Engineering topics

Lu, Dongping

Publications and source records attributed to Lu, Dongping.

44 records · Page 3

DOE OSTI2015

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

Li-S batteries hold great potential for next-generation, large-format power source applications; yet, the fundamental understanding of the electrochemical reaction pathways remains lacking to enable their functionality as promised. Here, in situ NMR technique employing a specially designed cylindrical micro battery was used to monitor the chemical environments around Li+ ions during repetitive charge-discharge process and track the transient electrochemical and chemical reactions occurring in the whole Li-S system. The in situ NMR provides real time, quantitative information related to the temporal concentration variations of the polysulfides with various chain lengths, providing important clues for the reaction pathways during both discharge and charge processes. The in-situ technique also reveals that redox reactions may involve transient species that are difficult to detect in ex-situ NMR study. Intermediate species such as charged free radicals may play an important role in the formation of the polysulfide products. Additionally, in situ NMR measurement simultaneously reveals vital information on the 7Li chemical environments in the electrochemical and parasitic reactions on the lithium anode that promotes the understanding of the failure mechanism in the Li-S system. These new insights could help design effective strategies to accelerate the development of Li-S battery technology.

Environmental Molecular Sciences Laboratory↗

DOE OSTI2015

Anodes for Rechargeable Lithium-Sulfur Batteries

In this work, we will review the recent developments on the protection of Li metal anode in Li-S batteries. Various strategies used to minimize the corrosion of Li anode and reducing its impedance increase will be analyzed. Other potential anodes used in sulfur based rechargeable batteries will also be discussed.

anode↗

DOE OSTI2015

Failure Mechanism of Fast-Charged Lithium Metal Batteries in Liquid Electrolyte

In recent years, lithium anode has re-attracted broad interest because of the necessity of employing lithium metal in the next-generation battery technologies such as lithium sulfur (Li-S) and lithium oxygen (Li-O2) batteries. Fast capacity degradation and safety issue associated with rechargeable lithium metal batteries have been reported, although the fundamental understanding on the failure mechanism of lithium metal at high charge rate is still under debate due to the complicated interfacial chemistry between lithium metal and electrolyte. Herein, we demonstrate that, at high current density, the quick growth of porous solid electrolyte interphase towards bulk lithium, instead of towards the separator, dramatically builds up the cell impedance that directly leads to the cell failure. Understanding the lithium metal failure mechanism is very critical to gauge the various approaches used to address the stability and safety issues associated with lithium metal anode. Otherwise, all cells will fail quickly at high rates before the observation of any positive effects that might be brought from adopting the new strategies to protect lithium.

Environmental Molecular Sciences Laboratory↗

DOE OSTI2015

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. Based on 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 towards 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 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 designing of cathode materials with both high capacity and voltage stability during cycling.

Environmental Molecular Sciences Laboratory↗

DOE OSTI2015

Direct Observation of Sulfur Radicals as Reaction Media in Lithium Sulfur Batteries

Lithium sulfur (Li-S) battery has been regaining tremendous interest in recent years because of its attractive attributes such as high gravimetric energy, low cost and environmental benignity. However, it is still not conclusively known how polysulfide ring/chain participates in the whole cycling and whether the discharge and charge processes follow the same pathway. Herein, we demonstrate the direct observation of sulfur radicals by using in situ electron paramagnetic resonance (EPR) technique. Based on the concentration changes of sulfur radicals at different potentials and the electrochemical characteristics of the cell, it is revealed that the chemical and electrochemical reactions in Li-S cell are driving each other to proceed through sulfur radicals, leading to two completely different reaction pathways during discharge and charge. The proposed radical mechanism may provide new perspectives to investigate the interactions between sulfur species and the electrolyte, inspiring novel strategies to develop Li-S battery technology.

25 ENERGY STORAGE↗

DOE OSTI2014

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 mAhg(-1) for 400 cycles at a high rate of 1,737mAg(-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.

Huang, C↗

DOE OSTI2013

Coordination Chemistry in magnesium battery electrolytes: how ligands affect their performance

Magnesium battery is potentially a safe, cost-effective, and high energy density technology for large scale energy storage. However, the development of magnesium battery has been hindered by the limited performance and the lack of fundamental understandings of electrolytes. Here, we present a coordination chemistry study of Mg(BH 4 ) 2 in ethereal solvents. The O donor denticity, i.e. ligand strength of the ethereal solvents which act as ligands to form solvated Mg complexes, plays a significant role in enhancing coulombic efficiency of the corresponding solvated Mg complex electrolytes. A new and safer electrolyte is developed based on Mg(BH4)2, diglyme and optimized LiBH4 additive. The new electrolyte demonstrates 100% coulombic efficiency, no dendrite formation, and stable cycling performance with the cathode capacity retention of ~90% for 300 cycles in a prototype magnesium battery.

25 ENERGY STORAGE↗

DOE OSTI2013

How to Obtain Reproducible Results for Lithium Sulfur Batteries

The basic requirements for getting reliable Li-S battery data have been discussed in this work. Unlike Li-ion batteries, electrolyte-rich environment significantly affects the cycling stability of Li-S batteries prepared and tested under the same conditions. The reason has been assigned to the different concentrations of polysulfide-containing electrolytes in the cells, which have profound influences on both sulfur cathode and lithium anode. At optimized S/E ratio of 50 g L-1, a good balance among electrolyte viscosity, wetting ability, diffusion rate dissolved polysulfide and nucleation/growth of short-chain Li2S/Li2S2 has been built along with largely reduced contamination on the lithium anode side. Accordingly, good cyclability, high reversible capacity and Coulombic efficiency are achieved in Li-S cell with controlled S/E ratio without any additive. Other factors such as sulfur content in the composite and sulfur loading on the electrode also need careful concern in Li-S system in order to generate reproducible results and gauge the various methods used to improve Li-S battery technology.

Cycling stability↗