Air- and Moisture Robust Surface Modification for Ni-Rich Layered Cathode Materials for Li-Ion Batteries.

The mainstream of high-energy cathode development is focused on increasing the Ni-ratio in layered structured cathode materials. The increment of the Ni portion in the layered cathode material escalates not only the deliverable capacity but also the structural degradation. High-Ni layered cathodes are highly vulnerable to exposure to air that contains CO2 and H2 O, forming problematic residual lithium compounds at the surface. In this work, a novel air- and moisture robust surface modification is reported for LiNi0.8 Co0.1 Mn0.1 O2 (NCM811) via the sol-gel coating method that selectively coats the internal surface area of the polycrystalline morphology secondary particles. Bare-, Li2 SnO3 -coated and LiCoO2 -coated NCM811 are exposed to different ambient environments (air, hot-air, and moisture-air) to systematically investigate the correlation between the internal/external coating morphology and performance degradations. The LiCoO2 -coated NCM811s exhibit high-capacity retention after exposure to all environments, due to the internal surface coating that prevents the penetration of harmful compounds into the polycrystalline NCM811. On the other hand, the Li2 SnO3 -coated NCM811s exposed to the ambient environments show gradual capacity fading, implying the occurrence of internal degradation. This paper highlights the impact of the internal degradation of polycrystalline NCM811 after environmental exposure and the correct coating mechanisms required to successfully prevent it.

Analysis of Electrochemical Performance with Dispersion Degree of CNTs in Electrode According to Ultrasonication Process and Slurry Viscosity for Lithium-Ion Battery.

Lithium-ion batteries (LIBs) continue to dominate the battery market with their efficient energy storage abilities and their ongoing development. However, at high charge/discharge C-rates their electrochemical performance decreases significantly. To improve the power density properties of LIBs, it is important to form a uniform electron transfer network in the cathode electrode via the addition of conductive additives. Carbon nanotubes (CNTs) with high crystallinity, high electrical conductivity, and high aspect ratio properties have gathered significant interest as cathode electrode conductive additives. However, due to the high aggregational properties of CNTs, it is difficult to form a uniform network for electron transfer within the electrode. In this study, to help fabricate electrodes with well-dispersed CNTs, various electrodes were prepared by controlling (i) the mixing order of the conductive material, binder, and active material, and (ii) the sonication process of the CNTs/NMP solution before the electrode slurry preparation. When the binder was mixed with a well sonicated CNTs/NMP solution, the CNTs uniformly adsorbed to the then added cathode material of LiNi0.6Co0.2Mn0.2O2 and were well-dispersed to form a flowing uniform network. This electrode fabrication process achieved > 98.74% capacity retention after 50 cycles at 5C via suppressed polarization at high current densities and a more reversible H1-M phase transition of the active material. Our study presents a novel design benchmark for the fabricating of electrodes applying well-dispersed CNTs, which can facilitate the application of LIBs in high current density applications.

Development of High-Energy Anodes for All-Solid-State Lithium Batteries Based on Sulfide Electrolytes.

All-solid-state Li batteries (ASSBs) promise better performance and higher safety than the current liquid-based Li-ion batteries (LIBs). Sulfide ASSBs have been extensively studied and considerably advanced in recent decades. Research on identifying suitable cathode materials for sulfide ASSBs is currently well established, with great progress being made in the commercialization of layered cathodes in the liquid-based LIBs. Research on anode materials for sulfide ASSBs is of great importance for enhancing the battery energy density. However, it seems that little has been published that summarizes studies of anode materials for sulfide ASSBs and suggests future research directions. Thus, within this Minireview, we aim to provide an overview of previous and current research focused on anode materials for sulfide ASSBs and to suggest a future research direction for developing suitable anode systems for sulfide ASSBs.

Nanosized and metastable molybdenum oxides as negative electrode materials for durable high-energy aqueous Li-ion batteries.

The development of inherently safe energy devices is a key challenge, and aqueous Li-ion batteries draw large attention for this purpose. Due to the narrow electrochemical stable potential window of aqueous electrolytes, the energy density and the selection of negative electrode materials are significantly limited. For achieving durable and high-energy aqueous Li-ion batteries, the development of negative electrode materials exhibiting a large capacity and low potential without triggering decomposition of water is crucial. Herein, a type of a negative electrode material (i.e., Li x Nb2/7Mo3/7O2) is proposed for high-energy aqueous Li-ion batteries. Li x Nb2/7Mo3/7O2 delivers a large capacity of ∼170 mA ⋅ h ⋅ g-1 with a low operating potential range of 1.9 to 2.8 versus Li/Li+ in 21 m lithium bis(trifluoromethanesulfonyl)amide (LiTFSA) aqueous electrolyte. A full cell consisting of Li1.05Mn1.95O4/Li9/7Nb2/7Mo3/7O2 presents high energy density of 107 W ⋅ h ⋅ kg-1 as the maximum value in 21 m LiTFSA aqueous electrolyte, and 73% in capacity retention is achieved after 2,000 cycles. Furthermore, hard X-ray photoelectron spectroscopy study reveals that a protective surface layer is formed at the surface of the negative electrode, by which the high-energy and durable aqueous batteries are realized with Li x Nb2/7Mo3/7O2 This work combines a high capacity with a safe negative electrode material through delivering the Mo-based oxide with unique nanosized and metastable characters.

Multiple Potentials of Maximum Entropy for a Na2Co[Fe(CN)6] Battery Electrode Material: Does the Electrolyte Composition Control the Interface?

Development of efficient schemes of energy storage is crucial for finding a solution for the "generation versus consumption" problem. Aqueous Na-ion batteries have been already recognized as one of the promising candidates for large-scale energy-storage systems. Despite noticeable progress in this field, the actual intercalation mechanisms governing these battery cells are yet to be fully comprehended. In this manuscript, we examine the electrode/electrolyte interface formed between electrodeposited Na2Co[Fe(CN)6] films and aqueous solutions. The investigated systems exhibit up to three potentials of maximum entropy (PMEs). To the best of our knowledge, the existence of multiple PMEs in electrochemical systems has never been reported in the literature. These unexpected results are, however, in line with the theory explaining the correlation between the water structure at the interface and the ease of the interfacial mass and charge transfer. Additionally, the obtained PMEs appear to largely depend on the anions' properties, most probably on the hydration energy of these species. This reveals the impact of the electrolyte composition on the interfacial processes in Na-ion batteries.

Multistage Mechanism of Lithium Intercalation into Graphite Anodes in the Presence of the Solid Electrolyte Interface.

A so-called solid electrolyte interface (SEI) in a lithium-ion battery largely determines the performance of the whole system. However, it is one of the least understood objects in these types of batteries. SEIs are formed during the initial charge-discharge cycles, prevent the organic electrolytes from further decomposition, and at the same time govern lithium intercalation into the graphite anodes. In this work, we use electrochemical impedance spectroscopy and atomic force microscopy to investigate the properties of a SEI film and an electrified "graphite/SEI/electrolyte interface". We reveal a multistage mechanism of lithium intercalation and de-intercalation in the case of graphite anodes covered by SEI. On the basis of this mechanism, we propose a relatively simple model, which perfectly explains the impedance response of the "graphite/SEI/electrolyte" interface at different temperatures and states of charge. From the whole data obtained in this work, it is suggested that not only Li+ but also negatively charged species, such as anions from the electrolyte or functional groups of the SEI, likely interact with the surface of the graphite anode.

Chromium(II) Hexacyanoferrate-Based Thin Films as a Material for Aqueous Alkali Metal Cation Batteries.

Identification and characterization of novel battery electrode materials are key factors in transitioning the grids to renewable energy provision. Given the scale of the challenge, special attention should be paid to safety and availability of resources. This paper presents a new electrode material for aqueous batteries and supercapacitors based on highly available resources: chromium(II) hexacyanoferrate (CrHCF) thin films. Electrodeposited CrHCF exhibited "half-charge" potentials (E 1/2) of ∼0.69 and ∼0.72 V versus silver/silver chloride (reference electrode) for Na and K intercalation, respectively, a high specific capacity of ∼88 mA h/g (10 C), and a good rate performance at fast C-rate (360 C). The electrolyte composition significantly influences the long-term cycling stability of the CrHCF electrodes and the choice of the intercalating alkali metal cations significantly impacts the E 1/2 potentials. Finally, a CrHCF-based symmetric cell (quasi-supercapacitor) was constructed and showed high specific energy of ∼4.6 W h/kg at 100 C.

What Do Laser-Induced Transient Techniques Reveal for Batteries? Na- and K-Intercalation from Aqueous Electrolytes as an Example.

Technological advancement has been revolutionized by rechargeable batteries, without which the use of various modern devices would not be possible. Aqueous Na ion batteries have lately garnered much attention, being recognized as a promising alternative to the commonly used Li ion batteries for the large-scale energy storage systems. However, further improvement and optimization of such systems require a more detailed understanding of intercalation mechanisms. In this work, we for the first time demonstrate the implementation of the laser-induced current transient (LICT) technique for in situ characterization of battery systems and investigate the interface between Na2Ni[Fe(CN)6] model battery electrodes and aqueous electrolytes in contact with aqueous electrolytes. Quite counterintuitively, the LICT method revealed that at the quasi-steady-state the electrode surface stays positively charged within the potential range where the intercalation/deintercalation of sodium as well as of potassium is possible, evidencing that the intercalation mechanism of the alkali-metal cations should be rather complex. Furthermore, the specific shape of the observed current transients indicates that the interfacial processes of intercalation/deintercalation have at least three different relaxation time constants. The relaxation behavior is highly influenced by the nature of the alkali-metal cations-most likely through their different solvation energy. In addition, we outline how the laser-based experiments can intensify detailed in situ investigations of battery systems.

Electrodeposited Na2VOx[Fe(CN)6] films As a Cathode Material for Aqueous Na-Ion Batteries.

The so-called Prussian blue analogues (PBAs) are spotlighted as promising cathode materials for aqueous Na-ion batteries regarding their good performance for the application in future large-scale energy storage systems. In this work, we demonstrate that one of the PBA representatives, namely Na2VOx[Fe(CN)6] thin films (VHCFs), is a promising cathode material for aqueous Na-ion batteries with very positive intercalation/deintercalation potentials, which might likely designate a new benchmark in the field. To maximize the material utilization, we have formed VHCF thin films on model current collectors from aqueous solutions. The resulting films demonstrated a very positive half-charge potential (ΔE1/2 ≈ 0.91 V vs Ag/AgCl reference electrode) in acidic media with a specific capacity of ∼80 mAh g-1 recorded at high C-rates (30 C) in 1 M LiNO3, 3 M NaNO3 and 3 M KNO3 electrolytes in the presence of 3.6 M H2SO4. It is also shown that well-known solvation effects related to the nature of the alkali metal cations during intercalation and deintercalation are surprisingly not pronounced in the case of VHCFs.

Synergistically Enhanced Electrochemical Performance of Hierarchical MoS2/TiNb2O7 Hetero-nanostructures as Anode Materials for Li-Ion Batteries.

As potential high-performance anodes for Li-ion batteries (LIBs), hierarchical heteronanostructures consisting of TiNb2O7 nanofibers and ultrathin MoS2 nanosheets (TNO@MS HRs) were synthesized by simple electrospinning/hydrothermal processes. With their growth mechanism revealed, the TNO@MS HRs exhibited an entangled structure both for their ionic and electronic conducting pathways, which enabled the synergetic combination of one- and two-dimensional structures to be realized. In the potential range of 0.001-3 V vs Li/Li+, the TNO@MS HR-based LIBs exhibited high capacities of 872 and 740 mAh g-1 after 42 and 200 cycles at a current density of 1 A g-1, respectively, and excellent rate performance of 611 mAh g-1 at 4 A g-1. We believe that the fabrication route of TNO@MS HRs will find visibility for the use of anode electrodes for high capacity LIBs at low cost.

The Mechanism of the Interfacial Charge and Mass Transfer during Intercalation of Alkali Metal Cations.

Intercalation of alkali metal cations, like Li+ or Na+, follows the same three-stage mechanism of the interfacial charge and mass transfer irrespective of the nature of the electrolyte, electrolyte composition or electrode material.