Dressing Paraffin Wax/Boron Nitride Phase Change Composite with a Polyethylene "Underwear" for the Reliable Battery Safety Management.

Phase change material (PCM) can provide a battery system with a buffer platform to respond to thermal failure problems. However, current PCMs through compositing inorganics still suffer from insufficient thermal-transport behavior and safety reliability against external force. Herein, a best-of-both-worlds method is reported to allow the PCM out of this predicament. It is conducted by combining a traditional PCM (i.e., paraffin wax/boron nitride) with a spirally weaved polyethylene fiber fabric, just like the traditional PCM is wearing functional underwear. On the one hand, the spirally continuous thermal pathways of polyethylene fibers in the fabric collaborate with the boron nitride network in the PCM, enhancing the through-plane and in-plane thermal conductivity to 10.05 and 7.92 W m-1 K, respectively. On the other, strong polyethylene fibers allow the PCM to withstand a high puncture strength of 47.13 N and tensile strength of 18.45 MPa although above the phase transition temperature. After this typical PCM packs a triple Li-ion battery system, the battery can be promised reliable safety management against both thermal and mechanical abuse. An obvious temperature drop of >10 °C is observed in the battery electrode during the cycling charging and discharging process.

Critical Effects of Insoluble Additives in Liquid Electrolytes for Metal Batteries.

Rechargeable metal batteries have received widespread attention due to their high energy density by using pure metal as the anode. However, there are still many fundamental problems that need to be solved before approaching practical applications. The critical ones are low charge/discharge current due to slow ion transport, short cycle lifetime due to poor anode/cathode stability, and unsatisfied battery safety. To tackle these problems, various strategies have been suggested. Among them, electrolyte additive is one of the most widely used strategies. Most of the additives currently studied are soluble, but their reliability is questionable, and they can easily affect the electrochemical process, causing unwanted battery performance decline. On the contrary, insoluble additives with excellent chemical stability, high mechanical strength, and dimensional tunability have attracted considerable research exploration recently. However, there is no timely review on insoluble additives in metal batteries yet. This review summarizes various functions of insoluble additives: ion transport modulation, metal anode protection, cathode amelioration, as well as battery safety enhancement. Future research directions and challenges for insoluble solid additives are also proposed. It is expected this review will stimulate inspiration and arouse extensive studies on further improvement in the overall performance of metal batteries.

Full-Dimensional Analysis of Gaseous Products to Unlocking In Depth Thermal Runaway Mechanism of Li-Ion Batteries.

In this study, state-of-the-art on-line pyrolysis MS (OP-MS) equipped with temperature-controlled cold trap and on-line pyrolysis GC/MS (OP-GC/MS) injected through high-vacuum negative-pressure gas sampling (HVNPGS) programming are originally designed/constructed to identify/quantify the dynamic change of common permanent gases and micromolecule organics from the anode/cathode-electrolyte reactions during thermal runaway (TR) process, and corresponding TR mechanisms are further perfected/complemented. On LiCx anode side, solid electrolyte interphase (SEI) would undergo continuous decomposition and regeneration, and the R-H+ (e.g., HF, ROH, etc.) species derived from electrolyte decomposition would continue to react with Li/LiCx to generate H2. Up to above 200 °C, the O2 would release from the charged NCM cathode and organic radicals would be consumed/oxidized by evolved O2 to form COx, H2O, and more corrosive HF. On the contrary, charged LFP cathode does not present obvious O2 evolution during heating process and the unreacted flammable/toxic organic species would exit in the form of high temperature/high-pressure (HT/HP) vapors within batteries, indicating higher potential safety risks. Additionally, the in depth understanding of the TR mechanism outlined above provides a clear direction for the design/modification of thermostable electrodes and non-flammable electrolytes for safer batteries.

In Situ Growth Strategy to Construct "Four-In-One" Separators with Functionalized Polyphosphazene Coatings for Safe and Stable Lithium-Sulfur Batteries.

Lithium-sulfur batteries (LSBs) are facing many challenges, such as the inadequate conductivity of sulfur, the shuttle effect caused by lithium polysulfide (LiPSs), lithium dendrites, and the flammability, which have hindered their commercial applications. Herein, a "four-in-one" functionalized coating is fabricated on the surface of polypropylene (PP) separator by using a novel flame-retardant namely InC-HCTB to meet these challenges. InC-HCTB is obtained by cultivating polyphosphazene on the surface of carbon nanotubes with an in situ growth strategy. First, this unique architecture fosters an enhanced conductive network, bolstering the bidirectional enhancement of both ionic and electronic conductivities. Furthermore, InC-HCTB effectively inhibits the shuttle effect of LiPSs. LSBs exhibit a remarkable capacity of 1170.7 mA h g-1 at 0.2 C, and the capacity degradation is a mere 0.0436% over 800 cycles at 1 C. Third, InC-HCTB coating serves as an ion migration network, hindering the growth of lithium dendrites. More importantly, InC-HCTB exhibits notable flame retardancy. The radical trapping action in the gas phase and the protective effect of the shielded char layer in the condensed phase are simulated and verified. This facile in situ growth strategy constructs a "four-in-one" functional separator coating, rendering InC-HCTB a promising additive for the large-scale production of safe and stable LSBs.

DNA Helix Structure Inspired Flexible Lithium-Ion Batteries with High Spiral Deformability and Long-Lived Cyclic Stability.

With the development of flexible devices, it is necessary to design high-performance power supplies with superior flexibility, durability, safety, etc., to ensure that they can be deformed with the device while retaining their electrochemical functions. Herein, we have designed a flexible lithium-ion battery inspired by the DNA helix structure. The battery structure is mainly composed of multiple thick energy stacks for energy storage and some grooves for stress buffers, which realized the spiral deformation of batteries. According to the results, the batteries exhibit less than 3% capacity degradation even after more than 31000 times of in situ dynamic mechanical loadings. Moreover, the mechanism of the battery with spiral deformability is further revealed. It is anticipated that this bioinspired design strategy could create unique opportunities for the commercialization of flexible batteries and fill the current gap in realizing battery-specific deformations to meet various requirements for future complex device designs.

Early Braking of Overwarmed Lithium-Ion Batteries by Shape-Memorized Current Collectors.

In the context of the constant impending energy crisis, the lithium-ion battery as a burgeoning energy storage means is showing extraordinary talents in many energy relevant investigations. However, fire and explosion would probably occur when the battery is encountered with overheating, at which the shrinking of the separator routinely causes an internal short circuit. Herein, we develop a kind of novel shape-memorized current collector (SMCC), which can successfully brake battery thermal runaway at the battery internal overheating status. Unlike traditional current collectors made of commercial copper foils, SMCC is made of a micropatterned shape memory micron-sized film with copper deposition. SMCC displays ideal conductivity at normal temperatures and turns to be insulative at overheating temperatures. Following this principle, the battery consisting of an SMCC can run normally at temperatures lower than 90 °C, while it quickly achieves self-shutdown before the occurrence of battery combustion and explosion.

Stabilized Solid Electrolyte Interphase Induced by Ultrathin Boron Nitride Membranes for Safe Lithium Metal Batteries.

Lithium-ion batteries (LIBs) are still facing safety problems, mainly due to dendrite growth on the anode that leads to combustion and explosion. Forming a stable solid electrolyte interface (SEI) layer is an effective way to suppress this. To induce the formation of stable SEI using simple methods at a low cost, we report an ultrathin and large-scale hexagonal boron nitride (h-BN)/polyimide (PI) layer that was coated on a commercial polypropylene (PP) separator. The formation of a stabilized SEI component induced by the h-BN coating layer is proposed, as suggested by theoretical calculations and confirmed by electrochemical analysis and spectroscopy. It effectively suppresses Li dendrite growth and reduces the consumption of active lithium. The separator also has good electrolyte wettability, excellent mechanical strength and thermal conductivity, and high thermal stability. When using the h-BN modified separator in a full cell, the capacity is extremely stable after long cycling and high temperature.

A Review on Lithium-Ion Battery Separators towards Enhanced Safety Performances and Modelling Approaches.

In recent years, the applications of lithium-ion batteries have emerged promptly owing to its widespread use in portable electronics and electric vehicles. Nevertheless, the safety of the battery systems has always been a global concern for the end-users. The separator is an indispensable part of lithium-ion batteries since it functions as a physical barrier for the electrode as well as an electrolyte reservoir for ionic transport. The properties of separators have direct influences on the performance of lithium-ion batteries, therefore the separators play an important role in the battery safety issue. With the rapid developments of applied materials, there have been extensive efforts to utilize these new materials as battery separators with enhanced electrical, fire, and explosion prevention performances. In this review, we aim to deliver an overview of recent advancements in numerical models on battery separators. Moreover, we summarize the physical properties of separators and benchmark selective key performance indicators. A broad picture of recent simulation studies on separators is given and a brief outlook for the future directions is also proposed.

The Boundary of Lithium Plating in Graphite Electrode for Safe Lithium-Ion Batteries.

Uncontrolled Li plating in graphite electrodes endangers battery life and safety, driving tremendous efforts aiming to eliminate Li plating. Herein we systematically investigate the boundary of Li plating in graphite electrode for safe lithium-ion batteries. The cell exhibits superior safety performance than that with Li dendrites by defining the endurable amount of uniform Li plating in graphite anode. The presence of "dead Li" can be eliminated owing to the uniform distribution of Li plating, and the average Coulombic efficiency for deposited Li during reversible plating/stripping process is decoupled as high as about 99.5 %. Attributing to the limited Li plating with superior Coulombic efficiency, the LiNi0.5 Mn0.3 Co0.2 O2 | graphite cell achieves a high capacity retention of 80.2 % over 500 cycles. This work sheds a different light on further improving the fast-charging capability, low-temperature performance, and energy density of practical lithium-ion batteries.

Prospect of Sulfurized Pyrolyzed Poly(acrylonitrile) (S@pPAN) Cathode Materials for Rechargeable Lithium Batteries.

Lithium-sulfur (Li-S) batteries are one of the most promising next-generation batteries owing to their ultra-high theoretical energy density and that sulfur is an abundant resource. During the past 20 years, various sulfur materials have been reported. As a molecular-scale sulfur-composite cathode, sulfurized pyrolyzed poly(acrylonitrile) (S@pPAN) exhibits several competitive advantages in terms of its electrochemical behavior. Although it was first reported in 2002 S@pPAN is currently attracting increasing attention. In this Minireview, we summarize its molecular model and explore the correlation between its structure and its exceptional electrochemical performance. We classify the modification strategies into three types, including material improvement, binder, and electrolyte screening. Several research and development directions are also suggested.

An Intrinsic Flame-Retardant Organic Electrolyte for Safe Lithium-Sulfur Batteries.

Safety concerns pose a significant challenge for the large-scale employment of lithium-sulfur batteries. Extremely flammable conventional electrolytes and dendritic lithium deposition cause severe safety issues. Now, an intrinsic flame-retardant (IFR) electrolyte is presented consisting of 1.1 m lithium bis(fluorosulfonyl)imide in a solvent mixture of flame-retardant triethyl phosphate and high flashpoint solvent 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl (1:3, v/v) for safe lithium-sulfur (Li-S) batteries. This electrolyte exhibits favorable flame-retardant properties and high reversibility of the lithium metal anode (Coulombic efficiency >99 %). This IFR electrolyte enables stable lithium plating/stripping behavior with micro-sized and dense-packing lithium deposition at high temperatures. When coupled with a sulfurized pyrolyzed poly(acrylonitrile) cathode, Li-S batteries deliver a high composite capacity (840.1 mAh g-1 ) and high sulfur utilization of 95.6 %.

Highly Reversible and Rechargeable Safe Zn Batteries Based on a Triethyl Phosphate Electrolyte.

Zinc metal is an attractive anode material for next-generation batteries. However, dendrite growth and limited Coulombic efficiency (CE) during cycling are the major roadblocks towards the widespread commercialization of batteries employing Zn anodes. In this work we report the novel adoption of triethyl phosphate (TEP) as a solvent and co-solvent with aqueous electrolytes to obtain a highly stable and dendrite-free Zn anode. Stable Zn plating/stripping for over 3000 h was obtained, accompanied by a CE of 99.68 %. SEM images of the Zn anodes revealed highly porous interconnected dendrite-free Zn deposits. The electrolyte displayed good compatibility with both Zn anodes and potassium copper hexacyanoferrate (KCuHCf) cathodes for Zn ion batteries (ZIBs). The full cell showed a long cycling stability and high rate capability. The present work is a contribution towards cost-effective and safe battery systems.

Simple battery armor to protect against gastrointestinal injury from accidental ingestion.

Inadvertent battery ingestion in children and the associated morbidity and mortality results in thousands of emergency room visits every year. Given the risk for serious electrochemical burns within hours of ingestion, the current standard of care for the treatment of batteries in the esophagus is emergent endoscopic removal. Safety standards now regulate locked battery compartments in toys, which have resulted in a modest reduction in inadvertent battery ingestion; specifically, 3,461 ingestions were reported in 2009, and 3,366 in 2013. Aside from legislation, minimal technological development has taken place at the level of the battery to limit injury. We have constructed a waterproof, pressure-sensitive coating, harnessing a commercially available quantum tunneling composite. Quantum tunneling composite coated (QTCC) batteries are nonconductive in the low-pressure gastrointestinal environment yet conduct within the higher pressure of standard battery housings. Importantly, this coating technology enables most battery-operated equipment to be powered without modification. If these new batteries are swallowed, they limit the external electrolytic currents responsible for tissue injury. We demonstrate in a large-animal model a significant decrease in tissue injury with QTCC batteries compared with uncoated control batteries. In summary, here we describe a facile approach to increasing the safety of batteries by minimizing the risk for electrochemical burn if the batteries are inadvertently ingested, without the need for modification of most battery-powered devices.

Li3PO4 Matrix Enables a Long Cycle Life and High Energy Efficiency Bismuth-Based Battery.

Bismuth is a lithium-ion battery anode material that can operate at an equilibrium potential higher than graphite and provide a capacity twice as high as that of Li4Ti5O12, making it intrinsically free from lithium plating that may cause catastrophic battery failure. However, the potential of bismuth is hampered by its inferior cyclability (limited to tens of cycles). Here, we propose an "ion conductive solid-state matrix" approach to address this issue. By homogeneously confining bismuth nanoparticles in a solid-state γ-Li3PO4 matrix that is electrochemically formed in situ, the resulting composite anode exhibits a reversible capacity of 280 mA hours per gram (mA h/g) at a rate of 100 mA/g and a record cyclability among bismuth-based anodes up to 500 cycles with a capacity decay rate of merely 0.071% per cycle. We further show that full-cell batteries fabricated from this composite anode and commercial LiFePO4 cathode deliver a stable cell voltage of ∼2.5 V and remarkable energy efficiency up to 86.3%, on par with practical batteries (80-90%). This work paves a way for harnessing bismuth-based battery chemistry for the design of high capacity, safer lithium-ion batteries to meet demanding applications such as electric vehicles.

Injury Surveillance and Safety Considerations for Large-Format Lead-Acid Batteries Used in Mining Applications.

Large lead-acid batteries are predominantly used throughout the mining industry to power haulage, utility, and personnel-carrier vehicles. Without proper operation and maintenance, the use of these batteries can introduce mechanical and electrical hazards, particularly in the confined, and potentially dangerous, environment of an underground coal mine. A review of the Mine Safety and Health Administration accident/illness/injury database reveals that a significant number of injuries occur during the maintenance and repair of lead-acid batteries. These injuries include burns from electrical arcing and acid exposure, as well as strained muscles and crushed hands. The National Institute for Occupational Safety and Health investigated the design and implementation of these batteries to identify safety interventions that can mitigate these inherent hazards. This paper promotes practical design modifications, such as reducing the size and weight of battery assembly lids in conjunction with lift assists, as well as using five-pole cable connectors to improve safety.

Oriented Structures for High Safety, Rate Capability, and Energy Density Lithium Metal Batteries.

Lithium metal batteries (LMBs) have emerged in recent years as highly promising candidates for high-density energy storage systems. Despite their immense potential, mutual constraints arise when optimizing energy density, rate capability, and operational safety, which greatly hinder the commercialization of LMBs. The utilization of oriented structures in LMBs appears as a promising strategy to address three key performance barriers: 1) low efficiency of active material utilization at high surface loading, 2) easy formation of Li dendrites and damage to interfaces under high-rate cycling, and 3) low ionic conductivity of solid-state electrolytes in high safety LMBs. This review aims to holistically introduce the concept of oriented structures, provide criteria for quantifying the degree of orientation, and elucidate their systematic effects on the properties of materials and devices. Furthermore, a detailed categorization of oriented structures is proposed to offer more precise guidance for the design of LMBs. This review also provides a comprehensive summary of preparation techniques for oriented structures and delves into the mechanisms by which these can enhance the energy density, rate capability, and safety of LMBs. Finally, potential applications of oriented structures in LMBs and the crucial challenges that need to be addressed in this field are explored.

Nano-Enhanced Graphite/Phase Change Material/Graphene Composite for Sustainable and Efficient Passive Thermal Management.

Passive battery thermal management systems (BTMSs) are critical for mitigation of battery thermal runaway (TR). Phase change materials (PCMs) have shown promise for mitigating transient thermal challenges. Fluid leakage and low effective thermal conductivity limit PCM adoption. Furthermore, the thermal capacitance of PCMs diminishes as their latent load is exhausted, creating an unsustainable cooling effect that is transitory. Here, an expanded graphite/PCM/graphene composite that solves these challenges is proposed. The expanded graphite/PCM phase change composite eliminates leakage and increases effective thermal conductivity while the graphene coating enables radiative cooling for PCM regeneration. The composite demonstrates excellent thermal performance in a real BTMS and shows a 26% decrease in temperature when compared to conventional BTMS materials. The composite exhibits thermal control performance comparable with active cooling, resulting in reduced cost and increased simplicity. In addition to BTMSs, this material is anticipated to have application in a plethora of engineered systems requiring stringent thermal management.

Mechanical Behavior of Lithium-Ion Battery Separators under Uniaxial and Biaxial Loading Conditions.

The mechanical integrity of two commercially available lithium-ion battery separators was investigated under uniaxial and biaxial loading conditions. Two dry-processed microporous films with polypropylene (PP)/polyethylene (PE)/polypropylene (PP) compositions were studied: Celgard H2010 Trilayer and Celgard Q20S1HX Ceramic-Coated Trilayer. The uniaxial tests were carried out along the machine direction (MD), transverse direction (TD), and diagonal direction (DD). In order to generate a state of in-plane biaxial tension, a pneumatic bulge test setup was prioritized over the commonly performed punch test in an attempt to eliminate the effects of contact friction. The biaxial flow stress-strain behavior of the membranes was deduced via the Panknin-Kruglov method coupled with a 3D Digital Image Correlation (DIC) technique. The findings demonstrate a high degree of in-plane anisotropy in both membranes. The ceramic coating was found to negatively affect the mechanical performance of the trilayer microporous separator, compromising its strength and stretchability, while preserving its failure mode. Derived from experimentally calibrated constitutive models, a finite element model was developed using the explicit solver OpenRadioss. The numerical model was capable of predicting the biaxial deformation of the semicrystalline membranes up until failure, showing a fairly good correlation with the experimental observations.

Effect of a Polypropylene Separator with a Thin Electrospun Ceramic/Polymer Coating on the Thermal and Electrochemical Properties of Lithium-Ion Batteries.

Lithium-ion batteries (LIBs) are well known for their energy efficiency and environmental benefits. However, increasing their energy density compromises their safety. This study introduces a novel ceramic-coated separator to enhance the performance and safety of LIBs. Electrospinning was used to apply a coating consisting of an alumina (Al2O3) ceramic and polyacrylic acid (PAA) binder to a polypropylene (PP) separator to significantly improve the mechanical properties of the PP separator and, ultimately, the electrochemical properties of the battery cell. Tests with 2032-coin cells showed that the efficiency of cells containing separators coated with 0.5 g PAA/Al2O3 was approximately 10.2% higher at high current rates (C-rates) compared to cells with the bare PP separator. Open circuit voltage (OCV) tests revealed superior thermal safety, with bare PP separators maintaining stability for 453 s, whereas the cells equipped with PP separators coated with 4 g PAA/Al2O3 remained stable for 937 s. The elongation increased from 88.3% (bare PP separator) to 129.1% (PP separator coated with 4 g PAA/Al2O3), and thermal shrinkage decreased from 58.2% to 34.9%. These findings suggest that ceramic/PAA-coated separators significantly contribute to enhancing the thermal safety and capacity retention of high-energy-density LIBs.

In Situ Polymerization Facilitating Practical High-Safety Quasi-Solid-State Batteries.

Quasi-solid-state batteries (QSSBs) are gaining widespread attention as a promising solution to improve battery safety performance. However, the safety improvement and the underlying mechanisms of QSSBs remain elusive. Herein, a novel strategy combining high-safety ethylene carbonate-free liquid electrolyte and in situ polymerization technique is proposed to prepare practical QSSBs. The Ah-level QSSBs with LiNi0.83Co0.11Mn0.06O2 cathode and graphite-silicon anode demonstrate significantly improved safety features without sacrificing electrochemical performance. As evidenced by accelerating rate calorimetry tests, the QSSBs exhibit increased self-heating temperature and onset temperature (T2), and decreased temperature rise rate during thermal runaway (TR). The T2 has a maximum increase of 48.4 °C compared to the conventional liquid batteries. Moreover, the QSSBs do not undergo TR until 180 °C (even 200 °C) during the hot-box tests, presenting significant improvement compared to the liquid batteries that run into TR at 130 °C. Systematic investigations show that the in situ formed polymer skeleton effectively mitigates the exothermic reactions between lithium salts and lithiated anode, retards the oxygen release from cathode, and inhibits crosstalk reactions between cathode and anode at elevated temperatures. The findings offer an innovative solution for practical high-safety QSSBs and open up a new sight for building safer high-energy-density batteries.