Doctor of Philosophy, Zhejiang University (2017)
Electrochemical generation of liquid and solid sulfur on two-dimensional layered materials with distinct areal capacities
View details for DOI 10.1038/s41565-019-0624-6
Ultrathin, flexible, solid polymer composite electrolyte enabled with aligned nanoporous host for lithium batteries.
The urgent need for safer batteries is leading research to all-solid-state lithium-based cells. To achieve energy density comparable to liquid electrolyte-based cells, ultrathin and lightweight solid electrolytes with high ionic conductivity are desired. However, solid electrolytes with comparable thicknesses to commercial polymer electrolyte separators (~10mum) used in liquid electrolytes remain challenging to make because of the increased risk of short-circuiting the battery. Here, we report on a polymer-polymer solid-state electrolyte design, demonstrated with an 8.6-mum-thick nanoporous polyimide (PI) film filled with polyethylene oxide/lithium bis(trifluoromethanesulfonyl)imide (PEO/LiTFSI) that can be used as a safe solid polymer electrolyte. The PI film is nonflammable and mechanically strong, preventing batteries from short-circuiting even after more than 1,000h of cycling, and the vertical channels enhance the ionic conductivity (2.3*10-4Scm-1 at 30°C) of the infused polymer electrolyte. All-solid-state lithium-ion batteries fabricated with PI/PEO/LiTFSI solid electrolyte show good cycling performance (200 cycles at C/2 rate) at 60°C and withstand abuse tests such as bending, cutting and nail penetration.
View details for DOI 10.1038/s41565-019-0465-3
View details for PubMedID 31133663
- Fast lithium growth and short circuit induced by localized-temperature hotspots in lithium batteries NATURE COMMUNICATIONS 2019; 10
In Situ X-ray Absorption Spectroscopic Investigation of the Capacity Degradation Mechanism in Mg/S Batteries.
The Mg/S battery is attractive because of its high theoretical energy density and the abundance of Mg and S on the earth. However, its development is hindered by the lack of understanding to the underlying electrochemical reaction mechanism of its charge-discharge processes. Here, using a unique in situ X-ray absorption spectroscopic tool, we systematically study the reaction pathways of the Mg/S cells in Mg(HMDS)2-AlCl3 electrolyte. We find that the capacity degradation is mainly due to the formation of irreversible discharge products, such as MgS and Mg3S8, through a direct electrochemical deposition or a chemical disproportionation of intermediate polysulfide. In light of the fundamental understanding, we propose to use TiS2 as a catalyst to activate the irreversible reaction of low-order MgS x and MgS, which results in an increased discharging capacity up to 900 mAh·g-1 and a longer cycling life.
View details for PubMedID 30932498
- An Interconnected Channel-Like Framework as Host for Lithium Metal Composite Anodes ADVANCED ENERGY MATERIALS 2019; 9 (7)
Wrinkled Graphene Cages as Hosts for High-Capacity Li Metal Anodes Shown by Cryogenic Electron Microscopy.
Lithium (Li) metal has long been considered the "holy grail" of battery anode chemistry but is plagued by low efficiency and poor safety due to its high chemical reactivity and large volume fluctuation, respectively. Here we introduce a new host of wrinkled graphene cage (WGC) for Li metal. Different from recently reported amorphous carbon spheres, WGC show highly improved mechanical stability, better Li ion conductivity, and excellent solid electrolyte interphase (SEI) for continuous robust Li metal protection. At low areal capacities, Li metal is preferentially deposited inside the graphene cage. Cryogenic electron microscopy characterization shows that a uniform and stable SEI forms on the WGC surface that can shield the Li metal from direct exposure to electrolyte. With increased areal capacities, Li metal is plated densely and homogeneously into the outer pore spaces between graphene cages with no dendrite growth or volume change. As a result, a high Coulombic efficiency (CE) of 98.0% was achieved under 0.5 mA/cm2 and 1-10 mAh/cm2 in commercial carbonate electrolytes, and a CE of 99.1% was realized with high-concentration electrolytes under 0.5 mA/cm2 and 3 mAh/cm2. Full cells using WGC electrodes with prestored Li paired with Li iron phosphate showed greatly improved cycle lifetime. With 10 mAh/cm2 Li metal deposition, the WGC/Li compositeanodewas able to provide a high specific capacity of 2785 mAh/g. With its roll-to-roll compatible fabrication procedure, WGC serves as a highly promising material for the practical realization of Li metal anodes in next-generation high energy density secondary batteries.
View details for PubMedID 30676759
Nanostructural and Electrochemical Evolution of the Solid-Electrolyte Interphase on CuO Nanowires Revealed by Cryogenic-Electron Microscopy and Impedance Spectroscopy
2019; 13 (1): 737–44
Battery performance is critically dependent on the nanostructure and electrochemical properties of the solid-electrolyte interphase (SEI) - a passivation film that exists on most lithium battery anodes. However, knowledge of how the SEI nanostructure forms and its impact on ionic transport remains limited due to its sensitivity to transmission electron microscopy and difficulty in accurately probing the SEI impedance. Here, we track the voltage-dependent, stepwise evolution of the nanostructure and impedance of the SEI on CuO nanowires using cryogenic-electron microscopy (cryo-EM) and electrochemical impedance spectroscopy (EIS). In carbonate electrolyte, the SEI forms at 1.0 V vs Li/Li+ as a 3 nm-thick amorphous SEI and grows to 4 nm at 0.5 V; as the potential approaches 0.0 V vs Li/Li+, the SEI on the CuO nanowires forms an 8 nm-thick inverted multilayered nanostructure in ethylene carbonate/diethyl carbonate (EC/DEC) electrolyte with 10 vol. % fluoroethylene carbonate (FEC) and a mosaic nanostructure in EC/DEC electrolyte. Upon Li deposition, the total SEI thickness grows to 16 nm and significant growth of the inner amorphous layer takes place in the inverted multilayered nanostructure, indicating electrolyte permeates the SEI. Using a refined EIS methodology, we isolate the SEI impedance on Cu and find that the SEI nanostructure directly correlates to macroscopic Li-ion transport through the SEI. The inverted layered nanostructure decreases the interfacial impedance upon formation, whereas the mosaic nanostructure continually increases the interfacial impedance during growth. These structural and electrochemical findings illustrate a more complete portrait of SEI formation and guide further improvements in engineered SEI.
View details for DOI 10.1021/acsnano.8b08012
View details for Web of Science ID 000456749900075
View details for PubMedID 30589528