Aqueous zinc-ion batteries, in terms of integration with high safety, environmental benignity, and low cost, have attracted much attention for powering electronic devices and storage systems. However, the interface instability issues at the Zn anode caused by detrimental side reactions such as dendrite growth, hydrogen evolution, and metal corrosion at the solid (anode)/liquid (electrolyte) interface impede their practical applications in the fields requiring long-term performance persistence. Despite the rapid progress in suppressing the side reactions at the materials interface, the mechanism of ion storage and dendrite formation in practical aqueous zinc-ion batteries with dual-cation aqueous electrolytes is still unclear. Herein, we design an interface material consisting of forest-like three-dimensional zinc-copper alloy with engineered surfaces to explore the Zn plating/stripping mode in dual-cation electrolytes. The three-dimensional nanostructured surface of zinc-copper alloy is demonstrated to be in favor of effectively regulating the reaction kinetics of Zn plating/stripping processes. The developed interface materials suppress the dendrite growth on the anode surface towards high-performance persistent aqueous zinc-ion batteries in the aqueous electrolytes containing single and dual cations. This work remarkably enhances the fundamental understanding of dual-cation intercalation chemistry in aqueous electrochemical systems and provides a guide for exploring high-performance aqueous zinc-ion batteries andmore »
Metal anode instability, including dendrite growth, metal corrosion, and hetero-ions interference, occurring at the electrolyte/electrode interface of aqueous batteries, are among the most critical issues hindering their widespread use in energy storage. Herein, a universal strategy is proposed to overcome the anode instability issues by rationally designing alloyed materials, using Zn-M alloys as model systems (M = Mn and other transition metals). An in-situ optical visualization coupled with finite element analysis is utilized to mimic actual electrochemical environments analogous to the actual aqueous batteries and analyze the complex electrochemical behaviors. The Zn-Mn alloy anodes achieved stability over thousands of cycles even under harsh electrochemical conditions, including testing in seawater-based aqueous electrolytes and using a high current density of 80 mA cm−2. The proposed design strategy and the in-situ visualization protocol for the observation of dendrite growth set up a new milestone in developing durable electrodes for aqueous batteries and beyond.
- Publication Date:
- NSF-PAR ID:
- 10209430
- Journal Name:
- Nature Communications
- Volume:
- 12
- Issue:
- 1
- ISSN:
- 2041-1723
- Publisher:
- Nature Publishing Group
- Sponsoring Org:
- National Science Foundation
More Like this
-
Abstract -
Lithium metal as an anode has been widely accepted due to its higher negative electrochemical potential and theoretical capacity. Nevertheless, the existing safety and cyclability issues limit lithium metal anodes from practical use in high-energy density batteries. Repeated Li deposition and dissolution processes upon cycling lead to the formation of dendrites at the interface which results in reduced Li availability for electrochemical reactions, disruption in Li transport through the interface and increased safety concerns due to short circuiting. Here, we demonstrate a novel strategy using Ionic Liquid Crystals (ILCs) as the electrolyte cum pseudo-separator to suppress dendrite growth with their anisotropic properties controlling Li-ion mass transport. A thermotropic ILC with two-dimensional Li-ion conducting pathways was synthesized and characterized. Microscopic and spectroscopic analyses elucidate that the ILC formed with a smectic A phase, which can be utilized for wide temperature window operation. The results of electrochemical studies corroborate the efficacy of ILC electrolytes in mitigating dendrite formation even after 850 hours and it is further substantiated by numerical simulation and the mechanism involved in dendritic suppression was deduced.
-
Solid-state-batteries (SSBs) present a promising technology for next-generation batteries due to their superior properties including increased energy density, wider electrochemical window and safer electrolyte design. Commercialization of SSBs, however, will depend on the resolution of a number of critical chemical and mechanical stability issues. The resolution of these issues will in turn depend heavily on our ability to accurately model these systems such that appropriate material selection, microstructure design, and operational parameters may be determined. In this article we review the current state-of-the art modeling tools with a focus on chemo-mechanics. Some of the key chemo-mechanical problems in SSBs involve dendrite growth through the solid-state electrolyte (SSE), interphase formation at the anode/SSE interface, and damage/decohesion of the various phases in the solid-state composite cathode. These mechanical processes in turn lead to capacity fade, impedance increase, and short-circuit of the battery, ultimately compromising safety and reliability. The article is divided into the three natural components of an all-solid-state architecture. First, modeling efforts pertaining to Li-metal anodes and dendrite initiation and growth mechanisms are reviewed, making the transition from traditional liquid electrolyte anodes to next generation all-solid-state anodes. Second, chemo-mechanics modeling of the SSE is reviewed with a particular focus on themore »
-
Suffering from critical instability of lithium (Li) anode, the most commercial electrolytes, carbonate-ester electrolytes, have been restrictedly used in high-energy Li metal batteries (LMBs) despite of their broad implementation in lithium-ion batteries. Here, abundant, natural corn protein, zein, is exploited as a novel additive to stabilize Li anode and effectively prolong the cycling life of LMBs based on carbonate-ester electrolyte. It is discovered that the denatured zein is involved in the formation of solid electrolyte interphase (SEI), guides Li+ deposition and repairs the cracked SEI. In specific, the zein-rich SEI benefits the anion immobilization, enabling uniform Li+ deposition to diminish dendrite growth; the preferential zein-Li reaction effectively repairs the cracked SEI, protecting Li from parasite reactions. The resulting symmetrical Li cell exhibits a prolonged cycling life to over 350 h from <200 h for pristine cell at 1 mA cm 2 with a capacity of 1 mAh cm^ 2. Paired with LiFePO4 cathode, zein additive markedly improves the electrochemical performance including a higher capacity of 130.1 mAh g^ 1 and a higher capacity retention of ~ 80 % after 200 cycles at 1 C. This study demonstrates a natural protein to be an effective additive for the most commercial electrolytesmore »
-
Flexible and low-cost poly(ethylene oxide) (PEO)-based electrolytes are promising for all-solid-state Li-metal batteries because of their compatibility with a metallic lithium anode. However, the low room-temperature Li-ion conductivity of PEO solid electrolytes and severe lithium-dendrite growth limit their application in high-energy Li-metal batteries. Here we prepared a PEO/perovskite Li 3/8 Sr 7/16 Ta 3/4 Zr 1/4 O 3 composite electrolyte with a Li-ion conductivity of 5.4 × 10 −5 and 3.5 × 10 −4 S cm −1 at 25 and 45 °C, respectively; the strong interaction between the F − of TFSI − (bis-trifluoromethanesulfonimide) and the surface Ta 5+ of the perovskite improves the Li-ion transport at the PEO/perovskite interface. A symmetric Li/composite electrolyte/Li cell shows an excellent cyclability at a high current density up to 0.6 mA cm −2 . A solid electrolyte interphase layer formed in situ between the metallic lithium anode and the composite electrolyte suppresses lithium-dendrite formation and growth. All-solid-state Li|LiFePO 4 and high-voltage Li|LiNi 0.8 Mn 0.1 Co 0.1 O 2 batteries with the composite electrolyte have an impressive performance with high Coulombic efficiencies, small overpotentials, and good cycling stability.