bluuebunny/crossref_metadata_2025_split huggingface dataset:
Structural, Compositional and Electrochemical Control of Integrated Layered-Layered-Spinel Cathodes
Authors: Park Joong Sun , Croy Jason R. , Lee Eungje , Blauwkamp Joel D. , Thackeray Michael M. 
Published: February 2020

A concerted effort is being made at Argonne National Laboratory to stabilize high capacity ‘layered-layered’ xLi2MnO3•(1-x)LiMO2 electrodes, in which M is typically Mn, Ni and Co, when cycled to high potentials. The strategy being adopted is to marginally reduce the lithium content in ‘layered-layered’ structures in order to induce the formation of a spinel component, thereby introducing stabilizing transition metal ion pillars in the lithium layers of structurally-integrated ‘layered-layered-spinel’ (1-y)[xLi2MnO3•(1-x)LiMO2]•yLi0.5MO2 electrodes. This approach, which follows earlier related work on the composite ‘layered-spinel’ system, xLi2MnO3•(1-x)LiMn2-zLizO4 (0≤z≤0.33) [1], has yielded positive results with improvements in first-cycle efficiency, discharge capacity, and cycling stability being reported, particularly when targeting 5-15% of spinel in the electrode structure [2, 3].
In this presentation, the results of structural studies of ‘layered-layered-spinel’ materials using a combination of X-ray and neutron diffraction, transmission electron microscopy techniques, coupled to complementary electrochemical data, will be reported. One of the major goals of the study is to determine at what value of y do the transition metal ions start to drop into the lithium layers for any given system and composition, and to what extent can a lithium deficiency in the ‘layered-layered’ structure be compensated by changes in the oxidation state of the M cations while keeping the layered configuration intact.

References

C. S. Johnson, N. Li, J. T. Vaughey, S. A. Hackney, M. M. Thackeray, Electrochem. Commun., 7, 528 (2005).

D. Kim, G. Sandi, J. R. Croy, K. G. Gallagher, S.-H. Kang, E. Lee, M. D. Slater, C. S. Johnson, M. M. Thackeray, J. Electrochem. Soc., 160, A31 (2013).

B. R. Long, J. R. Croy, J. S. Park, J. Wen, D. J. Miller, M. M. Thackeray, J. Electrochem. Soc, 161, A2160 (2014).

Acknowledgment

Support for this work from the Office of Vehicle Technologies of the U.S. Department of Energy, in particular, Tien Duong, David Howell and Peter Faguy, is gratefully acknowledged.
The submitted abstract 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.
Preparation and Preliminary Electrochemical Characteristics of Cooking Oil Based Nano Carbons As Electrode Materials for Lithium Ion Batteries
Authors: Arie Arenst Andreas , Kristianto Hans , Lee Joong Kee , Halim Martin 
Published: February 2020

In the past decades, the development of nano- carbon materials with well-defined characteristics such as fullerenes, nanotubes and graphene have been a very active area of research. Carbon nanospheres (CNSs) are other class of nanostructured carbon materials, and have shown good prospects for application as alternative LIB anodes. CNSs possess some remarkable characteristics such as high specific capacity and good rate capability as anode materials in LIB. Those specific characteristics are attributed to a combination of several factors, including a short diffusion paths for Li+ ions; good porosity and high surface area. In this study, carbon nanospheres (CNSs) were synthesized by thermal assisted pyrolysis process using palm oil as carbon precursors, Fe-catalyst and activated carbon support. Prior to the synthesis of carbon nanospheres, Fe-catalyst on carbon supports was prepared by deposition precipitation by varying the amount of catalyst (10%, 20% and 30% w with respect to the mass of carbon support). The effect of catalyst amount on the morphology and structural characteristics of carbon products was investigated by x-ray diffraction (XRD), Raman spectroscopy and transmission electron microscope (TEM). The study indicated that structural properties are changed when a Fe catalyst amount is increased from 10 to 30 wt%. The stable cycle performances of carbon products were demonstrated when they are utilized as anode materials in lithium ion batteries. However, it can be observed that the highest specific capacity was shown by the carbon samples produced at the highest content of Fe catalyst.
Constructing Well-Designed Conductive Network for Lithium-Ion Battery LiNixCoyMnzO2-Type Cathodes
Authors: Cho Inseong , Choi Jaecheol , Kim Kyuman , Ryou Myung-Hyun , Lee Yong Min 
Published: February 2020

Ternary transient metal component systems of Li-Ni-Co-Mn-O (NCM; LiNixMnyCozO2 with x + y + z = 1) have advantages of high energy density, lower toxicity, lower cost, and high safety performances. But, NCMs suffer from poor rate capability and cycling performance under high rate charge/discharge conditions due to their low electric conductivities. Constructing well-dispersed conductive network is an important approach to overcome the inherent limits in the performance of the active materials. A variety of carbon materials such as carbon black (Super-P), carbon nanotubes, vapor-grown carbon fibers (VGCFs) have been studied as conductive agents.[1,2] Herein, the effect of different types of conductive agents on the cathode performance of lithium ion batteries is investigated in more detail. Three types of cathode materials (LiCoO2, LiFePO4, LiNi0.6Co0.2Mn0.2O2) which are containing different ratios of VGCFs and Super-P are used. Pillar-like morphology of the VGCF makes them to efficiently connect to the active materials and therefore, when we use the electrodes composed of primary particles, these achieve the highest electric conductivity for LiCoO2 (1.721 S cm−1) and LiFePO4 (1.23 S cm−1). On the contrary, for LiNi0.6Co0.2Mn0.2O2, consisted of micro-sized secondary particles made up of nano-sized primary particles, a mixture of two kinds of conductive additives shows synergistically improved electric conductivity (1.403 S cm−1). Well-dispersed powdery Super-P can helps electron transfer over the constituent primary particles. For all the studied cathodes, the cathode with a higher electrical conductivity shows improved result for the both cycle performance and rate capability.

References

[1] B. Jin et al., Electrochem. Comm., 2008, 10, 1537
[2] I. Cho et al., RSC Adv., 2015, 5, 95073

Acknowledgements

This work was supported by the Human Resource Training Program for Regional Innovation and Creativity through the Ministry of Education and National Research Foundation of Korea(NRF-2014H1C1A1066977)
Using Synchrotron Radiation to Study Li-Ion Batteries
Authors: Alfredsson Maria , Mountjoy Gavin , Bras Wim , Brownrigg Alex , Dominko Robert , Bruce Peter G. , Armstrong Anthony Robert , Billaud Juliette Marie , Kelder Eric M. 
Published: February 2020

X-Ray Absorption Spectroscopy (XAS) is a powerful tool, which can be used to study the atomic local structure as well as oxidation state during battery cycling. Hence, XAS can be used to provide detailed atomic information for improvement of materials design.
Here we present in situ XAS results for Li2FeSiO4 and Li2.2Fe0.9SiO4, promising cathode materials for lithium-ion batteries. It provides a low cost solution and is considered as a safe electrode material for future electric transportation, as the Si–O bond provides stability similar to the P – O bond in LiFePO4 compounds. In theory, it is possible to remove two Li ions from Li2FeSiO4, by utilizing both Fe+2/Fe+3 and the Fe+3/Fe+4 redox couples and, thus, producing a higher capacity than 166 mAhg-1 for one Li ion. Although capacities greater than 200 mAhg-1 it has yet to be clarified whether it was due to Fe+4 formation or electrolyte degradation.
The aim was to establish the valence and local structure of Fe during charge and discharge. The valence state changes between Fe+2 and Fe+3, with no evidence of Fe+4 before the onset of electrolyte degradation. There is a reversible contraction and extension of the Fe–O bond lengths during cycling while the Fe-Si distance remains constant, which underlines the stability of the Li2FeSiO4 material. The same observations apply to Li2.2Fe0.9SiO4 cathode material indicating that changing the stoichiometry does not provide any additional structural stability.1

1. A.W. Brownrigg, G. Mountjoy, A.V. Chadwick, M. Alfredsson, W. Bras, J. Billaud, A.R. Armstrong, P.G. Bruce, R. Dominko and E.M. Kelder, J. of Mater. Chem. A, 2015, 3, 7314-7322
Effects of High Energy Ball Milling on Phase Stability of Li7La3Zr2O12
Authors: Jonson Rob A , McGinn Paul J 
Published: February 2020

Solid state batteries offer many potential advantages over their liquid electrolyte counterparts including improved safety, wider electrochemical voltage ranges, better chemical compatibility, and the possibility for structural batteries. Among the solid Li-ion electrolyte materials, Li7La3Zr2O12 (LLZO), a garnet structured compound with a relatively high room temperature ionic conductivity (~ 2 x 10-4 S cm-1), has attracted much research interest.
The solid state method is the most common route to synthesize LLZO. Long duration sintering at temperatures of 1200 °C or greater are used to obtain dense bodies of the highly conductive cubic phase of LLZO rather than the lower conductivity tetragonal structure.
The long time and high temperature sintering can also lead to Li loss requiring the LLZO part be covered in sacrificial mother powder. Stabilization of the cubic phase can be achieved through the addition of one or more dopants including Al, Ta and Nb.
LLZO electrolytes are thus energy intensive and materially inefficient to manufacture. Production scalability of LLZO batteries depends on developing methods to reduce sintering temperatures while maintaining desirable properties. High energy ball milling (HEBM) offers a relatively simple means to reduce particle size, improve microstructural homogeneity, and reduce sintering temperatures.
Here we report the effect of HEBM on phase stability in undoped LLZO. It is observed that HEBM is capable of causing undoped LLZO to transform from the tetragonal phase to the cubic phase at low temperatures ( <40oC). It is seen that the HEBM cubic undoped LLZO transforms back into tetragonal LLZO with heating. This transformation is not observed in HEBM (Al,Nb or Ta)-doped LLZO.
HEBM of (Al,Nb or Ta)-doped LLZO with Li3BO3 is also reported. Li3BO3 is added to promote low temperature sintering (< 900C) which greatly reduces Li losses. Li3BO3 is found to be compatible with LLZO. We observe that dopants may also be incorporated into LLZO through Li3BO3 sintering. This is demonstrated by heat treatment of HEBM undoped LLZO with Li3BO3 and Al2O3 additives. LLZO treated this way retains the cubic structure, rather than reverting to the tetragonal phase, indicating that Al has been incorporated into the lattice.
Fluorinated Carbonate As an Additive for High-Voltage Performance Lithium Ion Battery
Authors: Lee Jieun , Im Jinsol , Cho Kuk Young 
Published: February 2020

Increase of the operation voltage of lithium ion batteries (LIB) is one important approach to enhance the energy density. Generally, conventional organic electrolytes based on the carbonate solvents show oxidation at about 4.5 V.
This can lead to severe capacity decay during the charge-discharge cycling. Thus it is significant to suppress decomposition of electrolyte and stabilize the cathode.
Here we investigated fluorinated carbonate solvent as an additive for high-voltage performance of LiNi0.5Co0.2Mn0.3O2 cathode LiB. The effects of additive content and electrochemical performances of the LIB were studied.
Investigation of Local Structures and Dynamics of Li and Na Ions in Nasicon-Type Solid Electrolytes by NMR Spectroscopy
Authors: Indris Sylvio , Kaus Maximilian , Scheuermann Marco , Rhode Magnus , Guin Marie , Tietz Frank , Guillon Olivier , Knapp Michael , Ehrenberg Helmut 
Published: February 2020

We investigated the local structure and the dynamics of Li and Na ions in the solid electrolytes Li1.2Al0.6Ti1.4(PO4)3, Li1.6Al0.6Ge1.4(PO4)3, and Na3.4Sc2(SiO4)0.4(PO4)2.6 by NMR spectroscopy.
While 27Al MAS NMR spectroscopy reveals the presence of only octahedral [AlO6] environments for Li1.6Al0.6Ge1.4(PO4)3, Li1.2Al0.6Ti1.4(PO4)3 exhibits large amounts of Al located in tetrahedral [AlO4] environments. 31P MAS NMR measurements reveal multiple environments with different Al/Ge next nearest neighbor composition around P and the relative intensities are in good agreement with a statistical arrangement of Ge/Al on the octahedral sites for Li1.6Al0.6Ge1.4(PO4)3. For Li1.2Al0.6Ti1.4(PO4)3, the 31P MAS NMR results indicate the presence of structural disorder. These results are confirmed by X-ray diffraction and Rietveld refinements.
The dynamics of Li ions have been investigated by temperature-dependent static 7Li NMR lineshape analysis and 7Li NMR relaxometry. Jump rates of about 7∙108 s-1 can be estimated for Li1.6Al0.6Ge1.4(PO4)3 at 400 K and the activation barrier for a single Li ion jump is 0.14 eV. A Li diffusion coefficient of 10-11 m2/s and a Li ion conductivity of 3.6 mS/cm can be estimated at 400 K.
For Na3.4Sc2(SiO4)0.4(PO4)2.6, NMR spectroscopy reveals that Si and P are arranged statistically on the tetrahedral sites and Sc is exclusively located on octahedral sites. Temperature-dependent 23Na NMR measurements show a strong increase of the asymmetry of the local environment, consistent with XRD measurements which yield a strongly anisotropic thermal expansion. Jump rates of higher than 5∙103 s-1 can be estimated for the Na ions for temperatures above 300 K.
Permselective Membrane System As Ion Shield for Polysulfides Toward High-Stable Lithium Sulfur Battery
Authors: Huang Jia-Qi , Zhuang Tingzhou , Peng Hong-Jie , Zhang Qiang , Wei Fei 
Published: February 2020

Lithium sulfur batteries attract great attention due to their high energy density, while the real applications are still hindered by the rapid capacity degradation. Despite great effort devoted to solving the polysulfide shuttle between the cathode and anode electrodes, it remains as a serious challenge to build high-stable lithium sulfur battery, which related to the diffusion and reaction between polysulfides and the metal lithium anode.
We proposed a strategy of introducing an ion selective membrane to improve the stability and coulombic efficiency of lithium sulfur battery. Generally, porous polymer membrane serves as membranes in batteries to avoid the short circuit between anode and cathode electrodes, which cannot stop the shuttle effect. By the introduction of permselective functional layer, the polysulfide anions can be confined in the cathode side, which would favor the cyclic stability and lower self-discharge performance.
We replace the routine membrane with an ion selective membrane, in which the sulfonate-ended perfluoroalkyl ether groups on the ionic separators are connected by pores or channels that are around several nanometers in sizes. These -SO3
-- groups coated channels allow ion hopping of positive charge species (Li+) but reject hopping of negative ions, such as polysulfide anions (Sn
2-) in this specific case due to the coulombic interactions. Consequently, this cation permselective membrane acts as an electrostatic shield for polysulfide anions, and confines the polysulfides in the cathode side. An ultra-low decay rate of 0.08% per cycle is achieved within the initial 500 cycles for membrane developed in this work, which is less than half that of the routine membranes.
We also proposed a unique lithium-sulfur battery configuration with ultrathin graphene oxide (GO) membrane for high stability. The oxygen electronegative atoms modified GO into a polar plane and the carboxyl groups acted as ion hopping sites of positively charged species (Li+) while rejected the transportation of negatively charged species (Sn
2-) due to the electrostatic interactions. Such electrostatic repulsion and physical inhibition largely decreased the transference of polysulfides across the GO membrane in lithium-sulfur system. By the incorporation of permselective GO membrane, cyclic capacity decay rate is also reduced from 0.49 to 0.23 %/cycle.
Such ion selective membrane is versatile for various electrodes and working conditions, which is promising for the construction of high performance batteries.

References
:

Huang JQ, Zhang Q, Peng HJ, Liu XY, Qian WZ, Wei F, 2014. Ionic shield for polysulfides towards highly-stable lithium–sulfur batteries.
Energy & Environmental Science
2014, 7, 347.
Huang JQ, Zhuang TZ, Zhang Q, Peng HJ, Chen CM, Wei F. Permselective graphene oxide membrane for high-stable and anti-self-discharge lithium-sulfur batteries.
ACS Nano
2015, 9, 3002.
Free-Standing Graphene-Based Papers with Controlled Pore Structures for High-Performance Li-O2 Battery Cathodes
Authors: Kim Do Youb , KIM Dong Wook , Kang Yongku 
Published: February 2020

In this presentation, we report the fabrication of free-standing graphene-based paper electrodes with controlled pore structures for high-performance Li–O2 battery cathodes. Firstly, graphene nanoplatelet/graphene oxide (GNP/GO) papers were fabricated using a vacuum-assisted filtration method. The obtained GNP/GP paper electrodes had a highly wrinkled and disordered morphology and were highly flexible, which was attributed to the partial re-aggregation of the GNPs under the holding effect of the GOs during a drying process. Subsequently, the GNP/GO paper could be directly used as a Li–O2 battery cathode without any conducting additives and polymeric binders. The GNP/GO paper electrode showed a much higher discharge capacity (6910 mAh/g at a current density of 200 mA/g) in comparison to the reduced-GO paper and commercially available carbon papers due to its higher Brunauer–Emmett–Teller (BET) surface area and pore volume. However, the GNP/GO paper electrode suffered from huge irreversible volume expansion during discharge due to the formation of relatively large Li2O2 inside the pores. This irreversible volume expansion of the electrode made a Li–O2cell incapable in few cycles (< 20 cycles).
Secondly, in order to solve the volume expansion problem of the electrode, graphene papers with macropores within the paper that can accommodate relatively large discharge product were fabricated by using polystyrene particles as sacrificial templates. The as-prepared macroporous graphene paper (mp-GP) had a large BET surface area (ca. 373 m2/g), a large pore volume (ca. 10.9 cm3/g), and a high porosity (91.6%). Owing to the high surface area and large pore volume, a Li–O2 cell using the mp-GP electrode exhibited a high discharge capacity of ca. 12,200 mAh/g at a current density of 200 mA/g, as well as good rate capability. Moreover, the mp-GP showed good stability up to 100 and 78 cycles at a current density of 500 mA/g and 2000 mA/g respectively, with a limiting capacity of 1000 mAh/g. It was found that formation and decomposition of the discharge product, Li2O2, occured within the macropores, and thus, the mp-GP maintained its original structure without considerable expansion during cycling.
Assessment of All-Solid-State Lithium-Ion Batteries
Authors: Braun Philipp , Ender Moses , Illig Jörg , Ivers-Tiffée Ellen 
Published: February 2020

All-solid-state lithium-ion batteries (SLIBs) are considered as promising next generation energy storage system for electric vehicles [1]. However, as this application needs low internal cell resistance even at high charging/discharging currents, a meaningful selection of materials, material combinations and electrode design is absolutely essential. Commonly known prerequisites are (i) high ionic conductivity of the solid electrolyte, (ii) low charge transfer resistance at the electrode/electrolyte interface and (iii) large active surface area between electrolyte and electrode material.
This study aims on guidelines for selecting solid electrolytes and their electrode interfaces, and on determining targets for further SLIB development. A newly developed one-dimensional model for SLIBs is presented, based on a design concept with 3-D structured composite electrodes (see Fig.1). The expected performance is simulated by linking two phase transmission line models [2] for both composite electrodes with an ohmic resistance for the solid electrolyte. Variations of (i) electrical parameters, i.e. ionic and electronic conductivity, (ii) electrochemical parameters, i.e. charge transfer resistance, and (iii) microstructure parameters, i.e. active surface area and composite electrode thickness, indicate the most important material and design parameters for high-performance. Performance potential will be presented for various anorganic solid electrolytes, i.e., glassy types (Phosphates, Oxides and Sulfides (Li7P3S11)) and crystalline types (LISICON, Garnets (Li7La3Zr2O12), Perovskites (Li3xLa2/3-xTiO3)) and diverse electrode designs with different thickness and microstructure properties.

References:

[1] A. L. Robinson and J. Janek, Solid-state batteries enter EV fray, MRS Bulletin, 39, pp 1046-1047, (2014)

[2] J. Illig et al., Modelling Graphite Anodes with Serial and Transmission Line Models, Journal of Power Sources, 282, 335-347, (2015)

Figure 1
Development of All-Solid-State Lithium Secondary Batteries Using Garnet Solid Electrolyte Layer
Authors: Shishihara Daisuke , Takeuchi Yuki , Hikosaka Hideaki , Mizutani Hidetoshi 
Published: February 2020

Lithium ion secondary batteries have been used as power sources of various devices. The electrolyte of the lithium ion battery is needed to have high lithium ionic conductivity and wide electric potential window. In addition, it is favored to be nonflammable to enhance the safety of batteries. The oxide solid electrolyte is generally nonflammable, but the most oxide electrolyte has narrower potential window and lower ionic conductivity. In late years lithium garnet type oxide solid electrolyte (e.g. Li7La3Zr2O12[1]) is gaining attention due to have high Li+ ionic conductivity and electrochemical stability from 0 to 5V vs. Li/Li+. The development of the all-solid-state batteries using this garnet type electrolyte has been carried out, but there are various issues. The main issue of the all-solid-state batteries using oxide electrolyte is high internal resistance of electrodes, which originates from a poor contact not only between electrolyte particle and active material particle, but also among electrolyte particles.
We investigated all-solid-state lithium batteries using lithium oxide solid electrolyte ceramics layer (Li1.5Al0.5Ge1.5(PO4)3 or Li7La3Zr2O12). The internal resistance of electrodes was reduced by interposing sulfide solid electrolyte (Li2S-P2S5) between the oxide electrolyte layer and the active material (e.g. Sulfur or LiCoO2) (Figure 1). The cathode structure enabled the batteries to work at room temperature [2-4]. In this study, we have developed the garnet type lithium solid electrolyte which has higher ionic conductivity above 1.0 x 10-3 Scm-1at 25°C. The performance of the all-solid-state batteries, using the garnet electrolyte and the sulfide electrolyte which is interposed between the oxide electrolyte layer and the active material, will be presented.
References
[1] R.Murugan, V.Thangadurai, and W.Weppner, Angew. Chem. Int. Ed., 2007, 46, 7778
[2] D. Shishihara, 24th Fall meeting of the ceramic society of Japan,2J01(2011)
[3] D. Shishihara, 25th Fall meeting of the ceramic society of Japan,3A05(2012)
[4] D. Shishihara, 54th Battery symposium in Japan,2E25(2013)

Figure 1