Lithium metal batteries (LMBs) are one of the most promising candidates for next‐generation high‐energy‐density rechargeable batteries. Solid electrolyte interphase (SEI) on Li metal anodes plays a ...significant role in influencing the Li deposition morphology and the cycle life of LMBs. However, a thorough understanding on the mechanisms of SEI formation and evolution is still inadequate. In this review, the progress in understanding structures, properties, and influencing factors of SEI, as well as efficient strategies of tailoring SEI are focused upon. First, the compositions, models, and recent progress in characterizing atomic structures of SEI are summarized. Second, the properties of SEI, including electronic conduction, ionic conduction, stability, and mechanical properties are elucidated. Structures and properties of SEI are greatly affected by multiple factors, thus interactions between these factors and SEI are systematically discussed. Correlations of SEI with Li deposition morphology, rate capability, and cycle life are further summarized. Moreover, efficient strategies of tailoring SEI with desired properties, including in situ SEI and ex situ SEI, are also reviewed. Finally, future directions, including in‐operando techniques, multi‐modality approaches for characterization of SEI, and artificial intelligence assisted understanding of correlations between electrolyte components and SEI properties are proposed.
The solid electrolyte interphase (SEI) between lithium metal anodes and electrolytes is the most important element that determines Li deposition/dissolution behavior and the cycle life of Li metal batteries. SEI composition, SEI structure models, influencing factors on SEI formation, functions of different SEI components, and strategies for designing and improving SEI are summarized.
Interfacial reactions between electrode and electrolyte are critical, either beneficial or detrimental, for the performance of rechargeable batteries. The general approaches of controlling ...interfacial reactions are either applying a coating layer on cathode or modifying the electrolyte chemistry. Here we demonstrate an approach of modification of interfacial reactions through dilute lattice doping for enhanced battery properties. Using atomic level imaging, spectroscopic analysis and density functional theory calculation, we reveal aluminum dopants in lithium nickel cobalt aluminum oxide are partially dissolved in the bulk lattice with a tendency of enrichment near the primary particle surface and partially exist as aluminum oxide nano-islands that are epitaxially dressed on the primary particle surface. The aluminum concentrated surface lowers transition metal redox energy level and consequently promotes the formation of a stable cathode-electrolyte interphase. The present observations demonstrate a general principle as how the trace dopants modify the solid-liquid interfacial reactions for enhanced performance.
It remains a grand challenge to replace platinum group metal (PGM) catalysts with earth-abundant materials for the oxygen reduction reaction (ORR) in acidic media, which is crucial for large-scale ...deployment of proton exchange membrane fuel cells (PEMFCs). Here, we report a high-performance atomic Fe catalyst derived from chemically Fe-doped zeolitic imidazolate frameworks (ZIFs) by directly bonding Fe ions to imidazolate ligands within 3D frameworks. Although the ZIF was identified as a promising precursor, the new synthetic chemistry enables the creation of well-dispersed atomic Fe sites embedded into porous carbon without the formation of aggregates. The size of catalyst particles is tunable through synthesizing Fe-doped ZIF nanocrystal precursors in a wide range from 20 to 1000 nm followed by one-step thermal activation. Similar to Pt nanoparticles, the unique size control without altering chemical properties afforded by this approach is able to increase the number of PGM-free active sites. The best ORR activity is measured with the catalyst at a size of 50 nm. Further size reduction to 20 nm leads to significant particle agglomeration, thus decreasing the activity. Using the homogeneous atomic Fe model catalysts, we elucidated the active site formation process through correlating measured ORR activity with the change of chemical bonds in precursors during thermal activation up to 1100 °C. The critical temperature to form active sites is 800 °C, which is associated with a new Fe species with a reduced oxidation number (from Fe3+ to Fe2+) likely bonded with pyridinic N (FeN4) embedded into the carbon planes. Further increasing the temperature leads to continuously enhanced activity, linked to the rise of graphitic N and Fe–N species. The new atomic Fe catalyst has achieved respectable ORR activity in challenging acidic media (0.5 M H2SO4), showing a half-wave potential of 0.85 V vs RHE and leaving only a 30 mV gap with Pt/C (60 μgPt/cm2). Enhanced stability is attained with the same catalyst, which loses only 20 mV after 10 000 potential cycles (0.6–1.0 V) in O2 saturated acid. The high-performance atomic Fe PGM-free catalyst holds great promise as a replacement for Pt in future PEMFCs.
High-energy nickel (Ni)-rich cathode will play a key role in advanced lithium (Li)-ion batteries, but it suffers from moisture sensitivity, side reactions, and gas generation. Single-crystalline ...Ni-rich cathode has a great potential to address the challenges present in its polycrystalline counterpart by reducing phase boundaries and materials surfaces. However, synthesis of high-performance single-crystalline Ni-rich cathode is very challenging, notwithstanding a fundamental linkage between overpotential, microstructure, and electrochemical behaviors in single-crystalline Ni-rich cathodes. We observe reversible planar gliding and microcracking along the (003) plane in a single-crystalline Ni-rich cathode. The reversible formation of microstructure defects is correlated with the localized stresses induced by a concentration gradient of Li atoms in the lattice, providing clues to mitigate particle fracture from synthesis modifications.
Design and processing of advanced lightweight structural alloys based on magnesium and titanium rely critically on a control over twinning that remains elusive to date and is dependent on an explicit ...understanding on the twinning nucleation mechanism in hexagonal close-packed (HCP) crystals. Here, by using in-situ high resolution transmission electron microscopy, we directly show a dual-step twinning nucleation mechanism in HCP rhenium nanocrystals. We find that nucleation of the predominant {1 0 -1 2} twinning is initiated by disconnections on the Prismatic│Basal interfaces which establish the lattice correspondence of the twin with a minor deviation from the ideal orientation. Subsequently, the minor deviation is corrected by the formation of coherent twin boundaries through rearrangement of the disconnections on the Prismatic│Basal interface; thereafter, the coherent twin boundaries propagate by twinning dislocations. The findings provide high-resolution direct evidence of the twinning nucleation mechanism in HCP crystals.
Lithium (Li) metal has been extensively investigated as an anode for rechargeable battery applications due to its ultrahigh theoretical specific capacity and the lowest redox potential. However, ...significant challenges including dendrite growth and low Coulombic efficiency are still hindering the practical applications of rechargeable Li metal batteries. It is demonstrated that long‐term cycling of Li metal batteries can be realized by the formation of a transient high‐concentration electrolyte layer near the surface of Li metal anode during high rate discharge process. The highly concentrated Li+ ions in this transient layer will immediately be solvated by the available solvent molecules and facilitate the formation of a stable and flexible solid electrolyte interphase (SEI) layer composed of a poly(ethylene carbonate) framework integrated with other organic/inorganic lithium salts. This SEI layer largely suppresses the corrosion of Li metal anode attacked by free organic solvents and enables the long‐term operation of Li metal batteries. The fundamental findings in this work provide a new direction for the development of Li metal batteries that could be operated at high current densities for a wide range of applications.
A transient layer of highly concentrated electrolyte can be formed in the vicinity of a Li metal anode by fast lithium stripping or high C‐rate discharge. The highly concentrated Li+ ions in this transient layer immediately coordinate with the available solvents and facilitate the formation of a highly flexible and stable solid electrolyte interphase (SEI) layer on the Li surface, effectively mitigating the Li corrosion by free organic solvents and enabling the sustainable operation of Li metal batteries.
The solid-electrolyte interphase (SEI) dictates the performance of most batteries, but the understanding of its chemistry and structure is limited by the lack of in situ experimental tools. In this ...work, we present a dynamic picture of the SEI formation in lithium-ion batteries using in operando liquid secondary ion mass spectrometry in combination with molecular dynamics simulations. We find that before any interphasial chemistry occurs (during the initial charging), an electric double layer forms at the electrode/electrolyte interface due to the self-assembly of solvent molecules. The formation of the double layer is directed by Li
and the electrode surface potential. The structure of this double layer predicts the eventual interphasial chemistry; in particular, the negatively charged electrode surface repels salt anions from the inner layer and results in an inner SEI that is thin, dense and inorganic in nature. It is this dense layer that is responsible for conducting Li
and insulating electrons, the main functions of the SEI. An electrolyte-permeable and organic-rich outer layer appears after the formation of the inner layer. In the presence of a highly concentrated, fluoride-rich electrolyte, the inner SEI layer has an elevated concentration of LiF due to the presence of anions in the double layer. These real-time nanoscale observations will be helpful in engineering better interphases for future batteries.
Despite considerable efforts to stabilize lithium metal anode structures and prevent dendrite formation, achieving long cycling life in high-energy batteries under realistic conditions remains ...extremely difficult due to a combination of complex failure modes that involve accelerated anode degradation and the depletion of electrolyte and lithium metal. Here we report a self-smoothing lithium-carbon anode structure based on mesoporous carbon nanofibres, which, coupled with a lithium nickel-manganese-cobalt oxide cathode with a high nickel content, can lead to a cell-level energy density of 350-380 Wh kg
(counting all the active and inactive components) and a stable cycling life up to 200 cycles. These performances are achieved under the realistic conditions required for practical high-energy rechargeable lithium metal batteries: cathode loading ≥4.0 mAh cm
, negative to positive electrode capacity ratio ≤2 and electrolyte weight to cathode capacity ratio ≤3 g Ah
. The high stability of our anode is due to the amine functionalization and the mesoporous carbon structures that favour smooth lithium deposition.
The lithium‐ and manganese‐rich (LMR) layered structure cathodes exhibit one of the highest specific energies (≈900 W h kg−1) among all the cathode materials. However, the practical applications of ...LMR cathodes are still hindered by several significant challenges, including voltage fade, large initial capacity loss, poor rate capability and limited cycle life. Herein, we review the recent progress and in depth understandings on the application of LMR cathode materials from a practical point of view. Several key parameters of LMR cathodes that affect the LMR/graphite full‐cell operation are systematically analyzed. These factors include the first‐cycle capacity loss, voltage fade, powder tap density, and electrode density. New approaches to minimize the detrimental effects of these factors are highlighted in this work. We also provide perspectives for the future research on LMR cathode materials, focusing on addressing the fundamental problems of LMR cathodes while keeping practical considerations in mind.
An overview of current research activities addressing the key challenges of LMR cathodes is presented, focusing on discussion of the facile strategies to improve the initial Coulombic efficiency, working voltage stability, and rate capability. Promising perspectives for LMR studies are suggested by providing full‐cell data of LMR electrodes with commercialization specifications.
Layered lithium transition metal oxides (LTMO) are promising candidate cathode materials for next-generation high-energy density lithium ion battery. The challenge for using this category of cathode ...is the capacity and voltage fading, which is believed to be associated with the layered structure disordering, a process that is initiated from the surface or solid-electrolyte interface and facilitated by transition metal (TM) reduction and oxygen vacancy formation. However, the atomic level dynamic mechanism of such a layered structure disordering is still not fully clear. In this work, utilizing atomic resolution electron energy loss spectroscopy (EELS), we map, for the first time at atomic scale, the spatial evolution of Ni, Co and Mn in a cycled LiNi1/3Mn1/3Co1/3O2 layered cathode. In combination with atomic level structural imaging, we discovered the direct correlation of TM ions migration behavior with lattice disordering, featuring the residing of TM ions in the tetrahedral site and a sequential migration of Ni, Co, and Mn upon the increased lattice disordering of the layered structure. This work highlights that Ni ions, though acting as the dominant redox species in many LTMO, are labile to migrate to cause lattice disordering upon battery cycling, while the Mn ions are more stable as compared with Ni and Co and can act as pillar to stabilize layered structure. Direct visualization of the behavior of TM ions during the battery cycling provides insight for designing of cathode with high structural stability and correspondingly a superior performance.
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