is reached due to active material degradation. In this fashion, the active material is replaced in a straightforward deinjecting-injecting process allowing direct reuse of the inactive components of the device, thus contributing to reducing the replacement cost. This device is called Ion Pumping Injectable Cell (IPIC).
Moreover, the IPIC system is a tremendously versatile technology due to the simple and easy methodology employed to replace the electrodes. In this fashion, the system was tested using different types of lithium intercalation materials (LFP and LMO), different ion capturing such as potassium (Prussian Blue Analogs, PBA´s), sodium (NMO) or more conventional activated carbon electrodes (capacitive non-selective electrode). In addition to this feature, it is important to remark that the IPIC could be used in a symmetric (e.g. LFP-LFP) or asymmetric configuration (e.g. LFP-LMO). The main difference is that the asymmetric system has the ability of storing energy while capturing ions and deliver that energy in the subsequent step. This is so due to the different electrode potential. The selectivity toward specific ions is achieved by using a chemical ion-selective separator such as an ion exchange membrane (LFP-LFP or LFP-LMO systems), or by using ion selective intercalation materials such as LFP and PBA´s without the need of selective membranes.
In this work, the benefits of the injectable electrode cell architecture will be examined, the performance of different cell configurations will be discussed and the electrochemical ion separation mechanism will be analyzed for different applications.

Acknowledgements

: J.J. Lado and Alba Fombona-Pascual acknowledge Comunidad de Madrid for the fellowship (2020-T1/AMB-19799).
(Invited) Microwave Dielectric Relaxation Spectroscopy: A Technique to Inform Ion Transport in Hydrated Polymer Membranes
Authors: Geise Geoffrey M. 
Published: February 2024

Providing sustainable supplies of purified water and energy is a critical global challenge for the future, and polymer membranes will play a key role in addressing these clear and pressing global needs for water and energy. Polymer membrane-based processes dominate the desalination market because they are more energy efficient than thermal desalination processes, and polymer membranes are crucial components in several rapidly developing power generation and energy storage applications that rely on membranes to control, selectively, rates of ion transport. Much remains unknown about the influence of polymer structure on basic intrinsic transport properties, and these relationships are important for designing next generation polymer membrane materials.
Key to controlling ion transport in membranes for water purification and energy applications is engineering interactions between ions and the solvated polymer matrix. Microwave dielectric relaxation spectroscopy is a tool that enables study of hydrated polymer membranes because water molecule dipoles can be probed in the microwave frequency region. This technique can provide unique insight into hydrated polymer dielectric permittivity (or dielectric constant) properties, which are critical in emerging thermodynamic modeling of ion transport in hydrated polymers. This presentation discusses the use of microwave dielectric relaxation spectroscopy to uncover structure property relationships in hydrated polymers and, more broadly, presents an overview of research aimed at further understanding fundamental structure/property relationships that govern small molecule transport in polymeric materials considered for desalination and electric potential field-driven membrane applications that can help address global needs for clean water and energy.
(Invited) Layered Double Hydroxides with Enhanced Interlayer Space for Electrochemical Energy Storage and Deionization
Authors: Wang Yang , Pan Qianfeng , Qiao Yixuan , Peng Song 
Published: February 2024

Layered double hydroxides (LDHs) have been extensively studied as promising functional nanomaterials owing to their excellent electrochemical activity and tunable chemical composition. In this work, we presented a series of investigations on enhanced interlayer space of LDHs for electrochemical energy and deionization.
Firstly, using acetate anions (Ac-) as an intercalating element, NiCo-LDH nanosheets arraying on Ni Foam with different amounts of Ac- anions intercalation or volumes of hydrothermal solution were prepared by a simple hydrothermal method. The optimized amount of Ac- anions expanded the interlayer space of LDH nanosheets from 0.8 to 0.94 nm. An ultrahigh specific capacity of 1200 C g-1 at 1 A g-1 (690 C g-1 without Ac- anions), outstanding rate capability of 72.5% at 30 A g-1 and cycle stability of 79.90% after 4500 cycles, which were mainly attributed to the higher interlayer spacing of Ac- anions intercalation.
Moreover, CoAl-LDH nanosheets intercalated by sodium dodecyl sulfate (SDS) with an enhanced interlayer spacing from 0.76 to 1.33 nm are synthesized and used as an anode of electrosorption. The enlarged interlayer spacing provides an enhanced ion diffusion channel and improves the utilization of the interlayer electroactive sites, while heat treatment transferring LDHs to layered metal oxides offers additional active oxidation reaction sites to facilitate the electro-sorption rate, contributing to the high salt adsorption capacity (31.78 mg g-1) and average salt adsorption rate (3.75 mg g-1 min-1) at 1.2 V in 500 mg L-1 NaCl solution. In addition, the excellent long-term cycling stability (92.9%) after 40 cycles proves the strong electronic interaction between SDS and the host layer, which is validated by density functional theory calculations later on.
In addition, ionic surfactants like SDS and cetyl trimethyl ammonium bromide (CTAB) can be used to modify the morphology of LDH. The original LDH shows microspheres formed by nanorods, and LDH-CTAB is similar, yet more tangled, while LDH-SDS is like micro flowers consisting of interwoven nanosheets. LDH-SDS achieved better electrochemical performance (1003.6 C g-1 at 1 A g-1 and 73.84% after 3500 cycles) than LDHs-CTAB (430.54 C g-1, 57.3%), and both higher than the original LDH (278.5 C g-1, 54.3%), while the electrocatalytic performance like Tafel slope follows an opposite trend owing to the difficulty of bubbles detachment from the nanosheets or nanorods, clearly showing the importance of morphology regulation in the synthesis of nanomaterials.
A Two-Dimensional Transport Model of Bipolar Membrane Electrodialysis for the Electro-Regeneration of Carbon Capture Solvents
Authors: Ledingham Jack , Campbell Alasdair , Sedransk Campbell Kyra 
Published: February 2024

Bipolar membrane electrodialysis (BPMED) is a promising technology that uses an electric field to split water into H+ and OH- ions. A repeating stack of cation selective, anion selective, and bipolar membranes are placed between two electrodes, creating a repeating pattern of acid, base, and diluting flow chambers. A major application of BPMED is the electrochemical solvent regeneration of capture solutions used in CO2 point source (PS) or direct air capture (DAC). Protons generated using BPMED can be used to shift the acid-base equilibria back to CO2, providing a more sustainable alternative to traditional thermal regeneration methods when integrated with renewable electricity sources. This method combines electrosynthesis and separation, producing a pure stream of CO2 for sequestration and a concentrated base stream.
Despite its potential, current limitations to BPMED implementation for this application stem from a large power consumption and high membrane costs. In addition, gas bubbles in solution can cause high electrical resistances, and experimental studies of this phenomenon are challenging due to the small scale on which it occurs. To address these challenges, we present a two-dimensional model of BPMED for CO2 capture solvent recovery. This model depicts a single repeating cell triplet and was constructed using COMSOL Multiphysics version 6.1. The Navier-Stokes equations were implemented to compute a convection field, and the ionic species concentration was found by solving the Nernst-Planck equation. A source term in the concentration partial differential equations was implemented to account for ionic speciation and water splitting reactions, captured through kinetic rate expressions.
Experimental validation was conducted on a PC Cell BED 1-4 recirculating batch system with a stack of seven cell pairs of PC acid 60 (anion selective), PC SK (cation selective), and PC Bip (bipolar) membranes. Good agreement between the model and experimental results across a range of conditions and variables demonstrates accuracy and robustness. The calculated pH and concentration profiles revealed that the majority of the speciation reaction takes place inside, or directly adjacent to, the bipolar membrane, including bubble nucleation. Bubbles form inside membrane pores and displace the electrolyte, greatly increasing the electrical resistance of the membrane, particularly when membrane porosity is low. However, the reaction plane location where bubbles are generated can be manipulated by increasing the channel width or reducing the applied voltage.
Future research will focus on expanding to multiphase CFD simulations to investigate the effect on flow. Our two-dimensional model provides valuable insights into the complex and multifaceted nature of BPMED, offering a powerful tool for investigating small-scale processes and advancing the use of BPMED for CO2 capture solvent recovery.

Figure 1