bluuebunny/crossref_metadata_2025_split huggingface dataset:
Organic Pigment Electrode in Aqueous Magnesium Ion Batteries
Authors: Rodríguez Pérez Ismael Antonio , Wang Xingfeng , Ji Xiulei 
Published: February 2020

Lithium-ion batteries (LIBs) have made tremendous successes in powering electronics and electric vehicles. Yet, LIBs face an insurmountable challenge in sustainability for large-scale stationary applications. Lithium, without effective recycling strategies, is too rare to be used at the current pace, rendering a concern over this great technology. Efforts are, therefore, guaranteed to pursue inexpensive and sustainable energy storage solutions. As of today, Na-ion batteries have received tremendous attention; however, it faces its own hurdle before commercialization, which originated from the choice of anodes. Alike sodium and potassium, magnesium is a benign and extremely Earth abundant element. So far, most electrodes for Mg2+ ion storage have been studied in non-aqueous electrolytes, where intrinsic properties of Mg2+ ion storage might be covered up by factors, including instability of the electrolyte and large overpotentials of Mg metal counter/reference electrode. To date, Mg2+ ion electrodes are still limited to Chevrel compounds or metal oxides. Here, we, for the first time, report reversible Mg2+ ion storage properties in 3,4,9,10-perylenetetracaboxilicdianhydride (PTCDA) in an aqueous electrolyte. In the potential range of -0.6 to 0.2 V vs Ag/AgCl reference electrode, PTCDA is able to deliver a reversible specific capacity of 125 mAh g-1, a good rate capability with 75 mAh g-1 at 500 mA g-1 and a reasonable cycling stability for 100 cycles. This work opens up a new avenue to harvest high-density charge storage for Mg2+ ions in an aqueous medium, which presents a large potential in magnesium ion batteries.
Operando μ-Beam Diffraction Following the Decomposition of Individual Li2O2 Grains in a Non-Aqueous Li-O2 Battery
Authors: Ganapathy Swapna , Anastasaki Mariastella , Heringa Jouke R , van Hulzen Martijn , Adams Brian , Wright Jonathan P. , Nazar Linda F , van Dijk Niels H. , Wagemaker Marnix 
Published: February 2020

Fundamental research into the Li-O2 battery system has gone into high gear, gaining momentum due its very high theoretical specific energy. The electrochemical processes that drive this battery are represented by the total chemical reaction:. We report for the first time the technique of operando micro beam X-ray diffraction applied to monitor the decomposition of individual grains of Li2O2 in a working non-aqueous Li-O2 battery. Due to the extremely small beam size and bright X-rays, the diffraction rings break up into spots, each spot representing a grain of Li2O2 having nanometer dimensions. We have studied two kinds of Li2O2; the first, electrochemically generated toroids of Li2O2 comprising of Li2O2 platelets formed at a low discharge current density of (E-Li2O2) and the second, chemically prepared Li2O2 incorporated into a carbon electrode (C-Li­2O2). The most obvious difference the two is the shape and size of the primary crystallites. Using this technique, we have time-resolved information on the individual transformation of a number of grains of both E-Li2O2 and C-Li2O2, following their complete decomposition.

Figure 1 Voltage curve corresponding to the Oxygen Evolution Reaction (OER) using a current density of 100 mA/cm2, and the corresponding evolution of a 2D (100) reflection of Li2O2 following its decomposition.

Figure 1
Rechargeable Batteries Using Molecular Ions As a Charge Carrier
Authors: Yao Masaru , Sano Hikaru , Ando Hisanori , Kiyobayashi Tetsu , Takeichi Nobuhiko 
Published: February 2020

Is it possible to exceed the lithium redox potential in electrochemical systems? One may think the answer to be “No” because among all the elements the redox potential of the elemental lithium is the lowest, which leads to the high voltage characteristics of the widely used lithium ion batteries. However, the answer should turn “Yes” in principle when we use a molecule-based ion which is not reduced even at the lithium potential. Here we examined a model battery system using a few molecular ion charge carriers such as PF6
– and Me4N+with organic active materials. Although the potential of the negative-electrode is not yet lower than that of lithium at present, this study reveals that molecular ions can work as a “rocking chair” type charge carrier in a battery [1]. There are so far a few studies [2-5] describing the use of a molecular ion as the charge carrier; however, its stoichiometery has rarely been analyzed.
To construct a “rocking chair” type molecular ion battery using, for instance, an anion charge carrier, we used a PF6
–-based electrolyte solution with two redox polymers (poly(N-vinylcarbazole): PVK, poly(1,1'-pentyl-4,4'-bipyridinium dihexafluorophosphate): PBPy) (Fig. 1a) as active materials. As for the molecular ion battery which uses a cation charge carrier, we chose a Me4N+-based electrolyte with some low molecular weight quinone type organic active materials.
As shown in Fig.1b, the prepared sealed full cell using a PF6
–-based electrolyte system exhibited the potential difference of about 1.8 V with about 100 mAh/g(PVK). The cell exhibited a fairly good cycle stability; the cell maintained about 65% of the initial capacity after 100 cycles. The cell using the Me4N+-based electrolyte system also showed a repeatable charge/discharge behavior.
The concept of these molecular ion batteries was proved by energy dispersive X-ray (EDX) measurement: we evaluated the change in stoichiometry of PF6
– in the electrode of the former cell ex situ by EDX and found that the charge carrier in this system is PF6
– and the prepared system is certainly a PF6
–-based “rocking chair type” battery.
When succeeded in further developing the molecular ion battery, the benefits we would gain are: Breaking through the Li potential limitation, High ion conductivity in the electrolyte solution, Free from the dendrite risk, Minor metal free, and so on. To enjoy these benefits, the development in the active materials of both the positive- and negative-electrodes is indispensable. Searching for a negative electrode active material with a low redox potential is especially significant, which, we believe, will pave the way for the progress of this new battery system.

References:

[1] M. Yao, et al., Sci. Rep. 5, 10962 (2015).
[2] J.O. Besenhard, Carbon, 14, 111-115 (1976).
[3] P. Novák, et al., Chem. Rev.
97, 207-281 (1997).
[4] T. Boinowitz, et al., J. Power Sources, 56, 179-187(1995).
[5] H. Nakano et al., J. Mater. Chem. A, 2, 7588-7592 (2014).

Figure 1
Dual Electrolytes Rechargeable Li-Air and Li-Water Batteries
Authors: Kwon Nam Hee , Sheima Yauhen , Fromm Katharina M 
Published: February 2020

Lithium is the lightest metal with the most negative potential (-3 V vs. SHE). Combining oxygen and water as a cathode and an electrolyte with lithium, rechargeable Li-air and Li-water batteries provide higher energy densities than the conventional Li-ion batteries.
However, the redox reversible reactions and cyclability of those batteries are far below expectations. Among the several structures of Li-air batteries, using an aqueous electrolyte provides a higher efficiency and cyclability due to the high ionic mobility and the solubility of discharge products [1]. However, water must not contact lithium metal anode to avoid violent reaction, producing heat and gas evolution. Thus, we apply organic electrolyte on lithium metal anode and aqueous electrolyte on cathode to protect lithium metal and to make highly reversible electrochemical reactions, respectively.
During discharging, the value of pH increases due to the formation of LiOH, damaging the membranes [2,3] and the saturation of LiOH formation [4].
In the system of Li-air, the solubility of O2 in aqueous solution is a key parameter to obtain the highly reversible electrochemical reactions and high energy density.
We studied the O2 solubility in terms of the concentration of LiOH aqueous solution and other salts mixed solutions by means of the electrochemical techniques. Fig. 1 shows the O2 solubility increased with decreasing the concentration of LiOH. We will show the behavior of the O2 solubility of different salts mixed aqueous solutions and the charge/discharge behaviors in dual electrolytes systems.
Fig. 1. The concentrations of O2 in terms of the various concentrations of LiOH aqueous electrolyte.
References
[1] X. Wang, Y. Hou, Y. Zhu, Y. Wu, R. Holze, Scientific Reports 2013, 3, 1401.
[2] D.-J. Lee, O. Yamamoto, D.-M. Im, Y. Takeda, N. Imanishi, 2012, Patent Application No. 13/191769.
[3] J. Christensen, P. Albertus, R. S. Sanchez-Carrera, T. Lohmann, B. Kozinsky, R. Liedtke, J. Ahmed, A. Kojic, J. Electrochem. Soc. 2012, 159, R1-R30.
[4] Y. Wang, H. Zhou, J. Power Sources 2010, 195, 358-361.

Figure 1
Investigating Olivine Cathode for Rechargeable Magnesium Battery with Theoretical and Experiment Approach
Authors: Zhang Ruigang , Mizuno Fuminori , Ling Chen 
Published: February 2020

Lithium ion batteries (LIBs) are quickly becoming the mainstream power sources for environmentally friendly vehicles such as hybrid vehicles (HV), plug-in hybrid vehicles (PHV) and electric vehicles (EV) due to their high energy density. On the other hand, a battery system with even higher energy density is required for the long-range PHV and EV applications, and therefore, post lithium ion batteries (PLIB) such as Li-sulfur batteries and Li-air batteries have been getting more attention in recent years. Rechargeable magnesium batteries are also a candidate for the PLIB thank to the natural abundance of magnesium and the absence of dendrite formation when magnesium metal is used as the anode. In addition, the magnesium batteries are expected to have high energy density because of its divalent nature. However, there is not much progress on the development of novel cathodes since an innovation of Chevrel phase materials such as MgxMo6S8. The difficulty lies in the strong polarization character of the small and divalent Mg2+ and consequently the intercalation and diffusion of Mg2+ ions is somewhat difficult and complicated.
Because of the so-called “diagonal relationship” in the periodic table stating the chemical similarity between lithium and magnesium, significant amount of efforts have been attempted to use compounds analogous to classical Li-ion battery cathode as Mg-intercalation hosts. As olivine LiFePO4 is one of the commercialized Li-ion battery cathode, it is of great interest to examine the performance of olivine compounds as Mg battery cathode. In this work, a comprehensive study about the performance of olivine FePO4 as Mg battery cathode is performed. With a combined theoretical and experimental approach we show that the intercalation of magnesium does not occur in the electrochemical operations. On the contrary to the common belief that the intercalation of magnesium is critically determined by the mobility of Mg2+ ions in the lattice, we demonstrate that the failure of FePO4 cathode is due to the formation of amorphous layer in the electrochemical process that passivates the active particle, similar to the phenomenon that we reported before for α-MnO2 cathode. Our research provides new insight for the magnesiation mechanism of a classical cathode and elucidate several directions towards future rechargeable Mg battery.
Understanding the Good Kinetics of Mo6S8 As Cathode in Mg Ion Batteries By Key Electronic States
Authors: Yu Pengfei , Han Fudong , Feng Xuefei , Long Xinghui , Liu Xiaosong , Wang Chunsheng , Liu Zhi 
Published: February 2020

Mg rechargeable batteries are being considered as one of the most prospective alternatives for Li rechargeable batteries because of their merits including Mg abundance, absence of Mg dendrite and high theoretical specific capacity attributed to two-electron charge transfer reaction process. [1] However，the achievable performance of Mg rechargeable batteries is still limited regarding their practical application. The key limitation to this lies in cathode. To date, Chevrel phase Mo6(SxSe1-x)8 is the only cathode material in which Mg2+ can be efficiently intercalated/deintercalated. Extensive theoretical and experimental studies have been done to screen out promising cathode materials by constructing the crystal structure similar to Chevrel phase. However, successful research has been rarely reported. It indicates that only taking into account of the crystal structure is not sufficient enough to explore the Mg storage/transport behavior in the electrode. Given the facts that the two-electron charge transfer process was involved in Mg batteries while the great success has been made in the studies on lithium ion batteries through the key electronic states [2-5], the evolution of electronic structure in Chevrel phase might provide more important information to elucidate the physical nature of Mg storage/transport in the electrode. However, the experimental study on the evolution of electronic structure in Chevrel phase cathode is rare. In this report, the study on the unoccupied states of a typical Chevrel phase Mo6S8 including Mo L-edge and S K-edge were conducted by tender X-ray absorption spectroscopy. In contrast with the conventional understanding that only Mo cation is involved in the charge transfer process, the key electronic states at the pre-edge of S spectra were also found to be evolved regularly with different states of charge/discharge. It is assigned to the hybridization between Mo 4d states and S 3p states. The evolution of this state opens a gate to reveal the nature of good kinetics in Chevrel phase.
1. Aurbach, D., et al., Prototype systems for rechargeable magnesium batteries. Nature, 2000. 407(6805):
p.724-727.
2. Liu, G., et al., Polymers with Tailored Electronic Structure for High Capacity Lithium Battery Electrodes.
Advanced Materials, 2011. 23(40): p. 4679-4683.
3. Liu, X., et al., Phase Transformation and Lithiation Effect on Electronic Structure of LixFePO4: An In-Depth
Study by Soft X-ray and Simulations. Journal of the American Chemical Society, 2012. 134(33): p. 13708-13715.
4. Yang, W., et al., Key electronic states in lithium battery materials probed by soft X-ray spectroscopy. Journal of
Electron Spectroscopy and Related Phenomena, 2013. 190, Part A(0): p. 64-74.
5. Liu, X., W. Yang, and Z. Liu, Recent Progress on Synchrotron-Based In Situ Soft X-ray Spectroscopy for Energy
Materials. Advanced Materials, 2014: 7710-7729.
Kinetics of Alloying and Deposition in Multivalent Battery Anodes Using Real-Time X-Ray Diffraction
Authors: Fister Timothy T , Han Sang-Don , Kim Soojeong , Vaughey John T. , Hubaud Aude A. , Fenter Paul , Esbenshade Jennifer , Lundberg Kimberly E. , Gewirth Andrew A 
Published: February 2020

A multivalent successor to lithium ion batteries will likely incorporate a metal anode. However, many electrodeposition processes are prone to energy losses from side reactions and overpotentials for plating or stripping. To develop a link between the kinetics of crystal growth/dissolution with electrochemical data, we have followed electrodeposition of Mg and Zn with operando x-ray diffraction using a variety of electrolytes and current collectors. In some cases we find that alloying or passivation competes with metal deposition and can dramatically alter the morphology of the deposited metal, as seen by texture analysis of the diffraction.
Identifying Solution Based Catalysts for the Lithium-Oxygen Battery
Authors: Richardson William , Garcia-Araez Nuria 
Published: February 2020

Increasing demand for lighter and more powerful batteries has driven research into alternative technologies. One system that has received significant attention is Lithium-Oxygen. This system exploits the reduction of oxygen to lithium peroxide, by lithium metal, to provide a theoretical specific energy of 3500 Wh kg-1. One of the major problems facing the Lithium-Oxygen battery is the passivation of the air electrode caused by insoluble lithium oxides and lithium carbonate formed during cycling. These products are not completely oxidized during the charge step and therefore accumulate within the electrode causing the capacity to fade with each cycle1.
This work focuses on identifying solution based catalysts in non-aqueous electrolytes to facilitate the oxidation of these insoluble products2. The catalysts are oxidized at a higher potential than the lithium peroxide but undergo much faster electron transfer. Once oxidized the catalyst is able to oxidize any lithium peroxide or lithium carbonate remaining on the surface, unblocking the pores and therefore preserving the capacity over subsequent cycles. Analysis of the carbon electrode by x-ray diffraction is able to confirm Li2O2 as the discharge product. While the evolution and consumption of oxygen during cycling has been studied using on-line mass spectrometry. The figure included displays cyclic voltammograms of oxygen reduction and evolution with (black) and without (red) a catalyst. This demonstrates that that incorporation of such a catalyst can significantly reduce electrode passivation and therefore dramatically improve the cycle life of the cell.
[1] Garcia-Araez, N.; Novák, P. Critical Aspects in the Development of Lithium–air Batteries. J. Solid State
Electrochem.
2013, 17, 1793–1807.
[2] Lacey, M. J.; Frith, J. T.; Owen, J. R. A Redox Shuttle to Facilitate Oxygen Reduction in the Lithium Air Battery. Electrochem. commun.
2013, 26, 74–76.
Fig. 1. Cyclic voltammogram of oxygen reduction and evolution at 50mV s-1. Cell consisted of a two electrodes; a glassy carbon working electrode (3mm) and Lithium foil counter/ reference electrode.

Figure 1
Novel Electrolytes for Metal-Air Batteries
Authors: von Czarnecki Peter , Ahrens Maria , Rösler Sina , Schubert Thomas J. S. 
Published: February 2020

Ionic liquids (ILs) – salts that are liquid at temperatures below 100°C – show interesting profiles of physical and chemical properties which allows their use as safe electrolytes[1,2,3] in batteries. These properties include tunable viscosities and conductivities, chemical and thermal stability as well as large electrochemical windows, and incombustibility at temperatures below their decomposition point.
Fig. 1: Temperature-dependent influence of additive X on the viscosity of IL-mixtures
In this presentation we will report our latest developments in the field ionic liquid based electrolytes for different types of metal-air batteries. The focus will be the use of mixtures of ionic liquids as well as of mixtures of ionic liquids and solvents in order to increase performance and safety of metal-air batteries.

References:

[1] M. A. Taige, D. Hilbert, T. J. S. Schubert Z. Phys. Chem.
2012, 226, 129.
[2] M. Armand, F. Endres, D. R. MacFarlane, H. Ohno, B. Scrosati Nature

Materials
2009, 8, 621.
[3] D. Gelman, B. Shvartsev, Y. Ein-Eli
J. Mater. Chem. A

, 2014,
2
, 20237.

Figure 1
Thiol-Based Electrolyte Additives for High-Performance Lithium-Sulfur Batteries
Authors: Wu Heng-Liang , Shin Minjeong , Liu Yao-Min , See Kimberly A , Gewirth Andrew A 
Published: February 2020

Here, we propose thiol-based electrolyte additives (biphenyl-4,4’-dithiol (BPD)) to enhance the capacity retention of lithium-sulfur batteries. In-situ Raman and UV-Vis spectroscopy are used to investigate the effect of the additive on the sulfur reduction mechanism. Raman spectroscopy shows that long chain polysulfides (S8
2-) are formed via S8 ring opening in the first reduction process at ~2.4 V vs Li/Li+ and short chain polysulfides such as S4
2-, S4
-, S3
․
- and S2O4
2- are observed with continued discharge at ~2.0 V vs Li/Li+ in the second reduction process. In the Kinetic study, rate constants obtained for the appearance and disappearance polysulfide species show that short chain polysulfides are directly formed from S8 decomposition. The polysulfide oxidation and reduction is quasi-reversible. With the BPD additive, an additional reduction process is observed at ~2.1 V vs Li/Li+. This reduction is associated with the formation of BPD-polysulfide complexes. The BPD-polysulfide complexes form at ~2.1 V followed by the formation of short chain polysulfides upon further discharge. The reduction of these complexes is reversible during the charge process. The BPD additive inhibits the formation rate of short chain polysulfides, suggesting that there is a strong interaction between BPD and short chain polysulfides. In-situ UV-Vis spectroscopy shows that the polysulfide solubility decreases in the presence of the BPD additive and forms thiol-polysulfide complexes during the cycling. The (-)ESI-MS shows the formation of BPD-S and BPD-S2 and BPD-S3, suggesting that BPD interacts with short chain polysulfides. The decomposition of the thiol-based additive was found during the battery cycling and resulted in a dense and smooth SEI film on the Li anode.
References:
(1) Zhang, S.S. et al J. Power Sources 2013, 231, 153-162.
(2) Barchasz, C. et al., Anal. Chem. 2012, 84, 3973.
(3) Cuisinier, M. et al., J. Phys. Chem. Lett. 2013, 4, 3227.
(4) Hagen, M. et al., J. Electrochem. Soc. 2013, 160, A1205.
Self-Assembled MWCNT Interlayer for High-Performance Lithium-Sulfur Batteries
Authors: Kim Hee Min , Manthiram Arumugam , Sun Yang-Kook 
Published: February 2020

Rechargeable batteries are one of the prime approaches for electrical energy storage. The current lithium-ion battery technology based on transition-metal oxide cathodes and graphite anode have limited energy storage capacity, so there is immense interest to develop alternate high-capacity cathode and anode materials. Lithium-sulfur (Li-S) batteries are appealing in this regard as they offer a high energy density of 2500 Wh kg-1 when coupled with lithium-metal anode due to the large charge-storage capacity of sulfur.[1]
Moreover, sulfur is much more abundant, inexpensive, and non-toxic compared to the transition-metal oxide cathodes.
There are several challenges with the Li-S batteries, such as low electrical conductivity of sulfur and the discharge product Li2S and the migration of dissolved polysulfides from the cathode to the anode, resulting in low efficiency and inadequate cycle life.[2] Well-designed carbon-sulfur composites have been extensively explored to overcome these issues.[3] In these strategies, sulfur was entrapped in carbon structures using porous carbon, carbon nanotubes (CNT), and hollow carbon spheres. Carbon backbone serves as the electron conducting path for sulfur and reduce polysulfide migration by trapping the polysulfides during cycling. However, polysulfide migration still occurs and cycle life is inadequate for practical applications. Manthiram group and other groups introduced the use of carbon-paper interlayers in between the sulfur cathode and the polymer separator or carbon-coated membrane and demonstrated high sulfur utilization with better cycle life due to the suppression of polysulfide diffusion to the anode and the serving of the carbon-paper interlayer as a pseudo-upper current collector.[4]

We present here the fabrication of an interlayer consisting of MWCNT and the electrolyte in a single fabrication process. Such MWCNT-electrolyte-paper interlayers are much more effective compared to the bare MWCNT-paper interlayer due to the fast ionic and electronic transport and a better interface between the sulfur cathode and the interlayer as well as between the separator and the interlayer.

References

[1]. B. Scrosati, J. Hassoun, Y.-K. Sun, Energy Environ. Sci. 2011, 4, 3287.
[2]. Y.-X. Yin, S. Xin, Y.-G. Guo, L.-J. Wan, Angew. Chem. Int. Ed. 2013, 52, 13186-13200
[3]. A. Rosenman, E. Markevich, G. Salitra, D. Aurbach, A. Garsuch, F.F. Chesneau, Pan, Adv. Energy Mater. 2014,1500212.
[4]. Y.-S. Su, A. Manthiram, Chem Comm. 2012, 48, 8817-8819.