bluuebunny/crossref_metadata_2025_split huggingface dataset:
Characterization of LiMn0.3Co0.3Ni0.3Cr0.1O2 Cathode for an All Solid-State Thin Film Battery
Authors: Kamarulzaman Norlida , Rusdi Roshidah , Elong Kelimah , Badar Nurhanna 
Published: February 2020

Thin film fabrication is very important especially for device fabrication. For an all solid-state thin film battery, very low dimensional (of the order of sub-micron), high quality thin films are needed and the fabrication technique is a key criteria for producing good quality ultra-thin films. Pulse Laser deposition (PLD) is a suitable method for producing high quality finish of metals and metal oxides. Controlling the PLD deposition parameters can affect the characteristics of thin films such as crystal orientation, thickness and roughness which in turn influence the physical and chemical properties of the thin films. Producing thin film metal oxides with simple stoichiometries such as ZnO, MgO and Al2O3, may not be such a problem to fabricate. However, producing thin films of complex metal oxides such as LiCo0.3Ni0.3Mn0.3Cr0.1O2 for Li-ion battery cathodes can be a problem. The thin film deposition technique must be appropriate so that the thin film material produced will not suffer a change of phase, stoichiometry or purity. Not all gas phase or plasma based methods are suitable for deposition of this type of material. Reactive type thin film fabrication method may not produce the needed stoichiometry or phase and may produce multiphase samples with impurities. PLD may be the choice method for producing thin films of very complex stoichiometries.
This work explores the thin film method of PLD in the fabrication of thin film LiCo0.3Ni0.3Mn0.3Cr0.1O2 material. Characteristics such as phase, stoichiometry, crystal growth orientation, and surface roughness, are studied. For this type of complex metal oxide, it is very important for the thin film to be of the right phase and stoichiometry because this will affect the electrochemical behavior of the energy device that will then be fabricated. It is found that thin films of LiCo0.3Ni0.3Mn0.3Cr0.1O2 deposited by PLD have good qualities such as mirror finish, dimensionally thin and of correct stoichiometry and high smoothness. Cyclic voltametry result shows that the cathode film is electrochemically active.
From Lab Scale to Large Volume Production: Substitution of Toxic NMP/PVDF with H2o/CMC/SBR in Lithium-Ion Cells
Authors: Noll Pascal , Hörpel Gerhard , Schroeder Melanie 
Published: February 2020

Lithium-ion batteries (LIBs) are becoming more and more important for mobile energy storage devices, with respect to their energy density. For large size applications such as in electric vehicles (EVs) or hybrid electric vehicles (HEVs), both higher energy density and low-cost materials are required also taking environmental friendliness into account. In order to enhance the performance of lithium-ion batteries, researchers and battery-manufacturers are trying to create new electrode materials and new electrolyte compositions. Nevertheless, battery efficiency strongly depends on the electrode engineering and additionally on the production process with the optimization of each individual step.[1,2]

Polyvinylidene fluoride (PVDF) based electrodes on the cathode as well as on the anode side are widely used. One major drawback of PVDF based electrodes is the usage of volatile organic solvents that are often toxic (like N-methyl-2-pyrrolidone (NMP)) and are difficult to dispose at the end of the production process. Alternatively, water soluble natural and/or synthetical based binders have been proposed which also cope the increasing demand of a more environmentally-friendly production process and recycling of LIBs. Processing of active materials for negative as well as positive electrodes is possible using carboxy methyl cellulose (CMC) and/or styrene-butadiene (SBR).[3]

In our study we present the results of our experiments to substitute NMP/PVDF with a water based CMC/SBR binder solution. Moreover, the work comprises the development and adaption of mixing processes, coating techniques, and appropriate drying procedures. To optimize the mixing process for water based slurries we had to figure out ideal substitution grades, mixing ratios between CMC/SBR, and the right pH-value. With the focus on viscosity, mixer types, and shear rates we figured out an optimized slurry configuration for the adaption to our battery pilot plants including the manufacturing of different cell types. Furthermore, the adjustment of coating techniques is one essential issue towards large scale production processes. Nevertheless, we also had to pay attention to the challenging production step, the drying procedure by the combination of different drying duration and temperatures as well as the adapted drying technique.
This work demonstrates the difficulties and production steps going from lab scale to large scale manufacturing.
We kindly thank the European Regional Development Fund for the funding this project “ProLiBat” (EM-1041H) and also the project partners for support and cooperation.
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[2] X. Zhang, et al., J. Electrochem. Soc., 148 (2001), A463.
[3] Lux, S. F., et al J. Electrochem. Soc., 157.3 (2010), A320-A325.
Graphene/Li[Li0.2Ni0.2Mn0.6]O2 nanocomposite for Enhanced Cathode with High Rate Capability
Authors: Pyun MinHo , Park Yong Joon 
Published: February 2020

Recently, solid solution system, xLi2MnO3·(1-x)LiMO2 (M = Co, Ni, Mn etc.), which has been classified as a lithium rich layered oxide, has drawn much attention due to its extraordinarily large capacity[1]. However, there are a lot of problems to overcome for commercialization such as low rate capability due to small electronic and ionic conductivities, and low cyclic performance attributed to insufficient structural stability. Over the past year, extensive effort has been made to enhance the rate capability of the lithium-rich layered oxide. As an approach, the composition with carbon-based materials with high electronic conductivity has been tried to compensate for low conductivity of the lithium-rich layered oxide [2,3]. In this study, the nanoparticles of lithium-rich layered oxide (Li[Ni0.2Li0.2Mn0.6]O2) were composited with graphene. Small particle-size of Li[Ni0.2Li0.2Mn0.6]O2 may facilitate the movement of lithium ions and electrons during cycling due to high surface area of the cathode. Graphene could be applied as a base-matrix for the composition with cathode nanoparticle because it has high electronic conductivity, wide surface area, and good mechanical flexibility. The Graphene/Li[Ni0.2Li0.2Mn0.6]O2 nanocomposite is expected to offer high rate capability because of high surface area of cathode nanoparticles and good electronic conductivity attributed to the graphene.

References

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Y. Kobayashi, Nat. Mater. 5 (2006) 357-360.
3.Y.G. Wang, Y.R. Wang, E.J. Hosono, K.X. Wang, H.S. Zhou, Angew. Chem. Int. Ed. 47 (2008)
7461-7465.
Invited Presentation: Fluorophosphates As High Energy Density Positive Electrodes for Li and Na Batteries
Authors: Croguennec Laurence , Bianchini Matteo , Ateba Mba Jean-Marcel , Carlier Dany , Ménétrier Michel , Suard Emmanuelle , Masquelier Christian 
Published: February 2020

Development of new materials for high energy density batteries is essential as they power a wide range of devices ranging from portable electronics to transport and storage applications. Since they are still facing limitations (energy and power density, safety …), intense academic and industrial research activities are devoted to the development of better performing materials with in particular high voltage and safety. Beside the extensively studied layered and spinel oxides, polyanionic materials have aroused huge interest in the past ten years [1]. Among them, the so-called fluorophosphates, actually fluoride phosphates combining phosphate and fluoride anions in the same framework, are very attractive positive electrode materials with increased voltage versus Li and Na as compared to regular (oxide) phosphates for a given M(n+1)+/Mn+ redox couple. We will discuss results obtained recently in our groups for Tavorite-like phosphate materials LiMPO4X (M = V, Fe, Ti; X = F, OH, O) used as electrodes in Li-ion batteries, but also for Na3V2(PO4)2F3in Li and Na-ion batteries. The vanadium-rich compounds LiVPO4F and LiVPO4O have been shown to be of particular interest as V is stable at different oxidation states in similar environments (VII, VIII, VIV and VV) in these Tavorite-type structures, leading to a possible exchange of two electrons per vanadium [2-5]. Very distinct values are interestingly observed for the “same” V3+/V4+ redox couple in LiVPO4F and LiVPO4O: ~ 4.25 V vs. Li upon Li+ extraction from LiVPO4F versus ~ 2.3 V vs. Li upon Li+ insertion into LiVPO4O, showing that the potential can be tuned over a wide range moving from a V3+-rich material to a vanadyl (VO)2+-rich material. Na3V2(PO4)2F3 is also undoubtedly of high interest for the development of Na-ion batteries: it was shown recently to allow fast sodium diffusion, even at high rates (up to 20C) and despite the formation of successive intermediate phases with Na+/vacancy ordering [6]. The average potential observed for the V3+/V4+ redox couple in Na3V2(PO4)2F3 is around 3.9 V vs. Na+/Na, i.e. (as expected) significantly higher than that of the Nasicon phase Na3V2(PO4)3.

References

[1] C. Masquelier and L. Croguennec, Chem. Rev., 113, 6552 (2013)
[2] J. Barker, R.K.B. Gover, P. Burns, A. Bryan, M.Y. Saidi and J.L. Swoyer, J. Power Sources, 146, 516 (2005)
[3] J.M. Ateba Mba, C. Masquelier, E. Suard and L. Croguennec, Chem. Mater., 24, 1223 (2012)
[4] J.M. Ateba Mba, L. Croguennec, N.I. Basir, J. Barker and C. Masquelier, J. Electrochem. Soc., 159, A1171 (2012)
[5] M. Bianchini, J.M. Ateba Mba, P. Dagault, E. Bogdan, D. Carlier, E. Suard, C. Masquelier and L. Croguennec, submitted
[6] A. Ponrouch, R. Dedryvère, D. Monti, A.E. Demet, J.M. Ateba Mba, L. Croguennec, C. Masquelier, P. Johansson and M.R. Palacin, Energy and Environmental Science, 6, 2361 (2013)
Invited Presentation: Li-Ion Battery Safety Considerations during Transportation, Storage, and Disposal
Authors: Garche Juergen 
Published: February 2020

The energy of a Li-ion cell is in average about 3,250 kJ/kg. About ¼ of this energy is related to electrochemical energy (chemical energy convertible into electrical energy via normal use or short circuit) and ¾ to thermal energy (chemical energy convertible only in thermal energy released at suitable stimulation; e.g. short circuit).
The main safety related events are overcharge, external heating, external and internal short circuits, and mechanical deformations of the cell/battery case. These unpredictable events may leads to a temperature increase and at T > 120 °C by internal chemical processes (SEI layer breakup, anode-electrolyte reaction) with gas development and internal pressure increase to cell container rupture at predetermined breaking points. Gas and electrolyte will escape through the rupture holes into the environment and, eventually, inflame by an external ignition source. A further temperature increase till about 200 °C triggers high rate chemical reactions (cathode decomposition with oxygen development, oxygen reaction with the electrolyte, electrolyte decomposition) leading to a very rapid temperature rise (thermal runaway) followed by flames caused by reaching the self-ignition temperature of the electrolyte (~ 450 °C) and possibly explosions. The specific occurrence of most of the above described safety related events, that may occur during the Li-ion battery life cycle phases of transportation, storage, and disposal, will be discussed in this presentation.
During transportation and storage, external heating, external and internal short circuits, and mechanical deformations, are the events most likely to happen. Measures which can prevent them (e.g. reliable and low flammable packaging, thermal barriers) and transport related standards (e.g. UN 38.3) are described.
The safety hazard in the disposal phase of the cell/battery are also associated with external heating, external and internal short circuits, and mechanical deformations. After collections it is to proof whether the battery is defective (not all functions properly) or damaged (loss of physical integrity). Defective batteries with capacity ≤ 80 % of the nominal value (end-of-life by definition) could be still used in lower demanding applications, e.g. stationary storage in PV houses. Damaged batteries and defective batteries with << 80 % capacity and other malfunctions have to be recycled. In order to reduce the safety risk before the recycling process (including transport), it is advisable to de-energize the battery by low current discharge and finally short it permanently.
Invited Presentation: Holistic Approach to Battery Materials Innovation
Authors: Fischer Andreas 
Published: February 2020

Research and development of materials for lithium ion secondary batteries requires thinking across multiple disciplines and levels of complexity. The most important factor to consider is the interaction of materials in a battery cell during operation.
New active materials for the cathode may have an impact on the functionality of electrolyte, binder, and separator and might even mirror to the anode side of the cell. This can be problematic because it is time consuming to adapt other materials to e.g. a new cathode material. On the other hand it offers the chance early on to develop highly efficient optimized cell chemistries in parallel by taking possible interactions into account. A detailed understanding of cell design is a prerequisite for that challenging task. Furthermore the quality of electrode tapes and finally the test cell is crucial to distinguishing real effects from artefacts.
Research and development on high voltage cathode materials and respective electrolyte systems might serve as an example for a holistic approach. In addition to existing cell chemistries like lithium ion batteries, such an approach is of utmost importance for new cell chemistries like lithium/sulfur based systems.
In a holistic approach it is not sufficient to work only empirically. For a complete understanding, an approach from fundamental science on a molecular level to empirical development regarding cell design and resulting interaction of materials is required. A deep and scientifically profound understanding of structure / property relationship is a must. One part of that holistic approach can be accomplished by strong and trustful cooperation models of academic and industry research partners that allow open exchange of information or by industry on campus cooperation models.
High Performance Na-Ion Batteries Based on Novel O3 Layered Oxide Cathode Materials
Authors: Barker Jerry , Heap Richard John , Roche Noel , Tan Chaou , Sayers Ruth , Liu Yang 
Published: February 2020

Sodium-ion (Na-ion) batteries represent an attractive alternative to their lithium-ion counterparts, and are expected to offer some significant commercial advantages such as lower active material costs and improved safety characteristics [1,2]. In these systems Na-based layered oxides, NaxMO2(M = transition metal) have emerged recently as high performance and low cost cathode materials [3,4]. These oxide materials may be categorized into three main structural types using the classification proposed by Delmas and co-workers – i.e. O3, P2 and P3 types, where the alkali ions occupy either octahedral (O) or prismatic sites (P), respectively [5].
In this study single-phase O3-NaaNi(1-x-y-z)MnxMgyTixO2 materials have been prepared using conventional solid-state processing methods. In these as-made compositions nickel and magnesium are included as M2+ while manganese and titanium are present as M4+. Special attention was given to the product composition, precursor mixing and synthesis conditions to ensure no unwanted NiO impurity content. Figure 1 shows the XRD pattern for a typical O3-Na layered oxide composition and confirms that the material is essentially phase pure.
The electrochemical performance of the experimental O3-NaaNi(1-x-y-z)MnxMgyTixO2 phases was evaluated in full Na-ion test cells where the cathode materials were capacity balanced to a commercial hard carbon anode material. The electrolyte used was 0.5 M NaClO4 in propylene carbonate and testing was carried out at 30 oC.
In Figure 2 we depict the low rate (C/10) voltage profile derived from a typical constant current charge-discharge cycle. The cathode active material cycles reversibly at a specific capacity of 163 mAh/g and the Na-ion cell generates an average discharge voltage of around 3.0 V. The specific energy performance for the cathode is comparable to commercial Li-ion electrode materials.
Figure 3 shows a typical cycle life plot for a representative Na-ion cell. These data were collected at a C/10 charge/discharge rate using voltage limits of 4.2 and 1.0 V. Following 300 cycles the cell has retained over 70 % of the original discharge capacity. Most of this capacity loss is recoverable at lower discharge rates indicating importantly that the fade mechanism is associated with cell impedance changes rather than irreversible loss of active Na. Further performance data for the Na-ion system will be presented.
References:
[1] V. Palomares, P. Serras, I. Villaluenga, K. B. Hueso, J. Carretero-Gonzalez and T. Rojo, Energy Environ. Sci.
5, 5884, 2012
[2] J. Barker, M.Y. Saidi and J. Swoyer, Electrochem. Solid-State Chem.
6, A1, 2003
[3] M. Slater, D. Kim, E. Lee and C. S. Johnson, Adv. Funct. Mater.
23, 947, 2013
[4] S-W. Kim, D-H. Seo, X. Ma, G. Ceder and K. Kang, Adv. Energy Mater.
2, 710, 2012
[5] C. Delmas, C. Fouassier and P. Hagenmuller, Physica B+C, 99, 81-85, 1980.
Electrochemical Behaviours and Structure Evolution of High Capacity Li1.2Cr0.4Mn0.4O2 Cathode Material in a Wide Voltage Range
Authors: Lyu Yingchun , Xiao Dongdong , Gu Lin , Li Hong 
Published: February 2020

Li-rich materials have been widely studied as high-energy cathode materials, with a high specific capacity more than 300 mAh/g when charged beyond a voltage plateau of ∼4.5 V [1]. Excess capacity at the voltage plateau has been suggested to be partly compensated by oxidation of oxide ions, causing release of oxygen from the lattice to electrolyte [2]. Electrode performance is significantly influenced by the oxygen removal process. Besides xLi2MnO3·(1−x)LiMO2 (M=Ni, Co, Mn), Li1.2Cr0.4Mn0.4O2 has also been widely studied [3, 4]. The theoretical specific capacity of Li1.2Cr0.4Mn0.4O2 reaches to 387 mAh/g by utilizing the Cr3+/Cr6+ redox, which possibly suppresses the oxygen loss associated with the voltage plateau at ∼4.5 V. The process of Cr3+/Cr6+ redox is reversible at a wide range from 4.8 to 1.5 V [5].
In this work, Li1.2Cr0.4Mn0.4O2 cathode material has been cycled in the voltage range from 4.8 to 1.0 V. The charge-discharge profiles and open circuit voltage curve of Li1.2Cr0.4Mn0.4O2 have been recorded. The low-voltage electrochemical behaviour is similar with (x)LiMn0.5Ni0.5O2·(1−x)Li2TiO3 [6]. It shows a charge capacity of 297 mAh/g during the first charge. When discharged to 1V, the discharge capacity achieved up to 387 mAh/g. It is worthwhile to note that there is a long plateau at the voltage range from 1.7 to 1.0 V, in which part the capacity is reversible during the subsequent cycles. But the voltage profile is not symmetrical; the capacity in the charging process is much less than that of the discharge process at low voltage. GITT, in situ XRD, XAS and HAADF-STEM measurements have been done to clarify the electrochemical behaviors and structure evolution of Li1.2Cr0.4Mn0.4O2 in such wide voltage range.
Acknowledgement: Financial support from CAS project (KJCX2-YW-W26), "Strategic Priority Research Program" of the Chinese Academy of Sciences,Grant No. XDA01020304 and National project 973 (2012CB932900) are appreciated.
References:
[1] M. M. Thackeray, C. S. Johnson, J. T. Vaughey, N. Li and S. A. Hackney, Journal of Materials Chemistry, 2005, 15, 2257-2267.
[2] A. R. Armstrong, M. Holzapfel, P. Novák, C. S. Johnson, S.-H. Kang, M. M. Thackeray and P. G. Bruce, Journal of the American Chemical Society, 2006, 128, 8694-8698.
[3] Z. H. Lu and J. R. Dahn, Journal of the Electrochemical Society, 2002, 149, A1454-A1459.
[4] M. Balasubramanian, J. McBreen, I. J. Davidson, P. S. Whitfield and I. Kargina, Journal of The Electrochemical Society, 2002, 149, A176-A184.
[5] N. Yabuuchi, K. Yamamoto, K. Yoshii, I. Nakai, T. Nishizawa, A. Omaru, T. Toyooka and S. Komaba, Journal of The Electrochemical Society, 2013, 160, A39-A45.
[6] C. S. Johnson, J.-S. Kim, A. Jeremy Kropf, A. J. Kahaian, J. T. Vaughey and M. M. Thackeray, Electrochemistry Communications, 2002, 4, 492-498.
Electrochemical Properties of Cu Doped Lithium Manganese Silicate/PANI Composite As Cathode Material for Lithium-Ion Batteries
Authors: Lee Sol Nip , Palanichamy Sennu , An Jae Youn , Thangavel Ranjith , Lee Yun Sung 
Published: February 2020

Development of cathode materials for lithium battery application like electric vehicle (EV) and plug-in hybrid electric vehicle (PHEV) requires high capacity materials[1]. At the same time, cost, environmental concerns and safety issues cannot be excluded. Recently, lithium transition-metal silicates such as Li2MSiO4
(M=Fe, Mn and Co) have been extensively studied as cathode materials for lithium ion batteries, due to high theoretical capacity and better thermal stability than lithium transition metal oxides such as LiCoO2. Among them, Li2MnSiO4 cathode could be a better choice as a high capacity( ~330 mAh/g) cathode for lithium ion batteries than Li2FeSiO4 cathode material. Due to Mn2+/Mn3+ and Mn3+/Mn4+ redox couples, extraction of two lithium ions can be achieved from Li2MnSiO4. However, due to defects such as structure change after the first charge and low electronic conductivity(~ < 10-14S/cm), this material has poor cycle performance and lower capacity than the theoretical prediction [2-3].
In this regard, the current work is aimed on the improvement of capacity and cycle stability of Li2MnSiO4
cathode active material by applying Cu doping and poly-aniline composites. The Li2Mn0.95Cu0.05SiO4were prepared using the sol-gel synthesis. PANI was synthesized by oxidative polymerization.
XRD patterns as shown in Figure 1 exhibit that the Cu doping and PANI composite does not contribute to structure change of Li2MnSiO4. From the cycle performances as shown in Figure 2, the Li2Mn0.95Cu0.05SiO4/PANI cell shows a high discharge capacity, as well as improved cycle retention compared with pristine Li2MnSiO4 material. Synthesis methodology of Li2Mn0.95Cu0.05SiO4/PANI materials along with their physical, morphological and electrochemical characteristics will be discussed in detail.

References
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