Lithium-Ion-Conducting Ceramics-Coated Separator for Stable Operation of Lithium Metal-Based Rechargeable Batteries

AbstractUncontrollable dendrite growth resulting from the non-uniform lithium ion (Li+) flux and volume expansion in lithium metal (Li) negative electrode leads to rapid performance degradation and serious safety problems of lithium metal batteries. Although N-containing functional groups in carbon materials are reported to be effective to homogenize the Li+ flux, the effective interaction distance between lithium ions and N-containing groups should be relatively small (down to nanometer scale) according to the Debye length law. Thus, it is necessary to carefully design the microstructure of N-containing carbon materials to make the most of their roles in regulating the Li+ flux. In this work, porous carbon nitride microspheres (PCNMs) with abundant nanopores have been synthesized and utilized to fabricate a uniform lithiophilic coating layer having hybrid pores of both the nano- and micrometer scales on the Cu/Li foil. Physically, the three-dimensional (3D) porous framework is favorable for absorbing volume changes and guiding Li growth. Chemically, this coating layer can render a suitable interaction distance to effectively homogenize the Li+ flux and contribute to establishing a robust and stable solid electrolyte interphase (SEI) layer with Li-F, Li-N, and Li-O-rich contents based on the Debye length law. Such a physical-chemical synergic regulation strategy using PCNMs can lead to dendrite-free Li plating, resulting in a low nucleation overpotential and stable Li plating/stripping cycling performance in both the Li‖Cu and the Li‖Li symmetric cells. Meanwhile, a full cell using the PCNM coated Li foil negative electrode and a LiFePO4 positive electrode has delivered a high capacity retention of ∼ 80% after more than 200 cycles at 1 C and achieved a remarkable rate capability. The pouch cell fabricated by pairing the PCNM coated Li foil negative electrode with a NCM 811 positive electrode has retained ∼ 73% of the initial capacity after 150 cycles at 0.2 C.

Download Full-text

Effect of thickness of coating layer on polymer-coated separator on cycling performance of lithium-ion polymer cells

Journal of Power Sources ◽

10.1016/j.jpowsour.2003.09.073 ◽

2004 ◽

Vol 128 (2) ◽

pp. 256-262 ◽

Cited By ~ 62

Author(s):

Yeon-Bok Jeong ◽

Dong-Won Kim

Keyword(s):

Coating Layer ◽

Lithium Ion ◽

Cycling Performance ◽

Coated Separator

Download Full-text

PEO Infiltration of Porous Garnet-Type Lithium-Conducting Solid Electrolyte Thin Films

Ceramics ◽

10.3390/ceramics4030031 ◽

2021 ◽

Vol 4 (3) ◽

pp. 421-436

Author(s):

Aamir Iqbal Waidha ◽

Vanita Vanita ◽

Oliver Clemens

Keyword(s):

Thin Films ◽

Solid State ◽

Ionic Conductivity ◽

Electrochemical Impedance ◽

Three Dimensional ◽

Lithium Ion ◽

Interfacial Resistance ◽

Composite Electrolytes ◽

Ion Conducting ◽

Polymer Infiltration

Composite electrolytes containing lithium ion conducting polymer matrix and ceramic filler are promising solid-state electrolytes for all solid-state lithium ion batteries due to their wide electrochemical stability window, high lithium ion conductivity and low electrode/electrolyte interfacial resistance. In this study, we report on the polymer infiltration of porous thin films of aluminum-doped cubic garnet fabricated via a combination of nebulized spray pyrolysis and spin coating with subsequent post annealing at 1173 K. This method offers a simple and easy route for the fabrication of a three-dimensional porous garnet network with a thickness in the range of 50 to 100 µm, which could be used as the ceramic backbone providing a continuous pathway for lithium ion transport in composite electrolytes. The porous microstructure of the fabricated thin films is confirmed via scanning electron microscopy. Ionic conductivity of the pristine films is determined via electrochemical impedance spectroscopy. We show that annealing times have a significant impact on the ionic conductivity of the films. The subsequent polymer infiltration of the porous garnet films shows a maximum ionic conductivity of 5.3 × 10−7 S cm−1 at 298 K, which is six orders of magnitude higher than the pristine porous garnet film.

Download Full-text

Enhanced Li+ Conduction Within Single-Ion Conducting Crosslinked Gel via Reduced Cation-Polymer Interaction

10.26434/chemrxiv.11102762 ◽

2019 ◽

Author(s):

Hunter O. Ford ◽

Bumjun Park ◽

Jizhou Jiang ◽

Jennifer Schaefer

Keyword(s):

Lithium Ion ◽

High Conductivity ◽

Ion Concentration ◽

Design Parameters ◽

Lithium Metal ◽

Glycol Diacrylate ◽

Carbonate Solutions ◽

Polymer Interactions ◽

Ion Conducting ◽

Poly Ethylene

The development of advanced electrolytes compatible with lithium metal and lithium-ion batteries is crucial for meeting ever growing energy storage demands. One such class of materials, single-ion conducting polymer electrolytes (SIPEs), prevents the formation of ion concentration gradients and buildup of anions at the electrode surface, improving performance. One of the ongoing challenges for SIPEs is the development of materials that are conductive enough to compete with liquid electrolytes. Presented herein is a class of gel SIPEs based on crosslinked poly(tetrahydrofuran) diacrylate that present enhanced room temperature conductivities of 3.5 × 10-5 S/cm when gelled with lithium metal relevant 1,3-dioxolane/dimethoxyethane, 2.5 × 10-4 S/cm with carbonate solutions, and approaching 10-3 S/cm with dimethyl sulfoxide. Remarkably, these materials also demonstrate high conductivity at low temperatures, 1.8 × 10-5 S/cm at -20 °C in certain solvents. Most importantly however, when contrasted with identical SIPEs formulated with poly(ethylene glycol) diacrylate, the mechanisms responsible for the enhanced conductivity are elucidated: decreasing Li+-polymer interactions and gel solvent-polymer interactions leads to an increase in Li+ mobility, improving the ionic conductivity. These findings are generalizable to various SIPE chemistries, and can therefore be seen as an additional set of design parameters for developing future high conductivity SIPEs.

Download Full-text

Enhanced Li+ Conduction Within Single-Ion Conducting Crosslinked Gel via Reduced Cation-Polymer Interaction

10.26434/chemrxiv.11102762.v1 ◽

2019 ◽

Author(s):

Hunter O. Ford ◽

Bumjun Park ◽

Jizhou Jiang ◽

Jennifer Schaefer

Keyword(s):

Lithium Ion ◽

High Conductivity ◽

Ion Concentration ◽

Design Parameters ◽

Lithium Metal ◽

Glycol Diacrylate ◽

Carbonate Solutions ◽

Polymer Interactions ◽

Ion Conducting ◽

Poly Ethylene

The development of advanced electrolytes compatible with lithium metal and lithium-ion batteries is crucial for meeting ever growing energy storage demands. One such class of materials, single-ion conducting polymer electrolytes (SIPEs), prevents the formation of ion concentration gradients and buildup of anions at the electrode surface, improving performance. One of the ongoing challenges for SIPEs is the development of materials that are conductive enough to compete with liquid electrolytes. Presented herein is a class of gel SIPEs based on crosslinked poly(tetrahydrofuran) diacrylate that present enhanced room temperature conductivities of 3.5 × 10-5 S/cm when gelled with lithium metal relevant 1,3-dioxolane/dimethoxyethane, 2.5 × 10-4 S/cm with carbonate solutions, and approaching 10-3 S/cm with dimethyl sulfoxide. Remarkably, these materials also demonstrate high conductivity at low temperatures, 1.8 × 10-5 S/cm at -20 °C in certain solvents. Most importantly however, when contrasted with identical SIPEs formulated with poly(ethylene glycol) diacrylate, the mechanisms responsible for the enhanced conductivity are elucidated: decreasing Li+-polymer interactions and gel solvent-polymer interactions leads to an increase in Li+ mobility, improving the ionic conductivity. These findings are generalizable to various SIPE chemistries, and can therefore be seen as an additional set of design parameters for developing future high conductivity SIPEs.

Download Full-text

Novel Co3O4/Carbon Nanofiber Composite Electrode with High Li-Storage Capacity for Lithium Ion Batteries

Advanced Materials Research ◽

10.4028/www.scientific.net/amr.197-198.1113 ◽

2011 ◽

Vol 197-198 ◽

pp. 1113-1116 ◽

Cited By ~ 4

Author(s):

Wen Li Yao ◽

Jin Qing Chen ◽

An Yun Li ◽

Xin Bing Chen

Keyword(s):

Composite Materials ◽

Lithium Ion Batteries ◽

Electrode Materials ◽

Storage Capacity ◽

Carbon Nanofiber ◽

Negative Electrode ◽

Lithium Ion ◽

Reversible Capacity ◽

Cycling Performance ◽

Li Storage

The platelike Co3O4/carbon nanofiber (CNF) composite materials were synthesized by the calcination of β-Co(OH)2/CNF precursor prepared by a surfactant-free hydrothermal method. As negative electrode materials for lithium-ion batteries, the platelike Co3O4/CNF composites can deliver a high reversible capacity of 900 mAh g-1 for a life extending over hundreds of cycles at a current density of 100 mA g-1. The high Li-storage capacity and excellent cycling performance for Co3O4/CNF composite materials may mainly attribute to the beneficial effect of the CNFs addition on enhancing structural stability and electrical conductivity of Co3O4 platelets.

Download Full-text