bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) On the Importance of Statistics in Electrode Characterization Techniques for Failure Mechanism Analysis
Authors: Moreau Philippe , Grissa Rabeb , Castaing Rémi , Guyomard Dominique , Bayle-Guillemaud Pascale , Boniface Maxime 
Published: February 2020

Characterization techniques, when used on electrodes after cycling and/or post mortem, are crucial to the improvement of battery performance. They can indeed pinpoint which failure mechanism is involved and suggest ways to overcome it. Unfortunately, in order to be more precise or save time, objects of interest are rarely studied in large numbers. One might then wonder how representative of the “real” battery they are. In this presentation, examples based on electrochemistry, XPS and EELS spectroscopies will serve to resolve this problem.
In order to highlight of the importance of statistical treatment, we benefited from the analysis of variance (ANOVA) in order to identify pertinent parameters in the aging of Li-ion batteries. To this end, two battery systems: Li4Ti5O12|LiFePO4 and Li4Ti5O12|LiNi1/3Mn1/3Co1/3O2 cells, were aged. The aging conditions, i.e. the rates of charge and discharge and the usage profile, were chosen within an experimental design. It is noteworthy that, contrary to expectations, the evolutions of capacity and resistance are not generally influenced by the aging conditions…
Additionally, how a rarely-used technique, such as XPS imaging, can improve our understanding of the true repartition of chemical species at the surface of electrodes will also be shown. Electrode mixes (binder, active material, electron conductor) are often so complex that a single spectrum, however precise it may be, can lead to misinterpretation. For example, it might imply an interaction between species even though some of them are too far apart to interact, or lead to a compound composition even though two compounds should be considered. This will be demonstrated by virtue of XPS imaging, and by using lithium metal electrodes [R. Grissa et al., ACS Appl. Energy Mater. 2018, 1, 5694−5702] and solid electrolyte polymers that allow one to discriminate between these possibilities. The importance of PCA treatment of the data will be also indicated.
Finally, since microscopy techniques are notorious for obscuring the big picture when it comes to the electrode as a whole, and all the more so when high-level spectroscopy (Electron Energy Loss spectroscopy) is used, silicon electrodes were analyzed after cycling thanks to a very rapid and optimized phase analysis technique developed by M. Boniface et al. (Nano Lett. 2016, 16, 7381−7388). Although a technique of this kind is able to identify the reaction mechanism and solid electrolyte interphase in an aggregate, the universality of this behaviour in the electrode still needed to be demonstrated. The purpose of this part of the presentation is to prove that such is indeed the case, a conclusion resulting from the analysis of hundreds of particles, as well as a careful and absolute quantification of the species in the sample. Notably, the macroscopic characteristics of the electrode can be obtained from the sum of the microscopic data.
(IBA Technology Award) Energy Storage Batteries using Mn and Ti Based Elelctrode Materials
Authors: Xia Yong-Yao 
Published: February 2020

Renewable generation, such as solar and wind, is intermittent, which causes sudden and unanticipated changes to power output and contributes to electricity grid instability. The stability and reliability of electricity grids requires a continuous balance between energy supply and demand. The aqueous lithium-ion battery (LIB) may solve both the safety problem associated with lithium-ion batteries that use highly toxic and flammable organic solvents, and the poor cycling life associated with commercialized aqueous rechargeable batteries including lead-acid and nickel-metal hydride systems. Aqueous LIBs have been demonstrated to be one of the most promising stationary power sources for the sustainable energy such as wind and solar power.
As early as in 2005, we developed a new concept hybrid electrochemical supercapacitor in which a Li-ion intercalated compound was used as a positive electrode in combination with an activated carbon negative electrode in a Li2SO4 aqueous electrolyte (ZL. 200510025269.6). A hybrid cell consisting of a spinel LiMn2O4 positive and an AC negative electrode shows excellent reversibility with a sloping voltage profile from 0.8 to 1.8 V at an average voltage near 1.3 V, and delivers an 8 Wh/kg of 60000 F practical cell. In order to improve the specific energy, we employed LiTi2(PO4)3, but the cell shows poorer cycling stability compared with the pure AC anode. We found that, in the presence of oxygen, the discharged state of lithium-ion intercalated compounds (LIC) of all negative electrode materials will react with water and O2 despite of the pH value of the electrolyte, which is mainly responsible for the capacity fading of aqueous lithium-ion batteries during charge/discharge cycling. By eliminating the O2 (using a sealed cell), adjusting the pH values of the electrolyte, and using carbon-coated electrode materials; the LIB shows much cycling stability. A commercialized hybrid LIB shows a specific energy of ca. 30 Wh/kg, and exhibits a good cycling stability over 3500 cycles. In 2005, we also for the first time employed carbon coating technology to improve the electrode performance of Li4Ti5O4. By optimizing the graphitization and the coated carbon layer thickness, the nano-thickness carbon layer coated LTO shows excellent rate capability and less gas generation during cycling and storage. A LMO/LTO Li-ion battery show excellent cycling stability, high power and safety as stationary power source for smart-grid systems.
References:

Xia et al., TiP2O7 and Expanded Graphite Nanocomposite as Anode Material for Aqueous Lithium-Ion Batteries. ACS Appl. Mater. Interfaces, 9, 8075-8082 (2017).

Xia et al., Raising the Cycling Stability of Aqueous Lithium-Ion Batteries by Eliminating O2 in the Electrolyte ”,
Nat

.

Chem

.

,
2, 760-765 (2010).

Xia et al., Hybrid aqueous energy storage cells using activated carbon and lithium-intercalated compounds I. The C/LiMn2O4 system,
Electrochem. Soc.

, 153(2): A450-A454 (2006).
(Keynote) Low Temperature Processing Innovation and Structure Design of Li-Garnetsfor Solid State Batteries and Environmental Sensing of Chemicals
Authors: Rupp Jennifer L.M. 
Published: February 2020

Next generation of energy storage and sensors may largely benefit from fast Li+ ceramic electrolyte conductors to allow for safe and efficient batteries and real-time monitoring anthropogenic CO2. Recently, Li-solid state conductors based on Li-garnet structures received attention due to their fast transfer properties and safe operation over a wide temperature range. Through this presentation basic theory and history of Li-garnets will first be introduced and critically reflected towards new device opportunities demonstrating that these electrolytes may be the start of an era to not only store energy or sense the environment but also to emulate environmental data and information based on simple electrochemistry device architecture twists.
In the first part we focus on the fundamental investigation of the electro-chemo-mechanic characteristics and design of disordered to crystallizing Li-garnet structure types and their description. Understanding the fundamental transport in solid state and asking the provokative question: how do Li-amorphous to crystalline structures conduct?
New insights on degree of glassy to crystalline Li-garnet thin films are presented based on model experiments of the structure types. Here, the thermodynamic stability range of maximum Li-conduction, phase, nucleation and growth of nanostructure is discussed using high resolution TEM studies, near order Raman investigations on the Li-bands and electrochemical transport measurements.
In a second part, we focus on new processing opportunities to Lithiate thin film structures in crystalline state and to assure cubic and fast conducting garnet structures for thin film form. For this we will review the field of thin film processing and structure-property for garnet type films and reflect our recent new processing routes based on vacuum and wet-chemical techniques.
The insights provide novel aspects of glass and ceramic thin film processing and material structure designs for both the Li-garnet structures (bulk to films) and their interfaces to electrodes, which we either functionalize to store energy for next generation solid state batteries or ... make new applications such as Li-operated CO2 sensor tracker chips which we present in a final part.
(Invited) Present Status of Lithium Ion Batteries
Authors: Blomgren George E 
Published: February 2020

The specific energy of commercial lithium ion batteries has increased substantially, while the price of both cells and batteries have diminished since their introduction in 1991(Figure 1). The results of these improvements have led to wide acceptance of the batteries in a number of applications. In particular, hybrid, plug-in hybrid and pure electric vehicles have been widely developed with lithium ion batteries. In addition, lithium ion batteries in other vehicle types from scooters to bicycles to motorcycles as well as trucks and buses have also been developed and are becoming popular. Lithium ion cells are frequently used in drones or unmanned aerial systems (UAS). High to medium power applications such as power tools and mechanical devices such as mobile robots have also been strongly marketed. Energy storage devices related to electric grid applications are also on a strong growth trajectory.
The design and material changes which have enabled these advances will be discussed and the prospects for further growth in energy and power will be considered. Also, the need for higher charge rates and possible methods of improvement in charge rate will be considered in the search for improved charge times for vehicles and other higher power applications.
Figure 1 Development of lithium batteries during the period of 1970–2015, showing the cost (blue, left axis) and gravimetric energy density (from G. Crabtree, E. Kocs and L. Trahey, MRS Bulletin 40, 1067, 2015)

Figure 1
(Invited) Preserving a High Energy Density of the Lithium-Rich Layered Oxides (LLO) and New Lithium Diffusion Model for LLO
Authors: Kang Kisuk 
Published: February 2020

Lithium-rich layered oxides (LLOs) are considered promising cathode materials for lithium-ion batteries because of their high reversible capacity, which is attributed to the exploitation of the novel anionic redox in addition to the conventional cationic redox process. Cobalt-free layered lithium-rich nickel manganese oxides, Li[LixNiyMn1
−
x
−
y]O2, are one of the promising positive electrode materials for lithium rechargeable batteries because of their high energy density and low materials cost. However, substantial voltage decay is inevitable upon electrochemical cycling, which makes this class of materials less practical. It has been proposed that undesirable voltage decay is linked to irreversible structural rearrangement involving irreversible oxygen loss and cation migration. In the first part of my talk, we demonstrate that the voltage decay of the electrode is correlated to Mn4+/Mn3+ redox activation and subsequent cation disordering, which can be remarkably suppressed via simple compositional tuning to induce the formation of Ni3+ in the pristine material. By implementing our new strategy, the Mn4+/Mn3+ reduction is subdued by an alternative redox reaction involving the use of pristine Ni3+ as a redox buffer, which has been designed to be widened from Ni3+/Ni4+ to Ni2+/Ni4+, without compensation for the capacity in principle. Negligible change in the voltage profile of modified LLO is observed upon extended cycling, and manganese migration into the lithium layer is significantly suppressed.
In the second part of the talk, I will discuss about transition metal (TM) migration, which is now understood to be the critical factor triggering the anionic redox as well as the phase transition, although the origin is still under debate. A better understanding of the specific TM migration behavior and its effect during charge/discharge would thus enable further development of this class of materials. I will show that the unique TM migration during charge/discharge significantly alters the lithium diffusion mechanism/kinetics of LLO cathodes. I present clear evidence of the much more sluggish lithium diffusion occurring during discharge (lithiation) than during charge (de-lithiation), which contrasts with the traditional lithium diffusion model based on simple topotactic lithium intercalation/deintercalation in the layered framework. The reversible but asymmetric TM migration in the structure, which originates from the non-equivalent local environments around the TM during the charge and discharge processes, is shown to affect the lithium mobility. This correlation between TM migration and lithium mobility led us to propose a new lithium diffusion model for layered structures and suggests the importance of considering TM migration in designing new LLO cathode materials.
(Invited) Battery Durability and Reliability Under Electric Utility Grid Operations
Authors: Dubarry Matthieu , Baure George 
Published: February 2020

Battery Energy Storage Systems (BESSs) can facilitate renewable energy sources integration onto the grid. For this application, these systems are expected to last for a decade or more, but the actual battery degradation under different real-world conditions is still largely unknown. In this work, three years of lithium titanate BESS usage in Hawai'i were analyzed. In addition, the representative usage was subjected on individual cells under controlled laboratory conditions to study the degradation mechanisms and enable life prognosis.
The BESS was found to be operational 90% of the time and it stored a cumulative 1.5 GWh of energy, which represented more than 5000 equivalent full cycles on the cells. From this BESS usage data, an initial estimate of BESS degradation was provided and a representative duty cycle was developed. The analysis of the maintenance cycles indicated that these 5000 equivalent cycles induced an estimated 5-10% degradation of the single cells. The battery duty cycle was characterized based on 5 parameters: pulses duration, pulses intensity (current), state of charge (SOC) swing range, SOC event ramp rate, and temperature. The average usage consisted of several 9-second C/2 charge and discharge pulses organized to generate 5% SOC swings with a 0.75% SOC/min ramp rate at 35°C. However, extreme values such as currents up to 4C, swings of 100% SOC, and temperatures above 50°C were also recorded.
Laboratory testing and analysis, in conjunction with a more thorough SOH estimation protocol, resulted in a detailed description of degradation that improved the predictions of the remaining useful battery life. Based on the BESS representative usage profile, cycle-aging and calendar-aging experiments were designed to test the degradation of the associated Li-ion cells in a controlled fashion. It was proven that the cell temperature history had the strongest impact on battery degradation followed by the C-rate and the state of charge. Interestingly, the impact of SOC, both on the cycle-aging and the calendar-aging experiments, was revealed to be counterintuitive. During cycle aging, small SOC swings were more detrimental than larger ones. During calendar aging, batteries lost capacity faster at low SOC than at high SOC. The associated degradation mechanisms and their path dependency were analyzed using incremental capacity analysis.
(Invited) Swelling of Si Nano-Flake Anode for Advanced Lithium-Ion Batteries
Authors: Inaba Minoru , Haruta Masakazu , Doi Takayuki 
Published: February 2020

The poor cyclability of Si electrodes is attributed to crack formation and pulverization of Si active material due to a large volume expansion and contraction during charging and discharging, respectively. It is thus important to suppress the physical stress induced by the large volume changes to improve the cyclability of Si electrodes. We designed a Si powder with a flake shape (Si LeafPowderÒ, Si-LP, OIKE & Co., LTD.) with 100 nm in thickness and 3-5 mm in lateral dimension, and have reported that Si-LP electrodes have a high initial discharge capacity (ca. 2,500 mAh g-1) and good cycleability (Fig. 1) [1].
Another serious problem of Si anode is a swelling of the electrode owing to irreversible microstructural changes of Si nano-flakes upon cycling (Fig. 2). The Si-LP sheets in a composite electrode were substantially deformed during alloying/de-alloying cycling and formed the multi-folded layered structure on repeated cycling. Furthermore, many voids, which could accommodate volume changes of Si, were formed on repeated cycling. The multi-folded layered structure with many voids enabled the stable battery operation of the Si-LP electrodes. On the other hand, the thickness of the electrode remarkably increased with cycle number (Fig. 3), which was caused by the deformation of Si-LP sheets and growth of the SEI layer. The electrode swelling was suppressed by the presence of the additives, VC and FEC. The uniform SEI layer formed from the decomposition products of VC or FEC inhibited further decomposition of the electrolyte and suppressed the deformation of the Si-LP sheets. Unfortunately the suppression of the electrode swelling by the additives is not enough, and further suppression of the electrode swelling and/or a new cell design to manage the large volume changes of Si is necessary for practical applications of the Si-LP as a negative electrode in advanced LIBs.
This research was supported by Japan Science and Technology Agency (JST) ALCA-SPRING and Japan Society for the Promotion of Science (JSPS) KAKENHI Grant Number 16H04649.
References
[1] M. Haruta et al., Electrochim. Acta, 267, 94-101 (2018). DOI: 10.1016/j.electacta.2018.02.062

Figure 1
(Invited) 3D Imaging Options of Battery Electrodes
Authors: Lemmens Herman 
Published: February 2020

There are different ways to create a 3D image of the battery electrodes. MicroCT uses the absorption of X-rays to create a 3D reconstruction. The Field of View is large enough to be representative with regard to the grain sizes. However, the submicron porosity in the electrodes is typically not well captured by microCT because of its limited resolution.
The FIBSEM technique which uses a Galium ion beam for sectioning and an electron beam for imaging has high enough resolution to resolve all porosity. However, the Field of View is typically of the order of 10 micrometer; which is not always big enough to create a representative model of the pore space.
PlasmaFIB can fill the gap between the Gallium FIB and the microCT on most liquid electrolyte lithium ion cells. However, for some solid state batteries, an even bigger volume is needed. This is where slicing with a laser can be used. In this presentation examples are covered of 3D imaging with microCT, laser sectioning and both Gallium and Plasma FIB.
Polyaniline-Intercalated MnO2 As a High Performance Cathode Material for Zinc-Ion Battery
Authors: Huang Jianhang , Wang Yong-Gang , Xia Yong-Yao 
Published: February 2020

Metal-ion batteries based on aqueous electrolyte are attracting widespread attention in the field of large-scale energy storage due to the low cost, high safety and environmental friendliness. However, the development of the most studied aqueous Li+ and Na+ batteries are plagued by the low energy density, which mainly derived from the low capacity of electrode materials (<150 mAh g-1) and the limited voltage window of aqueous electrolyte (<1.8 V). The latter could be conquered by the water-in-salt electrolyte, and the operating voltage > 3V could be obtained1. But the capacity of electrode materials still needs to be enhanced.
Due to the high capacity of metal zinc anode (820 mAh g-1), aqueous Zinc-ion battery based on Zn2+ storage cathode and metal Zn anode holds immense potential to achieve high capacity. But the capacity of cathode still has much room for improvement. As the most used cathode materials for zinc-ion battery, manganese oxides exhibit high theoretical capacity (308 mAh g-1), low cost and low toxicity. Various manganese dioxides, including the α-MnO2, β-MnO2, γ-MnO2, δ-MnO2, etc. have been reported as host materials for Zn2+/H+ insertion in the mild aqueous electrolyte. However, all the crystalline form of manganese oxides undergo structure transformation to layered structure with interlaminar water molecules during zinc-ion insertion, leading to capacity fading of the cell. And the cycling stability of manganese oxides decreases dramatically when cycled at high depth of discharge2.
In this work, we proposed novel polyaniline-intercalated MnO2 nanolayers as a high performance cathode material for zinc-ion battery, which is prepared by a simple one-step inorganic/organic interface reaction3. With the typical nano-size (approximately 10 nm), expanded interlayer space, uniform meso-structure and polymer-reinforced layered structure, the polyaniline-intercalated MnO2 nanolayers show a high rate performance and excellent cycle stability at high charge/discharge depth (200 stable cycles with capacity of 280 mAh g-1, corresponding 90.9% utilization of theoretical capacity of 308 mAh g-1), which is much superior to previous reports. The polyaniline-reinforced layered structure efficiently eliminate the hydrated H+/Zn2+-insertion-induced phase transformation and the subsequent structure collapse, which is important to achieve long cycle life and high utilization simultaneously. In addition, a H+/Zn2+ co-insertion process in the layered MnO2 was proposed, and a self-regulating mechanism of electrolyte involving generation/dissolution of flake-like zinc hydroxide sulfate was clarified.

Reference:

1 C. Yang, J. Chen, T. Qing, X. Fan, W. Sun, A. von Cresce, M.S. Ding, O. Borodin, J. Vatamanu, M.A. Schroeder, N. Eidson, C. Wang, and K. Xu, Joule, 1, 122 (2017).
2 J. Huang, Z. Guo, Y. Ma, D. Bin, Y. Wang, and Y. Xia, Small methods, 1800272 (2018).
3 J. Huang, Z. Wang, M. Hou, X. Dong, Y. Liu, Y. Wang, and Y. Xia, Nature Communications, 9, 2906 (2018).