Functional Optical Fiber Sensors Detecting Imperceptible Physical/Chemical Changes for Smart Batteries

The battery technology progress has been a contradictory process in which performance improvement and hidden risks coexist.Now the battery is still a“black box”,thus requiring a deep understanding of its internal state.The battery should“sense its internal physical/chemical conditions”,which puts strict requirements on embedded sensing parts.This paper summarizes the application of advanced optical fiber sensors in lithium-ion batteries and energy storage technologies that may be mass deployed,focuses on the insights of advanced optical fiber sensors into the processes of one-dimensional nano-micro-level battery material structural phase transition,electrolyte degradation,electrode-electrolyte interface dynamics to three-dimensional macro-safety evolution.The paper contributes to understanding how to use optical fiber sensors to achieve“real”and“embedded”monitoring.Through the inherent advantages of the advanced optical fiber sensor,it helps clarify the battery internal state and reaction mechanism,aiding in the establishment of more detailed models.These advancements can promote the development of smart batteries,with significant importance lying in essentially promoting the improvement of system consistency.Furthermore,with the help of smart batteries in the future,the importance of consistency can be weakened or even eliminated.The application of advanced optical fiber sensors helps comprehensively improve the battery quality,reliability,and life.

Thermal Runaway of Lithium-Ion Batteries Employing Flame-Retardant Fluorinated Electrolytes

Fluorinated electrolytes possess good antioxidant capacity that provides high compatibility to high-voltage cathode and flame retardance;thus,they are considered as a promising solution for advanced lithium-ion batteries carrying both high-energy density and high safety.Moreover,the fluorinated electrolytes are widely used to form stable electrolyte interphase,due to their chemical reactivity with lithiated graphite or lithium.However,the influence of this reactivity on the thermal safety of batteries is seldom discussed.Herein,we demonstrate that the flame-retardant fluorinated electrolytes help to reduce the flammability,while the lithium-ion batteries with flame-retardant fluorinated electrolytes still undergo thermal runaway and disclose their different thermal runaway pathway from that of battery with conventional electrolyte.The reduction in fluorinated components(e.g.,LiPF 6 and fluoroethylene carbonate(FEC))by fully lithiated graphite accounts for a significant heat release during battery thermal runaway.The 13%of total heat is sufficient to trigger the chain reactions during battery thermal runaway.This study deepens the understanding of the thermal runaway mechanism of lithium-ion batteries employing flame-retardant fluorinated electrolytes,providing guidance on the concept of electrolyte design for safer lithium-ion batteries.

Unveiling the parasitic-reaction-driven surface reconstruction in Ni-rich cathode and the electrochemical role of Li_(2)CO_(3)

Nickel-rich transition-metal oxides are widely regarded as promising cathode materials for high-energydensity lithium-ion batteries for emerging electric vehicles. However, achieving high energy density in Ni-rich cathodes is accompanied by substantial safety and cycle-life obstacles. The major issues of Ni-rich cathodes at high working potentials are originated from the unstable cathode-electrolyte interface, while the underlying mechanism of parasitic reactions towards surface reconstructions of cathode materials is not well understood. In this work, we controlled the Li_(2)CO_(3) impurity content on LiNi_(0.83)Mn_(0.1)Co_(0.07)O_(2) cathodes using air, tank-air, and O_(2) synthesis environments. Home-built high-precision leakage current and on-line electrochemical mass spectroscopy experiments verify that Li_(2)CO_(3) impurity is a significant promoter of parasitic reactions on Ni-rich cathodes. The rate of parasitic reactions is strongly correlated to Li_(2)CO_(3) content and severe performance deterioration of Ni83 cathodes.The post-mortem characterizations via high-resolution transition electron microscope and X-ray photoelectron spectroscopy depth profiles reveal that parasitic reactions promote more Ni reduction and O deficiency and even rock-salt phase transformation at the surface of cathode materials. Our observation suggests that surface reconstructions have a strong affiliation to parasitic reactions that create chemically acidic environment to etch away the lattice oxygen and offer the electrical charge to reduce the valence state of transition metal. Thus, this study advances our understanding on surface reconstructions of Nirich cathodes and prepares us for searching for rational strategies.

Insight into the Electrochemical Behaviors of NCM811|SiO-Gr Pouch Battery through Thickness Variation

LiNi0.8Co0.1Mn0.1O2(NCM811)|SiOx-graphite(SiO-Gr.)battery chemistry is of intensive attention because its achievable practical energy density is approaching impressively 300 Wh Kg^(-1).However,it still suffers rapid capacity fades during repeated cycles,both chemical,electrochemical and mechanical irreversibility contribute.A comprehensive understanding behind the fading behavior of the cell chemistry is required before fully realize the benefits of this chemistry.Herein,the in-situ thickness variation is introduced as a diagnostic technique and is performed on 5-55 Ah NCM811|SiO-Gr cells.With the help of Li reference electrode and in-situ X-ray diffraction device,the correspondence between thickness variation and the electrode potential is carefully investigated.Firstly,the NCM811|SiO-Gr cell is characterized with the maximum cell thickness at around 80%state-of-charge(SOC)in the discharge process,rather than at 100%SOC.Secondly,the electrochemical behaviors during rate charge/discharge are diagnosed,and a Li platting signal is resolved from thickness variation profile at 2C.This work confirms that the thickness monitoring is a nondestructive and informative complement to conventional diagnostic techniques for failure analysis of pouch cells.

PDOL-Based Solid Electrolyte Toward Practical Application:Opportunities and Challenges

Polymer solid-state lithium batteries(SSLB)are regarded as a promising energy storage technology to meet growing demand due to their high energy density and safety.Ion conductivity,interface stability and battery assembly process are still the main challenges to hurdle the commercialization of SSLB.As the main component of SSLB,poly(1,3-dioxolane)(PDOL)-based solid polymer electrolytes polymerized in-situ are becoming a promising candidate solid elec-trolyte,for their high ion conductivity at room temperature,good battery elec-trochemical performances,and simple assembly process.This review analyzes opportunities and challenges of PDOL electrolytes toward practical application for polymer SSLB.The focuses include exploring the polymerization mechanism of DOL,the performance of PDOL composite electrolytes,and the application of PDOL.Furthermore,we provide a perspective on future research directions that need to be emphasized for commercialization of PDOL-based electrolytes in SSLB.The exploration of these schemes facilitates a comprehensive and profound understanding of PDOL-based polymer electrolyte and provides new research ideas to boost them toward practical application in solid-state batteries.

Perception of fundamental science to boost lithium metal anodes toward practical application

As a key material for lithium metal batteries(LMBs),lithium metal is one of the most promising anode materials to break the bottleneck of battery energy density and a commonly used active material for reference electrodes.Although lithium anodes are regarded as the holy grail of lithium batteries,decades of exploration have not led to the successful commercialization of LMBs,due mainly to the challenges related to the inherent properties of lithium metal.To pave the way for further investigation,herein,a comprehensive review focusing on the fundamental science of lithium are provided.Firstly,the natures of lithium atoms and their isotopes,lithium clusters and lithium crystals are revisited,especially their structural and energetic properties.Subsequently,the electrochemical properties of lithium metal are reviewed.Numerous important concepts and scientific questions,including the electronic structure of lithium,influence of high pressure and low temperature on the properties of lithium,factors influencing lithium deposition,generation of lithium dendrites,and electrode potential of lithium in different electrolytes,are explained and analyzed in detail.Approaches to improve the performance of lithium anodes and thoughtfulness about the electrode potential in lithium battery research are proposed.

碳纤维复合材料高温界面性能研究进展

碳纤维复合材料以其强度高、耐腐蚀、质量轻、抗疲劳等优良特性被广泛应用于航空航天及国防军工领域。然而,航空航天用复合材料结构部件在高温、湿热环境中会发生界面损伤和失效。上浆剂是碳纤维复合材料界面相的重要组成部分,研制可以增强界面强度和耐高温的上浆剂对提高复合材料的热力学性能具有重要意义。文中从碳纤维表面上浆剂的角度出发,重点介绍了碳纤维复合材料界面特性、上浆剂的作用机理以及高温下复合材料界面的破坏机制。最后,针对环氧上浆剂耐热性差的缺点,阐述了碳纤维耐高温涂层改性和纳米粒子改性,重点介绍了聚酰亚胺、聚醚醚酮、生物活性多巴胺及氧化石墨烯、多面体低聚倍半硅氧烷(POSS)纳米粒子等类型改性上浆剂的研究进展。指出发展环境友好型上浆剂和POSS纳米粒子改性将是下一步工作的重点。

A review of lithium-ion battery safety concerns:The issues,strategies,and testing standards

Efficient and reliable energy storage systems are crucial for our modern society.Lithium-ion batteries(LIBs)with excellent performance are widely used in portable electronics and electric vehicles(EVs),but frequent fires and explosions limit their further and more widespread applications.This review summarizes aspects of LIB safety and discusses the related issues,strategies,and testing standards.Specifically,it begins with a brief introduction to LIB working principles and cell structures,and then provides an overview of the notorious thermal runaway,with an emphasis on the effects of mechanical,electrical,and thermal abuse.The following sections examine strategies for improving cell safety,including approaches through cell chemistry,cooling,and balancing,afterwards describing current safety standards and corresponding tests.The review concludes with insights into potential future developments and the prospects for safer LIBs.

Surface modification of polyolefin separators for lithium ion batteries to reduce thermal shrinkage without thickness increase

Surface chemical modification of polyolefin separators for lithium ion batteries is attempted to reduce the thermal shrinkage, which is im- portant for the battery energy density. In this study, we grafted organic/inorganic hybrid crosslinked networks on the separators, simply by grafting polymerization and condensation reaction. The considerable silicon-oxygen crosslinked heat-resistance networks are responsible for the reduced thermal shrinkage. The strong chemical bonds between networks and separators promise enough mechanical support even at high temperature. The shrinkage at 150 ℃ for 30 min in the mechanical direction was 38.6% and 4.6% for the pristine and present graft-modified separators, respectively. Meanwhile, the grafting organic-inorganic hybrid crosslink networks mainly occupied part of void in the internal pores of the separators, so the thicknesses of the graft-modified separators were similar with the pristine one. The half cells prepared with the modified separators exhibited almost identical electrochemical properties to those with the commercial separators, thus proving that, in order to enhance the thermal stability of lithium ion battery, this kind of grafting-modified separators may be a better alternative to conventional silica nanoparticle layers-coated polyolefin separators.

Effect of silica nanoparticles/poly(vinylidene fluoride-hexafluoropropylene) coated layers on the performance of polypropylene separator for lithium-ion batteries

In an effort to reduce thermal shrinkage and improve electrochemical performance of porous polypropylene （PP） separators for lithium-ion batteries, a new composite separator is developed by introducing ceramic coated layers on both sides of PP separator through a dip-coating process. The coated layers are comprised of heat-resistant and hydrophilic silica nanoparticles and polyvinylidene fluoride-hexafluoropropylene （PVDF-HFP） binders. Highly porous honeycomb structure is formed and the thickness of the layer is only about 700 nm. In comparison to the pristine PP separator, the composite separator shows significant reduction in thermal shrinkage and improvement in liquid electrolyte uptake and ionic conduction, which play an important role in improving cell performance such as discharge capacity, C-rate capability, cycle performance and coulombic efficiency.

In-depth investigation of the exothermic reactions between lithiated graphite and electrolyte in lithium-ion battery

Thermal runaway is a critical issue for the large application of lithium-ion batteries.Exothermic reactions between lithiated graphite and electrolyte play a crucial role in the thermal runaway of lithium-ion batteries.However,the role of each component in the electrolyte during the exothermic reactions with lithiated graphite has not been fully understood.In this paper,the exothermic reactions between lithiated graphite and electrolyte of lithium-ion battery are investigated through differential scanning calorimetry(DSC) and evolved gas analysis.The lithiated graphite in the presence of electrolyte exhibit three exothermic peaks during DSC test.The reactions between lithiated graphite and LiPF_(6) and ethylene carbonate are found to be responsible for the first two exothermic peaks,while the third exothermic peak is attributed to the reaction between lithiated graphite and binder.In contrast,diethylene carbonate and ethyl methyl carbonate contribute little to the total heat generation of graphite-electrolyte reactions.The reaction mechanism between lithiated graphite and electrolyte,including the major reaction equations and gas products,are summarized.Finally,DSC tests on samples with various amounts of electrolyte are performed to clarify the quantitative relationship between lithiated graphite and electrolyte during the exothermic reactions.2.5 mg of lithiated graphite (Li_(0.8627)C_(6)) can fully react with around 7.2 mg electrolyte,releasing a heat generation of 2491 J g^(-1).The results presented in this study can provide useful guidance for the safety improvement of lithium-ion batteries.

Tailoring Practically Accessible Polymer/Inorganic Composite Electrolytes for All-Solid-State Lithium Metal Batteries:A Review

Solid-state electrolytes(SSEs)are widely considered the essential components for upcoming rechargeable lithium-ion batteries owing to the potential for great safety and energy density.Among them,polymer solid-state electrolytes(PSEs)are competitive candidates for replacing commercial liquid electrolytes due to their flexibility,shape versatility and easy machinability.Despite the rapid development of PSEs,their practical application still faces obstacles including poor ionic conductivity,narrow electrochemical stable window and inferior mechanical strength.Polymer/inorganic composite electrolytes(PIEs)formed by adding ceramic fillers in PSEs merge the benefits of PSEs and inorganic solid-state electrolytes(ISEs),exhibiting appreciable comprehensive properties due to the abundant interfaces with unique characteristics.Some PIEs are highly compatible with high-voltage cathode and lithium metal anode,which offer desirable access to obtaining lithium metal batteries with high energy density.This review elucidates the current issues and recent advances in PIEs.The performance of PIEs was remarkably influenced by the characteristics of the fillers including type,content,morphology,arrangement and surface groups.We focus on the molecular interaction between different components in the composite environment for designing high-performance PIEs.Finally,the obstacles and opportunities for creating high-performance PIEs are outlined.This review aims to provide some theoretical guidance and direction for the development of PIEs.

Polyimides as Promising Materials for Lithium-Ion Batteries:A Review

Lithium-ion batteries(LIBs)have helped revolutionize the modern world and are now advancing the alternative energy field.Several technical challenges are associated with LIBs,such as increasing their energy density,improving their safety,and prolonging their lifespan.Pressed by these issues,researchers are striving to find effective solutions and new materials for next-generation LIBs.Polymers play a more and more important role in satisfying the ever-increasing requirements for LIBs.Polyimides(PIs),a special functional polymer,possess unparalleled advantages,such as excellent mechanical strength,extremely high thermal stability,and excellent chemical inertness;they are a promising material for LIBs.Herein,we discuss the current applications of PIs in LIBs,including coatings,separators,binders,solid-state polymer electrolytes,and active storage materials,to improve high-voltage performance,safety,cyclability,flexibility,and sustainability.Existing technical challenges are described,and strategies for solving current issues are proposed.Finally,potential directions for implementing PIs in LIBs are outlined.

Impact of Lithium-Ion Coordination on Lithium Electrodeposition

The lithium dendrite and parasitic reactions are two major challenges for lithium(Li)metal anode—the most promising anode materials for high-energy-density batteries.In this work,both the dendrite and parasitic reactions that occurred between the liquid electrolyte and Li-metal anode could be largely inhibited by regulating the Li+-solvation structure.The saturated Li+-solvation species exist in commonly used LiPF 6 liquid electrolyte that needs extra energy to desolvation during Li-electrodeposition.Partial solvation induced high-energy state Li-ions would be more energy favorable during the electron-reduction process,dominating the competition with solvent reduction reactions.The Li-symmetric cells that are cycling at higher temperatures show better performance;the cycled lithium metal anode with metallic lustre and the dendrite-free surface is observed.Theoretical calculation and experimental measurements reveal the existence of high-energy state Li+-solvates species,and their concentration increases with temperature.This study provides insight into the Li+-solvation structure and its electrodeposition characteristics.

Prelithiation Enhances Cycling Life of Lithium-Ion Batteries:A Mini Review

During the last decade,the rapid development of lithium-ion battery(LIB)energy storage systems has provided significant support for the efficient operation of renewable energy stations.In the coming years,the service life demand of energy storage systems will be further increased to 30 years from the current 20 years on the basis of the equivalent service life of renewable energy stations.However,the life of the present LIB is far from meeting such high demand.Therefore,research on the next-generation LIB with ultra-long service life is imminent.Prelithiation technology has been widely studied as an important means to compensate for the initial coulombic efficiency loss and improve the service life of LIBs.This review systematically summarized the different prelithiation methods from anode and cathode electrodes.Moreover,the large-scale industrialization challenge and the possibility of the existing prelithiation technology are analyzed,based on three key parameters:industry compatibility,prelithiation efficiency,and energy density.Finally,the future trends of improvement in LIB performance by other overlithiated cathode materials are presented,which gives a reference for subsequent research.

High Ion-Selectivity of Garnet Solid Electrolyte Enabling Separation of Metallic Lithium

Ionic selectivity is of significant importance in both fundamental science and practical applications.For instance,an ion-selective material allows the passage of a particular kind of ions while blocking the others,which could be used for purification of materials.Herein,the Li-ion-selectivity of a garnet-type solid electrolyte is discussed by comparing the difference of activation energy between different ions migrating in solids.The high ion-selectivity is confirmed by harvesting high-purity metallic lithium(99.98 wt%)from low-lithium-purity sources(80 wt%)at a moderate temperature(190℃).This gives it huge potential in separating lithium with impurities especially alkali and alkali-earth elements.The cost of metallic lithium production is only 25%of the international lithium price.The proposed electrochemical metallic lithium separating method is advantageous compared with the traditional process in terms of efficiency,safety,and cost.

Engineering strategies for high-voltage LiCoO_(2)based highenergyLi-ion batteries

To drive electronic devices for a long range,the energy density of Li-ionbatteries must be further enhanced,and high-energy cathode materialsare required.Among the cathode materials,LiCoO_(2)(LCO)is one of themost promising candidates when charged to higher voltages over 4.3 V.However,high-voltage LCO materials are confronted with severe surfaceand bulk issues inducing poor cyclic stability.To completely unleash thepotential of LCO cathodes,a more comprehensive theoretical understandingof the underlying issues is necessary,along with active explorationof previous modifications.This paper mainly presents thedegradation mechanisms of LCO under high voltage,the formation andevolution mechanisms of the cathode electrolyte interface,and the surfaceengineering strategies employed to enhance the cell performance.By organizing and summarizing these modifications,this work aims toestablish associations among common research issues and to suggestfuture research priorities,thus facilitating the rapid development of highvoltageLCO.

Internal short circuit evaluation and corresponding failure mode analysis for lithium-ion batteries

Internal short circuit(ISC)is the major failure problem for the safe application of lithium-ion batteries,especially for the batteries with high energy density.However,how to quantify the hazard aroused by the ISC,and what kinds of ISC will lead to thermal runaway are still unclear.This paper investigates the thermal-electrical coupled behaviors of ISC,using batteries with Li(Ni_(1/3)CO_(1/3)Mn_(1/3))O_(2) cathode and composite separator.The electrochemical impedance spectroscopy of customized battery that has no LiPF6 salt is utilized to standardize the resistance of ISC.Furthermore,this paper compares the thermal-electrical coupled behaviors of the above four types of ISC at different states-of-charge.There is an area expansion phenomenon for the aluminum-anode type of ISC.The expansion effect of the failure area directly links to the melting and collapse of separator,and plays an important role in further evolution of thermal runaway.This work provides guidance to the development of the ISC models,detection algorithms,and correlated countermeasures.

New Insight on Graphite Anode Degradation Induced by Li-Plating

Graphite is the dominant anode material for lithium-ion batteries;however,it still suffers from Li-plating when charging fast or at low temperature,and Liplating is associated with performance fading and safety concerns.Herein,we clarify the mechanism of lithium evolution from graphite particles by overlithiation cycle test,in-situ XRD,and titration gas chromatography.We observe that the graphite intercalation compounds(GICs,LiC_(12) and LiC_(6)e.g.)gradually become inactive and wrapped by dead lithium or side reaction sediments,while the rate of this degradation will be accelerated as the overpotential of Liplating is decreased after initial Li metal nucleation.This understanding is contradictory to the popular one that the degradation of graphite anode after Li plating is mainly caused by the inferior SEI and dead Li induced hindering of Li-ion intercalation.The isolation of lithiated graphite particles leading to the fast vanishing of Li insertion/deintercalation process in graphite anodes.We further study the insertion/deintercalation vanishing process at low temperature and high rates,respectively.This work provides a insight on graphite anode degradation induced by Li-plating,and the new understanding can be used to guide the design of advanced materials and electrodes to avoid Li-plating and achieve extreme fast while safe charging.

Boron-doped Ketjenblack based high performances cathode for rechargeable Li–O2 batteries

Boron-doped Ketjenblack is attempted as cathode catalyst for non-aqueous rechargeable Li–O2 batteries. The boron-doped Ketjenblack delivers an extremely high discharge capacity of 7193 m Ah/g at a current density of 0.1 m A/cm2, and the capacity is about 2.3 times as that of the pristine KB. When the batteries are cycled with different restricted capacity, the boron-doped Ketjenblack based cathodes exhibits higher discharge platform and longer cycle life than Ketjenblack based cathodes. Additionally, the boron-doped Ketjenblack also shows a superior electrocatalytic activity for oxygen reduction in 0.1 mol/L KOH aqueous solution. The improvement in catalytic activity results from the defects and activation sites introduced by boron doping.