Delamination‐Free Multifunctional Separator for Long‐Term Stability of Lithium‐Ion Batteries

Next‐generation lithium‐ion batteries (LIBs) that satisfy the requirements for an electric vehicle energy source should demonstrate high reliability and safety for long‐term high‐energy‐density operation. This inevitably calls for a novel approach to advance major components such as the separator. Herein, a separator is designed and fabricated via application of multilayer functional coating on both sides of a polyethylene separator. The multilayer‐coated separator (MCS) has a porous structure that does not interfere with lithium ion diffusion and exhibits superior heat resistance, high electrolyte uptake, and persistent adhesion with the electrode. More importantly, it enables high capacity retention and reduced impedance build up during cycling when used in a coin or pouch cell. These imply its promising application in energy sources requiring long‐term stability. Fabrication of the MCS without the use of organic solvents is not only environmentally beneficial but also effective at cost reduction. This approach paves the way for the separator, which has long been considered an inactive major component of LIBs, to become an active contributor to the energy density toward achieving longer cycle stability.     

Effect of SiO2 coating on polyethylene separator with different stretching ratios for application in lithium ion batteries

To enhance the properties of polyethylene separators in lithium ion batteries, we tested separators with uni-axial stretching ratios of 180% and 300%. We also tested stretched separators coated with SiO₂ ceramic substance to increase ionic conductivity and thermal stability without sacrificing mechanical properties. To test the thermal and tensile properties, thermomechanical analyzer (TMA) is employed. CR 2032-type coin cells are prepared by sandwiching pristine and coated stretched separators, respectively, between the Li anode and Li[Ni_1/3Co_1/3Mn_1/3]O₂ cathode to evaluate the AC impedance and cycling performance. The coated separators are observed with superior ionic conductivity, thermal and tensile properties. The cells prepared with coated separator have slightly higher discharge capacity and a better capacity retention ratio than the cells with pristine separators. These results suggest that the coated separator is a better option for lithium ion batteries.     

Protected Lithium‐Metal Anodes in Batteries: From Liquid to Solid

High‐energy lithium‐metal batteries are among the most promising candidates for next‐generation energy storage systems. With a high specific capacity and a low reduction potential, the Li‐metal anode has attracted extensive interest for decades. Dendritic Li formation, uncontrolled interfacial reactions, and huge volume effect are major hurdles to the commercial application of Li‐metal anodes. Recent studies have shown that the performance and safety of Li‐metal anodes can be significantly improved via organic electrolyte modification, Li‐metal interface protection, Li‐electrode framework design, separator coating, and so on. Superior to the liquid electrolytes, solid‐state electrolytes are considered able to inhibit problematic Li dendrites and build safe solid Li‐metal batteries. Inspired by the bright prospects of solid Li‐metal batteries, increasing efforts have been devoted to overcoming the obstacles of solid Li‐metal batteries, such as low ionic conductivity of the electrolyte and Li–electrolyte interfacial problems. Here, the approaches to protect Li‐metal anodes from liquid batteries to solid‐state batteries are outlined and analyzed in detail. Perspectives regarding the strategies for developing Li‐metal anodes are discussed to facilitate the practical application of Li‐metal batteries.     

Anion‐Sorbent Composite Separators for High‐Rate Lithium‐Ion Batteries

Novel composite separators containing metal–organic‐framework (MOF) particles and poly(vinyl alcohol) are fabricated by the electrospinning process. The MOF particles containing opened metal sites can spontaneously adsorb anions while allowing effective transport of lithium ions in the electrolyte, leading to dramatically improved lithium‐ion transference number t_Li⁺ (up to 0.79) and lithium‐ion conductivity. Meanwhile, the incorporation of the MOF particles alleviates the decomposition of the electrolyte, enhances the electrode reaction kinetics, and reduces the interface resistance between the electrolyte and the electrodes. Implementation of such composite separators in conventional lithium‐ion batteries leads to significantly improved rate capability and cycling durability, offering a new prospective toward high‐performance lithium‐ion batteries.     

Flexible,High‐Wettability and Fire‐Resistant Separators Based on Hydroxyapatite Nanowires for Advanced Lithium‐Ion Batteries

Separators play a pivotal role in the electrochemical performance and safety of lithium‐ion batteries (LIBs). The commercial microporous polyolefin‐based separators often suffer from inferior electrolyte wettability, low thermal stability, and severe safety concerns. Herein, a novel kind of highly flexible and porous separator based on hydroxyapatite nanowires (HAP NWs) with excellent thermal stability, fire resistance, and superior electrolyte wettability is reported. A hierarchical cross‐linked network structure forms between HAP NWs and cellulose fibers (CFs) via hybridization, which endows the separator with high flexibility and robust mechanical strength. The high thermal stability of HAP NW networks enables the separator to preserve its structural integrity at temperatures as high as 700 °C, and the fire‐resistant property of HAP NWs ensures high safety of the battery. In particular, benefiting from its unique composition and highly porous structure, the as‐prepared HAP/CF separator exhibits near zero contact angle with the liquid electrolyte and high electrolyte uptake of 253%, indicating superior electrolyte wettability compared with the commercial polyolefin separator. The as‐prepared HAP/CF separator has unique advantages of superior electrolyte wettability, mechanical robustness, high thermal stability, and fire resistance, thus, is promising as a new kind of separator for advanced LIBs with enhanced performance and high safety.     

Clay-Originated Two-Dimensional Holey Silica Separator for Dendrite-Free Lithium Metal Anode

Lithium metal anode is the ultimate choice to obtain next-generation high-energy-density lithium batteries, while the dendritic lithium growth owing to the unstable lithium anode/electrolyte interface largely limits its practical application. Separator is an important component in batteries and separator engineering is believed to be a tractable and effective way to address the above issue. Separators can play the role of ion redistributors to guide the transport of lithium ions and regulate the uniform electrodeposition of Li. The electrolyte wettability, thermal shrinkage resistance, and mechanical strength are of importance for separators. Here, clay-originated two-dimensional (2D) holey amorphous silica nanosheets (ASN) to develop a low-cost and eco-friendly inorganic separator is directly adopted. The ASN-based separator has higher porosity, better electrolyte wettability, much higher thermal resistance, larger lithium transference number, and ionic conductivity compared with commercial separator. The large amounts of holes and rich surface oxygen groups on the ASN guide the uniform distribution of lithium-ion flux. Consequently, the Li//Li cell with this separator shows stable lithium plating/stripping, and the corresponding Li//LiFePO₄, Li//LiCoO_2, and Li//NCM523 full cells also show high capacity, excellent rate performance, and outstanding cycling stability, which is much superior to that using the commercial separator.     

Lithium-Ion Battery Separators for Ionic-Liquid Electrolytes: A Review

Ionic liquids (ILs) are widely studied as a safer alternative electrolyte for lithium-ion batteries. The properties of IL electrolytes compared to conventional electrolytes make them more thermally stable, but they also have poor wetting with commercial separators. In a lithium-ion battery, the electrolyte should completely wet out the separator and electrodes to reduce the cell internal resistance. Investigations of cell materials with IL electrolytes have shown that the wetting issues in IL–electrolyte cells are most likely due to poor separator compatibility, not electrode compatibility. A compatible separator must be developed before IL electrolytes can be used in commercial lithium-ion batteries. Herein, separators for IL electrolytes, including commercial and novel separators, are reviewed. Separators with different processing methods, polymers, additives, and different IL electrolytes are considered. Collated, the separator studies show a strong correlation between ionic conductivity and membrane porosity, even more than the electrolyte type. The challenge of a suitable separator for IL electrolytes is not solved yet. Herein, it is revealed that a separator for IL electrolytes will most likely require a combination of high thermal and mechanical stability polymer, ceramic additives, and an optimized manufacturing process.     

Designing a Multifunctional Separator for High‐Performance Li–S Batteries at Elevated Temperature

The practical applications of lithium–sulfur (Li–S) batteries are seriously limited by the undesirable polysulfide shuttling and lithium dendrite growth. Herein, a multifunctional membrane is designed and prepared by coating a lithiated Nafion (Li@Nafion) layer and an Al₂O₃ layer on the two sides of a routine polymer membrane (polypropylene/polyethylene/polypropylene, PEP). The Li@Nafion layer faced to the sulfur cathode builds a “polysulfide‐phobic” surface to restrain the shuttle effect via Coulomb repulsion, while the Al₂O₃ layer with a uniform porous structure aids in regulating homogeneous Li⁺ fluxes to achieve stable Li electrodeposition. As a result, the Li//Li symmetric cell with a Li@Nafion/PEP/Al₂O₃ (LNPA) separator realizes stable Li plating/striping even after 1000 h at a high current density (5 mA cm^?2). Moreover, the Li–S batteries incorporating LNPA separators not only can achieve excellent outstanding cyclic stability at an ultrahigh sulfur loading (7.6 mg cm^?2), but also exhibit impressive electrochemical performance at an elevated temperature (60 °C). The rational design of the LNPA separator presents new insights to develop high‐performance Li–S batteries.     

MoS2/Celgard Separator as Efficient Polysulfide Barrier for Long‐Life Lithium–Sulfur Batteries

A high lithium conductive MoS₂/Celgard composite separator is reported as efficient polysulfides barrier in Li–S batteries. Significantly, thanks to the high density of lithium ions on MoS₂ surface, this composite separator shows high lithium conductivity, fast lithium diffusion, and facile lithium transference. When used in Li–S batteries, the separator is proven to be highly efficient for depressing polysulfides shuttle, leading to high and long cycle stability. With 65% of sulfur loading, the device with MoS₂/Celgard separator delivers an initial capacity of 808 mAh g^?1 and a substantial capacity of 401 mAh g^?1 after 600 cycles, corresponding to only 0.083% of capacity decay per cycle that is comparable to the best reported result so far. In addition, the Coulombic efficiency remains more than 99.5% during all 600 cycles, disclosing an efficient ionic sieve preventing polysulfides migration to the anode while having negligible influence on Li⁺ ions transfer across the separator. The strategy demonstrated in this work will open the door toward developing efficient separators with flexible 2D materials beyond graphene for energy‐storage devices.     

Rational Integration of Polypropylene/Graphene Oxide/Nafion as Ternary‐Layered Separator to Retard the Shuttle of Polysulfides for Lithium–Sulfur Batteries

The reversible electrochemical transformation from lithium (Li) and sulfur (S) into Li₂S through multielectron reactions can be utilized in secondary Li–S batteries with very high energy density. However, both the low Coulombic efficiency and severe capacity degradation limits the full utilization of active sulfur, which hinders the practical applications of Li–S battery system. The present study reports a ternary‐layered separator with a macroporous polypropylene (PP) matrix layer, graphene oxide (GO) barrier layer, and Nafion retarding layer as the separator for Li–S batteries with high Coulombic efficiency and superior cyclic stability. In the ternary‐layered separator, ultrathin layer of GO (0.0032 mg cm^?2, estimated to be around 40 layers) blocks the macropores of PP matrix, and a dense ion selective Nafion layer with a very low loading amount of 0.05 mg cm^?2 is attached as a retarding layer to suppress the crossover of sulfur‐containing species. The ternary‐layered separators are effective in improving the initial capacity and the Coulombic efficiency of Li–S cells from 969 to 1057 mAh g^?1, and from 80% to over 95% with an LiNO₃‐free electrolyte, respectively. The capacity degradation is reduced from 0.34% to 0.18% per cycle within 200 cycles when the PP separator is replaced by the ternary‐layered separators. This work provides the rational design strategy for multifunctional separators at cell scale to effective utilizing of active sulfur and retarding of polysulfides, which offers the possibility of high energy density Li–S cells with long cycling life.     

Recent Development in Separators for High‐Temperature Lithium‐Ion Batteries

Lithium‐ion batteries (LIBs) are promising energy storage devices for integrating renewable resources and high power applications, owing to their high energy density, light weight, high flexibility, slow self‐discharge rate, high rate charging capability, and long battery life. LIBs work efficiently at ambient temperatures, however, at high‐temperatures, they cause serious issues due to the thermal fluctuation inside batteries during operation. The separator is a key component of batteries and is crucial for the sustainability of LIBs at high‐temperatures. The high thermal stability with minimum thermal shrinkage and robust mechanical strength are the prime requirements along with high porosity, ionic conductivity, and electrolyte uptake for highly efficient high‐temperature LIBs. This Review deals with the recent studies and developments in separator technologies for high‐temperature LIBs with respect to their structural layered formation. The recent progress in monolayer and multilayer separators along with the developed preparation methodologies is discussed in detail. Future challenges and directions toward the advancement in separator technology are also discussed for achieving remarkable performance of separators in a high‐temperature environment.     

Bending‐Tolerant Anodes for Lithium‐Metal Batteries

Bendable energy‐storage systems with high energy density are demanded for conformal electronics. Lithium‐metal batteries including lithium–sulfur and lithium–oxygen cells have much higher theoretical energy density than lithium‐ion batteries. Reckoned as the ideal anode, however, Li has many challenges when directly used, especially its tendency to form dendrite. Under bending conditions, the Li‐dendrite growth can be further aggravated due to bending‐induced local plastic deformation and Li‐filaments pulverization. Here, the Li‐metal anodes are made bending tolerant by integrating Li into bendable scaffolds such as reduced graphene oxide (r‐GO) films. In the composites, the bending stress is largely dissipated by the scaffolds. The scaffolds have increased available surface for homogeneous Li plating and minimize volume fluctuation of Li electrodes during cycling. Significantly improved cycling performance under bending conditions is achieved. With the bending‐tolerant r‐GO/Li‐metal anode, bendable lithium–sulfur and lithium–oxygen batteries with long cycling stability are realized. A bendable integrated solar cell–battery system charged by light with stable output and a series connected bendable battery pack with higher voltage is also demonstrated. It is anticipated that this bending‐tolerant anode can be combined with further electrolytes and cathodes to develop new bendable energy systems.     

Highly Safe Electrolyte Enabled via Controllable Polysulfide Release and Efficient Conversion for Advanced Lithium–Sulfur Batteries

Conventional lithium–sulfur batteries often suffer from fatal problems such as high flammability, polysulfide shuttling, and lithium dendrites growth. Here, highly‐safe lithium–sulfur batteries based on flame‐retardant electrolyte (dimethoxyether/1,1,2,2‐tetrafluoroethyl 2,2,3,3‐tetrafluoropropyl ether) coupled with functional separator (nanoconductive carbon‐coated cellulose nonwoven) to resolve aforementioned bottle‐neck issues are demonstrated. It is found that this flame‐retardant electrolyte exhibits excellent flame retardancy and low solubility of polysulfide. In addition, Li/Li symmetrical cells using such flame‐retardant electrolyte deliver extraordinary long‐term cycling stability (less than 10 mV overpotential) for over 2500 h at 1.0 mA cm^?2 and 1.0 mAh cm^?2. Moreover, bare sulfur cathode–based lithium–sulfur batteries using this flame retardant electrolyte coupled with nanoconductive carbon‐coated cellulose separator can retain 83.6% discharge capacity after 200 cycles at 0.5 C. Under high charge/discharge rate (4 C), lithium–sulfur cells still show high charge/discharge capacity of ≈350 mAh g^?1. Even at an elevated temperature of 60 °C, discharge capacity of 870 mAh g^?1 can be retained. More importantly, high‐loading bare sulfur cathode (4 mg cm^?2)–based lithium–sulfur batteries can also deliver high charge/discharge capacity over 806 mAh g^?1 after 56 cycles. Undoubtedly, the strategy of flame retardant electrolyte coupled with carbon‐coated separator enlightens highly safe lithium–sulfur batteries at a wide range of temperature.     

Lithium–Graphite Paste: An Interface Compatible Anode for Solid‐State Batteries

All‐solid‐state batteries (ASSBs) with ceramic‐based solid‐state electrolytes (SSEs) enable high safety that is inaccessible with conventional lithium‐ion batteries. Lithium metal, the ultimate anode with the highest specific capacity, also becomes available with nonflammable SSEs in ASSBs, which offers promising energy density. The rapid development of ASSBs, however, is significantly hampered by the large interfacial resistance as a matched lithium/ceramic interface that is not easy to pursue. Here, a lithium–graphite (Li–C) composite anode is fabricated, which shows a dramatic modification in wettability with garnet SSE. An intimate Li–C/garnet interface is obtained by casting Li–C composite onto garnet‐type SSE, delivering an interfacial resistance as low as 11 Ω cm². As a comparison, pure Li/garnet interface gives a large resistance of 381 Ω cm². Such improvement can be ascribed to the experiment‐measured increased viscosity of Li–C composite and simulation‐verified limited interfacial reaction. The Li–C/garnet/Li–C symmetric cell exhibits stable plating/striping performance with small voltage hysteresis and endures a critical current density up to 1.0 mA cm^?2. The full cell paired with LiFePO₄ shows stable cycle performance, comparable to the cell with liquid electrolyte. The present work demonstrates a promising strategy to develop ceramic‐compatible lithium metal‐based anodes and hence low‐impedance ASSBs.     

Dual‐Layered Film Protected Lithium Metal Anode to Enable Dendrite‐Free Lithium Deposition

Lithium metal batteries (such as lithium–sulfur, lithium–air, solid state batteries with lithium metal anode) are highly considered as promising candidates for next‐generation energy storage systems. However, the unstable interfaces between lithium anode and electrolyte definitely induce the undesired and uncontrollable growth of lithium dendrites, which results in the short‐circuit and thermal runaway of the rechargeable batteries. Herein, a dual‐layered film is built on a Li metal anode by the immersion of lithium plates into the fluoroethylene carbonate solvent. The ionic conductive film exhibits a compact dual‐layered feature with organic components (ROCO₂Li and ROLi) on the top and abundant inorganic components (Li₂CO₃ and LiF) in the bottom. The dual‐layered interface can protect the Li metal anode from the corrosion of electrolytes and regulate the uniform deposition of Li to achieve a dendrite‐free Li metal anode. This work demonstrates the concept of rational construction of dual‐layered structured interfaces for safe rechargeable batteries through facile surface modification of Li metal anodes. This not only is critically helpful to comprehensively understand the functional mechanism of fluoroethylene carbonate but also affords a facile and efficient method to protect Li metal anodes.     

A Scalable Approach to Dendrite‐Free Lithium Anodes via Spontaneous Reduction of Spray‐Coated Graphene Oxide Layers

Li‐metal batteries (LiMBs) are experiencing a renaissance; however, achieving scalable production of dendrite‐free Li anodes for practical application is still a formidable challenge. Herein, a facile and universal method is developed to directly reduce graphene oxide (GO) using alkali metals (e.g., Li, Na, and K) in moderate conditions. Based on this innovation, a spontaneously reduced graphene coating can be designed and modulated on a Li surface (SR‐G‐Li). The symmetrical SR‐G‐Li|SR‐G‐Li cell can run up to 1000 cycles at a high practical current density of 5 mA cm^?2 without a short circuit, demonstrating one of the longest lifespans reported with LiPF₆‐based carbonate electrolytes. More significantly, a practically scalable paradigm is established to fabricate dendrite‐free Li anodes by spraying a GO layer on the Li anode surface for large‐scale production of LiFePO₄/Li pouch cells, reflected by the continuous manufacturing of the SR‐G‐Li anodes based on the roll‐to‐roll technology. The strategy provides new commercial opportunities to both LiMBs and graphene.     

Bioinspired Nacre‐Like Alumina with a Metallic Nickel Compliant Phase Fabricated by Spark‐Plasma Sintering

Many natural materials present an ideal “recipe” for the development of future damage‐tolerant lightweight structural materials. One notable example is the brick‐and‐mortar structure of nacre, found in mollusk shells, which produces high‐toughness, bioinspired ceramics using polymeric mortars as a compliant phase. Theoretical modeling has predicted that use of metallic mortars could lead to even higher damage‐tolerance in these materials, although it is difficult to melt‐infiltrate metals into ceramic scaffolds as they cannot readily wet ceramics. To avoid this problem, an alternative (“bottom‐up”) approach to synthesize “nacre‐like” ceramics containing a small fraction of nickel mortar is developed. These materials are fabricated using nickel‐coated alumina platelets that are aligned using slip‐casting and rapidly sintered using spark‐plasma sintering. Dewetting of the nickel mortar during sintering is prevented by using NiO‐coated as well as Ni‐coated platelets. As a result, a “nacre‐like” alumina ceramic displaying a resistance‐curve toughness up to ≈16 MPa m^½ with a flexural strength of ≈300 MPa is produced.     

Separator‐Integrated,Reversely Connectable Symmetric Lithium‐Ion Battery

A separator‐integrated, reversely connectable, symmetric lithium‐ion battery is developed based on carbon‐coated Li₃V₂(PO₄)₃ nanoparticles and polyvinylidene fluoride‐treated separators. The Li₃V₂(PO₄)₃ nanoparticles are synthesized via a facile solution route followed by calcination in Ar/H₂ atmosphere. Sucrose solution is used as the carbon source for uniform carbon coating on the Li₃V₂(PO₄)₃ nanoparticles. Both the carbon and the polyvinylidene fluoride treatments substantially improve the cycling life of the symmetric battery by preventing the dissolution and shuttle of the electroactive Li₃V₂(PO₄)₃. The obtained symmetric full cell exhibits a reversible capacity of ≈87 mA h g^–1, good cycling stability, and capacity retention of ≈70% after 70 cycles. In addition, this type of symmetric full cell can be operated in both forward and reverse connection modes, without any influence on the cycling of the battery. Furthermore, a new separator integration approach is demonstrated, which enables the direct deposition of electroactive materials for the battery assembly and does not affect the electrochemical performance. A 10‐tandem‐cell battery assembled without differentiating the electrode polarity exhibits a low thickness of ≈4.8 mm and a high output voltage of 20.8 V.     

Graphene Oxide Sieving Membrane for Improved Cycle Life in High‐Efficiency Redox‐Mediated Li–O2 batteries

As soluble catalysts, redox‐mediators (RMs) endow mobility to catalysts for unconstrained access to tethered solid discharge products, lowering the energy barrier for Li₂O₂ formation/decomposition; however, this desired mobility is accompanied by the undesirable side effect of RM migration to the Li metal anode. The reaction between RMs and Li metal degrades both the Li metal and the RMs, leading to cell deterioration within a few cycles. To extend the cycle life of redox‐mediated Li–O₂ batteries, herein graphene oxide (GO) membranes are reported as RM‐blocking separators. It is revealed that the size of GO nanochannels is narrow enough to reject 5,10‐dihydro‐5,10‐dimethylphenazine (DMPZ) while selectively allowing the transport of smaller Li⁺ ions. The negative surface charges of GO further repel negative ions via Donnan exclusion, greatly improving the lithium ion transference number. The Li–O₂ cells with GO membranes efficiently harness the redox‐mediation activity of DMPZ for improved performance, achieving energy efficiency of above 80% for more than 25 cycles, and 90% for 78 cycles when the capacity limits were 0.75 and 0.5 mAh cm^‐2, respectively. Considering the facile preparation of GO membranes, RM‐sieving GO membranes can be cost‐effective and processable functional separators in Li–O₂ batteries.     

Effective Suppression of Lithium Dendrite Growth Using a Flexible Single‐Ion Conducting Polymer Electrolyte

A novel single‐ion conducting polymer electrolyte (SIPE) membrane with high lithium‐ion transference number, good mechanical strength, and excellent ionic conductivity is designed and synthesized by facile coupling of lithium bis(allylmalonato) borate (LiBAMB), pentaerythritol tetrakis (2‐mercaptoacetate) (PETMP) and 3,6‐dioxa‐1,8‐octanedithiol (DODT) in an electrospun poly(vinylidienefluoride) (PVDF) supporting membrane via a one‐step photoinitiated in situ thiol–ene click reaction. The structure‐optimized LiBAMB‐PETMP‐DODT (LPD)@PVDF SIPE shows an outstanding ionic conductivity of 1.32 × 10^?3 S cm^?1 at 25 °C, together with a high lithium‐ion transference number of 0.92 and wide electrochemical window up to 6.0 V. The SIPE exhibits high tensile strength of 7.2 MPa and elongation at break of 269%. Due to these superior performances, the SIPE can suppress lithium dendrite growth, which is confirmed by galvanostatic Li plating/stripping cycling test and analysis of morphology of Li metal electrode surface after cycling test. Li|LPD@PVDF|Li symmetric cell maintains an extremely stable and low overpotential without short circuiting over the 1050 h cycle. The Li|LPD@PVDF|LiFePO₄ cell shows excellent rate capacity and outstanding cycle performance compared to cells based on a conventional liquid electrolyte (LE) with Celgard separator. The facile approach of the SIPE provides an effective and promising electrolyte for safe, long‐life, and high‐rate lithium metal batteries.