Zn metal anodes stabilized by an intrinsically safe, dilute, and hydrous organic electrolyte

From Anode to Cell: Synergistic Protection Strategies and Perspectives for Stabilized Zn Metal in Mild Aqueous Electrolytes

Sn-doped BiOCl nanosheet with synergistic H+/Zn2+ co-insertion for “rocking chair” zinc-ion battery

Novel small sulfur heterocyclic quinones (6a,16a-dihydrobenzo[b]naphtho[2',3':5,6][1,4]dithiino[2,3-i]thianthrene-5,7,9,14,16,18-hexaone (4S6Q) and benzo[b]naphtho[2',3':5,6][1,4]dithiino[2,3-i]thianthrene-5,9,14,18-tetraone (4S4Q)) are developed by molecule structural design method and as cathode for aqueous zinc-organic batteries. The conjugated thioether (-S-) bonds as connected units not only improve the conductivity of compounds but also inhibit their dissolution by both extended π-conjugated plane and constructed flexible molecular skeleton. Hence, the Zn//4S6Q and Zn//4S4Q batteries exhibit satisfactory electrochemical performance based on 3.5 mol L-1 (M) Zn(ClO4)2 electrolyte. For instance, the Zn//4S6Q battery obtains 240 and 208.6 mAh g-1 of discharge capacity at 150 mA g-1 and 30 A g-1, respectively. The excellent rate capability is ascribed to the fast reaction kinetics. This system displays a superlong life of 20,000 cycles with no capacity fading at 3 A g-1. Additionally, the H+-storage mechanism of the 4S6Q compound is demonstrated by ex situ analyses and density functional theory calculations. Impressively, the battery can normally work at - 60 °C benefiting from the anti-freezing electrolyte and maintain a high discharge capacity of 201.7 mAh g-1, which is 86.2% of discharge capacity at 25 °C. The cutting-edge electrochemical performances of these novel compounds make them alternative electrode materials for Zn-organic batteries. 

https://link.springer.com/content/pdf/10.1007/s40820-022-01009-x.pdf

Molecular Engineering Design for High-Performance Aqueous Zinc-Organic Battery

Safety is a major challenge plaguing the use of Li-ion batteries (LIBs) in electric vehicle (EV) applications. A wide range of operating conditions with varying temperatures and drive cycles can lead to battery abuse. A dangerous consequence of these abuses is thermal runaway (TR), an exponential increase in temperature inside the battery caused by the exothermic decomposition of the cell materials that leads to fire and explosion. It is imperative to develop methodologies to accurately predict and mitigate thermal runway. Sodium-ion batteries (SIBs) are inherently safer than LIBs. In addition to offering better safety, SIBs are gaining momentum due to the abundance and low cost of their raw materials compared to the limited lithium resources and high cost of elements such as cobalt, copper, and nickel used in LIBs. However, the challenge of low energy density impedes the maturation of sodium-ion technology to the same level as lithium-ion technology. There are additional challenges to the acceptability of sodium-ion batteries due to the poor sodium kinetics during insertion reactions, leading to rapid material degradation. Additionally, the higher solubility of the solid electrolyte interface (SEI) observed in the case of SIBs may lead to undesired side reactions, causing increased heat generation. This paper presents a comprehensive review of the heat-release mechanisms, their differences, and prediction methodologies for the two battery chemistries. Various experimental and modeling approaches for TR detection from the literature are reviewed. Future research directions toward the development of a battery management system (BMS) with the capability to identify the precursors to thermal runaway and implement mitigation strategies are also discussed. 

Thermal Behavior of Lithium- and Sodium-Ion Batteries: A Review on Heat Generation, Battery Degradation, Thermal Runway – Perspective and Future Directions

Despite a promising outlook due to the intrinsic low cost and high safety, the practical application of aqueous Zn‐ion battery is impeded by the severe mutual problems of cathode dissolution, electrolyte parasitic reactions, and metallic anode dendrite growth. Herein, a triple‐functional strategy is proposed that a polyoxovanadate (POV) cluster of K10[VIV16VV18O82] as a promising Zn2+ host can concomitantly stabilize the cluster cathode, aqueous electrolyte, and metallic Zn anode. An in situ generated cathode electrolyte interface via anodic oxidation is identified as effective in preventing the dissolution of POV cathode. Molecular dynamics simulation and density functional theory calculation confirm that the [VIV16VV18O82]10− polyoxoanions can synergistically suppress electrolyte side reactions by modulating the primary solvation shell of Zn2+‐6H2O, and random anode dendrite growth by in situ constructing a stable solid electrolyte interface of Zn‐POV. As a result, the Zn//POV battery exhibits unprecedented cycling durability over 10 000 cycles at high rates of 5 and 12 A g−1. In a systematic consideration, the findings enlighten the origin of triple‐functional polyoxometalates and will significantly propel the practical development of aqueous batteries.

Triple‐Functional Polyoxovanadate Cluster in Regulating Cathode, Anode, and Electrolyte for Tough Aqueous Zinc‐Ion Battery

The safety, durability and power density of lithium‐ion batteries (LIBs) are currently inadequate to satisfy the continuously growing demand of the emerging battery markets. Rapid progress has been made from material engineering to system design, combining experimental results and simulations to enhance LIB performance. Limited by spatial and temporal resolution, state‐of‐the‐art advanced characterization techniques fail to fully reveal the complex multi‐scale degradation mechanism in LIBs. Strengthening interaction and iteration between characterization and modeling improves the understanding of reaction mechanisms as well as design and management of LIBs. Herein, a seed cyber hierarchy and interactional network framework is demonstrated to evaluate the overall lifecycle of LIBs. The typical examples of bridging the characterization techniques and modeling are discussed. The critical parameters extracted from multi‐scale characterization can serve as digital inputs for modeling. Furthermore, advanced computational techniques including cloud computing, big data, machine learning, and artificial intelligence can also promote the comprehensive understanding and precise control of the whole battery lifecycle. Digital twins techniques will be introduced enabling the real‐time monitoring and control of LIBs, autonomous computer‐assisted characterizations and intelligent manufacturing. It is anticipated that this work will provide a roadmap for further intensive research on developing high‐performance LIBs and intelligent battery management.

Bridging Multiscale Characterization Technologies and Digital Modeling to Evaluate Lithium Battery Full Lifecycle

Highly aligned lithiophilic electrospun nanofiber membrane for the multiscale suppression of Li dendrite growth

High‐level safety is of vital importance to the continuous pursuit of high‐energy‐density batteries in the increasingly electrified world. The thermal instability and dendrite‐induced issues of conventional polypropylene (PP) separators often cause internal short circuits and thermal runaway in batteries. Herein, a thermally stable and dendrite‐resistant separator (F‐PPTA@PP) is constructed using a dual‐functional and easy‐to‐commercialize design strategy of thermally safe poly‐p‐phenylene‐terephthamide nanofibers and plasma‐induced lithiophilic fluorine‐containing groups. In situ thermal monitoring, in situ optical observation, and multiphysics simulation demonstrate that F‐PPTA@PP can suppress thermal shrinkage of the separator and the formation of hotspots, and also promote uniform lithium deposition. Subsequently, lithium metal batteries are assembled, featuring an initial capacity of 194.1 mAh g–1 at 0.5 C with a low‐capacity attenuation of 0.02% per cycle over 1000 cycles. When operating under extreme conditions, i.e., −10 and 100 °C, ultrafast charging/discharging rates up to 30 C, lean electrolyte (2.4 µL mg–1)/high mass‐loading (10.77 mg cm–2) or lithium‐sulfur batteries, F‐PPTA@PP separator still enables competitive electrochemical performance, highlighting its plausible processing scalability for high‐safety energy storage systems.

Kai Yang

Papers

Triple‐Functional Polyoxovanadate Cluster in Regulating Cathode, Anode, and Electrolyte for Tough Aqueous Zinc‐Ion Battery

Bridging Multiscale Characterization Technologies and Digital Modeling to Evaluate Lithium Battery Full Lifecycle

Highly aligned lithiophilic electrospun nanofiber membrane for the multiscale suppression of Li dendrite growth

Thermally Stable and Dendrite‐Resistant Separators toward Highly Robust Lithium Metal Batteries

Design principles in MOF-derived electromagnetic wave absorption materials: Review and perspective