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Wu, Xianyang

Publications and source records attributed to Wu, Xianyang.

12 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Electrochemical reactivity and passivation of organic electrolytes at spinel MgCrMnO 4 cathode interfaces for rechargeable high voltage magnesium-ion batteries

Magnesium transition metal oxides such as MgCr 2−x Mn x O 4 are promising high-voltage and high-capacity cathode materials for rechargeable magnesium batteries (RMBs). Understanding and improving the chemical and electrochemical stability of the cathode–electrolyte interface (CEI) has been the primary technical emphasis to enable this category of cathode materials, which has been significantly underexplored. Herein, in this study, we focus on investigating the fundamental mechanism of parasitic reactions at the charged surface of the high-voltage MgCrMnO 4 model cathode with different organic electrolytes. The aim is to reveal the underlying effect of anions and solvents responsible for the passivation behavior of the cathode by using three exemplary anions: [(CF 3 SO 2 ) 2 N] − (TFSI − ), Al[OC(CF 3 ) 3 ] 4 − (TPFA − ), and [CB 11 H 12 ] − (MC) and three solvents: diglyme (G2), triglyme (G3), and 3-methoxypropylamine (MPA). High precision leakage current measurements during potentiostatic hold reveal that the electrolyte solvent chemistry has a more profound impact than anion's on the passivation of the MgCrMnO 4 cathode surface during deintercalation of Mg 2+ . X-ray photoelectron spectroscopy exhibits the differences in CEI composition. Amine solvents like MPA show poor passivation due to a higher degree of solvent decomposition, while the thin and anion-derived CEI in glyme-based electrolytes is directly linked with the better passivation behavior on the cathode. Furthermore, we leverage the knowledge from these findings to modify the electrolyte structure by adding a solvent additive, with the goal of reducing the parasitic reaction.

25 ENERGY STORAGE↗
DOE OSTI2024

Acidity-Governed Rules in the Electrochemical Performance of Fluorinated Benzenes for High-Voltage Lithium Metal Batteries

Judicious selection of the optimal fluorobenzene (FB) as a nonsolvating cosolvent for lithium metal batteries (LMBs) is reported. For this work, we found the key correlation between FB structures and cycling stabilities of cells: increased fluorine substitution of FBs results in higher anodic stability but at the expense of reduced reductive stability, and FBs containing three or more fluorine atoms exhibit insufficient anodic stability in the electrolyte system comprised of fluoroethylene carbonate (FEC) and ethyl methyl carbonate (EMC). More importantly, FBs with higher acidity (lower pK a ) due to protons located between two adjacent fluorine atoms tend to be more susceptible to side reactions during cycling. Our results indicate that difluorobenzenes with no “acidic” proton (DFB2 and DFB4) have emerged as the optimal choice with the desired redox stability in high-voltage LMBs. Nuclear magnetic resonance and X-ray photoelectron spectroscopy confirmed these findings, providing guidance for selecting the most suitable FB variants as nonsolvating cosolvents for high-voltage LMBs.

25 ENERGY STORAGE↗
DOE OSTI2023

Probing the Effectiveness in Stabilizing Lithium Metal Anodes through Functional Additives

A variety of electrolyte additives were comprehensively evaluated to understand their relative capability in stabilizing lithium metal anode. Although the Li||Cu test is an effective test to rule out ineffective additives, a reliable assessment of individual additives cannot be obtained just by a single evaluation method. Therefore, various methods must be combined to truly assess the stabilization of a lithium anode. Moreover, it was also discovered that a significant depletion of electrolytes occurred during the end-of-life of the lithium batteries, which partially contributed to the sudden failure of the lithium batteries during cycling. However, the main culprit of the sudden failure was identified as the significant increase in the resistance of the lithium metal anode. Further, when used as an additive, cyclic fluorinated carbonates are the most effective in stabilizing the lithium anode and improving the cycling performance of lithium batteries among all the common additives. Despite its cost-effectiveness, the additive in the conventional electrolyte approach provides insufficient protection for lithium metal due to the complete consumption of the additive materials, which is necessary to repair the solid-electrolyte interphase (SEI). Therefore, it is suggested that a larger ratio (>15 wt %) of the SEI former should be employed to achieve effective lithium stabilization.

25 ENERGY STORAGE↗
DOE OSTI2023

Understanding and Mitigating the Dissolution and Delamination Issues Encountered with High-Voltage LiNi 0.5 Mn 1.5 O 4

In our initial study on the high-voltage 5 V cobalt-free spinel LiNi 0.5 Mn 1.5 O 4 (LNMO) cathode, we discovered a severe delamination issue in the laminates when cycled at a high upper cut-off voltage (UCV) of 4.95 V, especially when a large cell format was used. This delamination problem prompted us to investigate further by studying the transition metal (TM) dissolution mechanism of cobalt-free LNMO cathodes, and as a comparison, some cobalt-containing lithium nickel manganese cobalt oxides (NMC) cathodes, as the leachates from the soaking experiment might be the culprit for the delamination. Unlike other previous reports, we are interested in the intrinsic stability of the cathode in the presence of a baseline Gen2 electrolyte consisting of 1.2 M of LiPF 6 in ethylene carbonate/ethyl methyl carbonate (EC/EMC), similar to a storage condition. The electrode laminates (transition metal oxides, transition metal oxides, TMOs, coated on an Al current collector with a loading level of around 2.5 mAh/cm 2 ) or the TMO powders (pure commercial quality spinel LNMO, NMC, etc.) were stored in the baseline solution, and the transition metal dissolution was studied through nuclear magnetic resonance, such as 1 H NMR, 19 F NMR, scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometry (ICP-MS). Significant electrolyte decomposition was observed and could be the cause that leads to the TM dissolution of LNMO. To address this TM dissolution, additives were introduced into the baseline electrolyte, effectively alleviating the issue of TM dissolution. The results suggest that the observed delamination is caused by electrolyte decompositions that lead to etching, and additives such as lithium difluorooxalato borate and p-toluenesulfonyl isocyanate can alleviate this issue by forming a firm cathode electrolyte interface. This study provides a new perspective on cell degradation induced by electrode/electrolyte interactions under storage conditions.

25 ENERGY STORAGE↗
DOE OSTI2023

A Novel High‐Performance Electrolyte for Extreme Fast Charging in Pilot Scale Lithium‐Ion Pouch Cells

Realizing extreme fast charging (XFC) in lithium-ion batteries for electric vehicles is still challenging due to the insufficient lithium-ion transport kinetics, especially in the electrolyte. Herein, a novel high-performance electrolyte (HPE) consisting of lithium bis(fluorosulfonyl)imide (LiFSI), lithium hexafluorophosphate (LiPF 6 ) and carbonates is proposed and tested in pilot-scale, 2-Ah pouch cells. Moreover, the origin of improved electrochemical performance is comprehensively studied via various characterizations, suggesting that the proposed HPE exhibits high ionic conductivity and excellent electrochemical stability at high charging rate of 6-C. Furthermore, the HPE-based pouch cells deliver improved discharge specific capacity and excellent long-term cyclability up to 1500 cycles under XFC conditions, which is superior to the conventional state-of-the-art baseline electrolyte.

25 ENERGY STORAGE↗
DOE OSTI2023

Prelithiation of Lithium Peroxide for Silicon Anode: Achieving a High Activation Rate

The use of lithium peroxide (Li2O2) as a cost-effective low-weight prelithiation cathode additive was successfully demonstrated. Through a series of studies on the chemical stability of Li2O2 and the activation process of Li2O2 on the cathode, we revealed that Li2O2 is more compatible with conventional electrolyte and cathode laminate slurry than lithium oxide. Due to the significantlysmaller size of commercial Li2O2, it can beused directly as a cathode additive. Moreover, the activation of Li2O2 on the cathode leads to the impedance growthof the cathode possibly resulting from the release of dioxygen andevacuation of Li2O2 inside the cathode. Withthe introduction of a new Li2O2 spread-coatingtechnique on the cathode, the capacity loss was suppressed. Si||NMCfull cells using Li2O2 spread-coated cathodedemonstrated a highly promising activation rate of Li2O2 and significantly enhanced specific capacity and cyclingstability compared to the uncoated full cells.

cathode additive↗
DOE OSTI2023

Effect of Si Content on Extreme Fast Charging Behavior in Silicon–Graphite Composite Anodes

Commercial Li-ion batteries typically incorporate a small amount of high-capacity silicon (Si)-based materials in the composite graphite-based anode to increase the energy density of the battery. However, very little is known about the effects of Si on the fast-charging behavior of composite anodes. Herein, we examine the effects of the Si/graphite ratio in the composite anode on the fast-charging behavior of full cells. We show that addition of Si increases the rate capability from 1C to 8C and improves the capacity retention in early cycles at 6C due to reduced overpotential in constant current charging cycles. The impacts of Si content on fast-charging aging were identified by Post-Test characterization. Despite realizing benefits of available capacity and reduced Li plating at 6C, silicon–electrolyte interactions lead the time-dependent cell performance to fade quickly in the long term. The Post-Test analysis also revealed the thickening of the electrode and nonuniform distribution of electrolyte decomposition products on the Si-containing anodes, as well as the organic-rich solid electrolyte interphase (SEI), which are the factors behind cell degradation. Our study sheds insight on the advantages and disadvantages of Si/graphite composite anodes when they are used in fast-charging applications and guides further research in the area by designing an optimized composition of Si incorporated in a mature graphite matrix.

25 ENERGY STORAGE↗
DOE OSTI2022

Understanding the effect of salt concentrations on fast charging performance of Li-ion cells

Here, different lithium salt (lithium bis(fluorosulfonyl) imide (LiFSI)/LiPF 6 9/1 mol ratio) concentrations in carbonate electrolyte were studied on the fast charging performance of LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622)/graphite pouch cells. The cells with electrolyte concentration from 0.75 M to 1.50 M showed similar fast charging capabilities. Further increase of the concentration to 1.75 M and 2.00 M decreased the attainable capacity in fast charging. In the long-term cycling test, the capacity retention after 200 fast charging cycles increased with the increase of salt concentration in electrolyte. Cells with 1.5 M electrolyte showed the best overall performance in fast charging capacity and long-term cycling. Li platings were observed in the cells with 0.75 M, 1.00 M and 1.25 M electrolyte. It was improved with greatly reduced Li plating area in 1.50 M, and no Li plating at all in 1.75 M and 2.00 M electrolyte. Post-mortem analysis such as neutron powder diffraction (NPD) and X-ray photoelectron spectroscopy (XPS) were used to characterize the electrode after cycling. It suggests that electrolyte concentration needs to be optimized for a given cell configuration with specific electrode and loading.

25 ENERGY STORAGE↗
DOE OSTI2021

Anionic redox induced anomalous structural transition in Ni-rich cathodes

Ni-rich cathodes have emerged as one of the most promising candidates for power next generation electric vehicles. However, they often suffer from poor capacity retention when charged to high voltages and the origin of this degradation remains elusive. Here, by using high throughput operando neutron diffraction, a universal four-stage structural evolution of Ni-rich cathodes is revealed during the initial cycle for the first time. Particularly, we discovered a universal structural transition in Ni-rich cathodes at ~75% delithiation irrespective of Ni or substituent contents. This transition is hallmarked by the anomalous increase of average TM–O bond lengths, contradicting the conventional wisdom that TM–O bond lengths decrease during charge (oxidation). This anomaly is induced by the direct oxidation of lattice oxygen ions, which is rooted in the drastic decrease of oxygen-to-TM charge transfer gap at high degrees of delithiation. The onset of this anomalous transition matches very well with the onset of oxygen gas release and severe decline of capacity retention in Ni-rich cathodes, suggesting that this bulk structural transition plays an indispensable role in the degradation process. These findings shed light on the elusive degradation mechanism of Ni-rich cathodes, providing valuable clues to stabilize oxidized oxygen ions for stable cycling of layered oxide cathodes at high voltages.

25 ENERGY STORAGE↗
DOE OSTI2021

Structural Evolution and Transition Dynamics in Lithium Ion Battery under Fast Charging: An Operando Neutron Diffraction Investigation

Abstract Fast charging (<15 min) of lithium‐ion batteries (LIBs) for electrical vehicles (EVs) is widely seen as the key factor that will greatly stimulate the EV markets, and its realization is mainly hindered by the sluggish diffusion of Li + . To have a mechanistic understanding of Li + diffusion within LIBs, in this study, structural evolutions of electrodes for a Ni‐rich LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) || graphite cylindrical cell with high areal loading (2.78 mAh cm −2 ) are developed for operando neutron powder diffraction study at different charging rates. Via sequential Rietveld refinements, changes in structures of NMC622 and Li x C 6 are obtained during moderate and fast charging (from 0.27 C to 4.4 C). NMC622 exhibits the same structural evolution regardless of C‐rates. For phase transitions of Li x C 6 , the stage I (LiC 6 ) phase emerges earlier during the stepwise intercalation at a lower state of charge when charging rate is increased. It is also found that the stage II (LiC 12 ) → stage I (LiC 6 ) transition is the rate‐limiting step during fast charging. The LiC 12 → LiC 6 transition mechanism is further analyzed using the Johnson–Mehl–Avrami–Kolmogorov model. It is concluded as a diffusion‐controlled, 1D phase transition with decreasing nucleation kinetics under increasing chargingrates.

25 ENERGY STORAGE↗
DOE OSTI2021

New Insights into Structural Evolution of LiNiO 2 Revealed by Operando Neutron Diffraction

LiNiO 2 (LNO) represents the end member in the compositional space of the LiNi 1-x-y Mn x Co y O 2 (as x and y approach zero) cathode system. Despite its high theoretical specific capacity (275 mAh/g), LNO suffers from phase transitions with large volume change and unfavorable reactions upon electrochemical cycling, which restricts its practical use in the application of lithium-ion batteries. While the contributing factor to the structural instability is commonly linked to the undesired volume collapse associated with the H2-H3 phase transition, detailed analysis of structural evolution following the entire route of phase transitions (H1-M-H2-H3) in real time under battery operating conditions remains a challenging task. In this work, we employ operando neutron diffraction to study the structural changes (crystal lattice, Li/Ni–O bond length, O–Ni–O bond angles, and LiO 2 /NiO 2 layer thickness) of LNO cathode in a home-built Li x NiO 2 || graphite full cell during Li + de-/intercalation. In particular, the anomalous increase(decrease) of Ni–O(Li–O) bond length at high SOC (>~85 %) in the H3 phase is discussed in the context of O 2- (2p)→Ni 4+ (3d) negative charge transfer.

25 ENERGY STORAGE↗