Lithium-ion batteries (LIBs) continue to draw vast attention as a promising energy storage technology due to their high energy density, low self-discharge property, nearly zero-memory effect, high open circuit voltage, and long lifespan. In particular, high-energy density lithium-ion batteries are considered as the ideal power source for electric vehicles (EVs) and hybrid electric vehicles (HEVs) in the automotive industry, in recent years. This review discusses key aspects of the present and the future battery technologies on the basis of the working electrode. We then discuss how lithium-ion batteries evolve to meet the growing demand on high charge capacity and electrode stability. An account of a stand-alone energy device (off-grid system) that combines an energy harvesting technology with a lithium-ion battery is also provided. The main discussion is categorized into three perspectives such as the evolution from the conventional to the advanced LIBs (e.g., Li-rich transition metal oxide and Ni-rich transition metal oxide batteries), to the state-of-the-art LIBs (e.g., Li–air, Li–sulfur batteries, organic electrode batteries, solid-state batteries, and Li–CO2 batteries), and to the hybridized LIBs (e.g., metal halide perovskite batteries).

Lithium-ion batteries: outlook on present, future, and hybridized technologies

Lithium- and manganese-rich layered electrode materials, represented by the general formula xLi2MnO3·(1 − x)LiMO2 in which M is Mn, Ni, and Co, are of interest for both high-power and high-capacity lithium ion cells. In this paper, the synthesis, structural and electrochemical characterization of xLi2MnO3·(1 − x)LiMn0.333Ni0.333Co0.333O2 electrodes over a wide compositional range (0 ≤ x ≤ 0.7) is explored. Changes that occur to the compositional, structural, and electrochemical properties of the electrodes as a function of x and the importance of using a relatively high manganese content and a high charging potential (>4.4 V) to generate high capacity (>200 mAh/g) electrodes are highlighted. Particular attention is given to the electrode composition 0.3Li2MnO3·0.7LiMn0.333Ni0.333Co0.333O2 (x = 0.3) which, if completely delithiated during charge, yields Mn0.533Ni0.233Co0.233O2, in which the manganese ions are tetravalent and, when fully discharged, LiMn0.533Ni0.233Co0.233O2, in which the average manganese ...

Synthesis, Characterization and Electrochemistry of Lithium Battery Electrodes: xLi2MnO3·(1 − x)LiMn0.333Ni0.333Co0.333O2 (0 ≤ x ≤ 0.7)

https://iopscience.iop.org/article/10.1149/2.0351701jes/pdf

Review—Recent Advances and Remaining Challenges for Lithium Ion Battery Cathodes I. Nickel-Rich, LiNixCoyMnzO2

Structural transformation of a lithium-rich Li1.2Co0.1Mn0.55Ni0.15O2 cathode during high voltage cycling resolved by in situ X-ray diffraction

Development and discovery of cathode materials with superior performance seem to be tremendous challenges for Li-ion battery scientists. Since the topotactic reaction was first demonstrated in the 1970s, layered Li transition metal oxides (LiMO2, M = Co, Ni, Mn) have been a shining star throughout the research and innovation in intercalation materials due to their appealing merits. Generally the basic LiMO2 with a single kind of transition metal ion suffers from safety concerns and structural instability and can not support high energy Li-ion batteries. Nowadays, Li-stoichiometric mixed metal oxides and Li-excess Mn-based oxides have been considered as the most promising families of cathode materials for large-scale Li-ion batteries with high energy density used for transportation. In the present paper, with the help of a phase diagram tetrahedron, we provide an overview of the major developments in the field of LiMO2 cathode materials. The changes in structure during Li extraction and the phase compatibility of Li mixed metal oxides are highlighted. The latest progress in the research of Li-excess Mn-based oxides is also included.

Layered lithium transition metal oxide cathodes towards high energy lithium-ion batteries

The conversion that occurs from layered LiMnO2 to spinel on electrochemical cycling has been studied by neutron diffraction and NMR. Neutron diffraction results indicate that the tetrahedral sites in the Li layers that share faces with octahedral sites in the transition metal layers are occupied even following the first charge to 4.6 V. NMR results are consistent with the conversion from the monoclinic, Jahn−Teller distorted, to the rhombohedral, layered phase on charging. On subsequent discharging, clear evidence for the monoclinic phase is seen by NMR indicating the presence of Jahn−Teller distorted domains in the material at 3.5 V and below. The fraction of monoclinic phase decreases gradually as a function of cycle number and disappears by 35 charge−discharge cycles. Diffraction patterns obtained as a function of cycle number were refined with a structural model that included both a layered phase (with octahedral and tetrahedral site occupancy) and a spinel phase, with the fraction of spinel increasin...

Combined Neutron Diffraction, NMR, and Electrochemical Investigation of the Layered-to-Spinel Transformation in LiMnO2

The conversion upon electrochemical cycling from a layered structure to a spinel in nonstoichiometric LixMnyO2 has been studied by neutron diffraction and NMR. This process occurs in all layered lithium manganate materials, irrespective of the ion-exchange route. The high temperature of the ion exchange under reflux in n-hexanol is sufficient to promote formation of some spinel within the as-synthesized material. Upon cycling, all the different layered LixMnyO2 compounds begin to transform to a spinel. In the first 50 or so cycles, the various layered LixMnyO2 compounds behave rather differently, with a higher spinel fraction being observed for materials ion-exchanged under more extreme conditions. However, the rate of this transformation is significantly slower than was observed in stoichiometric layered LiMnO2, with only 25% spinel observed after 100 cycles. Ultimately, upon extended cycling, the entire structure will form a well-ordered spinel phase.

Structural evolution of layered LixMnyO2 : Combined neutron, NMR, and electrochemical study

Earthabundant Na 0.67 [Mn 1xMg x]O 2 (0 ≤ x ≤ 0.2) cathode materials with the P2 structure have been synthesized as positive electrodes for sodiumion batteries. Na 0.67 MnO 2 exhibits a capacity of 175 mAh g 1 with good capacity retention. A Mg content of 5 % is sufficient to smooth the charge/discharge profiles without affecting the capacity, whilst further increasing the Mg content improves the cycling stability, but at the expense of a lower discharge capacity (~ 150 mAh g 1Na 0.67 Mn 0.8 Mg 0.2 O2). It was observed that the

Na 0.67 Mn 1x Mg x O 2 (0 ≤ x ≤ 0.2): A High Capacity Cathode for SodiumIon Batteries

Abstract While a relationship between ballast and carbon in sedimenting particles has been well-documented, the mechanistic basis of this interaction is still under debate. One hypothesis is that mineral ballast protects sinking organic matter from degradation. To test this idea, we undertook a laboratory experiment using the diatom Skeletonema marinoi to study in parallel the dissolution of one of the most common mineral ballasts, biogenic silica (bSiO2), and the associated degradation of organic matter. Three different models were applied to our results to help elucidate the mechanisms driving bSiO2 dissolution and organic compound degradation. Results of this modeling exercise suggest that the diatom frustule is made up of two bSiO2 phases that dissolve simultaneously, but at different rates. In our experiments, the first phase was more soluble ( k bSiO 2 = 0.27 d - 1 ) and made up 31% of the total bSiO2. In this phase, bSiO2 was mainly associated with membrane lipids and the amino acids glutamic acid, tyrosine, and leucine. The second phase was more refractory ( k bSiO 2 = 0.016 d - 1 ), and contained more neutral lipid alcohols and glycine. Until it dissolved, the first bSiO2 phase effectively protected much of the organic matter from degradation: particulate organic carbon (POC) degradation rate constants increased from 0.025 to 0.082 d−1 after the total dissolution of this phase, and particulate organic nitrogen (PON) degradation rate constants increased from 0.030 to 0.094 d−1. Similar to POC and PON, the total hydrolyzable amino acids (THAA) degradation rate constant increased from 0.054 to 0.139 d−1 after dissolution of the first bSiO2 phase. The higher THAA degradation rate constant is attributed to a pool of amino acids that was produced during silicification and enclosed between the two silica phases. This pool of amino acids might come from the incorporation of silica deposition vesicles into the diatom wall and might not be directly associated with bSiO2. In contrast, most lipid degradation was not prevented by association with the more soluble bSiO2 phase, as the average lipid degradation rate constant decreased from 0.048 to 0.010 d−1 after 17 d of degradation. This suggests that most lipids were associated with rather than protected by silica, except pigments that appeared resistant to degradation, independently from silica dissolution. When the only organic compounds remaining were associated with the second bSiO2 phase, degradation rate constants decreased greatly; concentrations changed only slightly after day 25.

A. Robert Armstrong

Papers

Combined Neutron Diffraction, NMR, and Electrochemical Investigation of the Layered-to-Spinel Transformation in LiMnO2

Structural evolution of layered LixMnyO2 : Combined neutron, NMR, and electrochemical study

Na 0.67 Mn 1x Mg x O 2 (0 ≤ x ≤ 0.2): A High Capacity Cathode for SodiumIon Batteries

SI-OC Interactions during degradation of the diatom Skeletonema marinoï

Composition and degradation of sinking particles with different settling velocities