bluuebunny/crossref_metadata_2025_split huggingface dataset:
Impact of Solvation Energetics on the Oxygen Reduction Reaction in Alkali-Metal/Oxygen Batteries
Authors: Sankarasubramanian Shrihari , Ramani Vijay 
Published: May 2020

Alkali-metal/Oxygen batteries are a potential high-energy alternative to Li-ion batteries1. In these systems, the critical performance bottleneck is the oxygen reduction reaction (ORR) which in turn depends on the non-aqueous electrolyte that mediates ion and oxygen transport2. Herein, we show that a multifold increase of the practical discharge power of these batteries can be achieved by tuning the tripartite interactions between the salt cation, anion and the solvent in the electrolyte3. A single descriptor of the solvation energetics, the solvent reorganization energy (λ), is shown to capture the influence of electrolyte composition on both reactant transport (DO2
) and reaction kinetics (k) at the electrode and found to be broadly applicable to alkali-metal/oxygen (i.e. Li-, Na- and K-O2) batteries. Increasing cation size (from Li+ to K+) doubled k/λ, indicating an increased sensitivity of k to the choice of anion, while variations in DO2
were minimal over this cation size range. These multifarious effects were captured in the Electrochemical Thiele Modulus incorporating Marcus-Hush kinetics and guidelines are presented for the choice of electrolyte solvent and salt when designing systems for high discharge rates. In a model symmetric K-O2 cell4, both the formation of solvent-separated ion-pairs and the existence of unsolvated anions reduced overpotential losses by 200mV compared to electrolytes with partial anion solvation, successfully demonstrating the rational, ab-initio design of electrolytes for high-power alkali-metal/Oxygen batteries.

References

1. N. Xiao, X. Ren, W. D. McCulloch, G. Gourdin, and Y. Wu, Acc. Chem. Res., 51, 2335–2343 (2018).
2. S. Sankarasubramanian, J. Seo, F. Mizuno, N. Singh, and J. Prakash, J. Phys. Chem. C, 121, 4789–4798 (2017).
3. S. Sankarasubramanian, J. Kahky, and V. Ramani, Proc. Natl. Acad. Sci. U. S. A., 116, 14899–14904 (2019).
4. S. Sankarasubramanian and V. Ramani, J. Phys. Chem. C, 122, 19319–19327 (2018).
Catalytic and Stability Performance of the Electrode and Electrolyte in Na-O2 Batteries: Electrochemical Insight
Authors: Hasan Maksudul , Ravikumar Ravikumar , Mamlouk Mohamed , Scott Keith 
Published: May 2020

Using a metal anode in a metal air battery should maximise the cell voltage and energy density compared to the counterpart metal-ion technology but currently is challenging [1]. In sodium and lithium air batteries sodium or lithium dendrite formation at the anode is problem both in terms of performance and safety [2]. Oxygen (O2) may also diffuse to the anode and partly passivate the metallic surface and increase the cell impedance [2]. Side reactions of the metallic anode with the liquid electrolyte, O2 can also take place at the anode surface [3].
Here, we report how the Na anode, the cathode and electrolyte limit the performance of Na-O2 batteries. The capacity limitation of the Na-O2 batteries not only relates to air blockage of the cathode by the discharge products but also to the metallic anode due to its side reactions with electrolyte and O2. A pX logged cyclic voltammetry studies showed that metallic Na is passivated significantly in aerated electrolyte as indicated by a shift in the Na/electrolyte interface's oxidation and reduction reaction potential to both positive and negative directions. Consequently, the overall cell potential decreases while the charging over potential increases (Fig. 1). The isolation by a solid-state electrolyte of the metallic anode from the direct contact of liquid electrolyte and O2 resulted in a long operating time with cell potential close to the theoretical value. A high stability was achieved at slower charge-discharge rates due to lower ionic conductivity of the solid-state electrolyte at room temperature. We will examine a number of solid-sate electrolytes for high performance Na-O2 batteries. This study will also analyse ex situ characterisation of the products formed at the metallic Na/electrolyte and non-precious metal oxide air-cathode/electrolyte interfaces that correlates the catalytic and stable performances of Na-O2 batteries.

References:

1. L. J. Hardwick and C. P. de Leon, Johnson Matthey Technology Review, 62, 134 (2018).
2. B. Sun, C. Pompe, S. Dongmo, J. Q. Zhang, K. Kretschmer, D. Schroder, J. Janek and G. X. Wang, Advanced Materials Technologies, 3 (2018).
3. I. Landa-Medrano, C. Li, N. Ortiz-Vitoriano, I. Ruiz de Larramendi, J. Carrasco and T. Rojo, Journal of Physical Chemistry Letters, 7, 1161 (2016).

Figure: CV’s in TEGDME containing 0.5 M NaFSI with N2 and O2 saturated; catalyst loading 1.5 mg cm-2 and scan rate 10 mV s-1. Three-electrode glass cell using Na foil wire as the counter, Ag/AgCl as the reference and Ni/TiC/NiCo2O4 as the working electrode were used. The counter electrode potential was measured vs Ag/AgCl using pX data logger.

Figure 1
Towards Moisture Tolerant Aprotic Lithium-air Batteries via Reversibly Cycling LiOH
Authors: Temprano Israel , Liu Tao , Petrucco Enrico , Kim Gunwoo , Ellison James , Jónsson Erlendur , Grey Clare P. 
Published: May 2020

In the light of recent commitments from several European countries to ban the sale of internal combustion engine vehicles in the coming decades, the race to develop electrical storage strategies beyond the capabilities of lithium ion batteries is intensifying considerably. Amongst the many different options, Li-air batteries (LABs) have attracted significant attention due to their comparable energy density to fossil fuels1. Despite of its potential, several fundamental challenges remain to be overcome for their successful development2-4. Amongst these challenges, the instability of the typical discharge products (LiO2 and Li2O2) in the presence of moisture and CO2 represents a fundamental stumbling block5.
The development of moisture-tolerant, LiOH-based non-aqueous Li-O2 batteries is a promising route to bypassing the inherent limitations caused by the instability of their typical discharge products6. The use of the I-/I3
- redox couple to mediate the LiOH-based oxygen reduction and oxidation reactions has proven challenging to develop due to the multiple reaction paths induced by the oxidation of I- on cell charging7. In this work we demonstrate a reversible LiOH-based Li-O2 battery cycling through a 4 e-/O2 process with low charging overpotential (below 3.5 V vs Li/Li+). This is achieved by increasing the oxidizing power of I3
-, which shifts the charging mechanism from IO-/IO3
- formation to O2 evolution.
1. C. P. Grey and J. M. Tarascon, Nature Materials, 2017, 16, 45–56.
2. G. Girishkumar, B. McCloskey, A. C. Luntz, S. Swanson and W. Wilcke, The Journal of Physical Chemistry Letters, 2010, 1, 2193-2203.
3. D. Aurbach, B. D. McCloskey, L. F. Nazar and P. G. Bruce, Nature Energy, 2016, 1, 16128.
4. D. G. Kwabi, N. Ortiz-Vitoriano, S. A. Freunberger, Y. Chen, N. Imanishi, P. G. Bruce and Y. Shao-Horn, MRS Bulletin, 2014, 39, 443-452.
5. N. Mahne, B. Schafzahl, C. Leypold, M. Leypold, S. Grumm, A. Leitgeb, Gernot A. Strohmeier, M. Wilkening, O. Fontaine, D. Kramer, C. Slugovc, Sergey M. Borisov and Stefan A. Freunberger, Nature Energy, 2017, 2, 17036.
6. T. Liu, M. Leskes, W. Yu, A. J. Moore, L. Zhou, P. M. Bayley, G. Kim and C. P. Grey, Science, 2015, 350, 530-533.
7. C. M. Burke, R. Black, I. R. Kochetkov, V. Giordani, D. Addison, L. F. Nazar and B. D. McCloskey, ACS Energy Letters, 2016, 1, 747-756.

Figure 1
Novel Methods for Coating Li4Ti5O12 Particles: Boosting Performances of Li-Ion Batteries
Authors: Daigle Jean-Christophe , Asakawa Yuichiro , Beaupré Mélanie , Trudeau Michel , Zaghib Karim 
Published: May 2020

One of the promising approaches for limiting climate changes is to use alternatives and greener sources of energy (wind, solar, etc.). However, the production of electricity from these sources is fluctuant and needs a solution for storage thus, the advent of energy storage for wind power, solar plant, etc., requires a new generation of batteries in order to optimize the use of these alternative sources of energy. To do so, the development of a battery with a high rate of charging and discharging, a longer cycle life and safe is imperative.
We devoted our efforts to develop LFP-LTO batteries; this presentation will highlight our avenues to limit the gas evolution in a battery; novel methods for coating will be presented, the use of polymers to protect the surface of the active inorganic particles in order to limit the degradation of the electrolyte. Two methods to graft polymers on particles (LTO) were applied with success for preventing degradation of LFP-LTO cells. Because battery environments are aggressive (HF formation, pH = 2), we developed a new robust method for grafting hydrophobic polymers on active particles (LTO) by Williamson Ether Synthesis, which is compatible with the manufacturing of electrodes, and prevented significant cell degradation over extensive cycling. They were able to limit the degradation of the battery by increasing the capacity retention and stabilizing the resistance of the electrode with the accelerated aging. The other method (grafting from) allows the formation of shells by a myriad of polymers, therefore particles become compatible with any kind of polymeric binders. Electrochemical performances will be shown with different compositions.
Moreover, we reported on the development of an economical, eco-friendly, and scalable method of making a homogenous 3D network coating of N-doped carbons on LTO particles. Our method makes it possible, for the first time, to fill the pores of secondary particles with carbons; we revealed that it is possible to cover each primary nanoparticle. This unique approach permited the creation of lithium-ion batteries with outstanding performances during ultra-fast charging (4 C and 10 C), and demonstrated an excellent ability to inhibit the degradation of cells over time. This new method allowed removal of conductive carbons in anode fabrication, therefore active materials compose up to 96 wt% in electrodes.
These methods are valuable for large production because it is inexpensive and easy to scale up.
Pulsed Current Based Fast Charging Methods for Li-Ion Battery
Authors: Khatokar Amarnath Rakesh , Thivel Pierre-Xavier , Leprêtre Jean-Claude , Bultel Yann , Roy Francis , Thorner Gentien 
Published: May 2020

The increasing rate of greenhouse gas emissions from conventional cars and its impact on global warming in the recent years has led to the technological advancements in the evolution of electric vehicles. Developing fast charging methods for Li-ion batteries is one such technological advancement and soon it will be imperative to promote the usage of electric vehicles in increased numbers. However, fast charging of Li-ion battery accelerates aging mechanisms [1] and triggers thermal runaway condition. As a result, this study investigates pulsed current based fast charging methods employed on C/NMC batteries. Pulses of current at low frequency (mHz) [2] and high frequency (KHz) are used with an extended pulse current period, thanks to higher voltage limit based on ohmic drop compensation [3]. The findings of the experimental investigation clearly establishes that a compromise has to be found between relaxation period and temperature in order to achieve fast charging. For instance, on one hand, a 2C current pulse with an on duration of 3s and relaxation duration of 1s allows to save 45% of recharging time when compared with standard constant current-constant voltage charging (CC-CV) at 0.5C as shown in the figure below. On the other hand, the temperature variation does not exceed 20°C beyond ambient which is lower than that of its counterpart CC-CV at 2C. Hence, the experimental investigation successfully opens the doors to implement fast charging methods on C/NMC batteries by limiting the temperature rise, there by arresting the ageing of batteries and thermal runaway condition.
Keyword: Li-ion, Fast charging, Current pulse, Ohmic drop compensation, Temperature, Thermal runaway.

Figure 1
Design Considerations for Charging Time Reduction in Lithium Ion Cells
Authors: Yourey William , Fu Yanbao , Li Ning , Battaglia Vince , Tong Wei 
Published: May 2020

As electric vehicles (EV) show an increased penetration into the transportation market, a challenging hurdle to overcome is a vehicle “refuel” time similar to that of refilling a gasoline vehicle tank. One pathway to accomplish this is fast charging lithium-ion cells. The majority of commercial Li-Ion cells manufactured today contain various positive electrode active materials, coupled with a graphite negative electrode. An advantage of graphite electrodes is that the lithiated graphite voltage lies close to that of Li/Li+, resulting in in increased cell voltage. This benefit also has a detrimental effect on fast charging cells with graphite electrodes, where a small polarization of the negative electrode can result in a condition favorable to lithium metal plating on the negative graphite electrodes1.
While modified high rate charging procedures for commercial lithium-ion cells with conventional graphite negative electrodes, such as multistage constant current charging and boost charging, have been implemented. These procedures rely on reducing charging currents when cell voltage limits are reached 2,3. Following the development of an accelerated charging procedure based solely on negative electrode lithiation rate and polarization 4, the presented work evaluates the effect of negative to positive (N:P) matching ratio on cell fast charge performance. Two varying N:P matching ratios of 1.2:1 and 1.7:1 are evaluated and the resulted impact on fast charge performance will be presented. Utilizing an accelerated charging procedure based solely on the limiting negative electrode results in an identical charging procedure being used for multiple cell designs when charging to the same degree of negative electrode lithiation. Theoretically the applied procedure should result in a reduction in recharge time to 80% state of charge from 58 minutes to 34 minutes by altering the cell N:P ratio. Actual cell performance is altered as increased irreversible capacity loss occurs in cells with increased N:P rations, but improvements in cell charge times can be accomplished from design changes, namely cell N:P ratios.

References

1. C. Uhlmann, J. Illig, M. Ender, R. Schuster, and E. Ivers-Tiffée, Journal of Power Sources, 279, 428–438 (2015).
2. D. Anseán et al., Journal of Power Sources, 321, 201–209 (2016).
3. P. H. L. Notten, J. H. G. O. het Veld, and J. R. G. van Beek, Journal of Power Sources, 145, 89–94 (2005).
4. W. Yourey, Y. Fu, N. Li, V. Battaglia, and W. Tong, J. Electrochem. Soc., 166, A1432–A1438 (2019).
Accurate in-Operando Quantitative Diagnostics of Lithium Ion Cells Using Heat Generation
Authors: Prosser Ryan 
Published: May 2020

As lithium ion cells are used, internal chemical and physical degradation processes occur which negatively impact cell performance. A key issue for battery systems engineers is extending the life of their battery pack which amounts to slowing down the rate of these degradation processes.
The first step in addressing this problem is being able to frequently and accurately diagnose cell degradation. With this knowledge of cell state, it is possible to make better decisions on how to adjust the operating conditions of the battery pack to optimise cell longevity and performance.
Current methods which are capable of accurate quantitative diagnostics employ thermodynamic models parameterised by different degradation modes. These models require very slow discharge rates or galvanic intermittent titration tests (GITT) to obtain the cell open circuit voltage (OCV) and therefore cannot be used in most commercial applications. Other methods which do not require OCV conditions involve an impedance model coupled to the thermodynamic model. This adds computational complexity of the methods as well as incurring an accuracy penalty compared to the thermodynamic models.
We present a novel technique which uses cell instantaneous heat generation rate obtained in operando to quantify the extent of cell degradation. The proposed method provides results comparable to those obtained from thermodynamic models using a model which is no more computationally intense. The method also decouples the thermodynamic and kinetic effects of degradation allowing for a full diagnosis to be obtained more accurately and in a fraction of the time compared to alternative methods.
(Invited) Multi-Functional Flexible Sensor Sheets
Authors: Takei Kuniharu 
Published: May 2020

Flexible and stretchable electronics are now widely studied for a next class of electric devices replaced from the silicon-based conventional inflexible devices. In particular, multi-functional e-skins can contribute to the applications for wearable healthcare devices and Internet of Things (IoT) concepts. For healthcare application, chemical information such as pH, glucose, sodium ion, and potassium ion levels are very important to monitor as well as physical information including activity, temperature, heartbeat, and electrocardiogram (ECG) signals. Furthermore, simultaneous multiple condition monitoring of physical and chemical information is a next class of wearable devices for convenient and safe human life. To realize the multi-functional flexible sensor system platforms, in this talk, flexible physical and chemical sensor sheets using mainly inorganic nanomaterials will be discussed by proposing low-cost, macroscale, and multi-functional material systems. Especially, human-interactive flexible sensors to detect human motion and health conditions are mainly introduced. After understanding the fundamental properties and mechanism of the flexible sensors such as a strain sensor, a temperature sensor, an ultraviolet sensor, a tactile pressure sensor, and a chemical sensor, integrated device applications with several sensors on a flexible film are demonstrated as proof-of-concepts for multi-functional e-skins.
Although a lot of researches and developments are still required for practical application, these studies may help to open a door for the next step of flexible electronics.
(Invited) Wireless Electrochemiluminescence Devices
Authors: Gao Wenyue , Qi Wenjing , Qi Liming , Yuan Fan , Ma Xiangui , Xia Yong , Zhang Wei , Lou Baohua , Muzyka Kateryna , Snizhko Dmytro V. , Xu Guobao 
Published: May 2020

Traditional electrochemical systems generally require the direct connection of working electrode with potentiostat. They often employ two electrodes (a working electrode and a counter electrode) or three electrodes (a working electrode, a counter electrode, and a reference electrode) for a single electrochemical experiment. Different from traditional electrochemical systems, wireless electrochemical systems do not require the direct connection of working electrode with potentiostat. Conventional ipolar electrochemical system is a well-known wireless electrochemical system. It exerts potential control over electrolyte solutions with driving electrodes and redox reactions occur at the two opposite poles of the bipolar electrode. This enables simultaneous control of many bipolar electrode arrays with only two driving electrodes for multiplex experiments.
Electrochemiluminescence, also called electrogenerated chemiluminescence (ECL), is light-emitting phenomenon generated from electrochemical reaction. The combination of bipolar electrochemical systems with ECL enables facile multiplex analysis.
We present here several new wireless ECL systems, including wireless electrochemiluminescence, single-electrode ECL system, and wireless single-electrode ECL system [1-5].
Acknowledgment
We are grateful for financial support from the National Key Research and Development Program of China (No. 2016YFA0201300), National Natural Science Foundation of China (Nos. 21804127,21874126,21675148), the Chinese Academy of Sciences (CAS)-the Academy of Sciences for the Developing World (TWAS), and President’s Fellowship Program, the CAS President's International Fellowship Initiative (PIFI) project.

References

Wenjing Qi, Jianping Lai, Wenyue Gao, Suping Li, Saima Hanif, Guobao Xu. Wireless Electrochemiluminescence with Disposable Minidevice. Chem., 2014, 86, 8927–8931.

Liming Qi, Yong Xia, Wenjing Qi, Wenyue Gao, Fengxia Wu, Guobao Xu. Increasing Electrochemiluminescence Intensity of a Wireless Electrode Array Chip by Thousands of Times Using a Diode for Sensitive Visual Detection by a Digital Camera Chem., 2016, 88, 1123–1127.

Fan Yuan, Liming Qi, Tadesse Haile Fereja, Dmytro V. Snizhko, Zhongyuan Liu, Wei Zhang, Guobao Xu. Regenerable bipolar electrochemiluminescence device using glassy carbon bipolar electrode, stainless steel driving electrode and cold patch. Electroc Acta, 2018, 262, 182-186.

Xiangui Ma, Liming Qi, Wenyue Gao, Fan Yuan, Yong Xia, Baohua Lou, Guobao Xu. A portable wireless single-electrode system for electrochemiluminescent analysis. Electroc Acta, 2019, 308, 20-24.

Wenyue Gao, Kateryna Muzyka, Xiangui Ma, Baohua Lou, Guobao Xu, A single-electrode electrochemical system for multiplex electrochemiluminescence analysis based on a resistance induced potential difference. Chem. Sci. 2018, 9, 3911-3916.
(Invited) Structural Modulation of 2D Carbon Nitride for Electrochemiluminescent Biosensing
Authors: Zhang Yuanjian 
Published: May 2020

As an emerging luminophore, metal free 2D carbon nitride demonstrate the advantages of low-cost, high biocompatibility and stability, easy functionalization, strong electrochemiluminescent (ECL) emission, and an unambiguous luminescence mechanism. Many ECL biosensors based on carbon nitride have been developed, with very promising performances. As chemical tailoring of 2D materials can effectively control the properties thus guiding their applications, our group recently explored the modulation of a diverse range of carbon nitrides with different dopants and nanostructures (e.g. nanosheets, nanofibers, and quantum dots). It not only tunes the optical properties of carbon nitride but also offer an effective way to engineer the surface properties of carbon nitride. Both are important in addressing the challenges of biosensing such as the development of new strategies for higher sensitivity and selectivity that involves signal transducer and multi-scale interfaces.

Acknowledgements

This work was financially supported in part by the National Natural Science Foundation of China (21775018), the Natural Science Foundation of Jiangsu Province (BK20160028), the Open Funds of the State Key Laboratory of Electroanalytical Chemistry (SKLEAC201909) and the Fundamental Research Funds for the Central Universities.

References

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2018, 47, 2298.
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2019, DOI: 10.1002/anie.201911822.
[3] Lv, Y.; Chen, S.; Shen, Y.; Ji, J.; Zhou, Q.; Liu, S.; Zhang, Y. J. Am. Chem. Soc.
2018,
140, 2801.
[4] Ji, J.; Wen, J.; Shen, Y.; Lv, Y.; Chen, Y.; Liu, S.; Ma, H.; Zhang, Y. J. Am. Chem. Soc. 2017, 139, 11698.
[5] Zhou, Z.; Wang, J.; Yu, J.; Shen, Y.; Li, Y.; Liu, A.; Liu, S.; Zhang, Y. J. Am. Chem. Soc. 2015, 137, 2179.