Lithium versus Mono/Polyvalent Ion Intercalation: Hybrid Metal Ion Systems for Energy Storage (original) (raw)
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Intercalation reaction in lithium-ion battery: effect on cell characteristics
The International Journal of Materials and Engineering Technology (TIJMET), 2023
Lithium-ion batteries (LIBs) are vital components in mobile devices and electric vehicles (EVs) due to their high energy density and long lifespan. However, to meet the rising demand for electrical devices, LIB energy density must be improved further. Anode materials, as a key component of lithium batteries, significantly improve overall energy density. LIBs are a widely utilized electrochemical power source in EVs and energy storage. LIBs have proven to be consistent because of their superior power density, which is directly related to the type of cathode, and extended lifespan in comparison to other types of rechargeable batteries. LIBs are developed with suitable electrolytes through a complex pathway that almost parallels advances in electrode chemistry. This work concentrates on the intercalation of alkali metal ions (Li +) into graphite, summarizing the important advances from experiments and theoretical calculations that underlie the close host-guest relationships and their underlying mechanics. This study elucidates the effect of the intercalation mechanism on the electrode surface to achieve high-performance LIBs. Lithium metal ions in graphite are intercalated into monovalent and multivalent ions in layered electrode materials. This will result in a better understanding of intercalation chemistry in host materials for storage and conversion applications. This review emphasizes the impact of lithium intercalation chemistry on the battery cell using different types of electrode materials to improve its performance. It also studies the influence of the electrode properties on the LIB technology.
Energy Environ. …, 2011
To evaluate the potential of Na-ion batteries, we contrast in this work the difference between Na-ion and Li-ion based intercalation chemistries in terms of three key battery properties-voltage, phase stability and diffusion barriers. The compounds investigated comprise the layered AMO 2 and AMS 2 structures, the olivine and maricite AMPO 4 structures, and the NASICON A 3 V 2 (PO 4 ) 3 structures. The calculated Na voltages for the compounds investigated are 0.18-0.57 V lower than that of the corresponding Li voltages, in agreement with previous experimental data. We believe the observed lower voltages for Na compounds are predominantly a cathodic effect related to the much smaller energy gain from inserting Na into the host structure compared to inserting Li. We also found a relatively strong dependence of battery properties on structural features. In general, the difference between the Na and Li voltage of the same structure, DV Na-Li , is less negative for the maricite structures preferred by Na, and more negative for the olivine structures preferred by Li. The layered compounds have the most negative DV Na-Li . In terms of phase stability, we found that open structures, such as the layered and NASICON structures, that are better able to accommodate the larger Na + ion generally have both Na and Li versions of the same compound. For the close-packed AMPO 4 structures, our results show that Na generally prefers the maricite structure, while Li prefers the olivine structure, in agreement with previous experimental work. We also found surprising evidence that the barriers for Na + migration can potentially be lower than that for Li + migration in the layered structures. Overall, our findings indicate that Na-ion systems can be competitive with Li-ion systems.
Nano letters, 2015
Intercalation of ions in electrode materials has been explored to improve the rate capability in lithium batteries and supercapacitors, due to the enhanced diffusion of Li(+) or electrolyte cations. Here, we describe a synergistic effect between crystal structure and intercalated ion by experimental characterization and ab initio calculations, based on more than 20 nanomaterials: five typical cathode materials together with their alkali metal ion intercalation compounds A-M-O (A = Li, Na, K, Rb; M = V, Mo, Co, Mn, Fe-P). Our focus on nanowires is motivated by general enhancements afforded by nanoscale structures that better sustain lattice distortions associated with charge/discharge cycles. We show that preintercalation of alkali metal ions in V-O and Mo-O yields substantial improvement in the Li ion charge/discharge cycling and rate, compared to A-Co-O, A-Mn-O, and A-Fe-P-O. Diffraction and modeling studies reveal that preintercalation with K and Rb ions yields a more stable inter...
Fast Diffusion of Multivalent Ions Facilitated by Concerted Interactions in Dual-Ion Battery Systems
Advanced Energy Materials, 2018
Seemingly, existing LIB knowledge and technology can be used for similarly structured multivalent-ion batteries. However, when constructing multivalent-ion batteries, we have to overcome many difficulties that arise from the unclear nature of multivalent carrier ions. [2-5] One of the major challenges is to find appropriate intercalation cathode materials. Compared with that of monovalent Li ions, multivalent ions, such as Mg 2+ , Zn 2+ , and Al 3+ , usually show sluggish solid-phase diffusion behaviors, which is usually caused by strong coulomb interactions between the inserted ions and the host materials. [2,5] This causes solid-phase diffusion to be the rate-determining process in the battery reactions, by which most intercalation electrode materials cannot work with multivalent ions. In the current rechargeable battery field, critical issues due to the intrinsic properties of the carrier ions, such as the dangerous dendritic growth of Li during charging, [6] as well as the sluggish diffusion behavior of multivalent ions, hinder the development of high-energy-density batteries. Since these issues cannot be solved in single-carrier ion battery systems, [2,7] combining different carrier ions seems to be an intriguing approach to solve these shortcomings and realize high-energydensity batteries. To verify our conjecture, we first proposed a new battery technology which we refer to as Li-Mg dual-salt batteries. [8] This technology was then followed and adopted by many independent researchers. Until now, the dual-salt technology in a wide range of battery systems has been reported, not only employing Li-Mg systems, [9-12] but also extending to Li-Na, [13] Na-Al, [14] Mg-I systems, etc. [15] In addition, the dualsalt technology is also successfully employed in Mg-S batteries, [16,17] where adding Li-salt into the electrolytes is proved to remarkably enhance the battery performances. Although effectiveness of the dual-salt technology contributing to the exceptional battery performance has been well confirmed, [9-17] there is still lack of awareness in knowledge and mechanisms behind the experimental phenomena. Furthermore, since the dual-salt batteries usually have a Daniell-type structure (in which each ion only participates in each side of half-cell reaction), large amount of electrolyte is intrinsically necessary to accommodate approximately half of carrier ions during the battery reactions, which results in a considerable decrease of the energy density. To achieve high energy densities, the dual-salt batteries must have a so-called
Lithium-Intercalation Oxides for Rechargeable Batteries
Since the introduction of the Li x C/LiCoO 2 cell, rechargeable lithium batteries have become the technology of choice for applications where volume or weight are a consideration (e.g., laptop computers and cell phones). The focus of current research in cathodeactive materials is on less-expensive or higherperformance materials than LiCoO 2 . This article illustrates how first-principles calculations can play a critical role in obtaining the understanding needed to design improved cathode oxides.
Advanced Energy Materials, 2015
rock-salt structures, with Li + /TM evenly sharing cation sites and close-packed anion arrays, may be a reasonable alternative for effi cient Li + storage. After Li + extraction, the TM may remain at the cation sublattice sites and uphold well the disordered rocksalt framework. A recent work based on ab initio computations revealed that Li + transport can be facile in a disordered cubic rock-salt oxide (Li 1.211 Mo 0.467 Cr 0.3 O 2 ) with Li-excess. [ 8 ] It was found that such framework is stable with a maximum of 45% of the cation sites vacant. Herein, we demonstrate that a new dilithium disordered rock-salt Li 2 VO 2 F intercalation material can deliver up to about 1.8 Li + capacity per TM (420 mAh g −1 ) at ≈2.5 V (1000 Wh kg −1 ) with only minor lattice volume change (≈3%). Such material with mixed O 2− /F − anion environment has been synthesized by a simple ball-milling method. The two Li + storage with V 3+ /V 5+ redox reactions (Li 2 VO 2 F ↔ 2 Li + + 2e − + VO 2 F) leads to an attractively high theoretical capacity of 462 mAh g −1 . Moreover, Li 2 VO 2 F shows good capacity retention and minor increase in polarization upon fast charging/discharging or upon low-temperature operation.
Solid-state chemistry of lithium power sources†
Chemical Communications, 1997
This article describes the solid-state chemistry of intercalation compounds that underpins a revolutionary new rechargeable lithium battery which has recently achieved phenomenal commercial success. The battery can store more than twice the energy compared with conventional alternatives of the same size and mass and holds the key to the future improvement of consumer electronic products (e.g. mobile telephones), electric vehicles and implantable medical devices (e.g. the artificial heart). Attention is focused on those lithium intercalation compounds that are useful as positive electrodes in rechargeable lithium batteries. The basic operation of the cell is summarised briefly and the structure/property relationships are developed that are important for the solid-state chemist when attempting to design and synthesise new lithium intercalation compounds capable of operating as positive electrodes. Finally, the structure, electronic structure and intercalation chemistry of several important positive intercalation electrodes are discussed including some which show considerable promise for applications in future generations of rechargeable lithium batteries.
Intercalation chemistry and energy storage
Journal of Solid State Chemistry, 1979
The reaction between lithium and titanium disulfide is used to show the relationship between intercalation chemistry and electrochemical energy storage. The maintenance of crystalline structure with only a 10% lattice expansion perpendicular to the sulfide sheets allows high rates of rektion with lithium and complete reversibility of the reaction. The behavior of TaSs and VSes are compared with that of TiS2. Many oxides and other chalcogenides of the early group transition metals are also able to react with lithium to form ternary compounds, but none of these have to date shown the high reversibility of titanium disulfide.
Progress into lithium-ion battery research
Journal of Chemical Research, 2023
Lithium-ion batteries have transformed our lives and are now found in everything from mobile phones to laptop computers and electric cars. In lithium-ion batteries, an adequate electrolyte was developed using a winding process nearly related to the progress of electrode chemistries. In this technology, a metal oxide is a cathode, and porous carbon is the anode. The electrochemical interaction of anode material with lithium could produce an intercalation product, which could form the basis of a revolutionary battery system. Structural retention causes this reaction to proceed quickly and with a high degree of reversibility at room temperature. Titanium disulfide is one of the latest solid cathode materials. In this review, the history of intercalation electrodes, electrolytes, and basic principles related to batteries based on intercalation processes and their effect on battery performance is reported.