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Here, Ag x Mn 8 O 16 (Ag-OMS-2) and K x Mn 8 O 16 (K-OMS-2) were investigated as high voltage cathode materials for Mg based batteries. Both M x Mn 8 O 16 materials delivered high initial capacities (>180 mA h g –1 ), and K x Mn 8 O 16 showed high cycle stability with a reversible capacity of >170 mA h g –1 after 20 cycles.
Significant capacity loss has been observed across extended cycling of lithium-ion batteries cycled to high potential. One of the sources of capacity fade is transition metal dissolution from the cathode active material, ion migration through the electrolyte, and deposition on the solid-electrolyte interphase on the anode. While much research has been conducted on the oxidation state of the transition metal in the cathode active material or deposited on the anode, there have been limited investigations of the oxidation state of the transition metal ions dissolved in the electrolyte. Here, in this work, X-ray absorption spectroscopy has been performed on electrolytes extracted from cells built with four different cathode active materials (LiMn 2 O 4 (LMO), LiNi 0.5 Mn 1.5 O 4 (LNMO), LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811), and (x Li 2 MnO 3 *(1-x) LiNi a Mn b Co c O 2 , with a+b+c=1) (LMRNMC)) that were cycled at either high or standard potentials to determine the oxidation state of Mn and Ni in solution. Inductively coupled plasma-mass spectrometry has been performed on the anodes from these cells to determine the concentration of deposited transition metal ions. While transition metal ions were found dissolved in all electrolytes, the oxidation state(s) of Mn and Ni were determined to be dependent on the cathode material and independent of cycling potential.
Mechanical integrity issues such as particle cracking are considered one of the leading causes of structural deterioration and limited long-term cycle stability for Ni-rich cathode materials of Li-ion batteries. Indeed, the detrimental effects generated from the crack formation are not yet entirely addressed. Here, applying physicochemical and electrochemical ex situ and in situ characterizations, the effect of Co and Mn on the mechanical properties of the Ni-rich material are thoroughly investigated. As a result, we successfully mitigate the particle cracking issue in Ni-rich cathodes via rational concentration gradient design without sacrificing the electrode capacity. Our result reveals that the Co-enriched surface design in Ni-rich particles benefits from its low stiffness, which can effectively suppress the formation of particle cracking. Meanwhile, the Mn-enriched core limits internal expansion and improve structural integrity. The concentration gradient design also promotes morphological stability and cycling performances in Li metal coin cell configuration.
Abstract Significant capacity loss has been observed across extended cycling of lithium‐ion batteries cycled to high potential. One of the sources of capacity fade is transition metal dissolution from the cathode active material, ion migration through the electrolyte, and deposition on the solid‐electrolyte interphase on the anode. While much research has been conducted on the oxidation state of the transition metal in the cathode active material or deposited on the anode, there have been limited investigations of the oxidation state of the transition metal ions dissolved in the electrolyte. In this work, X‐ray absorption spectroscopy has been performed on electrolytes extracted from cells built with four different cathode active materials (LiMn 2 O 4 (LMO), LiNi 0.5 Mn 1.5 O 4 (LNMO), LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811), and (x Li 2 MnO 3 *(1‐x) LiNi a Mn b Co c O 2 , with a+b+ c =1) (LMRNMC)) that were cycled at either high or standard potentials to determine the oxidation state of Mn and Ni in solution. Inductively coupled plasma‐mass spectrometry has been performed on the anodes from these cells to determine the concentration of deposited transition metal ions. While transition metal ions were found dissolved in all electrolytes, the oxidation state(s) of Mn and Ni were determined to be dependent on the cathode material and independent of cycling potential.
Microbial electrosynthesis is a promising strategy for the microbial conversion of carbon dioxide to transportation fuels and other organic commodities, but optimization of this process is required for commercialization. Cathodes which enhance electrode-microbe electron transfer might improve rates of product formation. To evaluate this possibility, biofilms of Sporomusa ovata, which are effective in acetate electrosynthesis, were grown on a range of cathode materials and acetate production was monitored over time. Modifications of carbon cloth that resulted in a positive-charge enhanced microbial electrosynthesis. Functionalization with chitosan or cyanuric chloride increased acetate production rates 6-7 fold and modification with 3-aminopropyltriethoxysilane gave rates 3-fold higher than untreated controls. A 3-fold increase in electrosynthesis over untreated carbon cloth cathodes was also achieved with polyaniline cathodes. However, not all strategies to provide positively charged surfaces were successful, as treatment of carbon cloth with melamine or ammonia gas did not stimulate acetate electrosynthesis. Treating carbon cloth with metal, in particular gold, palladium, or nickel nanoparticles, also promoted electrosynthesis, yielding electrosynthesis rates that were 6-,4.7- or 4.5-fold faster than the untreated control, respectively. Cathodes comprised of cotton or polyester fabric treated with carbon nanotubes yielded cathodes that supported acetate electrosynthesis rates that were similar to 3-fold higher than carbon cloth controls. Recovery of electrons consumed in acetate was similar to 80% for all materials. The results demonstrate that one approach to increase rates of carbon dioxide reduction in microbial electrosynthesis is to modify cathode surfaces to improve microbe-electrode interactions.
Aiming at the comprehensive understanding of the single sulfur poisoning effect and, eventually, the multiple impurities poisoning phenomena on the SOFC (Solid Oxide Fuel Cell) cathode materials, the sulfur poisoning effect on the (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 3 (LSCF-6428) has been investigated in the presence of 10 ppm SO 2 at 800, 900, and 1000°C, respectively, with a combined computational and experimental approach. The good agreement between the CALPHAD (Computer Coupling of Phase Diagrams and Thermochemistry) simulations and the XRD (X-Ray Diffraction), SEM (Scanning Electron Microscopy), and TEM (Transmission Electron Microscopy) characterization results support the reliability of the CALPHAD approach in the SOFC field. Furthermore, comprehensive simulations were made to understand the impact of temperature, P(SO 2 ), P(O 2 ), and Sr concentration on the threshold of SrSO 4 stability. Results showed that the formation of SrSO4 is thermodynamically favored at lower temperatures, higher P(SO 2 ), higher P(O 2 ), and higher Sr concentration. Finally, comparisons were also made between LSCF-6428 and LSM20 (La 0.8 Sr 0.2 MnO 3 ) using simulations, which confirmed that LSCF-6428 is a poor sulfur-tolerant cathode, in agreement with the literature.
Sodium ion batteries offer a low-cost, sustainable, and environment-friendly solution to large-scale electrochemical energy storage systems. Layered oxides represent a family of promising cathode materials with a potential to improve the energy and power densities while reducing the material cost of sodium ion batteries. However, due to the chemical and structural instability of layered oxides in an aqueous solution, the current battery electrode manufacturing requires expensive and hazardous organic solvents, which impedes the full benefit of the low-cost, sustainable, and eco-friendly advantages. We need an effective technology that empowers a cathode with water processable properties. In this study, we set a representative example, P2-Na0.67Ni0.22Cu0.11Mn0.56Ti0.11O2, to explore its performance under water-processing conditions. This material achieves a discharge capacity of 180 mAh/g and a discharge energy of 544 Wh/kg at 22 ?C. The aging experiments indicate its superior stability against water, having negligible bulk 2 structural or chemical changes. The surface sensitive soft X-ray absorption spectroscopy shows that the P2-Na0.67Ni0.22Cu0.11Mn0.56Ti0.11O2 has stable surface chemistry in the aqueous solution. Moreover, the cells with water-processed cathodes delivered stable cycling performance with minor voltage decay, originating from the decreased cell impedance. Therefore, the present study sets a refined example to establish a low-cost, sustainable, and eco-friendly solution by developing water-processable electrode materials for sodium ion batteries.
Potassium-ion batteries have recently attracted considerable attention as cost-effective alternatives to lithium-ion batteries for large-scale energy storage. However, a major obstacle to the practical application of this emerging technology is the lack of suitable cathode materials that are capable of delivering high gravimetric/volumetric energy, stable cycle life, and high rate capability. Here in this review article, we review the recent progress in cathodes development for potassium-ion batteries. These materials are categorized into four types: layered oxides, Prussian blue analogs, poly-anion, and organic compounds. Based on our critical review of the reported literature, we identify poly-anion compounds as a class of promising candidates among all types and provide suggestions for future optimization.
There is a growing appreciation for the role of surface reactivity and subsequent reconstruction affecting the performance of high-voltage, high-capacity Li-ion cathode materials. In particular, the promising Li-excess materials are known to exhibit significant vulnerability toward oxygen release, which can cause surface densification and impede Li intercalation. In this work, we focus on the end member, Li 2 MnO 3 , as a Li-excess, Mn-rich representative of this class of materials and systematically elucidate all possible stoichiometric low Miller index surfaces with various cation ordering on each surface. We apply surface cation reconstruction rules that depend on the local environment, including target Mn-Li site exchanges, and optimize the resulting surface Li configurations using metadynamics. The equilibrium Wulff shape shows dominant (001), (010) surface facets, and almost all facets exhibit favorable Mn reconstruction. Most importantly, we find that while all equilibrium Li x MnO 3 surfaces become unstable toward oxygen release for x < 1.7, some facets are consistently more resistant than others which may provide a design metric for more stable particle morphologies and enhanced surface oxygen retention.
Despite several reports on the surface phase transformations from a layered to a disordered spinel and a rock-salt structure at the surface of the Ni-rich cathodes, the precise structures and compositions of these surface phases are unknown. The phenomenon, in itself, is complex and involves the participation of several contributing factors. Of these factors, transition metal (TM) ion migration toward the interior of the particle and hence formation of TM-densified surface layers, triggered by oxygen loss, is thermodynamically probable. Here in this study, we simulate the thermodynamic phase equilibria as a function of TM ion content in the cathode material in the context of lithium nickel oxides, using a combined approach of first-principles density functional calculations, the cluster expansion method, and grand canonical Monte Carlo simulations. We developed a unified lattice Hamiltonian that accommodates not only rock-salt like structures but also topologically different spinel-like structures. Also, our model provides a foundation to investigate metastable cation compositions and kinetics of the phase transformations. Our investigations predict the existence of several Ni-rich phases that were, to date, unknown in the scientific literature. Our simulated phase diagrams at finite temperature show a very low solubility range of the prototype spinel phase. Finally, we find a partially disordered spinel-like phase with far greater solubility that is expected to show very different Li diffusivity compared to that of the prototype spinel structure.
A modified cluster-expansion treatment was developed recently to analyze atomic order in LiCo y Ni 1-y O 2 , a model cathode material for Li-ion batteries. In this treatment, referred to as a “spin-atom” cluster expansion, the occupant of a lattice site is identified by its spin state as well as its atomic species. Further, Effective Cluster Interaction (ECI) coefficients are derived from a large training data set (i.e., the set of atomic arrangements for which DFT calculations are performed) which is filtered by an anomaly detection algorithm to eliminate poorly converged DFT calculations. The cluster expansion incorporates Li-Ni (LN) exchange as well as intralayer Co-Ni (CN) exchange. Monte Carlo simulations based on the cluster expansion were applied to the Ni-rich part of the phase diagram. The simulations predict a miscibility gap between y = 0.05 and y = 0.65.
Rechargeable Ca-based batteries can potentially achieve higher energy capacity than Li-ion batteries. The development of Ca-ion batteries, however, remains in its infancy, especially due to the challenge of finding cathode materials with high reversible capacity. In this work, we investigate properties of Ca cobaltites as Ca-ion intercalation cathodes, by means of density functional theory calculations validated by synthesis and electrochemical measurements. Computationally, we accessed thermodynamic, diffusion properties, energy capacity, and the voltage profiles for four Ca cobaltite compounds of different stoichiometry and Co oxidation states: Ca 3 Co 2 O 6 , CaCo 2 O 4 , Ca 2 Co 2 O 5 , and [Ca 2 CoO 3 ][CoO 2 ] 1.62 . We found good stability and relatively low migration barriers of some Ca cobaltites during cycling with the layered CaCo 2 O 4 having the lowest Ca migration barrier of 0.7 eV and the highest theoretical capacity. To validate our calculations, we synthesized Ca 3 Co 2 O 6 , CaCo 2 O 4 , and [Ca 2 CoO 3 ][CoO 2 ] 1.62 with the Pechini method and, subsequently, to test the electrochemical extraction of Ca.
Mechanical degradation of Li-ion batteries caused by the repetitive swelling and shrinking of electrodes upon electrochemical cycles is now well recognized. Structural disintegration of the state-of-art cathode materials of a hierarchical structure is relatively less studied. In this paper, we track the microstructural evolution of different marked regimes in LiNi x Mn y Co z O 2 (NMC) electrodes after lithiation cycles. Decohesion of primary particles constitutes the major mechanical degradation in the NMC materials, which results in the loss of connectivity of the conductive network and impedance increase. We find that the structural disintegration is largely dependent on the charging rate – slow charging causes more damage, and is relatively insensitive to the cyclic voltage window. We use finite element modeling to study the evolution of Li concentration and stresses in a NMC secondary particle and employ the cohesive zone model to simulate the interfacial fracture between primary particles. Finally, we reveal that microcracks accumulate and propagate during the cyclic lithiation and delithiation at a slow charging rate.
Highlights: • Nanostructured Na{sub 1.08}V{sub 6}O{sub 15} was synthesized through additive-free sol-gel process. • Prepared Na{sub 1.08}V{sub 6}O{sub 15} demonstrated high capacity and sufficient cycling stability. • The reaction temperature was optimized to allow scalable Na{sub 1.08}V{sub 6}O{sub 15} fabrication. - Abstract: Developing high-capacity cathode material with feasibility and scalability is still challenging for lithium-ion batteries (LIBs). In this study, a high-capacity ternary sodium vanadate compound, nanostructured NaV{sub 6}O{sub 15}, was template-free synthesized through sol-gel process with high producing efficiency. The as-prepared sample was systematically post-treated at different temperature and the post-annealing temperature was found to determine the cycling stability and capacity of NaV{sub 6}O{sub 15}. The well-crystallized one exhibited good electrochemical performance with a high specific capacity of 302 mAh g{sup −1} when cycled at current density of 0.03 mA g{sup −1}. Its relatively long-term cycling stability was characterized by the cell performance under the current density of 1 A g{sup −1}, delivering a reversible capacity of 118 mAh g{sup −1} after 300 cycles with 79% capacity retention and nearly 100% coulombic efficiency: all demonstrating its significant promise of proposed strategy for large-scale synthesis of NaV{sub 6}O{sub 15} as cathode with high-capacity and high energy density for LIBs.
Using air-stable lithium cobalt oxide (LCO) as a prototypical system, we elucidate the role of crystallographic orientation and anisotropic transport in atom probe tomography (APT) for lithium transition metal oxide (LTMO) cathode materials.
In this work, a series of ordered rocksalt (OR) type Li-rich Li 2 Ru 1–x Ni x O 3-δ (LRN x O, 0.3 ≤ x ≤ 0.5) are successfully synthesized and investigated for the first time. X-ray diffraction and neutron powder diffraction patterns exhibit an obvious phase transition from layered to an OR structure as the Ni content gradually increases from x = 0 to x = 0.5, which leads to different electrochemical behaviors. In the case of OR-LRN 0.4 O, an ~350 mV decrease of the oxygen oxidation potential compared with Li 2 RuO 3 (LRO) is observed from around 4.2 to 3.85 V, which is confirmed by both X-ray photelectron O 1s spectra and dQ/dV results. Additionally, the role of Ni substitution on the oxygen redox reaction is studied by first-principles calculations, and it is concluded that the formation of the OR structure caused by Ni substitution is the main reason for lowering the oxygen oxidation potential. In addition, the average discharge voltage of OR-LRN 0.4 O is also enhanced compared with LRO. This work provides a novel innovative strategy to modulate and control the oxygen anion redox reaction for high-energy-density Li-rich materials, which shed light on the fundamental understanding and optimizing of the anion redox process in Li-rich materials.
Provided is a rechargeable alkali metal-sulfur cell comprising an anode active material layer, an electrolyte, and a cathode active material layer comprising multiple particulates, wherein at least one of the particulates comprises one or a plurality of sulfur-containing material particles being embraced or encapsulated by a thin layer of a conductive sulfonated elastomer composite having from 0.01% to 50% by weight of a conductive reinforcement material dispersed in a sulfonated elastomeric matrix material, wherein the conductive reinforcement material is selected from graphene sheets, carbon nanotubes, carbon nanofibers, metal nanowires, conductive polymer fibers, or a combination thereof and the composite has a recoverable tensile strain from 2% to 500%, a lithium ion conductivity from 10−7 S/cm to 5×10−2 S/cm, and a thickness from 0.5 nm to 10 μm. This battery exhibits an excellent combination of high sulfur content, high sulfur utilization efficiency, high energy density, and long cycle life.
Redox phase transformations are relevant to a number of metrics pertaining to the electrochemical performance of batteries. These phase transformations deviate from and are more complicated than the conventional theory of phase nucleation and propagation, owing to simultaneous changes of cationic and anionic valence states as well as the polycrystalline nature of battery materials. Herein, we propose an integrative approach of mapping valence states and constructing chemical topographies to investigate the redox phase transformation in polycrystalline layered oxide cathode materials under thermal abuse conditions. We discover that, in addition to the three-dimensional heterogeneous phase transformation, there is a mesoscale evolution of local valence curvatures in valence state topographies. The relative probability of negative and positive local valence curvatures alternates during the layered-to-spinel/rocksalt phase transformation. In conclusion, the implementation of our method can potentially provide a universal approach to study phase transformation behaviors in battery materials and beyond.