bluuebunny/crossref_metadata_2025_split huggingface dataset:
Anodic Dissolution of Aluminum in Sodium-Ion Batteries: A Comparison of Electrolyte and Solvent Composition
Authors: Colbin Lars Olow Simon , Hall Charles Aram , Etman Ahmed S. , Buckel Alexander , Nyholm Leif , Younesi Reza 
Published: February 2024

The anodic dissolution behavior of aluminum was studied in various sodium-based electrolyte solutions using cyclic voltammetry and chronoamperometry. The aim was to investigate how different electrolyte and solvent compositions affect the dissolution process. The electrolyte solutions tested included 0.284 m NaBOB in TEP, 1.00 m NaPF6 in TEP, 1.00 m NaPF6 in EC:DEC, 1.00 m NaPF6 in diglyme, 1.00 m NaFSI in PC, and 1.00 m NaFSI in TEP. SEM imaging was also performed to analyze the morphological changes of the aluminum surface during the dissolution process.
To emphasize any dissolution process, relatively large volumes (3-5 ml) of electrolyte solution was used in polytetrafluoroethylene beaker cells. A three-electrode configuration was used to obtain the desired accuracy in the electrochemical tests.
Severe anodic aluminum dissolution was not observed below 5.3 V vs. Na+/Na in electrolyte solutions containing NaBOB in TEP, NaPF6 in TEP, NaPF6 in EC:DEC, or NaPF6 in diglyme. Anodic dissolution was, however, detected in electrolyte solutions containing NaFSI in PC and NaFSI in TEP, affirming that caution should be exercised when using FSI-anions with aluminum current collectors.1,2 Yet, the choice of solvent used with NaFSI appeared to influenced the anodic dissolution behavior of aluminum. Here, TEP seemed to suppress the initial dissolution, compared to PC.
In summary, this study provides insights into the anodic dissolution behavior of aluminum in sodium-ion batteries, and highlights the significance of selecting appropriate solution compositions to mitigate potential anodic dissolution issues. The findings contribute to the understanding of the electrochemical behavior of aluminum in the context of sodium-ion batteries, and provides a foundation for further studies.
The authors acknowledge The Swedish Energy Agency via project no. 50177-1, VINNOVA via projects no. 2022-01465 and 2019-00064 (Batteries Sweden), and H2020 research and innovation programme under Grant agreements No 958174 and 963542 for financial support.
1. L. Otaegui, E. Goikolea, F. Aguesse, M. Armand, T. Rojo and G. Singh, J. Power Sources, 2015, 297, 168–173.
2. A. Bitner-Michalska, A. Krztoń-Maziopa, G. Żukowska, T. Trzeciak, W. Wieczorek and M. Marcinek, Electrochim. Acta, 2016, 222, 108–115.

Figure 1
Internally Connected Porous Polymer Electrolyte Membrane for Long-Lasting Flexible Zinc-Air Batteries
Authors: Kim Kwang Won , Yoon Ki Ro , Choi Seon-Jin 
Published: February 2024

The market of various wearable devices is rapidly growing in the recent. Accordingly, a light, safe, and flexible power source is also required to operate. The lithium-ion batteries (LIBs) are optimized for portable devices and can be miniaturized, but they are vulnerable due to the use of organic electrolytes and have limited theoretical energy density. The zinc-air battery (ZAB), as a next-generation battery, have garnered attention for its specific energy density (~1350 Wh/kg) and price competitiveness compared to the LIB. In particular, the use of an aqueous-based polymer electrolyte can provide safety and flexibility, making it a promising energy source for wearable devices. However, the open cathode structure of ZABs for breathing air as an active material leads to gradual loss of liquid components in the polymer electrolyte, resulting in decreased performance.
Herein, we developed a porous hybrid polymer membrane to overcome the aforementioned issues by means of the introduction of superabsorbent polymer (SAP) and the formation of internal network design of the membrane. First, a polyacrylic acid (PAA), one of the SAP, based fibrous network was constructed through an electrospinning process. Second, polyvinyl alcohol (PVA) as an ion conductive polymer was cast on the PAA framework, and subsequently impregnated with KOH electrolyte to form a gel-polymer electrolyte (GPE). Interestingly, the sacrificial PAA framework forms internal pores along with the fiber network, which can act as water pockets affording fast ionic conduction through the membranes and providing a higher electrolyte retention effect. As a result, the hybrid GPE had approximately three times higher ionic conductivity compared to pure PVA and better retention, resulting in outstanding electrochemical performance and cycle-life of the ZAB cell. We believe that our unique design approach for GPE can accelerate the commercialization of flexible ZABs and extend the market of wearable devices.

Figure 1
A Near Dimensionally Invariable Electrode Material: Li8/7Ti2/7V4/7O2
Authors: Konuma Itsuki , Yabuuchi Naoaki 
Published: February 2024

Our group has reported that Li-excess V-based oxide with Nb ions, Li1.25Nb0.25V0.25O2, delivers a large reversible capacity of over 250 mA g-1 with V3+/V5+ two-electron redox reaction.[1] Recently, Li8/7Ti2/7V4/7O2 has been also synthesized and examined as high-capacity positive electrode materials with V cationic redox.[2] Nanosized Li8/7Ti2/7V4/7O2 was also synthesized by high-energy mechanical milling. Nanosized Li8/7Ti2/7V4/7O2 delivers a high reversible capacity of ~300 mA h g-1 with no capacity deterioration for 100 cycles, which originates from a near dimensionally invariable nature as high-capacity electrode materials. Moreover, Li8/7Ti2/7V4/7O2 is used for as positive electrode materials for all-solid-state batteries with argyrodite-type electrolyte, Li6PS5Cl. An all-solid-state cell with Li8/7Ti2/7V4/7O2 and Li6PS5Cl delivers a large reversible capacity of 300 mA h g-1 with excellent retention for 700 cycles. From these results, the importance of a near dimensionally invariable character is discussed in detail.
[1] M. Nakajima and N. Yabuuchi, Chem. Mater.,
29, 6927 (2017)
[2] I. Konuma et al. and N. Yabuuchi, Nat. Mater., 22, 225 (2023)
An Insight into the Lithium Plating – Operando Gas Evolution Study
Authors: Sandra Amritha , Mattinen Ulriika , Lindstrom Rakel 
Published: February 2024

Lithium-ion batteries (LiBs) play a major role in the electrification of transportation systems as a step forward in achieving a sustainable carbon neutral society [1]. Fast-charging is regarded as one of the most necessary features for lithium-ion batteries in order to speed the widespread adoption of electric vehicles [2]. However, we have previously shown that charging LiBs at high C-rate cause the evolution of high amount of ethylene gas along with capacity fade [3]. It is well known that fast charging is also may result in lithium plating and allied parasitic reactions [4]. Since many of the side reactions in LiBs are associated with evolution of products in gaseous phase, operando mass spectrometric techniques can be used to better understand these unwanted reactions. We have developed an Online Electrochemical Mass Spectrometry (OEMS) set-up to study the gases formed on a Li-plated electrode, to provide the fundamental understanding of the reaction mechanism at the electrode/electrolyte interface.
References
[1]. Bibra, E. M. et al. Global EV Outlook 2021: Accelerating Ambitions Despite the Pandemic. (2021).
[2]. Huang, W., Ye, Y., Chen, H. et al. Onboard early detection and mitigation of lithium plating in fast-charging batteries. Nat Commun
13, 7091 (2022).
[3]. Mattinen, Ulriika, et al. "Gas evolution in commercial Li-ion battery cells measured by on-line mass spectrometry–Effects of C-rate and cell voltage." Journal of Power Sources 477 (2020): 228968.
[4]. Mussa, Abdilbari Shifa, et al. "Fast-charging to a partial state of charge in lithium-ion batteries: A comparative ageing study." Journal of Energy Storage 13 (2017): 325-333.
(Keynote) Evidence of the Interplay of Temperature on Local and Global Battery Phenomena
Authors: Love Corey T. , Carter Rachel Elizabeth , Kingston Todd A. , Mukherjee Partha P. , Dubarry Matthieu , Waller Gordon Henry 
Published: February 2024

Temperature is an important parameter in electrochemical processes and battery operation; for instance, open circuit voltage and resistance values of cells are temperature sensitive. Several recent studies have shown temperature within battery packs are not uniform. This non-uniformity of temperature produces localized thermal gradients within cells that can dictate cell construction, thermal management scheme, cell bussing, etc. Our research group has been working to understand how thermal gradients within battery cells effect material properties, electrochemical performance and stability. We have demonstrated through a range of electrochemical and materials characterization techniques, how dynamic external conditions, specifically thermal gradients and transients, can induce differing degradation modes of the positive and negative electrodes. The directionality and magnitude of thermal gradient dictate the degradation mode, whether loss of lithium inventory, loss of active material, etc.
We have also observed strong electrochemical-mechanical coupling the result of low temperature cycling, where lithium plating on the negative electrode causes a physical deformation and collapse of the cylindrical cell jellyroll. In this talk, we will present in-operando optical microscopy and X-ray computed tomography data to show how dynamic electrical and external thermal conditions can irreversibly effect the chemistry, structure and subsequent safety of lithium-ion battery materials, components and cells. Lastly, the importance of testing materials and cells outside of isothermal laboratory conditions in favor of operating under dynamic thermal conditions, to include austere and stressful operating conditions will be discussed.
A Study on Impedance Change of Lithium-Ion Batteries Depending on Charging Current Profile at Low Temperature
Authors: Lee Jaein , Ha Sang-Hyeon , Yoon Hyunki , Choi Yusong 
Published: February 2024

Lithium-ion batteries(LIBs) are used in various portable electronic devices due to their advantages such as high energy density, power, and long lifespan. Therefore, various studies are being conducted to improve the capacity and power of LIBs and to increase their stability. As a result, LIBs has become a key component of electric vehicles(EVs) and hybrid vehicles(HEVs), which are rapidly increasing in recent years. However, even in these LIBs, the electrochemical reaction and the diffusion rate of lithium ions rapidly decrease at low temperatures, resulting in serious performance degradation. Therefore, low-temperature charging causes lithium plating and dendrite formation to reduce cell life and in severe cases cause cell rupture. In particulary, in the case of EVs and HEVs that are charged outdoors, low-temperature charging can cause serious problems such as battery rupture as well as shortened lifespan. Therefore, in this study, we analyze the effect of various charging techniques such as CC-CV, multi-stage CC, and pulse on the low-temperature impedance change of LIB and propose an optimal charging technique for stable charging.
AT first, test cells for the experiment were fabricated and activated, and then capacity and impedance were measured at room temperature. After that, the charge/discharge cycle experiment of each test cell was performed by applying the CC-CV, multi-step CC, and pulse charging methods at low temperature. After the cycle experiment, the capacity and impedance change of each test cell were measured at room temperature, and the correlation between the capacitance change and the impedance change was analyzed. As a result, the greatest change occurred in the resistance and capacitance components of the SEI (Solid Electrolyte Interface) layer, which is common to all charging methods. However, among the three charging methods, the pulse charging method had the smallest change in capacity and impedance. This is because the repetitive rest period of pulse charging gives relaxation time for diffusion of Li-ions. Next, morphological changes of the LIB anode were confirmed using a scanning electron microscope (SEM). As a result, it was confirmed that the lithium plating and dendrite generated during low-temperature charging additionally reacted with the electrolyte to form an additional SEI layer, thereby changing the thickness and shape of the SEI layer. Therefore, it was confirmed that the change of the SEI layer caused the LIB impedance change. Finally, we confirmed that a low current density or charging current with sufficient break time such as pulse charging is most effective in maintaining the endurance of LIBs at low temperatures.
Improvement of Electrochemical Performances of Electrochromic-Zinc Ion Batteries System Utilizing V4+-V2O5 As a Cathode
Authors: KIM Yonghan 
Published: February 2024

Recently, many countries are practicing carbon neutrality to lower greenhouse gas emissions to "zero" by 2050. Therefore, zinc ion batteries (ZIBs) have been increasing attention as next-generation batteries due to low cost and high volumetric energy density. In addition, since ZIBs utilize a human-friendly water-based electrolyte, ZIBs has been proposed as an alternative to wearable energy storage systems. Above all, the electrochromic – ZIB system is gaining popularity as the next generation storage technology because it can visualize charging and discharging. Vanadium oxide(V2O5), one of the cathode materials of electrochromic ZIB, exhibits excellent electrochemical characteristics with excellent rate performance through intercalation in the layered structure. However, because of V2O5’s poor electronic and ionic conductivities, it is necessary to improve the structure improvement for increasing energy density.
To solve this problem, mixed multiple oxidation states of vanadium are essential to ZIB cathode. This mixed valence states are contributed to increase electrochemical performance and specific capacity.1 V4+-V2O5 exhibit higher electrochemical activity, faster ion transport, better electrical conductivity than Pure V2O5. Also, we can expect that V4+-V2O5 performs outstanding rate capability and long term-cyclic life.
In this study, we developed V4+-V2O5 based electrochromic-ZIB cathode to enhance electrochemical performance controlling the temperature for vanadium reduction heat treatment in H2 gas atmosphere. Furthermore, it will be determined whether vanadium oxide is suitable for electrochromic. Between the yellow V2O5 and the black Vanadium-based compounds, an appropriate point with excellent electrochemical and electrochromic properties will be found.
Visible Light Driven CO2 Photoreduction Using TiO2 Nanotube Arrays Embedded with Low Bandgap Carbon Nitride Nanoparticles
Authors: Vrushabendrakumar Damini , Alam Kazi , Chaulagain Narendra , Kumar Navneet , Shankar Karthik 
Published: February 2024

The extraordinary thermal and photochemical stability, superior charge transport, and tunable band positions of graphitic carbon nitride (g-CN), which is constituted of elements that are plentiful on Earth, renders g-CN an important semiconductor photocatalyst for heterogeneous catalysis [1,2]. Despite these advantages, carbon nitride-based semiconductors do not function effectively as freestanding photocatalysts or photoelectrodes due to a rapid carrier recombination rate and a slightly wide bandgap that only enables them to capture blue and UV photons [3,4]. Anodically formed TiO2 nanotube arrays (TNTAs) are semiconducting wide bandgap scaffolds with excellent photocatalytic properties due to the intrinsic orthogonalization of charge generation/transport and charge transfer processes. Herein, we use a novel in situ electrophoretic anodization to embed low bandgap carbon nitride nanoparticles (CNNPs) in the walls of titania nanotubes. The likelihood of the CNNPs leaching off the TNTA photoanode during photoelectrochemical processes was eliminated by encapsulating CN inside a TiO2 matrix. CNNPs were formed by the thermal condensation polymerization of carbon nitride utilizing citric acid and urea as the precursors, and exhibited some unusual properties, including a lower bandgap of 2.1 eV, a highly redshifted fluorescence emission maximum at 2.35 eV, surface carboxylate groups, and the emergence of unique structural characteristics corresponding to amorphous yet graphitic carbon [5]. In contrast to bulk g-CN, which has a C:N ratio of 0.75, the CNNPs possessed an elevated C:N ratio as high as 1.87 at the surface. The additional carbon was found to be both amorphous and graphitic, although the structural characteristics of g-CN were mostly unaffected, as validated by diffractometric and spectroscopic data. Even in the absence of a sacrificial agent, the CNNP@TNT nanocomposite demonstrated enhanced performance in sunlight-driven CO2 photoreduction. When compared to the freestanding TNT photocatalyst, the CO yield of photoreduction for the CN@TNT hybrid was more than three times higher. UV-filtered illumination of the CNNP@TNT heterojunction photocatalyst generated appreciable quantities of methane and CO (3.41 and 8.78 μmolg–1h–1 respectively). In situ electrophoretic anodization is an innovative approach to incorporate semiconductor quantum dots into TiO2 nanotubes or other electrochemically grown nanostructures.
REFERENCES
1. Kessler, F. K. et al., Nature Reviews Materials (2017) 2 (6), 1.
2. Chaulagain, N. et al., ACS Applied Materials & Interfaces (2022) 14 (21), pp.
24309-24320.
3. Kumar, P. et al., Advanced Optical Materials (2020) 8 (4), Art. No. 1901275.
4. Fu, J. et al., Advanced Energy Materials (2018) 8 (3), Art. No. 1701503.
5. Alam, K.M. et al., Chemical Engineering Journal (2023) 456, Art. No. 141067.
3D Printed Carbon Framework with the Graphene Aerogel for Microbial Fuel Cell Application
Authors: Nikolaev Konstantin G. , Wu Jiqiang , Leng Xuanye , Ivanov Artemii S. , Vazquez Ricardo J. , McCuskey Samantha R. , Bazan Guillermo C. , Novoselov Kostya S. , Andreeva Daria V. 
Published: February 2024

There is a high interest in living organism-compatible materials associated with electrically active interfaces. Bacteria/electrode interfaces implement smart, functional systems with responses, based on which it is possible to elaborate self-regulating energy generation systems. Carbon materials have a number of advantages, such as biocompatibility, low electrical resistance, and the possibility of increasing the electrode surface on an industrial scale. The most promising approach for the industrial production of electrodes is 3D printing. We propose a 3D-printed carbon electrode – a novel lightweight material for electrodes in bioelectrochemical systems for efficient bioelectricity utilization.
The pyrolytic process for manufacturing carbon electrodes is promising for upscaling and industrial applications. However, there is a problem of volume loss when 3D-printed polymers are pyrolyzed in an inert environment. We propose a new strategy for the thermal treatment of 3D-printed polymers that allow for reduced volume loss under pyrolytic carbonization. In addition, to achieve a higher electrode surface area, the graphene aerogel could be impregnated into the 3D-printed scaffolds. Chemical modification of graphene surface can enhance biocompatibility. Specifically, the oxidation of graphene leads to forming a hydrophilic and biocompatible material. We tune graphene hydrophilic properties and electrical conductivity via control over the thermal reduction of the oxidized form of graphene–graphene oxide1.
Such sponge morphology affords 3D-printed carbon scaffolds an excellent lightweight host scaffold for microorganisms, in which the graphene nanowalls are homogeneously occupied by S. oneidensis MR-1. We demonstrate a novel sustainable method to produce graphene-based lightweight 3D printed electrode materials for green energy production from biomass. The proposed technology creates the opportunity for novel, innovative, disruptive graphene applications that can lead to the establishment of new energy-related industries and facilitate many startups in the ecosystem.

Acknowledgments

This work was supported by the Ministry of Education (Singapore) through the Research Centre of Excellence program (grant EDUN C-33-18-279-V12, I-FIM).

References

Xuanye Leng, Ricardo J. Vazquez, Samantha R. McCuskey, Glenn Quek, Yude Su, Konstantin G. Nikolaev, Mariana C.F. Costa, Siyu Chen, Musen Chen, Kou Yang, Jinpei Zhao, Mo Lin, Zhaolong Chen, Guillermo C. Bazan, Kostya S. Novoselov, Daria V. Andreeva, Carbon, 205, 2023, 33-39.
Bioactive Ion-Based Switchable Supercapacitors
Authors: Li Panlong , Grothe Julia , Kaskel Stefan 
Published: February 2024

Switchable supercapacitors enable a reversible electrically driven uptake and release of bioactive ions by polarizing nanoporous carbon electrodes. In this work we demonstrate the first example of a bioactive ion-based switchable supercapacitor. Based on choline chloride and nanoporous carbons with defined porosity we unravel the mechanism of physisorption vs. electrosorption by nuclear magnetic resonance, Raman, and impedance spectroscopy. Weak physisorption leads to pronounced electrically driven electrolyte depletion enabling the release and capture of electrolyte ions in highly controllable and reversible manner. A new 4-terminal device structure is proposed, with a main capacitor and a smaller inserted detective capacitor for monitoring bioactive ions electrosorption in situ. Controlling the ion concentration in a printed switchable supercapacitor based on bioactive ions realizes switching down to 8.3% residual capacity.
The exploration of electrically driven adsorption mechanisms in printable microdevices will open an avenue of manipulating bioactive ions for the further application of drug delivery, neuromodulation, or neuromorphic devices.

Figure 1
Sustainable Laser Induced Supercapacitors from Cork Natural Substrates
Authors: Imbrogno Alessandra , Islam Jahidul , Santillo Chiara , Castaldo Rachele , Sygellou Lamprini , Larrigy Cathal , Murray Richard , Vaughan Eoghan , Hoque Khairul Md , Quinn Aidan J , Iacopino Daniela 
Published: February 2024

A novel type of eco-friendly and cost-effective supercapacitor has been developed by fabricating interdigitated and squared supercapacitors made of porous graphitic carbon electrodes and Polyvinyl alcohol (PVA) electrolyte. The electrodes were fabricated using a simple, fast, and low-cost laser engraving process, using visible irradiation wavelengths (450 nm) and performed under ambient conditions, resulting in highly three-dimensional, electrically conductive, and porous graphitic carbon structures.
By adjusting the laser power and wavelength, it was possible to produce electrode materials with highly porous and high surface area morphology, which are promising for electrochemical applications. Spectral investigation using Raman and FTIR spectroscopies confirmed the formation of graphitic carbon structures and the full conversion of the cork precursor under visible laser irradiation.
The obtained electrodes exhibited excellent supercapacitive behavior when exposed to a PVA electrolyte, achieving a specific areal capacitance of up to 11.24 mF/cm2 with PVA at 30% laser power. The supercapacitive properties showed excellent stability over time, with no significant loss after 10000 charge/discharge cycles.
To evaluate the performance of the new supercapacitors, linear electrodes were used as working electrodes in a three-electrode configuration electrochemical cell. The electrodes showed diffusion-limited electrochemical behavior with fast heterogeneous electron transfer rates (HET), which was superior to that of traditional glassy carbon electrodes.
The innovative and efficient electrode fabrication method presented in this study, which utilizes low-cost instrumentation, environmentally friendly fabrication methods, and Earth-abundant precursor materials, shows great promise for producing large-scale "green" electrochemical sensing platforms and devices in the future.