bluuebunny/crossref_metadata_2025_split huggingface dataset:
Using New Quasi in-Situ TEM Technique to Study Structural Changes of Electrode Materials for Li-Ion and Na-Ion Batteries
Authors: Lin Ruoqian , Hu Enyuan , Yu Xiqian , Yang Xiao-Qing , Xin Huolin L. 
Published: February 2020

In this poster, we report the development of a quasi in-situ TEM technique to study structural changes of electrode materials for Li-ion and Na-ion batteries. Some preliminary results about structural (ir)reversibility of NiO conversion anode materials relating to the materials’ size and morphology will be discussed as an example. Using a quasi in-situ TEM setup, we were able to track the structural changes of electrode materials in marked locations on a TEM grid repeatedly before and after electrochemical lithiation/delithiation in LiPF6/EC/DEC electrolyte. This method is a further development of the TEM grid-in-a-coin cell method reported in the literature (F Lin et al, Nat. Comms.,5, 3356 (2014)) with much improved capability to locate the same materials on the TEM grid before and after charging/discharging. Our results show that upon lithiation, NiO is converted into a three-dimensional nanoporous network of metallic Ni. However, we found that the structural reversibility of NiO upon delithiation is highly dependent on the initial size and morphology of the materials. Particularly in our 10 nm-thick NiO nanoplate materials, the nanoporous structure can be removed and the solid-form palette structure can be fully recovered when the material is delithiated. This study shows that that size effect can be an important parameter in dictating the structural reversibility of transition metal oxide conversion materials.
Acknowledgements
This work was supported by the U.S. Department of Energy, the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies under Contract Number DE-SC0012704. This research used resources of the Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility, at Brookhaven National Laboratory under Contract No. DE-SC0012704.
Fluoride-Phosphate Cathode Materials for Li-Ion Batteries: The Impact of Structure on Electrochemical Activity
Authors: Khasanova Nellie R. , Fedotov Stanislav S. , Manoilov Alexej I. , Samarin Aleksandr Sh. , Karakulina Olesia M. , Abakumov Artem M. , Antipov Evgeny V. 
Published: February 2020

Today researches in the field of cathode materials for Li-ion batteries are directed towards the development of new materials with high power and energy densities, especially to answer the requirements of large scale applications. In this respect, fluoride-phosphate materials are very attractive as they demonstrate wide structural diversity. Furthermore, they are expected to exploit the advantages of both anion species: the increase in the working potential due to inductive effect of the polyanion group and higher ionicity of the M−F bond, faster kinetics arising from lower affinity of lithium to the F-anion.1

In the search for new cathode materials for Li-ion batteries we have explored the A2MPO4F and AMPO4F (A=Li, Na, K, and M=Co, Mn, Fe, V) fluorophosphates families. The fluoride-phosphate phases were prepared through different synthetic routes depending on the chemistry of transition metal. Combination of X-ray/neutron diffraction and electron microscopy were applied for a thorough structural characterization. It was shown that in these systems the substitution on the alkali metal site leads to the wide range of adopted structures. Thus, in the Li2FePO4F system synthesis of sodium-containing counterpart, NaLiFePO4F, followed by subsequent electrochemical exchange of Na by Li leads to the cathode material with a 3D “stacked” structure.2 In the (Li,Na)2CoPO4F system it provides a new low-temperature polymorph adopting a complex layered structure, in contrast to the high-temperature phase with 3D “stacked” arrangement. The introduction of large potassium into the AMPO4F system gives a raise to a new cathode material with a KTP structure, which exhibits excellent rate capability.3 Reversible electrochemical activity demonstrated by these fluoride-phosphate materials in Li-cell will be discussed. A special attention will be given to the structure peculiarities and their impact on electrochemical properties, which is important for possible practical applications of these materials.
The work was partly supported by Russian Science Foundation (grant 16-19-00190), Skoltech Center for Electrochemical Energy Storage and Moscow State University Development Program up to 2020.
References

Antipov, E. V.; Khasanova, N. R.; Fedotov, S. S. International Union of Crystallography Journal 2015, 2, 85-94

Khasanova N. R., Drozhzhin O. A., Storozhilova D. A., Delmas C., Antipov E. V. Chem. Mater., 2012, 24, 4271–4273

Fedotov, S. S.; Khasanova, N. R.; Samarin, A. Sh.; Drozhzhin, O. A.; Batuk, D.; Karakulina, O. M.; Hadermann, J.; Abakumov, A. M; Antipov, E. V. Chem. Mater. 2016, DOI: 10.1021/acs.chemmater.5b04065
Unexpected Dilation and Dilation Relaxation Behavior of Graphite-Based Lithium-Ion Cells
Authors: Bauer Marius , Wachtler Mario , Persson Jon V. , Danzer Michael A. 
Published: February 2020

The dilation of lithium-ion cells is sensitive to swelling phenomena caused by both graphite staging processes and lithium plating on graphite anodes. In this work, the dilation behavior of graphite/NMC pouch cells is studied with a focus on relaxation phenomena occurring after current pulses.
Dilation data are recorded for quasi-equilibrium cycling as well as for current pulses at high rates. In the quasi-equilibrium case, the staging behavior is characterized based on dilation and voltage data. By comparison with a graphite half-cell measurement, the major effects in full cell dilation are confirmed to be anode-related. In the high rate case, the dilation responses to the actual pulse and the subsequent relaxation phases are recorded systematically for different SOCs and temperatures. Positive and negative relaxation phenomena are observed as exemplified in Fig. 1. They are ascribed to both graphite staging and lithium plating processes. A model is introduced explaining the unexpected relaxation effects in all SOC ranges by a temporary coexistence of three or more staging compounds during high-rate lithiation/delithiation. These data thereby confirm the shrinking annuli model recently introduced by Heß and Novák [1].
Additionally, the effects of thermal expansion on dilation data recorded on pouch cells are investigated. In order to prevent misleading interpretations due to thermal effects, thermal expansion is quantified and a method for the thermal compensation of dilation data is developed. It is shown that for measurements at constant ambient temperature, the bias from thermal expansion is small compared to the other dilation effects. With regard to the application of dilatometry at varying temperatures, however, it is crucial to compensate for thermal expansion in the measurement data.
Based on the findings presented in this work, dilation relaxation can be used as an indicator for kinetic limitations leading to deviations from the low-rate staging course during graphite lithiation. The results provide a basis for the development of a new dilation based approach to lithium plating prevention.

Acknowledgements

This research project is supported by the Federal Ministry for Economic Affairs and Energy (BMWi) under contract number 03ET4012C. All responsibilities for this publication rest with the authors.

Figure Caption

Figure 1: Relaxation of cell thickness after current pulses at I=1C from SOC=0% to SOC=25% for different temperatures.

References

[1] Heß, M., & Novák, P. (2013). Shrinking annuli mechanism and stage-dependent rate capability of thin-layer graphite electrodes for lithium-ion batteries. Electrochimica Acta, 106, 149–158. doi:10.1016/j.electacta.2013.05.056

Figure 1
Electrospun Membranes Based on PVdF-PEO Blends for Lithium Batteries
Authors: La Monaca Andrea , Arbizzani Catia , De Giorgio Francesca , Focarete Maria Letizia , Fabiani Davide , Zaccaria Marco 
Published: February 2020

Solid polymer electrolytes (SPEs) in lithium batteries have the dual function of electrolyte and separator to hinder lithium dendrite growth that causes hazardous short circuits during repeated charge/discharge cycles [1]. Polyethylene oxide (PEO), together with a lithium salt, would be a promising candidate as SPE for its good electrochemical and mechanical properties, but its low ionic conductivity at room temperature limits its use. In the last years the attention has been focused on gel polymer electrolytes (GPEs) for the high ionic conductivity at room temperature, good mechanical properties and safety improvements [2]. GPEs can consist of a flexible polymeric matrix as supporting network and a liquid phase containing a lithium salt [3]. Several polymers, like polyvinylidene difluoride (PVdF) for the high dielectric constant and the good electrochemical stability, and PEO have been used as matrix for GPEs.
Given the good compatibility between PVdF and PEO and with the aim to merge the properties of these two polymers, we prepared and characterized PVdF/PEO membranes that act as separators and as hybrid gel polymer electrolytes (HGPEs) when soaked in the liquid solvent with lithium salt. The membranes based on the polymer blends were prepared by electrospinning, a technique that yields micro-nanofibrous membranes with high porosity and, hence, huge values of electrolyte uptake [4]. PEO 100,000 and PEO 1,000,000 were used to prepare two blends with PVdF:PEO 90:10 w/w composition. Such membranes were soaked in 1M LiPF6 – ethylene carbonate:dimethyl carbonate (1:1 w/w) and the electrochemical performance of these HGPEs were tested in a Li/HPGE/LiFePO4 cell and discussed on the basis of their physical, mechanical, thermal and morphological properties.

Acknowledgments

Alma Mater Studiorum –Università di Bologna is acknowledged for RFO financial support

References

[1] Croce, F.; Focarete, M. L.; Hassoun, J.; Meschini, I.; Scrosati, B. Energy Environ. Sci.
2011, 4, 921-927
[2] Manuel Stephan, A. European Power Journal
2006, 42, 22.
[3] Marcinek, M.; Syzdek, J.; Marczewski, M.; Piszcz, M.; Niedzicki, L.; Kalita, M.; Plewa-Marczewska, A.; Bitner, A.; Wieczorek, P.; et al. Solid State Ionics
2015, 276, 115.
[4] Zaccaria, M.; Fabiani, D.; Cannucciari, G.; Gualandi, C.; Focarete, M. L.; Arbizzani, C.; De Giorgio, F.; Mastragostino, M. J. Electrochem. Soc.
2015, 162, A915.
Development of Sulfolane-Based Electrolytes for Li-ion batteries
Authors: Zhang Tong , Porcher Willy , Paillard Elie 
Published: February 2020

The quest for higher energy density Li-ion batteries pushes toward ‘high voltage’ cathode operating above 4.5V. However, if such materials have been proposed for many years in the case of LiNi0.5 Mn1.5 O4
1 or more recently for LiCoPO4F2, the implementation of such materials is currently prevented by the lack of adapted electrolyte. Several reports deal with high voltage electrolytes such as ionic liquids, dinitrile compounds or fluorinated carbonates. Yet, another class of solvents investigated are the alkyl sulfone, linear3 or cyclic4. Among them, sulfolane, despites its high viscosity has been reported to allow low potential anode operation (such as Li metal or graphite), while other reports point out the high oxidative stability of the electrolytes made thereof4, which was explained based on fundamental studies such as QC5 and MD6. Mixtures of sulfolane seem able to allow room temperature operation of both graphite and high voltage electrodes but no report can be found of a sulfolane-based electrolyte compatible, at the same time, with graphite and a high voltage electrodes. Thus, we examine here the possibility of forming new electrolyte system, based on sulfolane/DMC mixtures for room temperature operation. In particular, the role of the Li salt has been investigated as it is known to play a role on conductivity, via viscosity and dissociation in a solvent system that has a lower dielectric constant and higher viscosity than alkyl carbonate mixtures such as EC/DMC. In addition, keeping the application in mind, SEI building on graphite and aluminum current collector corrosion are also dependent on the Li salt or mixture used. Thus several inorganic and organic Li salts have been investigated in terms of conductivity and electrochemical stability and tested versus graphite and LiNi0.5 Mn1.5 O4 electrodes in a DMC/sulfolane mixed solvent.
References
1. Q. Zhong, A. Bonakclarpour, M. Zhang, Y. Gao, and J. R. Dahn, J Electrochem Soc, 144, 205–213 (1997).
2. S. Okada, M. Ueno, Y. Uebou, and J. I. Yamaki, J. Power Sources, 146, 565–569 (2005).
3. C. A. Xu, K. Angell, J. Electrochem. Soc., 145, L70 (1998).
4. A. Abouimrane, I. Belharouak, and K. Amine, Electrochem. commun., 11, 1073–1076 (2009)
5. O. Borodin, W. Behl, and T. R. Jow, J. Phys. Chem. C, 117, 8661–8682 (2013).
6. L. Xing, J. Vatamanu, O. Borodin, G. D. Smith, and D. Bedrov, J. Phys. Chem. C, 116, 23871–23881 (2012)
The research presented is part of the ‘SPICY’ project, funded by the European Union’s Horizon 2020 research and innovation programme under grant agreement No 653373.
Design on CFx Cathode for Sodium Secondary Batteries
Authors: Liu Wen , Shadike Zulipiya , Li Yong , Fu Zhengwen , Xie Jingying 
Published: February 2020

After investigations on many kinds of fluorides, carbon fluoride (or graphite fluoride, CFx) is the best material as cathode of primary lithium battery with ultrahigh energy density [1-2], while F2 gas is difficult to operate as cathode. And many attempts for extending the application concepts of CFx in lithium batteries were made to conclude no any evidence on its reversibility[3]. Since sodium batteries have been attracting much attention as one of the post-lithium ion battery[4]. CFx/Na cells were explored and the reversibility of these cells was also proved[5-6].
Here, we summarize these designed CFx materials for sodium secondary batteries, as shown in Figure 1. Commercial CFx and F-MWCNTs were synthesized by direct fluorination of graphite and mutil-wall carbon nanotubes (MWCNTs) using F2 gas. While CGF powders were prepared by simply ball-milling of the commercial CFx, FeF3 and GNS, with higher surface area, electronic conductivity, more active sites and specific channels for the transportation and storage of fluorine ions. Furthermore, disordered CFx exhibits excellent electrochemical performance due to its intrinsic amorphous character.
Figure 1 Three kinds of CFx materials for sodium secondary batteries:(a) commercialCFx, (b) CFx/GNS/FeF3(CGF) composite, (c) F-MWCNTs
Commercial CFx was first used in sodium secondary battery[5]; however, much larger overpotential(2000mV) between charge and discharge voltage and terrible cyclic performance (5 cycles) hindered its practice adoption. These drawbacks can be overcome by the introduce of catalysts and the change of the intrinsic characteristic of CFx materials[5-6], which results in a gap of only 0.8 volt and enhanced cycle life.
For practical uses, some popular approaches in nanotechnology and electrolyte chemistry such as the core-shell structure or encapsulation or coating composites, and using specially designed solid electrolytes will be expected to prevent the dissolution of fluorine for improving cycle life for Na-CFxbattery in the future.

Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (NSFC21373137) and Shanghai Science and Technology Development Fund (15DZ2282000).

Reference

[1] N. Watanabe, M. Fukuda, U.S. Patent 3 536 532, 1970 and 3 700502, 1972.
[2] M. Fukuda, Iijima, T. In Collins, D.H., Ed.; Power Sources 5;Academic Press: New York, 1975; p 713.
[3] G. G. Amatucci, N. J. Pereira, Fluorine Chem. 2007, 128, 243.
[4] D. S. Michael, K. Donghan,L. Eungje, and S. J. Christopher, Sodium-Ion Batteries, Adv. Funct. Mater. 2013, 23, 947.
[5] W. Liu, H. Li, J. Y.Xie, and Z. -W. Fu, ACS Appl. Mater. Interfaces, 2014, 6, 2209.
[6] W. Liu, Z. Shadike, Z. C. Liu, W. Y. Liu, J. Y.Xieand Z. -W. Fu, Carbon, 2015, 523.
[7] Y. Shao, H. Yue, Z. Gong and Y. Yang, The 18th National Conference on Electrochemistry. August, 2015, Haerbin, China.

Figure 1
Na2RuO3: A Model to Study the Extra Capacity of a
2
mO3 Type Cathodes
Authors: Mortemard de Boisse Benoit , Liu Guandong , Ma Jiangtao , Nishimura Shinichi , Chung Sai-Cheong , Kiuchi Hisao , Harada Yoshihisa , Kikkawa Jun , Yoshio Kobayashi , Okubo Masashi , Yamada Atsuo 
Published: February 2020

Li-ion batteries power almost all of today’s portable electronics as well as electric and hybrid vehicles thanks to their important energy density. However their high cost tend to prevent larger-scale application such as in power grids. On the other hand, Na is abundant, easily accessible and therefore cheaper than Li. As a consequence, Na-ion batteries draw a lot of attention since the 2000s.
Even though Nax
MO2 (x ≤ 1, M = transition metal) materials have been studied for a long time as positive electrode candidates, the available capacity is still limited. Partial substitution of M by Na+ is an appealing strategy to overcome this issue: the excess Na+ ions in the MO2 layer could participate in the (de)intercalation process while lowering the weight of the battery, thus greatly enhancing the gravimetric capacity. This strategy, applied to Li-ion batteries for many years, is still poorly transferred to Na-ion battery materials.
In order to establish a model for the study of Na2
MO3 – and A2
MO3 in general –, we prepared two polymorphs of O3-Na2RuO3 distinguished by the honeycomb-like ordering of the [Ru2/3Na1/3]O2 layers [1,2]. In both samples, we found that Na in the interlayer and in the [Ru2/3Na1/3]O2 layers is accessible. In ordered-Na2RuO3, the honeycomb ordering triggers the spontaneous formation of an ilmenite-type intermediate which facilitates highly reversible oxygen redox chemistry, associated to a large extra capacity (Figure 1) as well as noticeable structural stability upon cycling making it, to our knowledge, the first Ax
MO3 to do so.

Figure 1. Galvanostatic cycling curves for (a) disordered and (b) ordered O3-Na2RuO3 (first cycle highlighted in blue). The insets represent the coordination environment of Na at x = 1.

Figure 1
Chemical Intercalation and De-Intercalation Studies on Multivalent Ion Cathodes
Authors: Senguttuvan Premkumar , Burrell Anthony K. , Johnson Christopher 
Published: February 2020

As the lithium ion battery technology matures, it becomes apparent that the energy density is more limited by the materials used. Beyond-Li ion battery technology is now garnering more interest, and, as such, the search for new greater energy storage materials is underway. For us we are pursuing multivalent batteries [1] and are investigating new cathode materials, in hopes of discovering and designing new (de)intercalation hosts, or possibly cathodes that hold multivalent cations (Mg2+, Zn2+, Ca2+) by other storage mechanisms as well at high voltages. In particular, oxide cathodes, for example bilayer-V2O5 (BL-V2O5) [2]or alpha-MnO2(hollandite, 2x2 tunnel structure) [3], have been explored for high voltage intercalation. Unfortunately many problems abound, such as poor diffusion of multivalent cations due to strong electrostatic interactions with the oxide lattice.
The development of multivalent ion electrolytes is also at its infancy and it is required to exhibit high voltage stability, compatibility with cathode and inactivity towards cell components. Viable electrolytes for this battery task are hard to find, and thus limit our productivity. Nevertheless, the search and evaluation and synthesis will require the means to
chemically cycle
the materials. A few reagents like di-n-butyl magnesium, di-ethyl zinc have been reported to intercalate Mg2+ and Zn2+ions [4],[5]. In this work and poster, we will discuss and demonstrate a new method of utilizing novel reagents to intercalate multivalent cations into a variety of host materials.
References
[1] J. Muldoon et al., Chem. Rev. 114 (2014) 11683–11720.
[2] S. Tepavcevic et al., ACS Nano. 9 (2015) 8194–8205.
[3] R. Zhang et al., Electrochem. Commun. 23 (2012) 110–113.
[4] P.G. Bruce et al., Solid State Ionics 53–56, Part 1 (1992) 351–355.
[5] H. Wang et al., ECS Electrochem. Lett. 4 (2015) A90–A93.
Acknowledgments
This work was supported as part of the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the U. S. Department of Energy, Office of Science, Basic Energy Sciences. Work done at Argonne and use of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy Office of Science by Argonne National Laboratory, were supported by the U.S. Department of Energy under Contract No. DE-AC02-06CH11357.
Cathode to Cathode Lithium Ion Battery Recycling
Authors: Wang Yan , Gratz Eric , Heelan Joseph , Zheng Zhangfeng 
Published: February 2020

Due to their high energy density, long lifespan and light weight, lithium ion (Li-ion) batteries accounted for $11.8 billion dollars in sales in 2012, that makes up 60% of total portable battery sales and 37% of total battery sales. The same factors also make them the best candidate for use in hybrid electric vehicles (HEVs) and electric vehicles (EVs). Currently in the US almost all spent lithium ion batteries are land filled, compared to other types of batteries, such as lead acid batteries, in which 97% are recycled. This presents a large amount of environmental waste. Based on current trends in Li-ion battery use, if Li-ion batteries are not recycled, global lithium reserves are expected to be depleted by 2050. Additionally, recycling Li-ion batteries presents an economic opportunity in through the recovery of key valuable metals, such as cobalt, nickel and copper. Currently, most Li-ion battery recyclers focus on recovering cobalt from LiCoO2 cathode material or through the recovery of Co and Ni from the cathode materials via a high temperature pyrometallurgical approach. We propose a new methodology that uses a low temperature hydrometallurgical approach that has the advantage of having high efficiency of recovery. This process works regardless of the Li-ion batteries chemistry, shape and size and recovers Co, Ni, and Mn in the form of their hydroxides, which when sintered with recovered Li2CO3 produces new LiNixMnyCozO2 cathode materials. The regenerated cathode material, LiNixMnyCozO2 , has been tested and exhibits good electrochemical performance. In addition to the cathode material, copper, aluminium, steel, etc are also recycled.

Figure 1