bluuebunny/crossref_metadata_2025_split huggingface dataset:
Fabrication of All-Solid-State Batteries Using Li3BO3-Based Glass-Ceramic Electrolytes
Authors: Nagao Kenji , Hayashi Akitoshi , Tatsumisago Masahiro 
Published: February 2020

Safety and reliability are important factors for rechargeable batteries with high energy density. All-solid-state batteries using inorganic solid electrolytes without leakage and flammability are one of the solutions for rechargeable energy sources. Sulfide electrolytes exhibit very high lithium ion conductivities around 10-4-10-2 S cm-1 at room temperature, which is comparable to that of organic liquid electrolytes[1]. In spite of such good conductivities, sulfide electrolytes are not stable under ambient atmosphere. On the other hand, oxide-based solid electrolytes are very attractive for application in all-solid-state batteries with safety because of their high chemical stability. In general, it is difficult to use oxide solid electrolytes in all-solid-state batteries because of poor deformability, which results in a huge interfacial resistance between electrolytes and electrodes. Oxide glass electrolytes with low melting properties such as Li3BO3 are promising materials for application in all-solid-state batteries. Li3BO3 glass showed the conductivity of 3.4×10-7 S cm-1 at room temperature. To enhance the conductivity of the Li3BO3 glass, we have prepared lithium ion conducting glasses based on Li3BO3 by rapid melt-quenching and mechanochemical techniques [2-4]. Especially, by heating 90Li3BO3·10Li2SO4 (mol%) glass, solid solution between high temperature phase of Li3BO3 and Li2SO4 were precipitated. This glass-ceramic showed a high lithium ion conductivity of 1.4×10-5 S cm-1 and good deformability. The 33Li3BO3·33Li2SO4·33Li2CO3 glass-ceramic electrolyte was prepared. It showed a relatively high conductivity of 2.3×10-6 S cm-1 and excellent deformability achieving relative density of 90% by cold-press, which is comparable to the deformability of sulfide electrolytes such as Li3PS4 glass [5].
In this study, all-solid-state Indium / Li(Ni1/3Mn1/3Co1/3)O2 (NMC) cells using the 90Li3BO3·10Li2SO4 or 33Li3BO3·33Li2SO4·33Li2CO3 glass-ceramic electrolyte were fabricated. These cells operated as a secondary battery at 25-100oC. The first discharge capacity at 100oC of the cell using 90Li3BO3·10Li2SO4 glass-ceramic electrolyte was 100 mAh g-1, while the capacity using 33Li3BO3·33Li2SO4·33Li2CO3 glass-ceramic electrolyte was 150 mAh g-1. This capacity enhancement was caused by the better deformability of 33Li3BO3·33Li2SO4·33Li2CO3 electrolyte than that of 90Li3BO3·10Li2SO4 electrolyte.
References
[1] Y. Seino et al., Energy Environ. Sci., 7 (2014) 627.
[2] M. Tatsumisago et al., J. Ceram. Soc. Jpn., 95 (1987) 59.
[3] A. Hayashi et al., Phys. Chem. Glasses: Eur. J. Glass Sci. Technol. B, 54 (2013) 109.
[4] M. Tatsumisago et al., J. Power Sources, 270 (2014) 603.
[5] A. Sakuda et al., Sci. Rep., 3 (2012) 2261.
Mechanistic Studies of Fluorinated Electrolyte for High Voltage Lithium-Ion Battery
Authors: He Meinan , Su Chi-Cheung , Wang Yan , Zhang Zhengcheng , Peebles Cameron 
Published: February 2020

Lithium ion batteries have dominated the portable electronics market and have the potential to dominate large-scale battery applications including hybrid and electric vehicles as well as grid storage because of their high energy and power densities.[1] It is well known that conventional electrolytes (such as 1.2 M LiPF6 in EC/EMC 3/7) show poor anodic stabilities above 4.5 V versus Li/Li+.[2] However, high voltage electrolytes play an intrinsic role in many applications such as hybrid and electrical vehicles, aerospace uses and power grids. As a result, high voltage electrolytes are essential for the development of next generation lithium ion batteries. One possible solution is to develop fluorinated electrolytes which not only form kinetically stable SEI interphase, but also are resistant to oxidative decomposition due to their high oxidation potential. [3] In this work, a novel fluorinated electrolyte was introduced in a graphite-LiNi0.5Mn0.3Co0.2O2 full cell operated between 3.0 - 4.6 V. The electrolyte contains 1.0 M LiPF6 dissolved in a mixture of FEC and HFDEC solvent with 1wt % LiDFOB used as the additive. Compared to a conventional EC and EMC based electrolyte, the fluorinated electrolyte shows an excellent cycle life under a 4.6V cut off voltage. NMR and GC-MS were used to analyze the harvested electrolyte post-cycling while SEM, XPS and FTIR were employed to study the interface between the electrolyte and the bulk electrodes. Most importantly, HR-XRD and XANS were conducted to investigate and compare the cycled bulk cathode electrode in different electrolytes. To the best of our knowledge, the structural change of the cycled cathode material in different electrolytes has never been reported. Therefore, we believe this research is a crucial breakthrough for studying the interaction between the electrolyte and electrode. The methodology developed could be fundamental in the design and investigation of better electrolytes for next generation lithium ion batteries.
[1]Xu, Kang. "Nonaqueous liquid electrolytes for lithium-based rechargeable batteries." Chemical reviews 104.10 (2004): 4303-4418.
[2] Xu, Kang. "Electrolytes and interphases in Li-ion batteries and beyond." Chemical reviews 114.23 (2014): 11503-11618.
[3] Zhang, Zhengcheng, et al. "Fluorinated electrolytes for 5 V lithium-ion battery chemistry." Energy Environ. Sci. 6.6 (2013): 1806-1810.
Advanced Ceramic Li Ion Electrolytes for All-Solid-State Li Ion Batteries
Authors: Thangadurai Venkataraman 
Published: February 2020

At present, the energy supply around the world comes from fossil fuels and is one of the main causes of greenhouse gas emissions. Attempts have been made to generate electricity using renewable sources, such as wind and solar, but it could be realized through the use of reliable electrochemical storage systems. Batteries can be used in combination with renewable energies to store energy when the demand is low and supply to the grid when demand is high. Among the known secondary batteries, Li ion batteries (LIBs) find applications ranging from small mobile electronics to transportation and even to stationary, grid storage systems. LIBs exhibit the highest power and energy densities over other known batteries. The most frequently used cathodes in LIBs include LiCoO2, LiNi1/3Mn2/3Co1/3O12 and LiFePO4 and graphite is the most popular choice for anode. Typical electrolyte used in the LIB consists of lithium salt (e.g., LiPF6, LiBF4 or LiClO4) dissolved in an organic carbonate such as ethylene carbonate, diethyl carbonate or propylene carbonate.
The current LIB research is mainly focused on improving the practical gravimetric and volumetric energy densities by developing advanced Li ion electrolytes and electrodes. Attempts have been made to replace unstable polymer members with high temperature stable and highly conducting ceramic Li ion electrolytes, including Li3N, Li-β-alumina, A-site deficient perovskite-type and garnet-type metal oxides. These solid electrolytes offer the advantages of being safe and compatible with advanced electrode materials, as well as a having a wide temperature range of operation and high Li ion conductivity. In this talk, recent advances in most promising garnet-type Li5La3M2O12 (M = Nb,Ta) oxides will be discussed. Since their discovery as Li ion conductors, there has been an increased interest in the development of garnet-type Li ion electrolytes for all solid-state LIBs. Some of the members of the garnet have been proven to be stable against chemical reaction with Li, as well as electrochemically stable up to 6 V vs. Li/Li+. These attributes, together with the good total Li ion conductivity, make them ideal electrolyte candidates for all solid-state LIBs.
Development of Novel High Energy Density Sn-Doped Sodium Layered Oxide Cathode Materials
Authors: Smith Katherine , Gruar Robert , Kendrick Emma 
Published: February 2020

Sodium ion batteries are being developed as a lower cost alternative to lithium ion batteries which find application in consumer electronics, power tools , stationary energy storage and electric vehicles. The lower cost of sodium makes it an attractive technology r for application in stationary energy storage and other applications which require lower cost energy storage technologies. One of the limitations with sodium ion batteries for use in other applications is their low energy density. Sharp laboratories of Europe Ltd (SLE) have been developing and optimising higher energy density cathodes for sodium ion batteries.
Several layered oxide systems have been reported as potential cathodes [i],[ii] SLE has performed an optimisation of tin containing nickel based layered oxide materials which exhibit high specific capacities[iii]. In particular we have looked at the O3 type mixed nickel and manganese containing layered oxides of the formula NaυNi1
v M2
w M3
xO2±6wherein Μ2 comprises tin, optionally in combination with one or more transition metals, Μ3 comprises one or more transition metals. The incorporation of Sn is interesting because it leads to higher observed average voltages upon discharge, and exhibits higher specific capacities compared to other O3 type layered oxides with similar compositions. The main contribution to the higher average voltage upon discharge is the observation of a high voltage reversible plateaux. An optimisation of the material composition has been performed which looks at the effect of the different dopants and dopant levels upon the observed voltage and specific capacity. Here we discuss the optimisation of the high energy sodium ion cathode material, and the origin of the voltage plateaus and the mechanism for charge and discharge mechanism for the Sn containing layered oxide materials.

[i] X. Li et al. Electrochemistry Communications 49 (2014) 51–54
[ii] H. Yoshida, N. Yabuuchi and S. Komaba Electrochem. Commun., 34 (2013), pp. 60–6
[iii] Kendrick, Gruar et al, Tin containing compounds, WO2015177568A1, 2015-11-26

Figure 1
Characteristics of All-Solid-State Thin-Film Battery Using Amorphous LixMyPOz Cathode Material
Authors: Shimizu Keisuke , Hayashi Saori , Sato Susumu , Nakayama Norikazu , Kusanagi Susumu , Nagamine Masayuki 
Published: February 2020

A novel amorphous cathode material LixMyPOz for all-solid-state thin-film lithium-ion battery has been developed. Since a non-annealing process is employed, a thin-film lithium-ion battery can be fabricated by direct deposition of materials onto thin plastic film. LixMyPOz is formed through sputter deposition of Li3PO4 and metal or metal oxide targets. We have tested several metal elements (M = Ni, Mn, Co, Cu, Ag), and LiNiPO showed a high capacity of 330 mAh g−1 at 1C. In addition, a cell using this cathode material has demonstrated a high charge/discharge rate up to 30C.
Computational Modelling Study on Stability of Li-S/Se System
Authors: Masedi M. C. , Sithole H. M. , Ngoepe Phuti Esrom 
Published: February 2020

Li-ion batteries have transformed portable electronics and will play a key role in the electrification of transport. However, the highest energy storage possible for Li-ion batteries is insufficient for the long-term needs of society. Here we consider a study on rechargeable lithium−sulfur (Li−S) batteries which hold great potential for high-performance energy storage systems because they have a high theoretical specific energy, low cost, and are eco-friendly. This work employs computational modelling methods to explore stability, structural and electronic properties of discharge products formed in the Li-S/Se battery, especially Li2S/Se, which has potential to offer higher theoretical specific energy and remedies the challenges that Li-S battery encounters. First principle methods were used to calculate thermodynamic properties of Li2S and Li2Se, which agreed with available experimental results. A cluster expansion technique generated new stable phases of Li2S/Se system and Monte Carlo simulations determined concentration and temperature ranges in which the systems mix. Interatomic Born Meyer potential models for Li2S and Li2Se were derived and validated and used to explore high temperature structural and transport properties of Li2S/Se.
Storage and Effective Migration of Li-Ion for Defected Beta-LiFePO4 Phase Nanocrystals
Authors: Guo Hua , Song Xiaohe , Zheng Jiaxin , Pan Feng 
Published: February 2020

Lithium iron phosphate, a widely used cathode material, crystallizes typically in olivine-type phase, α-LiFePO4 (αLFP). However, the new phase β-LiFePO4 (βLFP), which can be transformed from αLFP under high temperature and pressure, is originally almost electrochemically inactive with no capacity for Li-ion battery, because the Li-ions are stored in the tetrahedral [LiO4] with very high activation barrier for migration and the one-dimensional (1D) migration channels for Li-ion diffusion in αLFP disappear, while the Fe ions in the β-phase are oriented similar to the 1D arrangement instead. In this work, using experimental studies combined with density functional theory calculations, we demonstrate that βLFP can be activated with creation of effective paths of Li-ion migration by optimized disordering. Thus, the new phase of βLFP cathode achieved a capacity of 128 mAh g−1 at a rate of 0.1 C (1C = 170 mA g−1) with extraordinary cycling performance that 94.5% of the initial capacity retains after 1000 cycles at 1 C. The activation mechanism can be attributed to that the induced disorder (such as FeLiLiFe antisite defects, crystal distortion, and amorphous domains) creates new lithium migration passages, which free the captive stored lithium atoms and facilitate their intercalation/ deintercalation from the cathode. Such materials activated by disorder are promising candidate cathodes for lithium batteries, and the related mechanism of storage and effective migration of Li-ions also provides new clues for future design of disordered electrode materials with high capacity and high energy density.
New Conversion Anode Material Utilizing Redox of Al3+ Ion
Authors: Sonoyama Noriyuki , Ogasawara Yoshitaka , Aoi Tomokatsu , Yoshida Satoshi , Tsukada Tetsuya 
Published: February 2020

A new conversion type anode material for lithium ion battery utilizing the redox activity of aluminum (III) ion has developed. Conversion type materials are known to have a serious weak point as anode materials, that is the high reaction voltage in spite of its high capacity (over 600 mAh/g). This high reaction voltage originates in high redox potential of transition metal oxide such as NiO or CoO, those are known as representative conversion anode materials for lithium ion battery. In order to improve this high reaction voltage, it is effective to use oxides of light metal with lower redox potentials such as aluminum oxides. However, aluminum oxides are difficult to use as the electrode materials owing to the low electric and ionic conductivity. We have synthesized solid solution of nickel oxide and aluminum oxide with nano level particle size by calcination of Ni-Al layered double hydroxides (LDH). The fine structure of calcinated materials are determined by XRD and XAFS: Ni2+ and Al3+ ions are randomly locating metal ion sites of NiO with rock salt structure and cation vacancies are introduced to compensate the excessive charges brought by the aluminum ions. In this structure, electron and lithium ion are expected to be supplied via NiO type host structure and cation vacancies, respectively.
The charging capacity of the half cell with lithium metal counter electrode from 0.03 V to I.5 V, that corresponds to the discharge capacity or the full cell was improved to 600 mAh/g, where as that for pristine NiO was 230 mAh/g. This improvement of capacity in the lower voltage region is expected to originate in redox of aluminum ion. The redox activity of aluminum ion was confirmed by ex-situ XANES measurement at Al K edge. The absorption edge of aluminum ion shifted to lower energy direction with discharge from 1560 keV to 1556 keV. With charging (the absorption edge of aluminum shifted back to the initial position. This dearly indicates the redox activity of aluminum ion during charge- discharge. This is the first report of anode material for lithium battery that utilizes redox of aluminum ion as far as we know.
In order to investigate the detailed reaction mechanism, ex-situ XRD and XAFS measurements were, carried out. On the basis of these results, the reaction mechanism of Ni-Al binary metal oxide was concluded as follows. In the higher voltage discharge process (OCV-1.0 V), lithium intercalation into the cation vacancy and lithium ion adsorption to the surface of Ni-Al binary metal oxide with the partial redaction of nickel ion is proceeding. In the lower voltage discharge (1.0-0.03 V), the conversion reaction proceeds with the reduction of Ni and Al ions. In the lower voltage charge process (0.03-1.0 V), only aluminum ion is oxidized to form an intermediate state, where aluminum ion makes complex with surrounding oxide ions. In the higher voltage charge process, nickel metal is oxidized to re-form the Ni-Al binary metal oxide with the rock salt structure.
Chemical Changes and Impedance Rise in Li4Ti5O12 - LiNi0.5Co0.2Mn0.3O2 Cells
Authors: Sahore Ritu , Tornheim Adam , Bareno Javier , Zhang Zhengcheng , Bloom Ira 
Published: February 2020

LiNi0.5Co0.2Mn0.3O2(NCM 523) is a promising cathode material for lithium-ion batteries due to its higher capacity, stability, and lower cost compared to LiCoO2, the other commonly used layered oxide. However, the high operating voltage of NCM523 (> 4.3V vs. Li/Li+) makes conventionally used electrolytes unstable. Their continuous electrochemical degradation at the electrodes surface adds to impedance rise, which is a major contributor to rapid capacity fade. High temperature conditions can accelerate these processes. Despite its practical and academic interest, there is no coherent model of cell degradation mechanisms responsible for the observed impedance changes.
In this work, lithium-ion cells consisting of an NCM523 cathode and a Li4Ti5O12(LTO) anode were prepared and subsequently aged at different temperatures and for different times after galvanostatically charging to a final hold potential of 4.6V vs. Li/Li+. Impedance increase and oxidation current were monitored as a function of aging time, hold voltage, temperature, and electrolyte additive concentrations. After aging, the cells were disassembled and chemical changes in the NCM523 electrode are characterized using a combination of techniques (including XPS, IR, and LC-MS) and correlated to the previously measured oxidation current and impedance increase.

Acknowledgement

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.
Optimization of Electrolytes for Si-Containing Full Cell
Authors: Chevrier Vincent L , Petibon Remi , Aiken Connor , Krause Larry J , Jensen Lowell , Xiao Ang , Le Dinh Ba , Eberman Kevin W , Dahn Jeff R 
Published: February 2020

Introduction

The Si/electrolyte interface is increasingly recognized as being a key factor in the successful implementation of Si-based materials in Li-ion batteries. Si-based negative electrode materials undergo massive volume changes during cycling. Pure Si expands by approximately 280% while 3M’s active/inactive Si alloys expand on the order of 135%. The expansion and contraction of Si has important consequences on the surface stability of these materials. This work will focus on the combined impact of material design and electrolyte choices on cell performance.

Results and Discussions

The 3M Si alloy is compared to pure Si in EC/EMC 3/7 + 10% FEC. Cross section SEM images are taken after 100 cycles in a half cell. While the 3M alloy shows a discernible SEI on distinct particles, the pure Si has dramatically expanded in size and completely lost its particle morphology. The impact of electrolyte choice on the surface morphology of the 3M Si alloy is then explored across a range of electrolytes compositions using cross section SEM images after 100 cycles.
Further testing is performed in 200 mAh pouch cells (Lifun), with a LiCoO2 positive electrode, a Si-alloy/graphite negative electrode, and approximately 3 mAh/cm2 of reversible capacity. In order to understand the impact of electrolyte composition as well as failure mechanisms, cells were studied by long term cycling, ultrahigh precision cycling, post-cycling gas chromatography/mass spectroscopy (GC/MS) of the electrolyte, in-situ volume measurements, and electrochemical impedance spectroscopy.
Fluorethylene carbonate (FEC) has long been recognized as an important electrolyte component for Si-containing full cells. GC/MS studies are used to study the consumption of FEC with cycle number as well as changes in electrolyte composition. FEC is found to be preferentially consumed relative to other electrolyte solvents and its depletion is found to generally cause sudden failure. A hierarchy of reactivity of electrolyte solvents is established.
An electrolyte additive in the new product introduction process at 3M will be presented. This additive is found to help delay sudden failure as well as suppress FEC gassing.

Conclusion

When implementing well-designed Si-based materials in commercially-relevant full cells, the electrolyte is a key parameter to be optimized. In this work, electrolyte optimizations lead to delayed sudden failure, suppressed gassing and reduced impedance growth. These findings suggest considerable gains are still attainable through further electrolyte optimizations, which will enable deeper penetration of Si-based materials into the marketplace.
Understanding Interfacial Resistance of Al-Substituted Li7La3Zr2O12 Solid Electrolyte
Authors: Chen Wei , Cheng Lei , Doeff Marca 
Published: February 2020

Cubic garnet phases based on Al-substituted Li7La3Zr2O12 (LLZO) exhibit superior ionic conductivity and outstanding electrochemical stability against metallic lithium anode, making them promising solid electrolyte for next-generation rechargeable battery systems. However, high interfacial impedances of LLZO have prevented their wide applications. The interfacial resistances of lithium cells containing Al-substituted LLZO solid electrolytes are sensitive to their microstructures and histories of exposure to air. Air exposure of LLZO samples with large grain sizes results in dramatically increased interfacial impedances in cells containing them, compared to those with pristine large-grained samples. In contrast, a much smaller difference is seen between cells with small-grained pristine and air-exposed LLZO samples. A combination of soft X-ray absorption (sXAS) and Raman spectroscopy, with probing depths ranging from nanometer to micrometer scales, revealed that the small-grained LLZO pellets are more air-stable than large-grained ones, forming far less surface Li2CO3 under both short- and long-term exposure conditions. Surface sensitive X-ray photoelectron spectroscopy (XPS) indicates that the better chemical stability of the small-grained LLZO is related to differences in the distribution of Al and Li at sample surfaces. Density functional theory thermodynamic calculations show that LLZO can react via different pathways to form Li2CO3. These observations have important implications for the operation of solid-state lithium batteries containing LLZO because the results suggest that the interfacial impedances of these devices is critically dependent upon specific characteristics of the solid electrolyte and how it is prepared.