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Li, Baohua

Publications and source records attributed to Li, Baohua.

17 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Designing lithium halide solid electrolytes

All-solid-state lithium batteries have attracted widespread attention for next-generation energy storage, potentially providing enhanced safety and cycling stability. The performance of such batteries relies on solid electrolyte materials; hence many structures/phases are being investigated with increasing compositional complexity. Among the various solid electrolytes, lithium halides show promising ionic conductivity and cathode compatibility, however, there are no effective guidelines when moving toward complex compositions that go beyond ab -initio modeling. Here, we show that ionic potential, the ratio of charge number and ion radius, can effectively capture the key interactions within halide materials, making it possible to guide the design of the representative crystal structures. This is demonstrated by the preparation of a family of complex layered halides that combine an enhanced conductivity with a favorable isometric morphology, induced by the high configurational entropy. This work provides insights into the characteristics of complex halide phases and presents a methodology for designing solid materials.

25 ENERGY STORAGE↗
DOE OSTI2023

The trans-regulatory landscape of gene networks in plants

The transcriptional effector domains of transcription factors play a key role in controlling gene expression; however, their functional nature is poorly understood, hampering our ability to explore this fundamental dimension of gene regulatory networks. To map the trans-regulatory landscape in a complex eukaryote, we systematically characterized the putative transcriptional effector domains of over 400 Arabidopsis thaliana transcription factors for their capacity to modulate transcription. We demonstrate that transcriptional effector activity can be integrated into gene regulatory networks capable of elucidating the functional dynamics underlying gene expression patterns. We further show how our characterized domains can enhance genome engineering efforts and reveal how plant transcriptional activators share regulatory features conserved across distantly related eukaryotes. Our results provide a framework to systematically characterize the regulatory role of transcription factors at a genome-scale in order to understand the transcriptional wiring of biological systems.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Non‐Flammable Ester Electrolyte with Boosted Stability Against Li for High‐Performance Li Metal Batteries

Abstract In traditional non‐flammable electrolytes a trade‐off always exists between non‐flammability and battery performance. Previous research focused on reducing free solvents and forming anion‐derived solid‐electrolyte interphase. However, the contribution of solvated anions in boosting the stability of electrolyte has been overlooked. Here, we resolve this via introducing anions into Li + solvation sheaths using anions with similar Gutmann donor number (DN) to that of solvents. Taking trimethyl phosphate fire‐retardant (DN=23.0 kcal mol −1 ) and NO 3 − (DN=22.2 kcal mol −1 ) as an example, NO 3 − is readily involved in the Li + solvation sheath and reduces the polarity of solvent. This results in boosted stability of electrolyte against Li. The developed non‐flammable electrolyte has low viscosity, high ionic conductivity and is low cost. The reversibility of Li‐Cu cell was improved to 99.49 % and the lifespan of practical LMBs was extended by >100 %.

Wang, Zhijie↗
DOE OSTI2022

Non‐Flammable Ester Electrolyte with Boosted Stability Against Li for High‐Performance Li Metal Batteries

Abstract In traditional non‐flammable electrolytes a trade‐off always exists between non‐flammability and battery performance. Previous research focused on reducing free solvents and forming anion‐derived solid‐electrolyte interphase. However, the contribution of solvated anions in boosting the stability of electrolyte has been overlooked. Here, we resolve this via introducing anions into Li + solvation sheaths using anions with similar Gutmann donor number (DN) to that of solvents. Taking trimethyl phosphate fire‐retardant (DN=23.0 kcal mol −1 ) and NO 3 − (DN=22.2 kcal mol −1 ) as an example, NO 3 − is readily involved in the Li + solvation sheath and reduces the polarity of solvent. This results in boosted stability of electrolyte against Li. The developed non‐flammable electrolyte has low viscosity, high ionic conductivity and is low cost. The reversibility of Li‐Cu cell was improved to 99.49 % and the lifespan of practical LMBs was extended by >100 %.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Efficient Construction of a C 60 Interlayer for Mechanically Robust, Dendrite-free, and Ultrastable Solid-State Batteries

Interfacial instability between solid electrolytes (SEs) and lithium metal remains a daunting challenge for solid-sate batteries. Here, a conformal C 60 interlayer is efficiently constructed on Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) SEs by physical vapor deposition, and an ideal interfacial contact is achieved via forming an ionically conducting matrix of LixC60 with lithium metal. The obtained Li x C 60 is beneficial to hinder the growth of lithium dendrites at interface and release the local stress during the lithiation and delithiation. As a result, the Li/LAGP-C 60 /Li symmetric cells demonstrate ultra-stable cycling performance for more than 4,500 h at a current density of 0.034 mA cm -2 . The Li/LAGP-C 60 /LiFePO 4 full cells deliver a reversible capacity of 152.4 mAh g -1 at room temperature, and the capacity retention rate is 85% after more than 100 cycles. This work provides a feasible and scalable strategy to improve the SEs/Li interface for high-performance solid-state batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

Revealing High Na-Content P2-Type Layered Oxides as Advanced Sodium-Ion Cathodes

Layered Na-based oxides with the general composition of Na x TMO 2 (TM: transition metal) have attracted significant attention for their high compositional diversity that provides tunable electrochemical performance for electrodes in sodium-ion batteries. The various compositions bring forward complex structural chemistry that is decisive for the layered stacking structure, Na-ion conductivity, and the redox activity, potentially promising new avenues in functional material properties. In this work, we have explored the maximum Na content in P2-type layered oxides and discovered that the high-content Na in the host enhances the structural stability; moreover, it promotes the oxidation of low-valent cations to their high oxidation states (in this case Ni 2+ ). This can be rationalized by the increased hybridization of the O(2p)-TM(3d-e g *) states, affecting both the local TM environment as well as the interactions between the NaO 2 and TMO 2 layers. These properties are highly beneficial for the Na storage capabilities as required for cathode materials in sodium-ion batteries. It leads to excellent Na-ion mobility, a large storage capacity (>100 mAh g –1 between 2.0-4.0 V), yet preventing the detrimental sliding of the TMO 2 layers (P2–O2 structural transition), as reflected by the ultralong cycle life (3000 (dis)charge cycles demonstrated). These findings expand the horizons of high Na-content P2-type materials, providing new insights of the electronic and structural chemistry for advanced cathode materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Cross-linked beta alumina nanowires with compact gel polymer electrolyte coating for ultra-stable sodium metal battery

Sodium metal batteries have potentially high energy densities, but severe sodium-dendrite growth and side reactions prevent their practical applications, especially at high temperatures. Herein, we design an inorganic ionic conductor/gel polymer electrolyte composite, where uniformly cross-linked beta alumina nanowires are compactly coated by a poly(vinylidene fluoride-co-hexafluoropropylene)-based gel polymer electrolyte through their strong molecular interactions. These beta alumina nanowires combined with the gel polymer layer create dense and homogeneous solid-liquid hybrid sodium-ion transportation channels through and along the nanowires, which promote uniform sodium deposition and formation of a stable and flat solid electrolyte interface on the sodium metal anode. Side reactions between the sodium metal and liquid electrolyte, as well as sodium dendrite formation, are successfully suppressed, especially at 60 °C. The sodium vanadium phosphate/sodium full cells with composite electrolyte exhibit 95.3% and 78.8% capacity retention after 1000 cycles at 1C at 25 °C and 60 °C, respectively.

Science & Technology - Other Topics↗
DOE OSTI2019

Evolution of Solid Electrolyte Interface on TiO 2 Electrodes in an Aqueous Li-Ion Battery Studied Using Scanning Electrochemical Microscopy

Scanning electrochemical microscopy (SECM) was applied for in situ visualization of solid electrolyte interface (SEI) evolution on the TiO 2 anode in a concentrated aqueous electrolyte during cycling. In nonaqueous electrolytes, the SEI is an electronic insulative layer composed of organic and inorganic components covering the electrode surface. However, in concentrated aqueous electrolytes, the SEI is mostly composed of inorganic compounds formed by electrolyte decomposition, such as LiF and Li 2 CO 3 , which are randomly distributed over the TiO 2 surface. In addition, the Ti 3+ and Li residuals accumulated through multiple cycling lead to an increase in the overall electronic conductivity of the TiO 2 anode. Furthermore during the resting period after cycling, an inverse process is observed with partial dissolution of the formed SEI and the diffusion of Li residuals back into the electrolyte.

25 ENERGY STORAGE↗
DOE OSTI2018

Compact 3D Copper with Uniform Porous Structure Derived by Electrochemical Dealloying as Dendrite-Free Lithium Metal Anode Current Collector

Here, the development of lithium (Li) metal anodes Li metal batteries faces huge challenges such as uncontrolled Li dendrite growth and large volume change during Li plating/stripping, resulting in severe capacity decay and high safety hazards. A 3D porous copper (Cu) current collector as a host for Li deposition can effectively settle these problems. However, constructing a uniform and compact 3D porous Cu structure is still an enormous challenge. Herein, an electrochemical etching method for Cu–Zinc (Zn) alloy is reported to precisely engrave a 3D Cu structure with uniform, smooth, and compact porous network. Such a continuous structure endows 3D Cu excellent mechanical properties and high electrical conductivity. The uniform and smooth pores with a large internal surface area ensures well dispersed current density for homogeneous Li metal deposition and accommodation. A smooth and stable solid electrolyte interphase is formed and meanwhile Li dendrites and dead Li are effectively suppressed. The Li metal anode conceived 3D Cu current collector can stably cycle for 400 h under an Li plating/stripping capacity of 1 mA h cm –2 and a current density of 1 mA cm –2 . The Li@3D Cu||LiFePO 4 full cells present excellent cycling and rate performances. The electrochemical dealloying is a robust method to construct 3D Cu current collectors for dendrite–free Li metal anodes.

25 ENERGY STORAGE↗
DOE OSTI2017

Dendrite-Free Potassium–Oxygen Battery Based on a Liquid Alloy Anode

The safety issue caused by the dendrite growth is not only a key research problem in lithium-ion batteries but also a critical concern in alkali metal (i.e., Li, Na, and K) oxygen batteries where a solid metal is usually used as the anode. Herein, we demonstrate the first dendrite-free K-O-2 battery at ambient temperature based on a liquid Na K alloy anode. The unique liquid liquid connection between the liquid alloy and the electrolyte in our alloy anode-based battery provides a homogeneous and robust anode electrolyte interface. Meanwhile, we manage to show that the Na K alloy is only compatible in K-O-2 batteries but not in Na-O-2 batteries, which is mainly attributed to the stronger reducibility of potassium and relatively more favorable thermodynamic formation of KO, over NaO2 during the discharge process. It is observed that our K-O-2 battery based on a liquid alloy anode shows a long cycle life (over 620 h) and a low discharge charge overpotential (about 0.05 V at initial cycles). Moreover, the mechanism investigation into the K-O-2 cell degradation shows that the 02 crossover effect and the ether electrolyte instability are the critical problems for K-O-2 batteries. In a word, this study provides a new route to solve the problems caused by the dendrite growth in alkali metal oxygen batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Systematic study of GeSn heterostructure-based light-emitting diodes towards mid-infrared applications

Temperature-dependent characteristics of GeSn light-emitting diodes with Sn composition up to 9.2% have been systematically studied. Such diodes were based on Ge/GeSn/Ge double heterostructures (DHS) that were grown directly on a Si substrate via a chemical vapor deposition system. Both photoluminescence and electroluminescence spectra have been characterized at temperatures from 300 to 77 K. Based on our theoretical calculation, all GeSn alloys in this study are indirect bandgap materials. However, due to the small energy separation between direct and indirect bandgap, and the fact that radiative recombination rate greater than non-radiative, the emissions are mainly from the direct Γ-valley to valence band transitions. The electroluminescence emissions under current injection levels from 102 to 357 A/cm{sup 2} were investigated at 300 K. The monotonic increase of the integrated electroluminescence intensity was observed for each sample. Moreover, the electronic band structures of the DHS were discussed. Despite the indirect GeSn bandgap owing to the compressive strain, type-I band alignment was achieved with the barrier heights ranging from 11 to 47 meV.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

The Effect of Potassium Impurities Deliberately Introduced into Activated Carbon Cathodes on the Performance of Lithium-Oxygen Batteries

Rechargeable lithium-air (Li-O 2 ) batteries have drawn much interest owing to their high energy density. We report on the effect of deliberately introducing potassium impurities into the cathode material on the electrochemical performance of a Li-O 2 battery. Small amounts of potassium introduced into the activated carbon (AC) cathode material in the synthesis process are found to have a dramatic effect on the performance of the Li-O 2 cell. An increased amount of potassium significantly increases capacity, cycle life, and round-trip efficiency. This improved performance is probably due to a larger amount of LiO 2 in the discharge product, which is a mixture of LiO 2 and Li 2 O 2 , resulting from the increase in the amount of potassium present. No substantial correlation with porosity or surface area in an AC cathode is found. Lastly, experimental and computational studies indicate that potassium can act as an oxygen reduction catalyst, which can account for the dependence of performance on the amount of potassium.

25 ENERGY STORAGE↗
DOE OSTI2015

Interfacial Effects on Lithium Superoxide Disproportionation in Li-O 2 Batteries

During the cycling of Li-O-2 batteries the discharge process gives rise to dynamically evolving agglomerates composed of lithium-oxygen nanostructures; however, little is known about their composition. In this paper, we present results for a Li-O-2 battery based on an activated carbon cathode that indicate interfacial effects can suppress disproportionation of a LiO2 component in the discharge product. High-intensity X-ray diffraction and transmission electron microscopy measurements are first used to show that there is a LiO2 component along with Li2O2 in the discharge product. The stability of the discharge product was then probed by investigating the dependence of the charge potential and Raman intensity of the superoxide peak with time. The results indicate that the LiO2 component can be stable for possibly up to days when an electrolyte is left on the surface of the discharged cathode. Density functional calculations on amorphous LiO2 reveal that the disproportionation process will be slower at an electrolyte/LiO2 interface compared to a vacuum/LiO2 interface. The combined experimental and theoretical results provide new insight into how interfacial effects can stabilize LiO2 and suggest that these interfacial effects may play an important role in the charge and discharge chemistries of a Li-O-2 battery.

interface↗
DOE OSTI2014

Raman Evidence for Late Stage Disproportionation in a Li–O 2 Battery

Raman spectroscopy is used to characterize the composition of toroids formed in an aprotic Li-O2 cell based on an activated carbon cathode. The trends in the Raman data as a function of discharge current density and charging cutoff voltage provide evidence that the toroids are made up of outer LiO2-like and inner Li2O2 regions, consistent with a disproportionation reaction occurring in the solid phase. The LiO2-like component is found to be associated with a new Raman peak identified in the carbon stretching region at ~1505 cm-1, which appears only when the LiO2 peak at 1123 cm-1 is present. The new peak is assigned to distortion of the graphitic ring stretching due to coupling with the LiO2-like component based on density functional calculations. The interface of the LiO2-like component with carbon surface should provide good electronic contact and is consistent with the low charge voltage plateau observed for it. These new results on the LiO2-like component from Raman spectroscopy provide evidence that a late stage disproportionation mechanism can occur during discharge and adds new understanding to the complexities of possible processes occurring in Li-O2 batteries.

25 ENERGY STORAGE↗
DOE OSTI2012

Formation and conversion mechanisms between single-crystal gamma-MnOOH and manganese oxides

Highlights: ► Single-crystal γ-MnOOH was obtained via hydrothermal method. ► α-MnO{sub 2} was transformed to γ-MnOOH by a dissolution-growth-recrystallization process. ► α-MnO{sub 2} preferred growth on (111{sup ¯}) crystal plane of γ-MnOOH. ► γ-MnOOH was a useful precursor to prepare manganese oxide via calcination. -- Abstract: Formation and conversion mechanisms between single-crystal gamma-MnOOH and manganese oxides had investigated systematically. Without extra surfactant or template, α-MnO{sub 2} nanorods and prismatic single crystalline γ-MnOOH rods had been synthesized under hydrothermal treatment in this study. The formation and conversion mechanisms of prismatic γ-MnOOH rod were investigated by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). It was found that the formation process includes three evolution stages: (1) formation of α-MnO{sub 2} nanorods whiskers; (2) transformation from α-MnO{sub 2} nanorods to prismatic γ-MnOOH rods by a dissolution-growth-recrystallization process; and (3) preferred growth on (111{sup ¯}) crystal plane. In addition, β-MnO{sub 2}, Mn{sub 2}O{sub 3} or Mn{sub 3}O{sub 4} rods could be obtained by calcination of the γ-MnOOH rods at different temperatures, which indicated that γ-MnOOH is an important precursor for preparing manganese oxides. The morphology and dimension of γ-MnOOH rods remained unchanged after converted to β-MnO{sub 2}, Mn{sub 2}O{sub 3} and Mn{sub 3}O{sub 4}.

36 MATERIALS SCIENCE↗