bluuebunny/crossref_metadata_2025_split huggingface dataset:
Raman Mapping for LiCoO2 Composite Positive Electrodes in All-Solid-State Lithium Batteries Using Li2S-P2S5 Solid Electrolytes
Authors: Otoyama Misae , Ito Yusuke , Hayashi Akitoshi , Tatsumisago Masahiro 
Published: February 2020

All-solid-state batteries with nonflammable inorganic solid electrolytes, an alternative to conventional inflammable organic liquid electrolytes, are widely studied as next generation batteries with low risk of leakage and explosion. Bulk-type batteries use composite electrodes of active materials and solid electrolytes. Solid electrolytes play a role of delivering Li ions to active materials. Bulk-type batteries are capable of having high energy density by adding large amounts of active materials into composite electrodes. We have investigated the electrochemical performance of bulk-type all-solid-state cells using a LiCoO2 composite positive electrode and a Li2S-P2S5 solid electrolyte [1]. Composite electrodes can be fabricated by mixing LiCoO2 particles and solid electrolyte particles. There are many solid-solid interfaces in composite electrodes. It is important that electrochemical reactions at LiCoO2-electrolyte solid-solid interfaces are clarified to improve the cell performance. Raman microscopy is one of the useful methods for investigating the reactions because of its feature of high spatial resolution and surface sensitivity. Raman spectral changes of composite electrodes are closely related to the structural changes of active material during charge-discharge cycling. In this study, Raman spectroscopy was carried out for LiCoO2 composite positive electrodes in all-solid-state cells before and after the charge-discharge process. Moreover, Raman mapping was conducted to evaluate state-of-charge (SOC) distributions of each active material in the electrodes.
The 75Li2S·25P2S5 (mol%) glass and indium foil were used as solid electrolyte and a negative electrode, respectively. A composite positive electrode was prepared by mixing LiCoO2 particles and 75Li2S·25P2S5 glass particles (80:20 wt.%). All-solid-state cells were charged and discharged with a cut-off voltage of 2.6-4.2 V (vs. Li+/Li) at 25 oC under a current density of 0.064 mA cm-2. Raman spectra were obtained for the surface part of composite positive electrodes prepared by an Ar ion-milling technique.
There are two strong Raman peaks at 486 and 596 cm-1, originating from the E
g and A
1g modes of oxygen vibration in LiCoO2, respectively. Those peaks shifted to the lower wavenumber side and their intensity decreased after the initial charging process. After the discharging process, those peaks returned to the original positions. Mapping images showed charge-discharge reactions did not proceed uniformly at the areas of insufficient contacts between LiCoO2 particles and solid electrolyte particles [2]. Our approaches to fabricate composite positive electrodes having uniform charge-discharge reactions will be demonstrated.

Acknowledgement

This research was financially supported by JST, ALCA-SPRING.

References

[1] T. Minami et al., Solid State Ionics, 177 (2006) 2715-2720.
[2] M. Otoyama et al., J. Power Sources, 302 (2016) 419-425.
Ni3Sn4 Based Anode Materials for Three-Dimensional Lithium/Sulfur Battery
Authors: Tolegen Beisen , Pidakhmet Aidyn , Mentbayeva Almagul , Hara Toru , Bakenov Zhumabay 
Published: February 2020

The development of renewable energy and ecological transport demands high energy density rechargeable batteries. Conventional battery technologies suffer from high cost, toxicity and performance limitations such as low capacity and capacity fading. Therefore, development of novel economically feasible high performance batteries is crucial for wider use and application of sustainable energy supply and electric vehicles. Lithium/sulfur (Li/S) batteries have the highest energy density among all known systems [1], and therefore are promising as the next generation batteries. However, these systems have disadvantages related to low conductivity of sulfur and its dissolution and shuttle during the battery operation.
Mosby and Prieto have demonstrated an innovative concept of economically feasible three-dimensional (3D) battery manufacturing concept [2]. The aim of our work is to develop an innovative battery by combining 3D battery architecture with outstanding performance of Li/S technology. In the current work focus was to construct a safe three-dimensional battery with high energy efficiency and stable cycling. Here we show that consistent progress has been achieved and three-dimensional anode was prepared: Ni3Sn4 alloys were successfully electrodeposited on nickel foam and their structural and electrochemical properties were examined. This 3D battery architecture will be combined with the Li/S battery technology, which will allow to overcome the large volume changes in the anode by making nano-sized anode crystals and tightly connecting these crystals to the 3D current collector. Sulfur cathode, which is converted into soluble catholite during charging/discharging, can be impregnated into the 3D architecture more easily than conventional cathode materials. This system is promising as a potential electric vehicle battery and the energy storage system for renewable energy sources.

Reference

[1] Y. Zhang, Y. Zhao, Z. Bakenov, “A novel lithium/sulfur battery based on sulfur/graphene nanosheet composite cathode and gel polymer electrolyte,” Nanoscale Res. Lett., 2014, 137.
[2] J. Mosby, L. Prieto, “Direct electrodeposition of Cu2Sb for lithium-ion battery anodes,” J. Am. Chem. Soc., 2008, 130, 10656-10661.

Acknowledgments

This work was supported by the research grant #4649/GF4 “Development of economically feasible three-dimensional lithium/sulfur battery” from the Ministry of Education and Science of the Republic of Kazakhstan.
A Surface Enhanced Raman Spectroscopy (SERS)-Active Cathode for Lithium-Oxygen Battery Discharge Product Investigation
Authors: Liu Kewei , Yu Zitian , Zhu Xiaowen , Zhang Shuo , Zhu Yu 
Published: February 2020

Nonaqueous Lithium-air (Li-O2) battery has attracted significant research interest in the past decade, because of its high theoretical specific energy far beyond conventional Li-ion battery. However, there are many challenges such as severe degradation during cycling that limits the practical utilization of Li-O2 battery. Hence, a powerful tool is necessary to be found to detect the intermediates and study side reactions in Li-O2 battery. In this work, we explored a method to fabricate larger-area regularly patterned gold nano-dots by using the mask of anodic aluminum oxide (AAO) membrane for surface enhanced Raman spectroscopy (SERS). The size effect of the small and large gold nano-dots on the enhancement of Raman signal was studied by Rhodamine 6G on Si. Small gold nano-dots on Au film and graphene were used as SERS-active cathodes in Li-O2 battery and showed great ability for detecting the component on planar electrode. After discharge, many peaks have been observed for the SERS-active gold electrode, which demonstrate the existence of Li2O2, LiOH and LiO2. On the other hand, when SERS-active graphene electrode was used as lithium oxygen battery cathode, Li2O2 and Li2CO3 were detected.
The Development of Sodium Sulfur Batteries for Energy Storage Application in China
Authors: Liu Yu 
Published: February 2020

Sodium sulfur batteries with a high energy density have been widely demonstrated by NGK INSULATORS, LTD, Japan, which is the only one maker for soduim sulfur batteries reported through the world Based on the technology developed from Shanghai Institute of Ceramics Chinese Academy of Sciences, a manufacture company of Shanghai Electric Sodium-sulfur Batteries Energy-Storage Technology Co.Ltd, abbreviated as SESSE, has been established at Jan., 2012. So far, the company has completed a 10 MW-per year scale for the fabrication of sodium sulfur batteries.The large size beta Al2O3 ceramic tubes are mass produced by the common ceramic fabrication technology such as dry bag molding and gas sintering. The market goal of sodium sulfur batteries developed currently is the energy storage application for renewable energy, emergency energy and smart grid. Based on the market requirement, such as power output, energy capacity, and system scale, different types of the modules such as 5Kw and 25 KW have been developed.The 1MWh power station of sodium sulfur batteries for energy storage located in Shanghai has been constructed and operated since March, 2015. The detailed information and situation will be introduced and presented in this conference.
Surface-Chemistry-Initiated Design of Host Materials for Sulfur Cathodes: From Nitrogen-Doped Carbon to Sulfiphilic Cobalt Disulfide
Authors: Peng Hong-Jie , Yuan Zhe , Hou Ting-Zheng , Huang Jia-Qi , Cheng Xin-Bing , Wei Fei , Zhang Qiang 
Published: February 2020

The development of lithium−sulfur batteries has become an important area of research to meet the growing demand of modern society for energy-storage devices as sulfur cathode is benefited from the excellent theoretical capacity of 1672 mAh g−
1, low cost, abundant reserves, and environmental benignity. However, its practical application is strongly impeded by the sluggish kinetics of sulfur redox within aprotic electrolytes and the shuttle effect of soluble intermediate polysulfides. The incompatibility between highly polar polysulfides and conventional carbonaceous conductive substrates is believed to be the main reason for both unfavorable redox activity and polysulfide “flooding”.1 Here two host materials for sulfur cathodes beyond typical nanocarbon are presented. (1) Nitrogen-doped carbon nanotubes were employed to build sulfur composite cathodes and to examine the heteroatom-doping effect on the sulfur electrochemistry. The electrochemical measurements combined with ab initio calculation validated an enhanced capacity of 1370 mAh g−
1 at 0.1 C, over eight-times extended cyclic life, and reduced polarization via only 1.8 % nitrogen incorporation.2 (2) The sulfiphilic surface properties of bulk cobalt disulfide (CoS2) was demonstrated by static adsorption and theoretical calculation. Further hybridization of 15 % CoS2 with graphene demonstrated a high capacity of 1368 mAh g−
1 at 0.5 C, low decay rate of 0.034% over 2000 cycles at 2.0 C, and 10 % increase in energy efficiency. More importantly, the electrocatalytic effect on liquid−liquid polysulfide redox was first verified by assembling symmetric cells.3The two surface-chemistry-initiated design is believed to bring new opportunity to propel the development of advanced sulfur lithium−sulfur batteries as well as other novel energy storage devices.

References:

Peng, H.-J.; Zhang, Q. Angew. Chem. Int. Ed.
2015, 54, 11018–11020

Peng, H.-J.; Hou, H.-Z.; et al. Adv. Mater. Interfaces
2014, 1, 1400227

Yuan, Z.; Peng, H.-J.; et al. Nano Lett.
2016, doi: 10.1021/acs.nanolett.5b04166
MoS2 Nanosheets Vertically Aligned on Carbon Paper: A Freestanding Electrode for Highly Reversible Sodium Ion Batteries
Authors: Xie Xiuqiang , Makaryan Taron , Zhao Mengqiang , Van Aken Katherine L , Gogotsi Yury , Wang Guoxiu 
Published: February 2020

The renaissance of sodium-ion batteries (SIBs) in the last few years provides a promising environmentally friendly alternative for energy storage and conversion (ESC).1
,
2 MoS2, a layered material with a large interlayer spacing along the c-axis (0.62 nm), has been attracting extraordinary attention as anode materials for SIBs. However, pure MoS2 exhibited poor rate capability and fast capacity decay upon cycling. Nanostructuring and hierarchical electrode architectures are required to facilitate transport of Na-ions within electrodes.3 Herein, we report on a rational design of freestanding anode materials for sodium-ion batteries, consisting of MoS2 nanosheets aligned vertically on carbon paper derived from paper towel.4 The hierarchical structure enables sufficient electrode/electrolyte interaction and fast electron transportation. Meanwhile, the unique architecture can minimize the excessive interface between carbon and electrolyte, enabling high ICE. When employed as freestanding electrodes for SIBs, the as-prepared MoS2@carbon paper composites delivered a high reversible capacity of 446 mA h g-1 at 20 mA g-1, high ICE (79.5%), and promising rate capability. Even at a high current density of 1000 mA g-1, a reversible capacity of 205 mA h g-1 was maintained.By exploiting in situ Raman spectroscopy, we observed the reversibility of the phase transition from 2H-MoS2 to 1T-MoS2 during the sodium-ion intercalation/de-intercalation process.
References
1. Xiuqiang Xie, Zhimin Ao, Dawei Su, Jinqiang Zhang and Guoxiu Wang, MoS2/graphene composite anodes with enhanced performance for sodium-ion batteries: the role of the two-dimensional heterointerface,
Advanced Functional Materials
, 2015, 25, 1393-1403.
2. Xiuqiang Xie, Katja Kretschmer, Jinqiang Zhang, Bing Sun, Dawei Su and Guoxiu Wang, Sn@CNT nanopillars grown perpendicularly on carbon paper: A novel free-standing anode for sodium ion batteries,
Nano Energy
, 2015, 13, 208-217.
3. Yury Gogotsi, What nano can do for energy storage,
ACS Nano
, 2014, 8, 5369-5371.
4. Xiuqiang Xie, Taron Makaryan, Mengqiang Zhao, Katherine L. Van Aken, Yury Gogotsi and Guoxiu Wang, MoS2 nanosheets vertically aligned on carbon paper: a freestanding electrode for highly reversible sodium-ion batteries,
Advanced Energy Materials
, 2015, DOI: 10.1002/aenm.201502161.

Figure 1
Voltage Fade Phenomenon and Structural Stability of Lithium- and Manganese-Rich Nickel-Manganese-Cobalt Oxides
Authors: Bareno Javier , Li Yan , Vu Anh , Phillips Patrick J , Bettge Martin , Klie Robert F , Chen Zonghai , Abraham Daniel P , Bloom Ira 
Published: February 2020

Lithium- and Manganese-Rich Nickel-Manganese-Cobalt Oxides (LMR-NMC), nominally of composition xLi2MnO3
•(1-x)LiMO2 (with M a combination of Ni, Mn, and/or Co), present a high-voltage plateau (~4.5 V vs. Li/Li+) in their capacity-voltage profile during the first delithiation cycle. This plateau is believed to result from activation of the Li2MnO3component, which makes additional lithium available for electrochemical cycling. Once activated (i.e., cycled beyond the activation plateau) the voltage v. capacity characteristic of LMR-NMC oxides is known to decrease continuously with cycling, resulting in a progressive loss of energy density. This phenomenon, commonly referred to as voltage fade, results in a gradual loss of energy density with cycling and constitutes one of the main barriers toward broad application of LMR-NMC as cathode materials for automotive applications.
In this work we show evidence of voltage fade well below the activation plateau and its relation to structural changes during LMR-NMC cycling. We argue that voltage fade results from a gradual accumulation of spinel environments in the crystal structure. Some of these spinel sites result from lithium deficiencies during oxide synthesis and are likely to be at the particle surfaces; other sites result from the migration of transition metal atoms in the partially-delithiated LiMO2component into the lithium planes during electrochemical cycling. We also present evidence that these structural changes are related to the oxygen-to-metal ratio and could be driving oxygen evolution from LMR-NMC materials which, as a potential trigger of thermal runaway, is a process of fundamental concern for safety.

Acknowledgment: The submitted issue has been created by the University of Chicago as Operator of Argonne National Laboratory (“Argonne”) under Contract No. W-31-109-Eng-38 with the U.S. Department of Energy. The U.S. Government retains for itself, and others acting on its behalf, a paid-up, non-exclusive, 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.
Novel Method of Contrast Improvement Applied to Lithium Ion Battery Electrode Materials Enabling Multi Modal and Super-High Resolution 3D Imaging and Advanced Quantification
Authors: Biton Moshiel , Yufit Vladimir , Tariq Farid , Kishimoto Masashi , Brandon Nigel P. 
Published: February 2020

The authors present for the first time a new methodology of contrast enhancement for multi modal 3D imaging including novel advanced quantification for a commercial Lithium Iron Phosphate (LFP) LiFePO4 cathode. The research aim of this work is to improve the 3D imaging of challenging battery materials by developing methods to increase the contrast between otherwise previously poorly differentiated phases. This is necessary to enable the capture of the real geometry of electrode microstructures, which allows measurement of a wide range of microstructural properties such as pore/particle size distributions, surface area, tortuosity and porosity. Those properties play vital roles in determining the performance of battery electrodes. In this study we present a novel method of sample preparation which is introduced here for the first time for this purpose and found suitable for multi modal imaging, for both FIB-SEM tomography and X-ray tomography. This novel method improves image contrast, which enables higher FIB-SEM resolution (3D image) the highest yet reported for carbon containing electrode materials (e.g. composite LFP cathodes) using FIB-SEM. It means that all the particles are well defined and the size distribution of each phase can be analysed very accurately from the complex 3D electrode microstructure using an advanced novel quantification algorithm.
Study the Performance of LiCoO2 for 4.5V Lithium Ion Battery
Authors: Han Guangshuai , Li Wei , Xie Jingying 
Published: February 2020

As the world into the era of 3G/4G, 3G/4G phones and netbooks gradually popular, mobile Internet, games, video more extensive application of all these applications need to be on the phone for a long time operation, the need of mobile phone battery can support a long time, it puts forward higher requirements on lithium ion batteries, thus to improve the specific energy of lithium ion battery has become one of the problems to be solved1-2. At present mainly in order to improve the specific energy of lithium ion battery by boosting voltage of LiCoO2 material, while it will also bring adverse effect to LiCoO2 materials. So it is necessary to study the evolution of the LiCoO2under high voltage cycling.
In this paper, we used the three electrodes to monitor the potential changes of LiCoO2 and graphite from the battery initial state charged to 4.5 V (as shown in figure 1), and before and after cycling. Study the morphology, structure and surface changes of LiCoO2before and after cycling under 4.5V high voltage by using differential capacitance, scanning electron microscopy, X-Ray Diffraction (as shown in figure 2), Raman, IR and differential scanning calorimetry analysis characterization methods.

Acknowledgements

The project was supported by the Shanghai Science and Technology Development Fund (15DZ2282000) and (14JC1491800)

References

[1]. A. Aboulaich*, K. Ouzaouit, H. Faqir, A. Kaddami, I. Benzakour, I. Akalay. Materials Research Bulletin 73 (2016) 362-368.
[2]. Y. Ito, Y. Sakurai, S. Yubuchi, A. Sakuda, A. Hayashi∗,and M. Tatsumisago, J. Electrochem. Society, 162 (8) (2015) A1610-A1616.

Figure 1
Electronic-Structure Analyses of Li-Ion-Battery Electrodes By Soft X-Ray Absorption/Emission Spectroscopy Including Operando experiments
Authors: Asakura Daisuke , Hosono Eiji , Niwa Hideharu , Kiuchi Hisao , Miyawaki Jun , Nanba Yusuke , Okubo Masashi , Matsuda Hirofumi , Oshima Masaharu , Harada Yoshihisa 
Published: February 2020

Improving the energy density and power density of electrode materials for Li-ion batteries (LIBs) is highly important to further develop electric and hybrid-electric vehicles. For the improvements, understanding the charge-discharge mechanisms from a viewpoint of the electronic structure is indispensable. Recently, electronic-structure analyses of the electrode materials using soft x-ray spectroscopy have been of particular importance.
In this study we demonstrate operando Mn L
3 soft x-ray emission spectroscopy (XES) for LiMn2O4 [1] which is a typical cathode material of LIB. We developed an operando cell consisting of the LiMn2O4 cathode, a counter electrode and an electrolyte solution [2] by modifying the in situ cell for fuel cell catalysts [3]. The charge-discharge experiments were performed by cyclic voltammetry. The operando XES experiments were carried out using ultrahigh-resolution x-ray emission spectrometer [4] at BL07LSU of SPring-8. The XES spectra were analyzed by theoretical analyses based on the configuration-interaction full-multiplet (CIFM) calculation [5-7].
In the operando Mn L
3 XES study for LiMn2O4, we revealed that the open-circuit voltage (OCV) state is almost the same as the initial state consisting of the Mn3+ and Mn4+ states. For the charged state, the Mn L
3 XES spectrum largely changed corresponding to the oxidation of Mn3+ to Mn4+ state at the Mn3+ site for the OCV. The spectrum for the discharged state almost returned to the spectrum for the OCV, while the small difference indicates that the Mn3+ state is slightly enhanced for the discharged state. Thus, the Mn 3d electronic states were reversibly changed for the charge-discharge process [2]. Moreover, charge-transfer (CT) effects between the Mn 3d and O 2p orbitals for each valence state were clarified. For the Mn4+ state, a negative CT energy was determined by the CIFM calculation, suggesting a very strong CT effect from the O 2p to Mn 3d orbitals.
In the presentation, XES and soft X-ray absorption spectroscopy studies for other electrode materials will also be reported, and the relationship between the electronic structure and electrochemical performance will be discussed.

References

[1] M. M. Thackeray, Prog. Solid St. Chem. 25, 1 (1997).
[2] D. Asakura et al., Electrochem. Commun. 50, 93 (2015).
[3] H. Niwa et al., Electrochem. Commun. 35, 57 (2013).
[4] Y. Harada et al., Rev. Sci. Instrum. 83, 013116 (2012).
[5] Y. Nanba et al., J. Phys. Chem. C 116, 24896 (2012).
[6] Y. Nanba et al., Phys. Chem. Chem. Phys. 16, 7031 (2014).
[7] D. Asakura et al., J. Phys. Chem. Lett. 5, 4008 (2014).
Hybrid Flow Battery/Mediator Supercapacitor Using Iron Cyanide Redox Materials
Authors: Zhou Xiangyang , Pape Marie , Narasimhan Swati , Zhang Chen 
Published: February 2020

Flow batteries have very high specific energy but low specific power and slow response while mediator supercapacitors give high specific power and fast response but relatively low specific energy. A hybrid flow-battery/supercapacitor is fabricated and operated under different conditions in order to provide both high specific energy and power. The porous electrodes of the consisted of catalysts for redox reactions (Ni, Pt, Ru, etc.), mediators (NaI/I2, VOSO4, K4Fe(CN)6, etc.), and polymer electrolytes as binders. An ion exchange membrane was used as the separator. An array of complex iron cyanide compound were synthesized and used as the redox materials in slurry reservoirs. This investigation focuses on the effects of flow rate, temperature, pressure, and mediator concentration on the performance of the energy storage device. Cyclic voltammetry (CV) and galvanostatic charge/discharge (GCD) measurements were conducted under a wide range of flow rate and mediator concentration. The redox potential of the slurry was monitored using an electrochemical redox sensor. The electrochemical kinetics of the mediators and redox materials were evaluated using linear polarization methods. The results indicate that at a given scan rate for CV or current for GCD, both flow rate and mediator concentration greatly impact the charge/discharge behaviour, the total energy, and efficiency. There is a critical flow rate at which a capacitor-like behaviour transits to battery-like behaviour. A simple numerical model is created to analyse the experimental data and provide an explanation of the observations.