bluuebunny/crossref_metadata_2025_split huggingface dataset:
Recycling of LIB: A New Separation Process for Lithium Ion Electrodes and Electrode Production Scraps
Authors: Hanisch Christian , Stieger Alexander Mathias , Loellhoeffel Thomas , Diekmann Jan , Haselrieder Wolfgang , Kwade Arno 
Published: February 2020

The increasing demand of lithium ion batteries (LIBs), especially from growth in electric vehicle (EV) production, presents the need for recovery of active materials from spent lithium ion batteries and production rejects. To prevent a future shortage of lithium and other valuable raw materials, development of recycling processes for both the spent LIBs and the production rejects becomes crucial.
In contrast to existing recycling processes, the main goal of the presented process (Fig. 1) is to achieve a high recycling yield and to recover battery materials at battery grade quality. Lithium and electrolyte components should be recycled in addition to copper, cobalt and nickel.
The project spams the entire recycling process starting from the discharging and disassembly stages, and following through with mechanical, chemical and thermal processing (e.g. crushing, grinding, classification, sorting, and extraction) used to separate the battery into recyclable fractions.
In order to match the high purity standards of hydro-metallurgical processes for the production of battery active materials, the battery active materials have to be separated from the current collector foil very purely (Fig. 2).
For this purpose, a new separation process has been developed: Adhesion Neutralization via Incineration and Impact Liberation (ANVIIL). Firstly, a thermal degradation of the polyvinylidene fluoride (PVDF) binder of the electrodes is induced by heat under different atmospheres. Secondly, a new separation apparatus is used to apply impact stress on the electrode compounds to separate coating from foil and to integrate a fine classification step.
Using this separation process separation rates of over 99 % are reached. Furthermore, the separated coating can be re-gained with a very low contamination of aluminum from scraps of the current collector of under 0.1 % w/w. Subsequently, new battery active materials have been produced and characterized in battery test cells.
Invited Presentation: New Aspects of Ionic Liquid Based Electrolytes for Battery Applications
Authors: Forsyth Maria , Howlett Patrick C , MacFarlane Douglas R 
Published: February 2020

Reliable, safe and high performance electrolytes are a critical step in the advancement of high energy density secondary batteries such as lithium or sodium based devices. Ionic liquids (ILs) and their solid state cousins, organic ionic plastic crystals (OIPCs), offer unique and attractive properties (such as low volatility and flammability, high electrochemical stability, and high conductivity) that make them important candidates for a number of battery applications. ILs and OIPCs based on the Bis(trifluoromethanesulfonyl)amide (NTf2or TFSI) and the Bis(fluorosulfonyl)imide (FSI) anions coupled with pyrrolidinium or phosphonium cations have shown particularly advantageous properties in lithium metal cells, with respect to stability and reversibility.
Recently, FSI based electrolytes containing a high Li salt concentration (up to 3.2 mol.kg-1) were shown to successfully cycle Li | LiCoO2cells, with fast charging and discharging rate capability (up to 5 C rate at 25 °C), in spite of the high viscosity and relatively low conductivity of these solutions. This suggests that an alternative transport mechanism may be responsible for more rapid lithium transport in these highly concentrated electrolytes and further investigation of the physicochemical properties of these materials has been undertaken. On the other hand, OIPC solid state electrolytes based on FSI have also shown remarkably high stability and cyclability in lithium metal batteries. Phase behavior, dynamics and transport in these lithium containing OIPCs and ILs will be presented in addition to cell performance.
In recent years concerns about the sustainability of lithium supplies, and therefore its cost, have prompted researchers to consider other anodic metals such as sodium. This paper will also present temperature and concentration dependence of structure, dynamics and electrochemical behaviour in these sodium ion containing IL electrolytes based on NTF2 and FSI anions. For example cyclic voltammetry indicated a stable sodium cycling behavior with the current of 5 mA.cm-2 at 25 oC to 20 mA.cm-2 at 100 oC, with high reversibility in such an IL electrolyte.
Silicon@Graphene-Embedded Nanofibers As High-Performance Anodes for Lithium-Ion Batteries
Authors: G Kannan Aravindaraj , Kim Dong-Won 
Published: February 2020

The growing demand for high-performance energy storage devices for applications in electric vehicles and grid-scale energy storage devices requires dramatic improvement in the energy density as well as power density. Silicon-based anodes hold promise for such high-end applications due to its high theoretical capacity and its abundant availability in earth’s crust. However, silicon anodes are well-known to exhibit problems such as electrode pulverization due to its huge volume expansion during cycling, poor cycle life and unstable solid-electrolyte interphase (SEI) layer. Much research has been focused on improving the performance of silicon anodes using novel materials design such as controlling the particle dimension (0D, 1D and 2D), particle embedded in hollow carbon spheres as well as alloying with metals. Here, we adopt the strategy of covalent attachment of silicon nanoparticles on graphene surface, which are embedded in the polymer matrix to form nanofibrous structures. Graphene sheets covalently anchoring uniform-sized silicon nanoparticles act as conducting matrix as well as buffer to accommodate volume expansion. In addition, the nanofibrous structure along with the polymer layer further suppresses pulverization of the electrode upon cycling. Detailed characterization of the prepared hybrid material and its performance as an anode in lithium ion cell will be presented.

[References]

[1] H. Wu, G. Zheng, N. Liu, T. J. Carney, Y. Yang, Y. Cui, Nano Lett., 12 (2012) 904.
[2] S. Murugesan, J. T. Harris, B. A. Korgel, K. J. Stevenson, Chem. Mater. 24 (2012) 1306.
[3] C. K. Chan, H. Peng, G. Liu, K. McIlwrath, X. F. Zhang, R. A. Huggins, Y. Cui, Nat. Nanotechnol. 3 (2008) 31.
Effect of Current Density on Nucleation and Morphology of Lithium during Electrodeposition in Ionic Liquids
Authors: Sano Hikaru , Sakaebe Hikari , Senoh Hiroshi , Matsumoto Hajime 
Published: February 2020

Lithium metal is very attractive anode material but the dendrite formation during charging prevents the batteries with lithium metal anode from wide commercialization. Our group has focused on some room-temperature ionic liquids as electrolytes from the viewpoint of high stability at the negative potential of Li/Li+. In the present study, the morphology of electrodeposited lithium in the ionic liquids was investigated by ex situ SEM observations. The effect of current density on lithium dendrite formation was figured out.
The electrolytes are prepared by addition of 10 wt.% of Li[Tf2N] to [C3mpip][Tf2N], [C4mpyr][Tf2N], and [N6,1,1,1][Tf2N] (see Figure). Two-electrode cells were fabricated, using nickel foils as working electrodes and lithium foils as counter electrodes. Lithium metal was electrodeposited with the current density from 5 to 200 μA cm-2 for total coulomb amount of 3 C cm-2. The morphology of electrodeposited lithium on each working electrode was observed by ex situ SEM after washing with dimethylcarbonate (see Figure).
For the cell with [C3mpip][Tf2N], when the current density was higher than 50 μA cm-2, the needle like deposits were observed and the deposits were apparently thought to have grown from a semisphere-like nuclei.1 When the current density was higher than 50 μA cm-2 for the cell with [N6,1,1,1][Tf2N], and was higher than 100 μA cm-2 with [C4mpyr][Tf2N], the needle like deposits were also observed and the deposits were thought to have grown from a semisphere like nuclei.1

The results for the lithium deposit morphology obtained from each cell with three ionic liquids were discussed with lithium-ion diffusion coefficient of the electrolytes, and we concluded as follows; The deposits were better distributed with decreased size when the current density was increased in the current range where the deposition was charge-transfer controlled. With higher current density where the deposition was diffusion controlled, deposits were more distributed but large and dendritic. The current density dependency of the lithium deposition behavior from ionic liquid are very similar to the case with noble metal deposition from aqueous solution, which is due to the high stability of the ionic liquid used in this study at the negative potential of Li/Li+.
[1] H. Sano, et al., ECS Electrochem. Lett., to be submitted.
Synthesize and Application of Novel Nano-Hierarchical Hollow Manganese Oxide Anode Material with Outstanding Performance for Sodium Ion Battery
Authors: Weng Yu-Ting , Kuo Chao-Yen , Hwang Bing-Joe , Wu Nae-Lih 
Published: February 2020

Based on the wide availability and low cost of sodium, ambient temperature sodium–ion batteries (SIBs) have the potential for meeting large scale grid energy storage needs. In addition, since sodium is so abundant, SIBs could provide an alternative chemistry to lithium batteries. However, many anode materials for lithium–ion batteries (LIBs) have not yet been explored for SIBs. Among several kinds of metal oxide anode materials, manganese (Mn) salts are naturally abundant, inexpensive, and environmentally friendly. The utilization of MnOx or their composites as anode material for SIBs is a prospect that should not be neglected. However, most of transition metal oxide anodes suffer from low rate performance and fast capacity fade due to their poor electronic conductivity and large volume changes during the conversion reaction. Nanostructured materials have the potential for achieving high capacity and rate capability resulting from the large specific surface area and the short electronic and ionic transport length in nanoscale.
For the first time, we have prepared hierarchical hollow MnO2 by utilizing a SiO2-templating hydrothermal process. Different from the conventional methods, the SiO2 was only partially dissolved so that the residue serves as a framework to support MnO2. The results revealed that the novel hollow nanostructure MnO2 electrode had a specific charge capacity as large as 499 mAh/g at 0.1 C-rate, and it unprecedentedly demonstrates good cycling stability, retaining 89.4% capacitance after 500 cycles at 1 C-rate at 50 oC.
Study on the Cathode Material Composed of LiCo1/3Ni1/3Mn1/3O2 and LiMn2O4
Authors: Qiu Jingyi , Yu Zhongbao , Li Meng , Zhan Shang 
Published: February 2020

Electric vehicles and energy storage will become the main application fields of next generation lithium-ion batteries, which require excellent performances such as high safety, large capacity and high power density for lithium-ion batteries. However, currently single cathode materials for lithium-ion batteries, such as LiCoO2、LiMn2O4、LiFePO4、LiCo1/3Ni1/3Mn1/3O2,could not meet these requests at the same time. Mixing different structures of cathode materials together is one practical way to improve performances of materials by complementary advantages of each other.
This work is to improve electronic conductivity and capacity of LiMn2O4 by adding LiCo1/3Ni1/3Mn1/3O2 in, and meanwhile the existence of LiMn2O4 could lower danger bringing from LiCo1/3Ni1/3Mn1/3O2. Different proportional mixtures with LiCo1/3Ni1/3Mn1/3O2 and LiMn2O4 were used as cathode materials for lithium ion battery. The results of charge-discharge tests show that the cyclic performance becomes better with the increase of LiCo1/3Ni1/3Mn1/3O2 until the proportion is higher than 5:5. The battery has better cyclic capability and kkk impedance when the proportion of LiCo1/3Ni1/3Mn1/3O2 and LiMn2O4 is 5:5,Itsinitial discharge specific capacity is 154.4 mAh/g, after 60 times charge-discharge, specific capacity is 143.0mAh/g, the capacity retention rate is92.62%; And the average voltage is 3.92 V(vs. Li + / Li),significantly higher than the discharge voltage platform of LiCo1/3Ni1/3Mn1/3O2 which is 3.80 V (vs. Li + / Li).
Approach of “Electrodes to Electrodes”: Challenges for Recycling Advanced Lithium-Ion Batteries for e-Mobility
Authors: Tedjar Farouk 
Published: February 2020

Lithium ion sector is the most dynamic among the battery segment. several omposition of li-ion batteries are now on the market while basic composition is moving from lithium cobalt oxides / carbon portable segment to several kinds of cathodes materials, electrolytes and anodes materials. This means that we are in the need of new flexible processes while maintaining high recycling rate linked mainly to:
1- Process in safe way high capacity batteries
2- Achieve resource conservation in general and lithium in particular
3- Provide process with low environment impact mainly on fluoride/solvent emissions while having improved carbon print avoiding any CO2 production.
A new process will be presented . Work are coming our from several R&D programs such as:
1-National French Networks Project ELLISUP and PROCYON
2- 7th FP European Cluster AMELIE, SOMABAT, MARS-EV
New process obtained during those projects will be presented.
Approach of “electrodes to electrodes” will be considered.
Effect of the Iron Doping on the Crystal Structure and Electrochemical Performances of LiCoPO4
Authors: Di Lecce Daniele , Brutti Sergio , Panero Stefania 
Published: February 2020

Current research in lithium-ion battery field focuses on the improvement of energy density and power performances. One way to increase the battery energy is the use of high voltage cathode materials with a large charge capacity and cycling capability. The LiCoPO4 olivine is an interesting candidate as high-voltage cathode for lithium cells due to its high working potential cells (4.8 V vs. Li/Li+), still within the working limits of the carbonate-based liquid electrolytes, its flat voltage profile and a theoretical capacity of about 167 mAh g-1. However the poor electronic conductivity and the low Li-ion diffusion coefficient limit its practical application [1].
Herein we present our recent results about the study of the synthesis of lithium cobalt phosphate materials and the effect of the iron doping on its structural features and electrochemical properties in lithium cell. In particular X-ray diffraction experiments have been carried out at the MCX beamline in the ELETTRA facility in order to elucidate the role played by iron doping on the lattice structure and local ordering of the cation sublattice. Furthermore a careful analysis of the performances in lithium cells have been carried out by comparing materials prepared in different experimental conditions with and without iron doping, in order to decouple the concurrent effects that drive the ability of this material to reversibly cycle lithium (e.g. particle size, lattice disorder, iron doping).
[1] S.Brutti, S.Panero, Recent Advances in the Development of LiCoPO4 as High Voltage Cathode Material for Li-Ion Batteries in “Nanotechnology for Sustainable Energy”, ACS Symposium Series, Vol. 1140, Chapter 4, pp 67–99
A Novel Electrolyte Additive for High-Voltage LiNi0.5Mn1.5O4 Positive Electrode
Authors: Lee Tae Jin , Yoon Taeho , Jung Jiwon , Lee Jaegil , Chae Oh B. , Ryu Ji Heon , Oh Seung M. 
Published: February 2020

The Ni-doped manganese spinel (LiNi0.5Mn1.5O4, LNMO) has been projected as a high-voltage positive electrode for lithium-ion batteries (LIBs). The high working voltage (> 4.6 V vs. Li/Li+) with an outstanding structural stability must be beneficial with respect to energy density and cycle life, but this advantage is offset by the instability of cell constituents. For instance, the commonly used electrolytes are decomposed and surface films deposit.1 Once surface films deposit, polarization increases to eventually cause a capacity fading.2,3

In order to mitigate the electrolyte decomposition/film growth, LNMO electrode should be passivated. A simple approach is the addition of film-forming agents, which decompose to form a protective layer to suppress additional electrolyte decomposition.
As a film-forming agent for LNMO electrodes, tris(pentafluorophenyl)silane (TPFPS) was tested in this work. Addition of TPFPS (0.1 wt. %) into the conventional electrolyte (1.3 M LiPF6in EC:EMC:DEC = 3:2:5 in vol. ratio) improves both the cycle performance and coulombic efficiency at 25°C and 60°C (Fig. 1a and 1b). TPFPS is oxidatively decomposed (< 4.7 V) prior to the electrolyte (Fig. 1c). The surface film derived from the additive shows a good passivating ability. The film growth and polarization increase are not serious. In contrast, the surface film derived from the additive-free electrolyte is poorly passivating. Surface film steadily grows due to continued electrolyte decomposition, which eventually leads to capacity fading due to ever-increasing electrode polarization (Fig. 1d).

References

1. J. B. Goodenough and Y. Kim, Journal of Power Sources, 196, 6688 (2011).
2. D. Aurbach, B. Markovsky, Y. Talyossef, G. Salitra, H.-J. Kim and S. Choi, Journal of Power Sources, 162, 780 (2006).
3. T. Yoon, S. Park, J. Mun, J. H. Ryu, W. Choi, Y.-S. Kang, J.-H. Park and S. M. Oh, Journal of Power Sources, 215, 312 (2012).

Fig. 1. Cycle performance and coulombic efficiency at 25°C (a) and 60°C (b). The differential capacity plot in the 1stcharging (c) and electrochemical impedance data obtained after 200 cycles (d).
Relation Between Pore Size Distribution and Discharge Capacity in Carbons Used As Li-O2 Cathodes with an Ionic Liquid-Based Electrolyte
Authors: Tonti Dino , Olivares-Marín Mara , Palomino Pablo , Enciso Eduardo 
Published: February 2020

A method for relating the experimental pore size distribution with the discharge capacity of carbons used in Li-O2 cells was developed.
Four porous carbons with similar composition and specific area, but with pores peaking in different points of the mesoporous region (i.e. average pore diameter in the range of 5 - 55 nm) were obtained from a resorcinol-formaldehyde route. These were used as cathodes for Li-O2 batteries using an ionic liquid electrolyte (LiTFSI in PYR14TFSI) at room temperature and 60 ºC. Discharge capacities were related to the experimental pore size distribution determined from N2 adsorption.
The method consisted in testing a linear fit between discharge capacity and the volume occupied by the discharge products. These are assumed distributed in a layer of constant thickness on the pore walls. In addition, the model assumes that pores below a threshold size do not participate to the capacity, because their access becomes clogged much faster than for large pores. Thus, the occupied volume is calculated from the experimental cumulative pore volume and the two parameters, layer thickness and threshold pore size.
The fit quality was mapped as a function of these parameters. No constraints or other fixed parameters were used. Best fits, with a coefficient of determination R2>0.95 were obtained when the layer thickness was of the order of 7 nm, which is consistent with the thickness of an insulating passivation layer. The method also allowed estimating the penetration depth of the discharge reaction in the electrode thickness, which in our electrochemical test conditions resulted of the order of 20 nm at RT and 40 nm at 60 ºC.
The extension of applicability of this method will be discussed.

Acknowledgement

The research leading to these results has received funding from the European Union’s Seventh Framework Programme under EC-GA No. 265971 ‘LABOHR’, and from the Spanish Government under contract MAT2012-39199-C02-01. M.O. acknowledges CSIC for a JAE-DOC research contract.
Excellent Cycle Performance of Pouch Cells at a High Rate Investigated By a Combination of Synchrotron Based X-Ray Diffraction and Absorption Spectroscopy
Authors: Fey George Ting Kuo , Lin Yi-Chuan , Wu Pin Jiun , Huang Kai Pin , Pai Chih Tung 
Published: February 2020

Lithium-ion batteries are widely developed for vehicle applications and energy storage systems owing to their high power density, long cycle life, and lack of memory effect. The cycling stability of a Li-ion battery plays an important role in its practical application, especially for use in electric vehicles, which is generally affected by the types of electrode materials [1], binder properties [2], and electrolyte compositions [3].
Li-ion cells based on LiFePO4cathodes have been considered as one of the most promising candidates for large-scale application due to its low cost, low toxicity, good electrochemical and excellent thermal stability. However, the tendency for capacity degradation behaviour of LFP cells is still seen as a problem for practical application.
The capacity fading mechanism of a laminated pouch type 1.0 Ah cell consisting of a graphite anode and an olivine LiFePO4 cathode during a long-term cycling test was studied in this report. The LiFePO4cathodes have a mole ratio of iron to phosphorus in the range of 0.93 to 0.99. As shown in Fig. 1, the LFP cell with a Fe/P ratio of 0.99 has the best cyclic performance at the charge/discharge rate of 2 C/5 C. The cycle life curves of the pouch cell show the number of cycles increases to 2269 cycles with the capacity retention (C.R.) of 80% as the Fe/P ratio increases from 0.93 to 0.99.
To investigate the aging mechanism of the LiFePO4 cathode and graphite anode, changes in the crystalline structure through the charge/discharge reactions were analysed by the synchrotron based X-ray diffraction (XRD) experiments. After long-term cycling tests, the appearance of LiOH and LiOH．H2O phases in the cycled anodes reveals that some Li ion released from the LiFePO4 phase during the charge process did not come back to the FePO4 phase, as shown in Fig. 2. Due to fewer lithium ions, some of the cathode material lost electrochemical activity and this brought down the reversible capacity significantly. In addition, the anode with the Fe/P ratio of 0.95 after 506 cycles has relatively stronger peaks than those of the other samples in Fig. 2(b). It indicates that the decrease in the Fe concentration of stoichiometric LiFePO4resulted in a shortage of lithium ion for the cathode material, and consequently the capacity fading rate accelerated.
In this study, a combination of X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and electrochemical testing are used to understand the physical and electrochemical characterizations of the graphite anode and the LiFePO4cathode with the different Fe/P mole ratios during long-term cycling tests.

References

[1] X. Han, M. Ouyang, L. Lu, J. Li, Y. Zheng, Z. Li, Journal of Power Sources,251 (2014) 38-54.
[2] Z. Zhang, T. Zeng, C. Qu, H. Lu, M. Jia, Y. Lai, J. Li, Electrochimica Acta,80 (2012) 440–444.
[3] S.S. Zhang, Journal of
Power Sources, 162 (2006) 1379-1394.