bluuebunny/crossref_metadata_2025_split huggingface dataset:
Metals Recovery from Spent Lithium-Ion Batteries: Synthesis and Physicochemical Properties of New Extractants for Solvent Extraction Processes
Authors: Omelchuk Kateryna , Haddad Mansour , Cote Gerard , Chagnes Alexandre 
Published: February 2020

Cobalt, nickel, lithium and manganese are strategic metals from many applications including alloys manufacturing, electrode materials for lithium-ion batteries (LIBs), etc. Their recovery from spent materials is a good opportunity from economical and geopolitical viewpoints. Indeed, these metals are expensive and recycling will reduce considerably their supply risks in the forthcoming years due to likely emergence of electric vehicles. Therefore, recovery of cobalt, nickel manganese and lithium from LiBs is strategic and development of efficient and economic processes is coming to the fore.
Several research activities were carried out to recycle strategic metals from spent batteries by different methods such as pyrometallurgy, hydrometallurgy and biohydrometallurgy. Pyrometallurgical processes are however energy intensive and release gases like sulfur dioxide and carbon dioxide which are harmful to the environment. In recent past, metallurgical industry has been searching for hydrometallurgical processes due to some advantages such as possibility of treating low-grade resources, easier control of wastes and lower energy consumption. Hydrometallurgical processes are based on physical separation, leaching, purification, precipitation and in some cases electrowining. The demand for high purity metals and recent trends towards environmentally friendly technologies have focused more attention onto solvent extraction because this technology is mature and permits to achieve high extraction efficiency at low operating costs. Although extractant molecules are at the center of concern to achieve high efficiency and high selectivity of metal recovery in hydrometallurgical recycling processes, only few teams focus their research on the synthesis of new extractants.
In this paper, extraction properties of new extracting agents for the recovery of cobalt, nickel, manganese and lithium will be presented after a brief overview of challenges and drawbacks in the development of lithium-ion batteries recycling processes. Extraction equilibria and relationships between their chemical structures and their extraction properties will be discussed. A flow sheet will be then deduced from experimental data provided in this paper to recover lithium, cobalt, nickel and manganese from spent cathodes contained in LiBs.

A. Chagnes, B. Pospiech, "A brief review on hydrometallurgical technologies for recycling spent lithium-ion batteries”, Journal of Chemical Technology and Biotechnology 88, 1191-1199 (2013).

A. Chagnes, J. Swiatowska (Ed), “Lithium Process Chemistry: Resources, Extractions, Batteries and Recycling”, http://dx.doi.org/10.1016/B978-0-12-801417-2.00005-0, ISBN 978-0-12-801417-2, Elsevier (2015).
Electroplating Three Dimensional Lithium Ion Batteries
Authors: Zhang Huigang 
Published: February 2020

The request for high energy lithium ion density batteries pushes forward the research on materials which could store more lithium atoms such as Si, Sn and so on. For example, Si and Sn could store 9786 and 7246 mAh/cm3. However, high capacity materials have the large volume changes during charge/discharge and leads to rapid degradation (Figure a). 3D scaffolded electrodes could accommodate the volume change and mitigate capacity loss. We have developed a route of fabricating 3D bicontinuous electrodes which consist of an inactive 3D scaffold and a conformal coating of active materials[1-6]. The nickel scaffold is derived from polystyrene opal templates (Figure b). Sn alloy is electrodeposited onto the 3D scaffold (Figure c). Such a scaffolded structure could hold the active material, efficiently conduct electrons, and partly manage the stress-induced capacity decay. The electrochemical analysis confirms that the inert 3D metal scaffold could stabilize the alloy electrode and significantly improve the cyclability of high capacity anodes. With the progress in the Sn anode[4], we also applied the similar concepts to silicon and metal oxide anodes, which are coated to the scaffold by CVD and hydrothermal methods[5-6]. Summarizing the research on Sn, Si, metal oxide leads to a conclusion that well-design scaffold structure and conformal coating are two key factors which contribute to the performance improvement of high capacity anodes.

References

[1]. Zhang, H.; Braun, P.V. Nature Nanotechnol. 2011, 6, 277.
[2]. Pikul, J.H.; Zhang, H.; Cho, J.; Braun, P.V.; King W. Nature Commun. 2013, 4, 1732.
[3]. Yu, X; Zhang, H.; Oliverio, J.K.; Braun, P.V. Nano Lett. 2009, 9, 4424.
[4] Zhang, H.; Shi, T.; Wetzel, D.J.; Nuzzo R.; Braun, P.V. Adv. Mater. 2015, DOI: 10.1002/adma.201504780
[5]. Zhang, H.; Braun, P.V. Nano Lett. 2012, 12, 2778.
[6] Liu, J.; Zhang, H.; Wang, H.; Cho, J.; Pikul, J.H.; Epstein, E.S.; Huang, X.; Liu, J.; King, W.P.; Braun, P.V. Adv. Mater. 2014, 26, 7096-7101.

Figure 1
A Statistical Model of the Voltage Fade Phenomenon in Lithium-, Manganese-Rich XLiMnO3·(1-x)LiNiaMnbCocO2 Materials
Authors: Bloom Ira , Vu Anh , Qin Yan , Lin Chi-Kai , Abouimrane Ali , Burrell Anthony K. , Bloom Samuel , Bass Dean A , Bareno Javier 
Published: February 2020

The effect of composition in the lithium- and manganese-rich region of (Li2MnO3)a(LiNiO2)b(LiMnO2)c(LiCoO2)d — where 0≤a≤0.83, 0.15≤b≤0.42, 0≤c≤0.85, and 0≤d≤0.30 (a + b + c + d = 1) — on the phase relations and the voltage fade phenomenon was probed using combinatorial synthesis methods. The observed values of voltage fade indicated that it was not very sensitive to composition. These values were found to be amenable to statistical modeling using the methods of Scheffé [1, 2]. The model indicated that it may be possible to markedly reduce voltage fade, but these potential compositions would be relatively low in lithium content and may not have the layered-layered structure.
The work at Argonne National Laboratory was performed under the auspices of the U.S. Department of Energy (DOE), Office of Vehicle Technologies, under Contract No.
DE-AC02-06CH11357.
The submitted manuscript has been created by UChicago Argonne, LLC, Operator of Argonne National Laboratory (“Argonne”). Argonne, a U.S. Department of Energy Office of Science laboratory, is operated under Contract No. DE-AC02-06CH11357. The U.S. Government retains for itself, and others acting on its behalf, a paid-up nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the Government. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan. http://energy.gov/downloads/doe-public-access-plan
In Situ Measurements of Solid Electrolyte Interphase Evolution on Silicon Electrodes
Authors: Yoon Insun , Abraham Daniel P , Lucht Brett L , Bower Allan F , Guduru Pradeep R. 
Published: February 2020

We report in situ measurements of initial solid electrolyte interphase (SEI) evolution on silicon negative electrode and also the lithiation-induced silicon volume changes in lithium ion half-cells. Thin film amorphous silicon (a-Si) electrodes are designed to enable unambiguous measurement of SEI thickness evolution and silicon thickness evolution. The thin film electrode samples are assembled into a custom-designed electrochemical cell integrated with an atomic force microscope (AFM) to facilitate real time measurements. The films are subjected to two potentiostatic lithiation and delithiation cycles by applying a series of constant potential values against lithium metal, which serves as the counter and reference electrode. The thickness changes are measured after a state of equilibrium is reached at each potential value. Experiments are carried out with two electrolytes – 1.2M lithium hexafluoro-phosphate (LiPF6) in ethylene carbonate (EC) and 1.2M LiPF6 in propylene carbonate (PC) – to investigate the influence of electrolyte compositions on SEI formation and electrochemical performance. The results reveal that the predominant SEI thickness evolution occurs during the first cycle, and reaches steady values of approximately 17nm with EC electrolyte and 10nm with PC electrolyte. Despite the thinner SEI layer, capacity loss due to SEI formation is larger with PC electrolyte compared to that of EC electrolyte. Si volume change shows approximately 21% of irreversible volume expansion during the first cycle and no appreciable irreversible volume expansion was observed in the subsequent cycle. In addition, silicon volume expansion shows an approximate linear relationship with the state of charge. Volume change and capacity of silicon films show hysteresis as functions of equilibrium potential. We seek to explain such hysteretic behavior in terms of the stress-potential coupling in silicon, which shows both qualitative and quantitative agreement. Beyond the specific materials systems considered here, the in situ AFM based experimental technique developed in this work has broader applications to investigate the role of electrolyte composition in the SEI formation kinetics.

Figure 1
Spray Drying-Assisted Synthesis of Hollow Spherical Li3VO4/C Composites for High-Performance Lithium Ion Battery Anodes
Authors: Yang Yang , Li Jiaqi , He Xinyi , Wang Jing , Sun Dong , Zhao Jinbao 
Published: February 2020

Recent studies showed that Li3VO4 intercalates Li-ions mainly between 0.5 ~ 1.0 V versus Li+/Li, lower than Li4Ti5O12, and at the same time can deliver a much higher theoretical capacity (~394 mAh g-1) than Li4Ti5O12 (~175 mAh g-1).[1] Therefore, Li3VO4 might be a better anode candidate for higher energy-density cell than Li4Ti5O12 as well as better safety cell than graphite.[2] However, its low electrode kinetics and poor electronic conductivity results in large resistance polarization and poor rate performance, preventing it from being widely used.[3, 4] In this study, we developed a method to solve these two issues simultaneously. The unique hollow spherically structured Li3VO4/C (H-LVO/C) composite was synthesized via a facile spray drying process and subsequent heat treatment (as shown in Figure 1a). TEM images (Figure 1b and c) clearly reveal the hollow structure of LVO/C microspheres, and the LVO particles are coated with a layer of carbon with thickness about 5 nm.
The surfaced coated carbon layer can enhance the electronic conductivity. Meanwhile, the hollow spherical geometry of the particles is effective for increasing the wetting area for electrolyte and decreasing the Li-ion diffusion length, both are beneficial for fast charge transport. Consequently, the composite exhibits exceeding rate capability (a stable capacity of 125 mAh g-1 even at 80 C) and long-life performance with a capacity retention of 97 % (a reversible capacity of 275 mAh g-1) after 3000 cycles at 10 C.

Figure captions

Figure 1 (a) The formation mechanism of hollow spherical LVO/C composite. (b) The TEM image and (c) the HRTEM image of the H-LVO/C. (d) Long-term cycling performance of the H-LVO/C at 10 C.

References

[1] C. K. Zhang, H. Q. Song, C. F. Liu, Y. G. Liu, C. P. Zhang, X. H. Nan, G. Z. Cao, Adv. Funct. Mater. 2015, 25, 3497.
[2] H. Li, X. Liu, T. Zhai, D. Li, H. Zhou, Advanced Energy Materials 2013, 3, 428.
[3] Q. Li, J. Sheng, Q. Wei, Q. An, X. Wei, P. Zhang, L. Mai, Nanoscale 2014, 6, 11072.
[4] Z. Jian, M. Zheng, Y. Liang, X. Zhang, S. Gheytani, Y. Lan, Y. Shi, Y. Yao, Chem. Commun. 2015, 51, 229.

Figure 1
Theoretical and Experimental Studies on Stabilization of P4332-Type LiNi0.5Mn1.5O4 with Oxygen Deficiencies through the Metal-Substitution
Authors: Shiiba Hiromasa , Zettsu Nobuyuki , Kida Satoru , Nakayama Masanobu , Teshima Katsuya 
Published: February 2020

Spinel-type LiNi0.5Mn1.5O4 (LNMO) have been attracted many attentions as a cathode material for 5V-level lithium-ion secondary batteries. LNMO is possibly crystalized into two different atomic arrangements (space groups). These two differences showed different characteristics. Ni/Mn ordered P4332 offers high specific energy density and disordered Fd-3m provide high electron conductivity. The origin of their electron conductivity in the Fd-3m type LNMO is strongly connected with the oxygen deficiencies in the spinel lattice, which is accompanying the reduction of Mn4+ to Mn3+. In order to realize electron conductivity enhancement of the P4332 type LNMO, we performed both theoretical and experimental studies on phase stabilities of metal-doped oxygen-deficient LiNi0.5Mn1.5O4-δ
crystalized in spinel lattices and corresponding electrochemical properties.
We point out that LiNi0.5Mn1.5-y
Cu
y
O4-δ

is the most plausible candidate which provides stable P4332 phase with oxygen deficiency. Computational studies of difference in the defect formation energies between P4332 and Fd-3m revealed that the Fd-3m became lower than that in P4332. Especially, the partial substitution of Cu2+ with Mn4+ effectively contributed to reduce oxygen vacancy formation energy in P4332, comparing to that of Fd-3m. In addition, Mn3+ is absent when oxygen vacancy concentration is equivalent to Cu2+ concentration, even though oxygen deficiency was formed in the spinel lattice. P4332 type LiNi0.5Mn1.5-y
Cu
y
O4-δ
potentially responsible to offer no appearance of plateau at 4 V in the charge-discharge profiles, no dissolution of Mn3+ species during the charge-discharge cycling and improve electronic conductivity due to the d-electron doping by Cu2+ substitution.
Based on our theoretical calculation, we performed the flux growth of LiNi0.5Mn1.5-y
Cu
y
O4-δ

crystals. X-ray diffraction pattern and Raman spectroscopy revealed that the substation of Cu2+ highly stabilized the P4332 type LiNi0.5Mn1.5-y
Cu
y
O4-δ
. The galvanostatic charge-discharge tests at 25 ̊C, ranging from 3.5 and 4.8 V of cut-off voltage showed the appearance of flat plateau at 4.7 V attributed to Ni2+/4+ redox couple. The discharge capacities were 137 mAh g-1 at 0.2C rate and 100 mAh g-1 at 10C rate, respectively. Furthermore, no current peaks from the Mn3+/4+ redox couples were observed at 4 V by cyclic voltammetry measurements. These findings strongly suggest that the substitution of Cu2+ with Mn4+ LNMO stabilize P4332 type structure even though the oxygen deficient may contain in the spinel lattice.

Acknowledgement

This work was partially supported by CREST, JST.
Surface Structure Design of Lithium-Rich Layered Cathode Materials Based on Framework and Interlayer Structures
Authors: Kim Sangryun , Cho Woosuk , Zhang Xiaobin , Oshima Yoshifumi , Choi Jang Wook 
Published: February 2020

The limited specific capacity of cathode materials is one of the main issues for further enhancement of the energy density of the rechargeable lithium ion batteries. Lithium-rich layered oxides are considered one of the most promising cathode materials because their specific capacities often exceed 200 mAh g-1 due to the additional lithium occupation in the transition metal layers [1]. However, this lithium arrangement, in turn, triggers cation mixing with the transition metals, driving a phase transition of the overall crystal framework to spinel and/or rocksalt structures during cycling and thereby causing a decrease in the operation voltage and specific capacity [2]. Surface modification has been one of the primary remedies because the given phase transition is typically initiated from the surface of the particle and well-designed surface structures can suppress this transition process from the initial step. In this study, we report an artificially designed high performance surface structure (Li2MnO3) bearing a consistent lithium-rich layered framework with the host, in which nickel is regularly arranged between the transition metal layers. X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), scanning transmission electron microscopy (STEM), and electrochemical impedance spectroscopy (EIS) characterizations reveal that the prepared surface structure effectively suppresses unwanted phase transitions, leading to substantially improved cycling and rate performance. The structure and electrochemical properties of the surface-modified lithium-rich layered oxide electrode will be discussed, along with a detailed reaction mechanism.
[1] C. S. Johnson et al., Electrochem. Commun. 6, 1085 (2004).
[2] K. G. Gallagher et al., Electrochem. Commun. 33, 96 (2013).
Effect of Local Strcutral Changes on Rate Capability of LiNi0.5Mn1.5O4-a Cathode Material for Lithium Ion Batteries
Authors: Yoon Jaesang , Um Ji Hyun , Kim Hyunchul , Jeong Mihee , Choi Woo Sung , Lee Hayeon , Yoon Won-Sub 
Published: February 2020

Due to its high working voltage (4.7 V vs. Li/Li+ for Ni2+/Ni4+ redox couple), high theoretical capacity (147 mAh/g), and inherent cyclic stability (no Jahn-Teller distortion from Mn3+), LiNi0.5Mn1.5O4 is a promising cathode material for the practical application in high energy density lithium ion batteries [1-3]. The cation ordering, the degree of presence of Mn3+ in the spinel structure, is regarded as an important factor influencing the electrochemical properties of LiNi0.5Mn1.5O4 [4, 5].
With a simply strategy of cooling rate, the degree of ordering in disordered spinel LiNi0.5Mn1.5O4-δ structure is controlled at 0.5 oC/min for slow cooled spinel and at 5 oC/min for fast cooled spinel. From XRD and FTIR analyses and charge/discharge profiles, it is confirmed that the fast cooled spinel develops more disordered structure than the slow cooled spinel, retaining more oxygen vacancies and more abundant Mn3+. Moreover, through in situ XRD analysis, the more disordered spinel follows the extended solid-solution reaction in favor of Li+transport, which results in an improved rate capability. But, the local structure information of interesting atoms without a destructive interference which can arise from long-range structural order is highly related to the electrochemical performance. Therefore, the examination in local structural variations of interesting atoms is essential for understanding their electrochemical properties.
In this work, we investigate local structural changes in the vicinity of Mn and Ni cations at various C-rates by using ex situ XAS analysis and quantify the structural changes by fitting a theoretical model to the extended X-ray absorption fine structure data. This finding will propose that a change of structural distortion can be another platform to understand the enhanced Li+transport in the disordered spinel and offer valuable guidance for developing LiNi0.5Mn1.5O4, a promising cathode material with high rate capability for next generation rechargeable batteries. More detailed discussion will be presented at the 2016 IMLB meeting.
[1]. X. Liu, D. Li et al., J. Alloys Compd.,2014, 609, 54-59.
[2]. X.-W. Gao, Y.-F. Deng et al., J. Mater, Chem. A.,2015, 3, 404-411.
[3]. H. Xia, Y.S. Meng et al., J. Electrochem. Soc., 2007, 154, A737-A743.
[4]. M. Kunduraci and G.G Amatucci, J. Electrochem. Soc.,2006, 153, A1345-A1352
[5]. L. Wang, H. Li et al., Solid State Ionics., 2011, 193, 32-38
X-Ray Scattering Analysis of the Morphology of TiO2 (B) Nanoparticles
Authors: Hua Xiao , Liu Zheng , Bruce Peter G. , Grey Clare P. 
Published: February 2020

The morphological characteristics of a nanomaterial, i.e., geometric shape and dimension, and the arrangement of atoms, which both vary depending on specific nanostructures, have a considerable impact on properties such as electronic structure, ionic diffusion, and surface structure. It is, therefore, essential to determine the nanomorphology of the electrode materials so as to link shape with the electrochemical performance.
Conventional microscopy methods used to characterize the morphology of nanomaterials sometimes involve practical challenges arising from the aggregation of nanoscopic structure. In order to determine the morphology of a TiO2 (B) nanoparticle sample that shows excellent electrochemical performance1,2, we have performed a comprehensive X-ray scattering analysis of SAXS, PDF and XRPD data. The scattering pattern within a particular angular range encodes distinct structural features of the materials ranging from mesoscale to nanoscale. The combination of small- and wide-angle measurements therefore covers a full angular range that enables us to access a complete set of morphological and structural characteristics including size and shape via SAXS, particle asymmetry and long-range structure via XRPD, and short-range atomic ordering via PDF.
From the analyses, we conclude that the particles are oblate-shaped, contracted along the [010] direction. This particular morphology provides not only a plausible rationale for the excellent electrochemical behavior of these TiO2(B) nanoparticles, but also a structural foundation to model the strain-driven distortion induced by lithiation. A more complex displacement model incorporating this lithiation-induced strain was developed making use of the oblate particle model. It clearly shows the importance of determining the morphology of the nanoparticle so as to understand the lithiation mechanism and rationalize the rate performance of nanostructured materials.
Reference:
[1] Ren, Y.; Liu, Z.; Pourpoint, F.; Armstrong, A. R.; Grey, C. P.; Bruce, P. G. Angew. Chem. Int. Ed. 51 (2012) 2164-2167.
[2] Andreev, Y. G.; Panchmatia, P. M.; Liu, Z.; Parker, S. C.; Islam, M. S.; Bruce, P. G. J. Am. Chem. Soc. 136 (2014) 6306-6312.
System Considerations for the Application of Thermal Management Solutions to Electrified Vehicle Traction Batteries: Benchmarks and Technical Specification Development
Authors: Robert Brian 
Published: February 2020

With an increasing demand in traction battery performance for electrified vehicles, thermal management definition and temperature uniformity specifications are a moving target for supplier product development and OEM system integration. Alternative cell formats, integration schemes and cell-to-pack scaling are trending stop-gaps to this challenge. Highlights of select vehicle system benchmarks and the evolving demands for lithium-ion battery thermal management will be discussed with focus on scaled temperature gradients, heat transfer efficiency, as well as system volume, weight, and cost. Recent efforts by the United States Advanced Battery Consortium to define such targets and SAE standards defining battery thermal management systems will be also be explored.