Dongping Lu

Manipulating surface reactions in lithium–sulphur batteries using hybrid anode structures

Lithium-sulphur batteries have high theoretical energy density and potentially low cost, but significant challenges such as severe capacity degradation prevent its widespread adoption. Here we report a new design of lithium-sulphur battery using electrically connected graphite and lithium metal as a hybrid anode to control undesirable surface reactions on lithium. Lithiated graphite placed in front of the lithium metal functions as an artificial, self-regulated solid electrolyte interface layer to actively control the electrochemical reactions and minimize the deleterious side reactions, leading to significant performance improvements. Lithium-sulphur cells incorporating this hybrid anodes deliver capacities of >800 mAh g(-1) for 400 cycles at a high rate of 1,737 mA g(-1), with only 11% capacity fade and a Coulombic efficiency >99%. This simple hybrid concept may also provide scientific strategies for protecting metal anodes in other energy-storage devices.

Evolution of lattice structure and chemical composition of the surface reconstruction layer in Li1.2Ni0.2Mn0.6O2 cathode material for lithium ion batteries

Voltage and capacity fading of layer structured lithium and manganese rich (LMR) transition metal oxide is directly related to the structural and composition evolution of the material during the cycling of the battery. However, understanding such evolution at atomic level remains elusive. On the basis of atomic level structural imaging, elemental mapping of the pristine and cycled samples, and density functional theory calculations, it is found that accompanying the hoping of Li ions is the simultaneous migration of Ni ions toward the surface from the bulk lattice, leading to the gradual depletion of Ni in the bulk lattice and thickening of a Ni enriched surface reconstruction layer (SRL). Furthermore, Ni and Mn also exhibit concentration partitions within the thin layer of SRL in the cycled samples where Ni is almost depleted at the very surface of the SRL, indicating the preferential dissolution of Ni ions in the electrolyte. Accompanying the elemental composition evolution, significant structural evolution is also observed and identified as a sequential phase transition of C2/m → I41 → Spinel. For the first time, it is found that the surface facet terminated with pure cation/anion is more stable than that with a mixture of cation and anion. These findings firmly established how the elemental species in the lattice of LMR cathode transfer from the bulk lattice to surface layer and further into the electrolyte, clarifying the long-standing confusion and debate on the structure and chemistry of the surface layer and their correlation with the voltage fading and capacity decaying of LMR cathode. Therefore, this work provides critical insights for design of cathode materials with both high capacity and voltage stability during cycling.

Following the Transient Reactions in Lithium–Sulfur Batteries Using an In Situ Nuclear Magnetic Resonance Technique

A fundamental understanding of electrochemical reaction pathways is critical to improving the performance of Li-S batteries, but few techniques can be used to directly identify and quantify the reaction species during disharge/charge cycling processes in real time. Here, an in situ (7)Li NMR technique employing a specially designed cylindrical microbattery was used to probe the transient electrochemical and chemical reactions occurring during the cycling of a Li-S system. In situ NMR provides real time, semiquantitative information related to the temporal evolution of lithium polysulfide allotropes during both discharge/charge processes. This technique uniquely reveals that the polysulfide redox reactions involve charged free radicals as intermediate species that are difficult to detect in ex situ NMR studies. Additionally, it also uncovers vital information about the (7)Li chemical environments during the electrochemical and parasitic reactions on the Li metal anode. These new molecular-level insights about transient species and the associated anode failure mechanism are crucial to delineating effective strategies to accelerate the development of Li-S battery technologies.

Formation of Reversible Solid Electrolyte Interface on Graphite Surface from Concentrated Electrolytes

Li-ion batteries (LIB) have been successfully commercialized after the identification of ethylene-carbonate (EC)-containing electrolyte that can form a stable solid electrolyte interphase (SEI) on carbon anode surface to passivate further side reactions but still enable the transportation of the Li+ cation. These electrolytes are still utilized, with only minor changes, after three decades. However, the long-term cycling of LIB leads to continuous consumption of electrolyte and growth of SEI layer on the electrode surface, which limits the batterys life and performance. Herein, a new anode protection mechanism is reported in which, upon changing of the cell potential, the electrolyte components at the electrode-electrolyte interface reorganize reversibly to form a transient protective surface layers on the anode. This layer will disappear after the applied potential is removed so that no permanent SEI layer is required to protect the carbon anode. This phenomenon minimizes the need for a permanent SEI layer and prevents its continuous growth and therefore may lead to largely improved performance for LIBs.

Li+-Desolvation Dictating Lithium-Ion Battery’s Low-Temperature Performances

Lithium (Li) ion battery has penetrated almost every aspect of human life, from portable electronics, vehicles, to grids, and its operation stability in extreme environments is becoming increasingly important. Among these, subzero temperature presents a kinetic challenge to the electrochemical reactions required to deliver the stored energy. In this work, we attempted to identify the rate-determining process for Li+ migration under such low temperatures, so that an optimum electrolyte formulation could be designed to maximize the energy output. Substantial increase in the available capacities from graphite∥LiNi0.80Co0.15Al0.05O2 chemistry down to -40 °C is achieved by reducing the solvent molecule that more tightly binds to Li+ and thus constitutes a high desolvation energy barrier. The fundamental understanding is applicable universally to a wide spectrum of electrochemical devices that have to operate in similar environments.

Minimizing Polysulfide Shuttle Effect in Lithium-Ion Sulfur Batteries by Anode Surface Passivation

Lithium-ion sulfur batteries use nonlithium materials as the anode for extended cycle life. However, polysulfide shuttle reactions still occur on the nonmetal anodes (such as graphite and Si), and result in undesirable low Coulombic efficiency. In this work, we used Al2O3 layers coated by atomic layer deposition (ALD) technique to suppress the shuttle reactions. With the optimal thickness of 2 nm Al2O3 coated on graphite anode, the Coulombic efficiency of the sulfur cathode was improved from 84% to 96% in the first cycle, and from 94% to 97% in the subsequent cycles. As a result, the discharge capacity of the sulfur cathode was increased to 550 mAh g-1 in the 100th cycle, as compared with 440 mAh g-1 when the pristine graphite anode was used. The Al2O3 passivation layer minimizes the formation of insoluble sulfide (Li2S2, Li2S) on the surface of graphite anode and improves the efficiency and capacity retention of the graphite-sulfur batteries. The surface passivation strategy could also be used in other sulfur based battery systems (with Li, Si, and Sn anodes), to minimize side reactions and enable high-performance sulfur batteries.

Enabling High-Energy-Density Cathode for Lithium–Sulfur Batteries

High-energy lithium-sulfur (Li-S) battery is built on high loading and dense sulfur electrodes. Unfortunately, these electrodes usually suffer from a low sulfur utilization rate and limited cycle life due to the gap in scientific knowledge between the fundamental research and the application at relevant scales. In this work, effects of electrode porosity on the electrode energy density, cell cycling stability, Li anode interface, and electrolyte/sulfur ratio were investigated on the basis of high-loading sulfur electrodes. Using electrodes with sulfur loading of 4 mg cm-2 and thickness at ∼60 μm, a high energy density of over 1300 Wh L-1 has been obtained at electrode level, which provides a decent basis for high-energy Li-S cell development. In addition, Li-S cells with the high-loading and dense electrodes demonstrate promising cycling stability (∼80% capacity retention for 200 cycles). These significant improvements are contributed by the synergistic effects of dense sulfur cathode, improved electrode wetting, and suppressed quick growth of the interphase layer on Li-metal anode. This study sheds light on rational design of sulfur cathode for balanced cell energy density and cycling life.