bluuebunny/crossref_metadata_2025_split huggingface dataset:
Enabling Aqueous Processing for Low/No-Cobalt Lithium-Ion Battery Cathode Active Materials
Authors: Hawley William Blake , Parejiya Anand , Bai Yaocai , Meyer Harry M , Wood David L. , Li Jianlin 
Published: December 2020

Industrially, lithium-ion battery cathodes are manufactured through a wet slurry mixing and coating process. There is great interest in replacing the presently-used N-methyl-2-pyrrolidone (NMP) solvent with water due to the cost and toxicity associated with NMP. In this study, the modifications made to the active materials as a result of water exposure were studied and two materials, LiMn2O4 (LMO) and LiNi0.8Co0.15Al0.05O2 (NCA), were assembled in high-performing aqueous-processed cathodes for the first time.
Five cathode active materials were the subject of this study: LiCoO2 (LCO), LiFePO4 (LFP), LMO, NCA, and LiNi0.5Mn0.3Co0.2O2 (NMC532). All materials exposed to DI water exhibited rapid increases in pH over the first 10 min, with stable pH values ranging from 9.0 (LFP and LMO) to 12.5 (NCA). Given that the protective aluminum oxide layer on the current collector breaks down at a pH of 8.5, corrosion is predicted for all materials, with NCA being the most extreme case. Pristine samples of the same five materials were submerged in water for 24 h, then the moisture was dried in a vacuum oven. The crystal structures of these materials (henceforth referred to as the wetted samples) were evaluated using X-ray diffraction and compared with pristine samples. No changes were observed in the crystal structure of any material as confirmed by Rietveld refinement. X-ray photoelectron spectroscopy was used to evaluate the changes of the surface composition of each wetted and pristine material.
Based on inductively coupled plasma-mass spectrometry results, the amount of Li and transition metal leaching in water was found to be independent of time in excess of 1 h, and the amount of Li leaching in water for NCA was found to be five times that of NMC532 and more than 30 times that of the other materials. As a result, using a traditional aqueous slurry formulation (active material, carbon black, emulsion binder, carboxymethylcellulose thickener) resulted in a severely cracked and unusable NCA cathode. By including high-molecular weight polyacrylic acid (PAA), the adhesion of the cathode was restored. Half coin cells of this PAA-processed and an NMP-processed NCA cathode were constructed using punches with 1.7 mAh·cm-2 areal capacity and a charge and discharge rate of C/3 between 3.0-4.3 V. The initial capacity of the PAA-processed NCA cathode was slightly lower (176.3 mAh·g-1 to 185.2 mAh·g-1), though it did exhibit better capacity retention through 100 cycles (84.2% to 78.1%).
Hydrogen Evolution and Oxygen Reduction Reactions on Conducting Polymers
Authors: Vagin Mikhail Yu. , Gueskine Viktor , Crispin Xavier 
Published: December 2020

The electrocatalytic processes for the energy conversion are the key aspects in the development of sustainable economy. Being one of the main technological stimuli of electrocatalysis research, the direct chemical-to-electrical energy interconversion is employed in a variety of applications from the electrical transportation to the balancing of the grid. Among the examples of the electrocatalytic processes, where the wide commercialization is limited by the cost of catalysts, the oxygen reduction reaction (ORR) and the hydrogen evolution reaction (HER) are the most critical for the development of technological infrastructure of fuel cells. This stipulates the intensive research on noble-metal-free electrocatalysts.
The quantification of ORR and HER on the intrinsically conducting polymers allows the rational design of catalyst, systematic investigation of mass transport phenomena and mechanistic evaluation of electrocatalysis due to the open material architecture. Firstly, the landscape of ORR phenomena happening on conjugated polymers is discussed at the mechanistic and device levels. The effects of co-catalyst and proton supply on ORR efficiency and the pathway is illustrated on the examples of poly(3,4-ethylenedioxythiophene) (PEDOT) [1-4] and other polymers as organic ORR catalyst. Secondly, the effect of proton supply is rationalized at both mechanistic and device levels for HER on PEDOT-triflate [5].
References
1. V. Gueskine, A. Singh, M. Vagin, X. Crispin, I. Zozoulenko. Molecular Oxygen Activation at a Conducting Polymer: Electrochemical Oxygen Reduction Reaction at PEDOT Revisited, a Theoretical Study. The Journal of Physical Chemistry C, 2020, accepted
2. E. Mitraka, M.J. Jafari, M. Vagin, X. Liu, M. Fahlman, T. Ederth, M. Berggren, M.P. Jonsson, X. Crispin. Oxygen-induced doping on reduced poly(3,4-ethylenedioxythiophene). Journal of Materials Chemistry A, 2017, 5(9):4404.
3. E. Mitraka, M. Gryszel, M. Vagin, M.J. Jafari, A. Singh, M. Warczak, M. Mitrakas, M. Berggren, T. Ederth, I. Zozoulenko, E.D. Głowacki, X. Crispin. Electrocatalytic production of hydrogen peroxide with poly(3,4-ethylenedioxythiophene) electrodes. Advanced Sustainable Systems, 2019, 3(2), 1800110.
4. E. Mitraka, M. Vagin, A. Sjöstedt, M. Berggren, K. Håkansson, M. Jonsson X. Crispin. PEDOT-Cellulose Gas Diffusion Electrodes for Disposable Fuel Cells. Advanced Sustainable Systems, 2019 3(12), 1900097
5. R. Valiollahi, M. Vagin, V. Gueskine, A. Singh, S. A. Grigoriev, A. S. Pushkarev, I. V. Pushkareva, M. Fahlman, X. J. Liu, Z. Khan, M. Berggren, I. Zozoulenko, X. Crispin. Electrochemical hydrogen production on a metal-free polymer. Sustainable Energy & Fuels, 2019, 3(12), 3387-3398.
Long-Range Surface Plasmon Enhanced Raman Spectroscopy at Catalytic Platinum Electrodes
Authors: Ikeda Katsuyoshi 
Published: December 2020

Surface enhanced Raman scattering (SERS) is recognized as a powerful method for in-situ observation of electrode/electrolyte interfaces, due to the high chemical sensitivity and surface selectivity. However, the applicability of this technique is limited by the nature of surface plasmon resonances at the interface. Although platinum group metals (PGMs) are one of the most interesting materials for electrocatalysis, surface plasmon polaritons are largely damped at these metal surfaces by their localized d-electrons near the Fermi level. Thus, the plasmon enhanced Raman spectroscopy is normally useless for studying such catalytic surfaces. So far, the signal enhancement factors reported at PGM surfaces are in the order of 102 while those at coinage metal surfaces can reach the order of 106 to 1010. In order to gain more intensity at highly damping PGM surfaces, the intensity-borrowing method is a common method; for example, when a large number of Au nanoparticles are deposited on a PGM surface, Raman scattering signals are largely enhanced by the sphere-plane type coupled plasmon modes [1,2]. However, such a nanostructure may influence mass transport, selectivity, and reactivity of electrochemical reactions. For spectro-electrochemistry, it is necessary to reduce the plasmon damping without suffering from such a nanoscale effect. In this work, the attenuation of surface plasmons at highly damping Pt surface is reduced using a symmetric slab mode, which is a strongly coupled surface plasmons excited at both interfaces of a thin metal film [3]. The prolonged propagation of surface plasmons in this double-interface configuration leads to a substantial enhancement of local fields even at lossy Pt surface. The theoretical calculation indicates that the enhancement factor of Raman scattering intensity can reach the order of 104 at Pt/solution interfaces in this coupled plasmon mode. We experimentally demonstrate that Raman scattering signals are significantly enhanced at Pt surface under electrochemical conditions. This strategy provides us a novel surface-specific spectroscopic method for the molecular-scale investigation of electrocatalytic reactions.
[1] J. Hu, N. Hoshi, K. Uosaki, K. Ikeda, Nano Lett., 15, 7982-7986 (2015).
[2] J. Hu, M. Tanabe, J. Sato, K. Uosaki, K. Ikeda, J. Am. Chem. Soc.,136, 10299-10307 (2014).
[3] S. Ikegaya, K. Motobayashi, K. Ikeda, J. Raman Spectrosc. DOI: 10.1002/jrs.5925 (2020)
(Invited) Recovering from Precipitation Events in Redox Flow Batteries
Authors: Saraidaridis James , Yang Zhiwei , Darling Robert M. 
Published: December 2020

Liquid electrolyte solutions containing dissolved active material imbue Redox Flow Batteries (RFBs) with many unique benefits relative to solid-state electrochemical energy storage devices: long shelf-life, long system life-time, de-coupled rated energy and power, ease of recyclability.1 Operating a RFB system with flowing electrolyte solutions presents unique concerns as well, with one notable concern arising from possible precipitation of electrolyte. Precipitation of active material can have many consequences including sensor inaccuracy, inaccessible storage capacity, partially- or fully-blocked reactor electrode regions, and system clogging.
Aqueous vanadium RFBs, a leading chemistry in commercial systems, has a precipitation mechanism at high temperatures for battery solutions containing commercially relevant vanadium concentrations >1.5 M. At elevated temperatures (> 40°C), positive electrolyte solutions can precipitate V2O5 dimers, first as a gel-like substance and eventually as solid particles.2 The Raytheon Technologies Research Center team has developed recovery procedures for systems that may succumb to such precipitation events; in the case for aqueous vanadium RFBs, exposure of precipitate to lower oxidation state forms of vanadium (i.e. negative electrolyte) reduces and redissolves precipitated V2O5. This electrolyte takeover process (ETP) can successfully redissolve precipitates and recover performance from precipitate-induced cell/stack under-performance.
As Raytheon Technologies Research Center pursues alternative low-cost flow chemistries, the same ETP principles are applied to other chemistries such as polysulfide-based systems, known for sulfur crossover and precipitation of elemental sulfur in positive electrode volumes.3 This abstract will discuss the progress made at the Research Center to recover from precipitation events in such chemistries, which, unlike aqueous vanadium, do not permit simple mixing of negative and positive electrolytes.

Acknowledgements:

The authors gratefully acknowledge support from Vionx Energy Corporation. Some of the work presented herein was funded in part by the Advanced Research Projects Agency-Energy (ARPA-E), U.S. Department of Energy, under Award Number DE-AR000994. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.

References:

Chalamala, B. R.; Soundappan, T.; Fisher, G. R.; Anstey, M. R.; Viswanathan, V. V.; Perry, M. L., Redox Flow Batteries: An Engineering Perspective. Proceedings of the IEEE
2014,
102 (6), 976-999.

Skyllas‐Kazacos, M.; Menictas, C.; Kazacos, M., Thermal Stability of Concentrated V(V) Electrolytes in the Vanadium Redox Cell. Journal of The Electrochemical Society
1996,
143 (4), L86-L88.

Su, L.; Badel, A. F.; Cao, C.; Hinricher, J. J.; Brushett, F. R., Toward an Inexpensive Aqueous Polysulfide–Polyiodide Redox Flow Battery. Industrial & Engineering Chemistry Research
2017,
56 (35), 9783-9792.
Performance Survey for Li-Ion Battery in a Hybrid Vehicle with 105,000 Km Driving
Authors: Koshika Kenichiroh , Suzuki Hisakazu 
Published: December 2020

A global technical regulation for vehicle environmental performance such as exhaust gases, fuel economy and range has appeared in the issue of WP29 in the United Nations Economic Commission for Europe (UN-ECE). [1] One of major concerns is that battery degradation may influence on the fuel economy deterioration of electrified vehicles such as HEVs. However, numbers of report from automakers about the relation between a fuel economy change and battery performance change are limited. In this paper, we demonstrate the battery performance change in a hybrid vehicle with 105,000 km driving and its fuel economy change.
Fuel consumptions of the hybrid vehicle with 1.5 L gasoline engine and 105,000 km driving were compared before and after battery pack replacement. The type of the battery was Lithium-ion. The fuel consumptions with the “state of charge correction” were measured by a chassis dynamometer with Japanese driving test cycle of “JC08 mode” (Fig.1). Before replacing the battery pack, the hybrid vehicle ran with a fuel consumption of 29.24 km/L. Then after replacing the battery ran with a fuel consumption of 29.96 km/L.
After the fuel consumption test, the battery pack with 105,000 km driving was disassembled to battery cells. Discharge capacities and internal resistances of the cells were measured. We will discuss the battery performance change and its influence on the fuel consumption rates of the vehicles.
[1]https://www.unece.org/trans/main/wp29/introduction.html

Figure 1
(Invited) Statistical Distribution and Feasibility for Re-Use of A123 LiFePO4 Cells from a Hybrid-Bus Battery Pack
Authors: Ramirez-Meyers Katrina , Rawn Barry , Whitacre Jay 
Published: December 2020

Second-use applications for batteries can play an important role in reducing the environmental impacts and life-cycle costs of electrochemical energy storage. The economic feasibility of re-using a battery pack is strongly influenced by the state-of-health (SOH) of its modules and cells after primary use. Thus, there is a strong incentive to optimize procedures for diagnosing SOH based on parameters such as calendar life, cycle life, internal resistance, and capacity fade. In this paper, we analyze the statistical distribution of the SOH cells extracted from a retired BAE-Systems ESS-A123 hybrid bus battery pack. The pack consists of 16 modules in series, each containing 96 lithium-iron-phosphate 26650 cells in a 12s8p configuration. Most of the modules use ANR26650M1-A (M1-A) cells. Two modules use M1-B cells—a newer version of the same battery—indicating that these two modules were installed as replacements. The M1-A and M1-B cells have nominal capacities of 2.3 and 2.5 Ah, respectively. We randomly sampled one cell from each of the 192 sub-modules that result from the 8p design and performed a comprehensive SOH assessment.
We will summarize the data by presenting internal resistance, discharge capacity, Warburg diffusion coefficient, and charge-transfer resistance as a function of cell location and type. Results show that the M1-A cells display widely varying SOH, while the M1-B cells are in much better condition. The wide range in SOH parameters suggest re-use of all parts of the pack may not be economically reasonable.
We will also present an analysis of the duty profile of the bus battery. We will then discuss the implications of our findings for the economic feasibility of re-using the cells and modules, in light of available data and modeling techniques.
Sensing Elevated Carbon Dioxide Levels for Detecting Battery Cell Venting in Packs
Authors: Cai Ting , Engle Brian , Stefanopoulou Anna G , Siegel Jason B 
Published: December 2020

Li-ion battery thermal runaway is a critical safety issue for large-scale battery packs, and gas venting of a battery cell is a precursor of an imminent thermal runaway. The proposed global technical regulation No.20 on Electric Vehicle Safety requires an advance warning 5 minutes prior to hazardous conditions caused by a thermal runaway event. Voltage-based detection methods are less effective in large packs with many parallel connected cells, and temperature-based methods provide slow and sparse information when fewer than 10% of the cells are instrumented. To achieve immediate detection for thermal runaway, vent-gas detection methods are promising due to their fast response and easy implementation in a pack. The composition of battery vent-gas during faults that can lead to a thermal runaway event include CO2, CO, H2, and volatile organic compounds (VOCs). The best gas species to target for a detection strategy is still debated. The composition of the vent-gas depends on cell chemistry, abuse condition, and cell state of charge. For robustness, the detection strategy needs to be sensitive to all possible failure mechanisms, be inexpensive, and require no maintenance. A Non-Dispersive Infrared (NDIR) CO2 sensor can meet these requirements, because the detection can be made immediately when the presence of CO2 is observed from the first venting event, and the sensor type has low cost and with some sensor’s lifetime over 15 years.
To check the NDIR sensor responsiveness, an overcharging test for a prismatic 4.9 Ah cell was performed and the gas venting is observed before thermal runaway is triggered. Quickly after the occurrence of gas venting, the NDIR CO2 sensor showed a strong response with maximum gas concentration exceeding 30,000 ppm as shown in the figure. In a battery pack, the fast velocity of the ejected gas from cell venting ensured the fast response of the gas sensor. To apply the gas detection strategies for large battery packs, the volume and average CO2 concentration can be modeled to set the gas detection threshold.

Figure 1
Robust Performance and Safety Advantages of Large Cells for Energy Storage Based on HE3DA (3D) Electrode Concept - from a Lab Sample to a Gigafactory
Authors: Prochazka Jan , Zukalova Marketa 
Published: December 2020

The HE3DA® concept of several millimeters thick electrodes (3D) gives the lithium battery incomparable safety and brings a number of new technical attributes, which are not achievable by the existing thin film technology (2D).
The safe and robust construction with multifunctional frames, easy degassing, low internal resistance and electrolyte regeneration make this new lithium accumulator technology ideal for high capacity batteries and large energy storage modules, optionally with an internal cooling system, which radically shrinks the battery pack size and extends the battery life.
The 3D construction of HE3DA technology provides an efficient thermal management and inherited safety to the batteries, enabling construction of very large cells on hundred KWh level and modules on hundreds of MWh scale. Incomparable safety, cheap manufacturing process and performance robustness make this technology ideal for the Smart Grid applications, stabilizing solar and wind power generation, changing this type of renewable energy from unpredictable to predictable. HE3DA technology platform has been developed from a lab sample into a mass scale production on Gigawatt hour scale in the past 10 years.
Typical performance data will be introduced.

Figure 1
Cost and Economic Analysis of a Polymer Sealed Planar Na-NiCl2 Battery for ESS
Authors: Lee Jung Seung , Yang Choongmo , Jung Keeyoung 
Published: December 2020

In order to commercialize the battery-based ESS, it is necessary to consider not only the technical characteristics of stability and long life, but also the economic characteristics of manufacturing cost. This study aims to analyze the manufacturing cost of a polymer sealed planar Na-NiCl2 battery that is currently being researched and developed for safe, long life and untra low cost energy storage and to predict economic efficiency.
Manufacturing cost analysis was calculated by dividing a number of technically feasible alternatives for each layer of cells, modules, packages, and applications into fixed, variable, and indirect costs. The economic feasibility analysis calculated the cost-benefit ratio by comparing the cost of the next 10 years and the purchase price and purchase plan of the ESS consumer derived from the manufacturing cost analysis. Data required for manufacturing cost analysis and economic analysis include public data such as power consumption patterns and weather data, as well as internal data from research and development institutions such as material and processing costs, as well as external data from suppliers, consumers and competitors. This study obtained relevant data by intensively interviewing the research and development personnel of Na-NiCl2 battery and the stakeholders located in the supply chain of this battery, and utilized secondary data already processed and published, such as the London Metal Exchange and the Statistics Korea.
As a result of analysis, we found that the proposed ESS based on a polymer sealed planar Na-NiCl2 battery has a comparative advantage economically compared to the competitive LiB-based ESS and ZEBRA ESS. Looking at the results of this study, we expect to be able to commercialize safe, long life and untra low cost energy storage in the near future.
Dissolution Stability of Photoanodes and Co-Catalysts in Photoelectrochemical Water Splitting
Authors: Knöppel Julius , Kormanyos Attila , Mayerhöfer Britta , Hofer André , Speck Florian Dominik , Bachmann Julien , Thiele Simon , Cherevko Serhiy 
Published: December 2020

In the future energy scenario, production of hydrogen is a promising solution for the storage of renewables.
Photoelectrochemical water splitting with integrated devices can be engaged for the production of hydrogen with the
advantage of less space consumption and saving power lines to the production site. Current devices have already
come close to the efficiency of an electrolyzer coupled to a solar cell [1]. However, to be profitable in commercial use
several challenges have to be resolved. One of the most pressing issues is photostability of materials during operation.
Even so photoelectrodes are able to reach lifetimes of several days in lab conditions, it is still a long way until real
device lifespans of several years are possible.
While efforts in the field of photoelectrochemical water splitting is mainly focused on achieving higher activity, research
on stability is still at the very beginning. Evaluation of photostability is typically done by rather short (only few hours)
chronoamperometry measurements and post mortem analysis. One option to study degradation processes in-situ is to
use on-line inductively coupled plasma mass spectrometry (on-line ICP-MS) which became available recently and
revealed photocorrosion of WO3 [2] and BiVO4 [3].
In this study, we aim to achieve a better understanding of the key factors driving photocorrosion. It has already been
shown, that WO3 exhibits significant differences in faradaic efficiency towards the oxygen evolution reaction (OER) in
various electrolytes [4]. One reason behind this behavior might be degradation processes driven by the electrolyte. To
study the effect of electrolytes on stability, dissolution of spray-coated WO3 films was investigated in four electrolytes
(HClO4, H2SO4, HNO3 and CH3SO3H). Additionally, the influence of protective iridium co-catalyst layers on stability,
synthesized in various thicknesses by atomic layer deposition (ALD) was explored.
1. Cheng, W.-H., et al., Monolithic Photoelectrochemical Device for Direct Water Splitting with 19% Efficiency. ACS
Energy Letters, 2018. 3(8): p. 1795-1800.
2. Knöppel, J., et al., Time-resolved analysis of dissolution phenomena in photoelectrochemistry – A case study of
WO3 photocorrosion. Electrochemistry Communications, 2018. 96: p. 53-56.
3. Zhang, S., et al., Dissolution of BiVO4 Photoanodes Revealed by Time-Resolved Measurements Under
Photoelectrochemical Conditions. The Journal of Physical Chemistry C, 2019.
4. Reinhard, S., F. Rechberger, and M. Niederberger, Commercially Available WO3 Nanopowders for
Photoelectrochemical Water Splitting: Photocurrent versus Oxygen Evolution. ChemPlusChem, 2016. 81: p.
935-940.