Solid polymer electrolytes(SPEs), such as polyethylene oxide(PEO), are characteristic of good flexibility and excellent processability, but they suffer from low ionic conductivity and small Li+transference number at a...Solid polymer electrolytes(SPEs), such as polyethylene oxide(PEO), are characteristic of good flexibility and excellent processability, but they suffer from low ionic conductivity and small Li+transference number at ambient temperature. Inorganic solid electrolytes(ISEs), garnet-type Li7La3Zr2O12 and its derivatives(LLZO-based) in particular, possess high ionic conductivity at room temperature, wide electrochemical stability window, large Li+transference number as well as good stability against Li metal anode.Nevertheless, lithium dendrites growth, interfacial contact issue and brittle nature of LLZO-based ceramic electrolytes prevent their practical applications. In response to these shortcomings, LLZO-based/polymer solid composite electrolytes(SCEs), taking complementary advantages of two kinds of electrolytes, and thus simultaneously improving the electrode wettability, ionic conductivity and mechanical strength, have been made to develop high-performance SCEs in recent years. Herein, the intrinsic properties and research progress of LLZO-based/polymer SCEs, including LLZO-based/PEO SCEs(LLZO-based/PEO SCEs with uniform dispersion of LLZO-based fillers and LLZO-based/PEO layered SCEs) and LLZO-based/novel polymers SCEs, are summarized. Besides, comprehensive updates on their applications in solid-state batteries are also presented. Finally, challenges and perspectives of LLZO-based/polymer SCEs for advanced allsolid-state lithium batteries(ASSLBs) are suggested. This review paper aims to provide systematic research progress of LLZO-based/polymer SCEs, to allow for more efficient and target-oriented research on improving LLZO-based/polymer SCEs.展开更多
Anion-immobilized solid composite electrolytes(SCEs)are important to restrain the propagation of lithium dendrites for all solid-state lithium metal batteries(ASSLMBs).Herein,a novel SCEs based on metal-organic framew...Anion-immobilized solid composite electrolytes(SCEs)are important to restrain the propagation of lithium dendrites for all solid-state lithium metal batteries(ASSLMBs).Herein,a novel SCEs based on metal-organic frameworks(MOFs,UiO-66-NH_(2))and superacid ZrO_(2)(S-ZrO_(2))fillers are proposed,and the samples were characterized by X-ray diffraction(XRD),scanning electron microscope(SEM),energy dispersive X-ray spectroscopy(EDS),thermo-gravimetric analyzer(TGA)and some other electrochemical measurements.The-NH_(2) groups of UiO-66-NH_(2) combines with F atoms of poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)chains by hydrogen bonds,leading to a high electrochemical stability window of 5 V.Owing to the incorporation of UiO-66-NH_(2) and S-ZrO_(2) in PVDF-HFP polymer,the open metal sites of MOFs and acid surfaces of S-ZrO_(2) can immobilize anions by strong Lewis acid-base interaction,which enhances the effect of immobilization anions,achieving a high Li-ion transference number(t_(+))of 0.72,and acquiring a high ionic conductivity of 1.05×10^(-4) S·cm^(-1) at 60℃.The symmetrical Li/Li cells with the anion-immobilized SCEs may steadily operate for over 600 h at 0.05 mA·cm^(-2) without the shortcircuit occurring.Besides,the solid composite Li/LiFePO_(4)(LFP)cell with the anion-immobilized SCEs shows a superior discharge specific capacity of 158 mAh·g^(-1) at 0.2 C.The results illustrate that the anion-immobilized SCEs are one of the most promising choices to optimize the performances of ASSLMBs.展开更多
The research of poly(ethylene oxide)(PEO)-based solid composite electrolyte with high ionic conductivity and excellent interfacial stability is the key to the development of all-solid-state lithium-ion batteries(ASSLI...The research of poly(ethylene oxide)(PEO)-based solid composite electrolyte with high ionic conductivity and excellent interfacial stability is the key to the development of all-solid-state lithium-ion batteries(ASSLIBs). Herein, uniform nanorod structured CeO_(2) fillers were controllably synthesized by electrospinning, which were subsequently filled into PEO polymer to prepare CeO_(2)/PEO solid composite electrolyte. The addition of CeO_(2) nanorods can reduce both the glass transition temperature and the melting point of PEO polymer, and also interact with PEO and lithium bis(trifluoromethanesulphonyl)imide(LITFSI) by Lewis acid—base reaction. Therefore, the solid composite electrolyte exhibits a high ionic conductivity of 4.52 × 10^(-4)S/cm, a wide electrochemical stability window of about 4.8 V, and a good interfacial stability with Li at 55℃. Moreover, the LiFePO_4/Li ASSLIB divulges the discharging specific capacity of 165, 162, 156 and 146 mA,h/g at 0.2, 0.5, 1 and 2 C, respectively, and achieves the capacity retention of 90.3% after 150 cycles at 0.5 C. Consequently, one dimensional CeO_(2) nanorods can be considered as an alternative filler for polymeric solid electrolyte.展开更多
To address the limitations of contemporary lithium-ion batteries,particularly their low energy density and safety concerns,all-solid-state lithium batteries equipped with solid-state electrolytes have been identified ...To address the limitations of contemporary lithium-ion batteries,particularly their low energy density and safety concerns,all-solid-state lithium batteries equipped with solid-state electrolytes have been identified as an up-and-coming alternative.Among the various SEs,organic–inorganic composite solid electrolytes(OICSEs)that combine the advantages of both polymer and inorganic materials demonstrate promising potential for large-scale applications.However,OICSEs still face many challenges in practical applications,such as low ionic conductivity and poor interfacial stability,which severely limit their applications.This review provides a comprehensive overview of recent research advancements in OICSEs.Specifically,the influence of inorganic fillers on the main functional parameters of OICSEs,including ionic conductivity,Li+transfer number,mechanical strength,electrochemical stability,electronic conductivity,and thermal stability are systematically discussed.The lithium-ion conduction mechanism of OICSE is thoroughly analyzed and concluded from the microscopic perspective.Besides,the classic inorganic filler types,including both inert and active fillers,are categorized with special emphasis on the relationship between inorganic filler structure design and the electrochemical performance of OICSEs.Finally,the advanced characterization techniques relevant to OICSEs are summarized,and the challenges and perspectives on the future development of OICSEs are also highlighted for constructing superior ASSLBs.展开更多
Solid-state batteries(SSBs)with thermal stable solid-state electrolytes(SSEs)show intrinsic capacity and great potential in energy density improvement.SSEs play critical role,however,their low ionic conductivity at ro...Solid-state batteries(SSBs)with thermal stable solid-state electrolytes(SSEs)show intrinsic capacity and great potential in energy density improvement.SSEs play critical role,however,their low ionic conductivity at room temperature and high brittleness hinder their further development.In this paper,polypropylene(PP)-polyvinylidene fluoride(PVDF)-Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)-Lithium bis(trifluoromethane sulphonyl)imide(LiTFSI)multi-layered composite solid electrolyte(CSE)is prepared by a simple separator coating strategy.The incorporation of LATP nanoparticle fillers and high concentration LiTFSI not only reduces the crystallinity of PVDF,but also forms a solvation structure,which contributes to high ionic conductivity in a wide temperature.In addition,using a PP separator as the supporting film,the mechanical strength of the electrolyte was improved and the growth of lithium dendrites are effectively inhibited.The results show that the CSE prepared in this paper has a high ionic conductivity of 6.38×10^(-4)S/cm at room temperature and significantly improves the mechanical properties,the tensile strength reaches 11.02 MPa.The cycle time of Li/Li symmetric cell assembled by CSE at room temperature can exceed 800 h.The Li/LFP full cell can cycle over 800 cycles and the specific capacity of Li/LFP full cell can still reach 120 m Ah/g after 800 cycles at 2 C.This CSE has good cycle stability and excellent mechanical strength at room temperature,which provides an effective method to improve the performance of solid electrolytes under moderate condition.展开更多
The interface instability between composite solid electrolytes(CSEs)and lithium anode significantly shortens the lifespan of all-solid-state lithium batteries(ASSLBs)with high areal capacity.In this work,a CSE featuri...The interface instability between composite solid electrolytes(CSEs)and lithium anode significantly shortens the lifespan of all-solid-state lithium batteries(ASSLBs)with high areal capacity.In this work,a CSE featuring a trilayer architecture is developed by incorporating a thin polyethylene(PE)separator into a blending polymer matrix of poly(ethylene oxide)and poly(vinylidene fluoride)(PEO-PVDF)through a hot pressing technique.This structural design provides complementary functions:the flexible outer layers confine lithium deposition within a restricted area,while the robust interlayer prevents lithium dendrite penetration.Additionally,the incorporation of LiNO_(3) significantly enhances the stability of the CSE/Li interface by gradually forming a Li_(3)N-rich interfacial film,which promotes uniform lithium deposition.Consequently,the assembled Li||Li symmetrical cell demonstrates stable cycling for over 6000 h at a current density of 0.2 mA cm^(–2)with an areal capacity of 1.2 mAh cm^(–2).More attractively,ASSLBs constructed with the designed CSEs,high mass loading LFP/NCM811(LFP:LiFePO_(4);NCM811:LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2))cathodes(≥12 mg cm^(–2)),and lithium metal anodes deliver superior cycling performance without short-circuiting at current densities of 0.3/0.2 mA cm^(–2),respectively.This work offers critical insights for the design of high-performance ASSLBs with improved durability at high areal capacities.展开更多
Recently,high-entropy materials are attracting enormous attention in battery applications,encompassing both electrode materials and solid electrolytes,due to the pliability and diversification in material composition ...Recently,high-entropy materials are attracting enormous attention in battery applications,encompassing both electrode materials and solid electrolytes,due to the pliability and diversification in material composition and electronic structure.Theoretically,the rapid ion transport and the abundance of surface defects in high-entropy materials suggest a potential for enhancing the performance of composite solid-state electrolytes(CPEs).Herein,using a high-entropy oxide(HEO)filler to assess its potential contributions to CPEs is proposed.The distinctive structural distortions in HEO significantly improve the ionic conductivity(5×10^(−4) S·cm^(−1) at 60℃)and Li-ion transference number(0.57)of CPEs.Furthermore,the enhanced Li-ion transport capability extends the critical current density from 0.6 to 1.5 mA·cm^(−2) in Li/Li symmetric cells.In addition,all-solid-state batteries incorporating the HEO-modified CPEs exhibit superior rate performance and cycling stability.The work will enrich the application of HEOs in CPEs and provide fundamental understanding.展开更多
Composite solid electrolytes(CSEs)are promising for solid-state Li metal batteries but suffer from inferior room-temperature ionic conductivity due to sluggish ion transport and high cost due to expensive active ceram...Composite solid electrolytes(CSEs)are promising for solid-state Li metal batteries but suffer from inferior room-temperature ionic conductivity due to sluggish ion transport and high cost due to expensive active ceramic fillers.Here,a host–vip inversion engineering strategy is proposed to develop superionic CSEs using cost-effective SiO_(2) nanoparticles as passive ceramic hosts and poly(vinylidene fluoride-hexafluoropropylene)(PVH)microspheres as polymer vips,forming an unprecedented“polymer vip-in-ceramic host”(i.e.,PVH-in-SiO_(2))architecture differing from the traditional“ceramic vip-in-polymer host”.The PVH-in-SiO_(2) exhibits excellent Li-salt dissociation,achieving high-concentration free Li+.Owing to the low diffusion energy barriers and high diffusion coefficient,the free Li+is thermodynamically and kinetically favorable to migrate to and transport at the SiO_(2)/PVH interfaces.Consequently,the PVH-in-SiO_(2) delivers an exceptional ionic conductivity of 1.32.10−3 S cm−1 at 25℃(vs.typically 10−5–10−4 S cm−1 using high-cost active ceramics),achieved under an ultralow residual solvent content of 2.9 wt%(vs.8–15 wt%in other CSEs).Additionally,PVH-in-SiO_(2) is electrochemically stable with Li anode and various cathodes.Therefore,the PVH-in-SiO_(2) demonstrates excellent high-rate cyclability in LiFePO4|Li full cells(92.9%capacity-retention at 3C after 300 cycles under 25℃)and outstanding stability with high-mass-loading LiFePO4(9.2 mg cm−1)and high-voltage NCM622(147.1 mAh g−1).Furthermore,we verify the versatility of the host–vip inversion engineering strategy by fabricating Na-ion and K-ion-based PVH-in-SiO_(2) CSEs with similarly excellent promotions in ionic conductivity.Our strategy offers a simple,low-cost approach to fabricating superionic CSEs for large-scale application of solid-state Li metal batteries and beyond.展开更多
Li_(6)PS_(5)Cl is a highly wanted sulfide-solid-electrolyte(SSE)for developing all-solid-state lithium batteries,due to its high ionic conductivity,good processability and abundant compositional elements.However,its c...Li_(6)PS_(5)Cl is a highly wanted sulfide-solid-electrolyte(SSE)for developing all-solid-state lithium batteries,due to its high ionic conductivity,good processability and abundant compositional elements.However,its cyclability is poor because of harmful side reactions at the Li_(6)PS_(5)Cl/Li interface and growth of lithium dendrites inside Li_(6)PS_(5)Cl phase.Herein,we report a simple interface-engineering remedy to boost the electrochemical performance of Li_(6)PS_(5)Cl,by coating its surface with a Li-compatible electrolyte Li3OCl having low electronic conductivity.The obtainedLi_(6)PS_(5)Cl@Li_(3)OCl core@shell structure exhibits a synergistic effect.Consequently,compared with the bare Li_(6)PS_(5)Cl,this composite electrolyte exhibits great performance improvements:1)In Li|electrolyte|Li symmetric cells,the critical current density at 30℃gets increased from 0.6 mA cm^(-2)to 1.6 mA cm^(-2),and the lifetime gets prolonged from 320 h to 1400 h at the cycling current of 0.2 mA cm^(-2)or from 10 h to 900 h at the cycling current of 0.5 mA cm^(-2);2)In Li|electrolyte|NCM721 full cells running at 30℃,the cycling capacity at 0.2 C(or 0.5 C)gets enhanced by 20%(or from unfeasible to be feasible)for 100 cycles and the rate capability reaches up to 2 C from 0.2 C;and in full cells running at 60℃,the cycling capacity is increased by 7%at 0.2 C and the rate capability is enhanced to 3.0 C from 0.5 C.The experimental studies and theoretical computations show that the performance enhancements are due to the confined electron penetration and suppressed lithium dendrites growth at theLi_(6)PS_(5)Cl@Li_(3)OCl interface.展开更多
Composite solid electrolytes(CSEs)with poly(ethylene oxide)(PEO)have become fairly prevalent for fabricating high-performance solid-state lithium metal batteries due to their high Li~+solvating capability,flexible pro...Composite solid electrolytes(CSEs)with poly(ethylene oxide)(PEO)have become fairly prevalent for fabricating high-performance solid-state lithium metal batteries due to their high Li~+solvating capability,flexible processability and low cost.However,unsatisfactory room-temperature ionic conductivity,weak interfacial compatibility and uncontrollable Li dendrite growth seriously hinder their progress.Enormous efforts have been devoted to combining PEO with ceramics either as fillers or major matrix with the rational design of two-phase architecture,spatial distribution and content,which is anticipated to hold the key to increasing ionic conductivity and resolving interfacial compatibility within CSEs and between CSEs/electrodes.Unfortunately,a comprehensive review exclusively discussing the design,preparation and application of PEO/ceramic-based CSEs is largely lacking,in spite of tremendous reviews dealing with a broad spectrum of polymers and ceramics.Consequently,this review targets recent advances in PEO/ceramicbased CSEs,starting with a brief introduction,followed by their ionic conduction mechanism,preparation methods,and then an emphasis on resolving ionic conductivity and interfacial compatibility.Afterward,their applications in solid-state lithium metal batteries with transition metal oxides and sulfur cathodes are summarized.Finally,a summary and outlook on existing challenges and future research directions are proposed.展开更多
In comparison with lithium-ion batteries(LIBs)with liquid electrolytes,all-solid-state lithium batteries(ASSLBs)have been considered as promising systems for future energy storage due to their safety and high energy d...In comparison with lithium-ion batteries(LIBs)with liquid electrolytes,all-solid-state lithium batteries(ASSLBs)have been considered as promising systems for future energy storage due to their safety and high energy density.As the pivotal component used in ASSLBs,composite solid polymer electrolytes(CSPEs),derived from the incorporation of inorganic fillers into solid polymer electrolytes(SPEs),exhibit higher ionic conductivity,better mechanical strength,and superior thermal/electrochemical stability compared to the single-component SPEs,which can significantly promote the electrochemical performance of ASSLBs.Herein,the recent advances of CSPEs applied in ASSLBs are presented.The effects of the category,morphology and concentration of inorganic fillers on the ionic conductivity,mechanical strength,electrochemical window,interfacial stability and possible Li+transfer mechanism of CSPEs will be systematically discussed.Finally,the challenges and perspectives are proposed for the future development of high-performance CSPEs and ASSLBs.展开更多
Compared with commercial lithium batteries with liquid electrolytes,all-solidstate lithium batteries(ASSLBs)possess the advantages of higher safety,better electrochemical stability,higher energy density,and longer cyc...Compared with commercial lithium batteries with liquid electrolytes,all-solidstate lithium batteries(ASSLBs)possess the advantages of higher safety,better electrochemical stability,higher energy density,and longer cycle life;therefore,ASSLBs have been identified as promising candidates for next-generation safe and stable high-energy-storage devices.The design and fabrication of solid-state electrolytes(SSEs)are vital for the future commercialization of ASSLBs.Among various SSEs,solid polymer composite electrolytes(SPCEs)consisting of inorganic nanofillers and polymer matrix have shown great application prospects in the practice of ASSLBs.The incorporation of inorganic nanofillers into the polymer matrix has been considered as a crucial method to achieve high ionic conductivity for SPCE.In this review,the mechanisms of Li+transport variation caused by incorporating inorganic nanofillers into the polymer matrix are discussed in detail.On the basis of the recent progress,the respective contributions of polymer chains,passive ceramic nanofillers,and active ceramic nanofillers in affecting the Li+transport process of SPCE are reviewed systematically.The inherent relationship between the morphological characteristics of inorganic nanofillers and the ionic conductivity of the resultant SPCE is discussed.Finally,the challenges and future perspectives for developing high-performance SPCE are put forward.This review aims to provide possible strategies for the further improvement of ionic conductivity in inorganic nanoscale filler-reinforced SPCE and highlight their inspiration for future research directions.展开更多
Single-ion conducting solid polymer electrolytes are expected to play a vital role in the realization of solid-state Li metal batteries.In this work,a lithiated Nafion(Li-Nafion)-garnet ceramic Li6.25La3 Zr2 Al0.25O12...Single-ion conducting solid polymer electrolytes are expected to play a vital role in the realization of solid-state Li metal batteries.In this work,a lithiated Nafion(Li-Nafion)-garnet ceramic Li6.25La3 Zr2 Al0.25O12(LLZAO)composite solid electrolyte(CSE)membrane with 30μm thickness was prepared for the first time.By employing X-ray photoelectron spectroscopy and transmission electron microscope,the interaction between LLZAO and Li-Nafion was investigated.It is found that the LLZAO interacts with the Li-Nafion to form a space charge layer at the interface between LLZAO and Li-Nafion.The space charge layer reduces the migration barrier of Li-ions and improves the ionic conductivity of the CSE membrane.The CSE membrane containing 10 wt%LLZAO exhibits the highest ionic conductivity of2.26×10-4 S cm-1 at 30℃among the pristine Li-Nafion membrane,the membrane containing 5 wt%,20 wt%,and 30 wt%LLZAO,respectively.It also exhibits a high Li-ion transference number of 0.92,and a broader electrochemical window of 0-+4.8 V vs.Li+/Li than that of 0-+4.0 V vs.Li+/Li for the pristine Li-Nafion membrane.It is observed that the CSE membrane not only inhibits the growth of Li dendrites but also keeps excellent electrochemical stability with the Li electrode.Benefitting from the above merits,the solid-state LiFePO4/Li cell fabricated with the CSE membrane was practically charged and discharged at 30℃.The cell exhibits an initial reversible discharge specific capacity of 160 mAh g-1 with 97%capacity retention after 100 cycles at 0.2 C,and maintains discharge specific capacity of 126 mAh g-1 after500 cycles at 1 C.The CSE membrane prepared with Li-Nafion and LLZAO is proved to be a promising solid electrolyte for advanced solid-state Li metal batteries.展开更多
The rapid development of new energy vehicles and 5G communication technologies has led to higher demands for the safety,energy density,and cycle performance of lithium-ion batteries as power sources.However,the curren...The rapid development of new energy vehicles and 5G communication technologies has led to higher demands for the safety,energy density,and cycle performance of lithium-ion batteries as power sources.However,the currently used liquid carbonate compounds in commercial lithium-ion battery electrolytes pose potential safety hazards such as leakage,swelling,corrosion,and flammability.Solid electrolytes can be used to mitigate these risks and create a safer lithium battery.Furthermore,high-energy density can be achieved by using solid electrolytes along with high-voltage cathode and metal lithium anode.Two types of solid electrolytes are generally used:inorganic solid electrolytes and polymer solid electrolytes.Inorganic solid electrolytes have high ionic conductivity,electrochemical stability window,and mechanical strength,but suffer from large solid/solid contact resistance between the electrode and electrolyte.Polymer solid electrolytes have good flexibility,processability,and contact interface properties,but low room temperature ionic conductivity,necessitating operation at elevated temperatures.Composite solid electrolytes(CSEs) are a promising alternative because they offer light weight and flexibility,like polymers,as well as the strength and stability of inorganic electrolytes.This paper presents a comprehensive review of recent advances in CSEs to help researchers optimize CSE composition and interactions for practical applications.It covers the development history of solid-state electrolytes,CSE properties with respect to nanofillers,morphology,and polymer types,and also discusses the lithium-ion transport mechanism of the composite electrolyte,and the methods of engineering interfaces with the positive and negative electrodes.Overall,the paper aims to provide an outlook on the potential applications of CSEs in solid-state lithium batteries,and to inspire further research aimed at the development of more systematic optimization strategies for CSEs.展开更多
All-solid-state lithium batteries(ASSLBs) employing sulfide electrolyte and lithium(Li) anode have received increasing attention due to the intrinsic safety and high energy density.However,the thick electrolyte layer ...All-solid-state lithium batteries(ASSLBs) employing sulfide electrolyte and lithium(Li) anode have received increasing attention due to the intrinsic safety and high energy density.However,the thick electrolyte layer and lithium dendrites formed at the electrolyte/Li anode interface hinder the realization of high-performance ASSLBs.Herein,a novel membrane consisting of Li_(6)PS_(5) Cl(LPSCl),poly(ethylene oxide)(PEO) and Li-salt(LiTFSI) was prepared as sulfide-based composite solid electrolyte(LPSCl-PEO3-LiTFSI)(LPSCl:PEO=97:3 wt/wt;EO:Li=8:1 mol/mol),which delivers high ionic conductivity(1.1 × 10^(-3) S cm^(-1)) and wide electrochemical window(4.9 V vs.Li^(+)/Li) at 25 ℃.In addition,an ex-situ artificial solid electrolyte interphase(SEI) film enriched with LiF and Li3 N was designed as a protective layer on Li anode(Li(SEI)) to suppress the growth of lithium dendrites.Benefiting from the synergy of sulfide-based composite solid electrolyte and ex-situ artificial SEI,cells of S-CNTs/LPSCI-PEO3-LiTFSI/Li(SEI) and Al_(2)O_(3)@LiNi_(0.5)Co_(0.3)Mn_(0.2)O_(2)/LPSCl-PEO3-LiTFSI/Li(SEI) are assembled and both exhibit high initial discharge capacity of 1221.1 mAh g^(-1)(135.8 mAh g^(-1)) and enhanced cycling stability with 81.6% capacity retention over 200 cycles at 0.05 C(89.2% over 100 cycles at 0.1 C).This work provides a new insight into the synergy of composite solid electrolyte and artificial SEI for achieving high-performance ASSLBs.展开更多
Developing laminar composite solid electrolyte with ultrathin thickness and continuous conduction channels in vertical direction holds great promise for all-solid-state lithium batteries.Herein,a thin,laminar solid el...Developing laminar composite solid electrolyte with ultrathin thickness and continuous conduction channels in vertical direction holds great promise for all-solid-state lithium batteries.Herein,a thin,laminar solid electrolyte is synthesized by filtrating–NH 2 functionalized metal-organic framework nanosheets and then being threaded with poly(ethylene oxide)chains induced by the hydrogen-bonding interaction from–NH_(2) groups.It is demonstrated that the threaded poly(ethylene oxide)chains lock the adjacent metal-organic framework nanosheets,giving highly enhanced structural stability(Young’s modulus,1.3 GPa)to 7.5-μm-thick laminar composite solid electrolyte.Importantly,these poly(ethylene oxide)chains with stretching structure serve as continuous conduction pathways along the chains in pores.It makes the non-conduction laminar metal-organic framework electrolyte highly conductive:3.97×10^(−5) S cm^(−1) at 25℃,which is even over 25 times higher than that of pure poly(ethylene oxide)electrolyte.The assembled lithium cell,thus,acquires superior cycling stability,initial discharge capacity(148 mAh g^(−1) at 0.5 C and 60℃),and retention(94% after 150 cycles).Besides,the pore size of nanosheet is tailored(24.5–40.9˚A)to evaluate the mechanisms of chain conformation and ion transport in confined space.It shows that the confined pore only with proper size could facilitate the stretching of poly(ethylene oxide)chains,and meanwhile inhibit their disorder degree.Specifically,the pore size of 33.8˚A shows optimized confinement effect with trans-poly(ethylene oxide)and cis-poly(ethylene oxide)conformation,which offers great significance in ion conduction.Our design of poly(ethylene oxide)-threaded architecture provides a platform and paves a way to the rational design of next-generation high-performance porous electrolytes.展开更多
Composite solid electrolytes(CSEs)have emerged as promising candidates for safe and high-energy–density solid-state lithium metal batteries(SSLMBs).However,concurrently achieving exceptional ionic conductivity and in...Composite solid electrolytes(CSEs)have emerged as promising candidates for safe and high-energy–density solid-state lithium metal batteries(SSLMBs).However,concurrently achieving exceptional ionic conductivity and interface compatibility between the electrolyte and electrode presents a significant challenge in the development of high-performance CSEs for SSLMBs.To overcome these challenges,we present a method involving the in-situ polymerization of a monomer within a self-supported porous Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZT)to produce the CSE.The synergy of the continuous conductive LLZT network,well-organized polymer,and their interface can enhance the ionic conductivity of the CSE at room temperature.Furthermore,the in-situ polymerization process can also con-struct the integration and compatibility of the solid electrolyte–solid electrode interface.The synthesized CSE exhibited a high ionic conductivity of 1.117 mS cm^(-1),a significant lithium transference number of 0.627,and exhibited electrochemical stability up to 5.06 V vs.Li/Li+at 30℃.Moreover,the Li|CSE|LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) cell delivered a discharge capacity of 105.1 mAh g^(-1) after 400 cycles at 0.5 C and 30℃,corresponding to a capacity retention of 61%.This methodology could be extended to a variety of ceramic,polymer electrolytes,or battery systems,thereby offering a viable strategy to improve the electrochemical properties of CSEs for high-energy–density SSLMBs.展开更多
Solid electrolytes have received widespread attention due to their higher safety than liquid electrolytes in the past decades.In particular,organic-inorganic composite solid electro-lytes(CSEs)in which inorganic fller...Solid electrolytes have received widespread attention due to their higher safety than liquid electrolytes in the past decades.In particular,organic-inorganic composite solid electro-lytes(CSEs)in which inorganic fllers dispersed in polymer solid electrolytes are consid-ered to be one of the most promising candidate electrolytes for high-performance solid-state lithium batteries.Understanding the local environments and the conduction pathway/dynamics of Lit is essential for the design of high-performance CSEs.Nuclear magnetic resonance(NMR)is a non-invasive quantitative technique that has unique ca-pabilities in providing molecular structure information,morphological evolution,and measuring the movement of ions at different time scales.Therefore,for battery re-searchers,an accurate and comprehensive under standing of the basic principles and experimental design of solid-state NMR(SSNMR)is of great significance for investigating the abundant molecular structure and dynamics information in CSEs.The specific appli-cations of the SSNMR technique in CSEs are briefly introduced in this present review.展开更多
Traditional lithium-ion batteries(LIBs)employing liquid electrolytes face inherent safety risks,motivating the development of solid polymer electrolytes(SPEs)like polyethylene oxide(PEO).However,pure PEO suffers from ...Traditional lithium-ion batteries(LIBs)employing liquid electrolytes face inherent safety risks,motivating the development of solid polymer electrolytes(SPEs)like polyethylene oxide(PEO).However,pure PEO suffers from low room-temperature ionic conductivity and poor mechanical strength.Composite solid electrolytes(CSEs)incorporating inorganic filler offer promise but are hindered by poor interfacial compatibility.This study addresses this critical issue through surface engineering.Mercaptopropyl trimethoxysilane(MPTMS)is used to modify garnet-type Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)particles,introducing thiol groups(-SH)onto their surface.Subsequently,thiol-functionalized LLZTO(LLZTO@MPTMS)participate in the insitu copolymerization of polyethylene glycol methyl methacrylate(PEGMEMA)and crosslinker polyethylene glycol dimethacrylate(PEGDMA),yielding a novel PEO-based CSE(PCSE).The effects of PEGMEMA molecular weight,PEGMEMA/PEGDMA ratio,and LLZTO@MPTMS content have been systematically examined to optimize the electrolyte.The resulting PCSE exhibits an ionic conductivity of 1.20×10^(-4)S·cm^(-1)at 30℃,a lithium-ion transference number of 0.36,and a wide electrochemical stability window up to 5.1 V(vs.Li^(+)/Li).Li/PCSE/Li symmetric cells demonstrate stable cycling for nearly 240 h at 0.05 mA·cm^(-2),indicating enhanced interface compatibility with lithium metal and effective dendrite suppression.Furthermore,LiFePO_(4)/PCSE/Li full cells deliver a high initial discharge capacity of 155.0 mAh·g^(-1)at 0.1 C and retain 76.0%capacity after 100 cycles,alongside excellent rate capability.These results confirm that the combined strategy of LLZTO surface modification with MPTMS and in-situ copolymerization effectively mitigates interfacial issues,presenting a promising material system for high-performance solid-state LIBs.展开更多
Composite solid electrolytes(CSEs) containing polymer matrices and inorganic fillers hold promise for the next generation of solid-state batteries.However,the role of residual solvents in CSEs remains controversial.Th...Composite solid electrolytes(CSEs) containing polymer matrices and inorganic fillers hold promise for the next generation of solid-state batteries.However,the role of residual solvents in CSEs remains controversial.This study investigated the evolution and function of the residual solvent in a polymer-Li_2B_(12)H_(12) CSE.A partial reaction occurred between Li_2B_(12)H_(12) and solvent N,N-dimethylformamide(DMF),which produced dimethylaminomethanol(DMAM) in the CSE.Density functional theory calculations have revealed that DMA M forms stronger hydrogen bonds with polyvinylidene fluoride chains than DMF,which can have a plasticizing effect on the polymer matrix,leading to lower crystallinity and quicker segment motion.Therefore,this CSE exhibited improved Li-ion conducting properties,enabling the stable cycling of Li‖LiFePO_(4) solid-state batteries.This study provided insights into the role of residual solvents in CSEs.展开更多
基金the National Natural Science Foundation of China(Grant No.21875071)the National Natural Science Foundation of China-Hong Kong Research Grant Council(NSFC-RGC)Joint Research Scheme(Grant No.21661162002 and N_HKUST601/16)the Guangzhou Scientific and Technological Planning Project(Grant No.201704030061)。
文摘Solid polymer electrolytes(SPEs), such as polyethylene oxide(PEO), are characteristic of good flexibility and excellent processability, but they suffer from low ionic conductivity and small Li+transference number at ambient temperature. Inorganic solid electrolytes(ISEs), garnet-type Li7La3Zr2O12 and its derivatives(LLZO-based) in particular, possess high ionic conductivity at room temperature, wide electrochemical stability window, large Li+transference number as well as good stability against Li metal anode.Nevertheless, lithium dendrites growth, interfacial contact issue and brittle nature of LLZO-based ceramic electrolytes prevent their practical applications. In response to these shortcomings, LLZO-based/polymer solid composite electrolytes(SCEs), taking complementary advantages of two kinds of electrolytes, and thus simultaneously improving the electrode wettability, ionic conductivity and mechanical strength, have been made to develop high-performance SCEs in recent years. Herein, the intrinsic properties and research progress of LLZO-based/polymer SCEs, including LLZO-based/PEO SCEs(LLZO-based/PEO SCEs with uniform dispersion of LLZO-based fillers and LLZO-based/PEO layered SCEs) and LLZO-based/novel polymers SCEs, are summarized. Besides, comprehensive updates on their applications in solid-state batteries are also presented. Finally, challenges and perspectives of LLZO-based/polymer SCEs for advanced allsolid-state lithium batteries(ASSLBs) are suggested. This review paper aims to provide systematic research progress of LLZO-based/polymer SCEs, to allow for more efficient and target-oriented research on improving LLZO-based/polymer SCEs.
基金financially supported by National Natural Science Foundation of China(No.21701083)Zhenjiang Key Laboratory of Marine Power Equipment Performance(SS2018006)+1 种基金The Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.SJCX19_0612)Project of Jiangsu University(High-Tech Ship)Collaborative Innovation Center(2019,1174871801-11).
文摘Anion-immobilized solid composite electrolytes(SCEs)are important to restrain the propagation of lithium dendrites for all solid-state lithium metal batteries(ASSLMBs).Herein,a novel SCEs based on metal-organic frameworks(MOFs,UiO-66-NH_(2))and superacid ZrO_(2)(S-ZrO_(2))fillers are proposed,and the samples were characterized by X-ray diffraction(XRD),scanning electron microscope(SEM),energy dispersive X-ray spectroscopy(EDS),thermo-gravimetric analyzer(TGA)and some other electrochemical measurements.The-NH_(2) groups of UiO-66-NH_(2) combines with F atoms of poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)chains by hydrogen bonds,leading to a high electrochemical stability window of 5 V.Owing to the incorporation of UiO-66-NH_(2) and S-ZrO_(2) in PVDF-HFP polymer,the open metal sites of MOFs and acid surfaces of S-ZrO_(2) can immobilize anions by strong Lewis acid-base interaction,which enhances the effect of immobilization anions,achieving a high Li-ion transference number(t_(+))of 0.72,and acquiring a high ionic conductivity of 1.05×10^(-4) S·cm^(-1) at 60℃.The symmetrical Li/Li cells with the anion-immobilized SCEs may steadily operate for over 600 h at 0.05 mA·cm^(-2) without the shortcircuit occurring.Besides,the solid composite Li/LiFePO_(4)(LFP)cell with the anion-immobilized SCEs shows a superior discharge specific capacity of 158 mAh·g^(-1) at 0.2 C.The results illustrate that the anion-immobilized SCEs are one of the most promising choices to optimize the performances of ASSLMBs.
基金Project supported by the Education Department of Henan Province(22A170017)the Science and Technology Department of Henan Province(232102240011)+1 种基金Henan Institute of Science and Technology(2016034)National College Students'Innovation and Entrepreneurship Training Program(202211071012)。
文摘The research of poly(ethylene oxide)(PEO)-based solid composite electrolyte with high ionic conductivity and excellent interfacial stability is the key to the development of all-solid-state lithium-ion batteries(ASSLIBs). Herein, uniform nanorod structured CeO_(2) fillers were controllably synthesized by electrospinning, which were subsequently filled into PEO polymer to prepare CeO_(2)/PEO solid composite electrolyte. The addition of CeO_(2) nanorods can reduce both the glass transition temperature and the melting point of PEO polymer, and also interact with PEO and lithium bis(trifluoromethanesulphonyl)imide(LITFSI) by Lewis acid—base reaction. Therefore, the solid composite electrolyte exhibits a high ionic conductivity of 4.52 × 10^(-4)S/cm, a wide electrochemical stability window of about 4.8 V, and a good interfacial stability with Li at 55℃. Moreover, the LiFePO_4/Li ASSLIB divulges the discharging specific capacity of 165, 162, 156 and 146 mA,h/g at 0.2, 0.5, 1 and 2 C, respectively, and achieves the capacity retention of 90.3% after 150 cycles at 0.5 C. Consequently, one dimensional CeO_(2) nanorods can be considered as an alternative filler for polymeric solid electrolyte.
基金supported by the National Natural Science Foundation of China(Grant No.22075064,52302234,52272241)Zhejiang Provincial Natural Science Foundation of China under Grant No.LR24E020001+2 种基金Natural Science of Heilongjiang Province(No.LH2023B009)China Postdoctoral Science Foundation(2022M710950)Heilongjiang Postdoctoral Fund(LBH-Z21131),National Key Laboratory Projects(No.SYSKT20230056).
文摘To address the limitations of contemporary lithium-ion batteries,particularly their low energy density and safety concerns,all-solid-state lithium batteries equipped with solid-state electrolytes have been identified as an up-and-coming alternative.Among the various SEs,organic–inorganic composite solid electrolytes(OICSEs)that combine the advantages of both polymer and inorganic materials demonstrate promising potential for large-scale applications.However,OICSEs still face many challenges in practical applications,such as low ionic conductivity and poor interfacial stability,which severely limit their applications.This review provides a comprehensive overview of recent research advancements in OICSEs.Specifically,the influence of inorganic fillers on the main functional parameters of OICSEs,including ionic conductivity,Li+transfer number,mechanical strength,electrochemical stability,electronic conductivity,and thermal stability are systematically discussed.The lithium-ion conduction mechanism of OICSE is thoroughly analyzed and concluded from the microscopic perspective.Besides,the classic inorganic filler types,including both inert and active fillers,are categorized with special emphasis on the relationship between inorganic filler structure design and the electrochemical performance of OICSEs.Finally,the advanced characterization techniques relevant to OICSEs are summarized,and the challenges and perspectives on the future development of OICSEs are also highlighted for constructing superior ASSLBs.
基金supported by National Natural Science Foundation of China(No.22209075)。
文摘Solid-state batteries(SSBs)with thermal stable solid-state electrolytes(SSEs)show intrinsic capacity and great potential in energy density improvement.SSEs play critical role,however,their low ionic conductivity at room temperature and high brittleness hinder their further development.In this paper,polypropylene(PP)-polyvinylidene fluoride(PVDF)-Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)-Lithium bis(trifluoromethane sulphonyl)imide(LiTFSI)multi-layered composite solid electrolyte(CSE)is prepared by a simple separator coating strategy.The incorporation of LATP nanoparticle fillers and high concentration LiTFSI not only reduces the crystallinity of PVDF,but also forms a solvation structure,which contributes to high ionic conductivity in a wide temperature.In addition,using a PP separator as the supporting film,the mechanical strength of the electrolyte was improved and the growth of lithium dendrites are effectively inhibited.The results show that the CSE prepared in this paper has a high ionic conductivity of 6.38×10^(-4)S/cm at room temperature and significantly improves the mechanical properties,the tensile strength reaches 11.02 MPa.The cycle time of Li/Li symmetric cell assembled by CSE at room temperature can exceed 800 h.The Li/LFP full cell can cycle over 800 cycles and the specific capacity of Li/LFP full cell can still reach 120 m Ah/g after 800 cycles at 2 C.This CSE has good cycle stability and excellent mechanical strength at room temperature,which provides an effective method to improve the performance of solid electrolytes under moderate condition.
基金financially supported by the National Natural Science Foundation of China(Nos.22178125 and 22478130).
文摘The interface instability between composite solid electrolytes(CSEs)and lithium anode significantly shortens the lifespan of all-solid-state lithium batteries(ASSLBs)with high areal capacity.In this work,a CSE featuring a trilayer architecture is developed by incorporating a thin polyethylene(PE)separator into a blending polymer matrix of poly(ethylene oxide)and poly(vinylidene fluoride)(PEO-PVDF)through a hot pressing technique.This structural design provides complementary functions:the flexible outer layers confine lithium deposition within a restricted area,while the robust interlayer prevents lithium dendrite penetration.Additionally,the incorporation of LiNO_(3) significantly enhances the stability of the CSE/Li interface by gradually forming a Li_(3)N-rich interfacial film,which promotes uniform lithium deposition.Consequently,the assembled Li||Li symmetrical cell demonstrates stable cycling for over 6000 h at a current density of 0.2 mA cm^(–2)with an areal capacity of 1.2 mAh cm^(–2).More attractively,ASSLBs constructed with the designed CSEs,high mass loading LFP/NCM811(LFP:LiFePO_(4);NCM811:LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2))cathodes(≥12 mg cm^(–2)),and lithium metal anodes deliver superior cycling performance without short-circuiting at current densities of 0.3/0.2 mA cm^(–2),respectively.This work offers critical insights for the design of high-performance ASSLBs with improved durability at high areal capacities.
基金supported by the National Natural Science Foundation of China(No.52002094)Shenzhen Science and Technology Program(Nos.JCYJ20210324121411031,JSGG202108021253804014 and RCBS20210706092218040)Shenzhen Steady Support Plan(Nos.GXWD20221030205923001 and GXWD20201230155427003-20200824103000001).
文摘Recently,high-entropy materials are attracting enormous attention in battery applications,encompassing both electrode materials and solid electrolytes,due to the pliability and diversification in material composition and electronic structure.Theoretically,the rapid ion transport and the abundance of surface defects in high-entropy materials suggest a potential for enhancing the performance of composite solid-state electrolytes(CPEs).Herein,using a high-entropy oxide(HEO)filler to assess its potential contributions to CPEs is proposed.The distinctive structural distortions in HEO significantly improve the ionic conductivity(5×10^(−4) S·cm^(−1) at 60℃)and Li-ion transference number(0.57)of CPEs.Furthermore,the enhanced Li-ion transport capability extends the critical current density from 0.6 to 1.5 mA·cm^(−2) in Li/Li symmetric cells.In addition,all-solid-state batteries incorporating the HEO-modified CPEs exhibit superior rate performance and cycling stability.The work will enrich the application of HEOs in CPEs and provide fundamental understanding.
基金financial support from the National Natural Science Foundation of China(Nos.52250010 and 52201242)the 261 Project of MIIT,Natural Science Foundation of Jiangsu Province(No.BK20240179)the Young Elite Scientists Sponsorship Program by CAST(No.2021QNRC001).
文摘Composite solid electrolytes(CSEs)are promising for solid-state Li metal batteries but suffer from inferior room-temperature ionic conductivity due to sluggish ion transport and high cost due to expensive active ceramic fillers.Here,a host–vip inversion engineering strategy is proposed to develop superionic CSEs using cost-effective SiO_(2) nanoparticles as passive ceramic hosts and poly(vinylidene fluoride-hexafluoropropylene)(PVH)microspheres as polymer vips,forming an unprecedented“polymer vip-in-ceramic host”(i.e.,PVH-in-SiO_(2))architecture differing from the traditional“ceramic vip-in-polymer host”.The PVH-in-SiO_(2) exhibits excellent Li-salt dissociation,achieving high-concentration free Li+.Owing to the low diffusion energy barriers and high diffusion coefficient,the free Li+is thermodynamically and kinetically favorable to migrate to and transport at the SiO_(2)/PVH interfaces.Consequently,the PVH-in-SiO_(2) delivers an exceptional ionic conductivity of 1.32.10−3 S cm−1 at 25℃(vs.typically 10−5–10−4 S cm−1 using high-cost active ceramics),achieved under an ultralow residual solvent content of 2.9 wt%(vs.8–15 wt%in other CSEs).Additionally,PVH-in-SiO_(2) is electrochemically stable with Li anode and various cathodes.Therefore,the PVH-in-SiO_(2) demonstrates excellent high-rate cyclability in LiFePO4|Li full cells(92.9%capacity-retention at 3C after 300 cycles under 25℃)and outstanding stability with high-mass-loading LiFePO4(9.2 mg cm−1)and high-voltage NCM622(147.1 mAh g−1).Furthermore,we verify the versatility of the host–vip inversion engineering strategy by fabricating Na-ion and K-ion-based PVH-in-SiO_(2) CSEs with similarly excellent promotions in ionic conductivity.Our strategy offers a simple,low-cost approach to fabricating superionic CSEs for large-scale application of solid-state Li metal batteries and beyond.
基金supported by the National Key Research and Development Program of China (2018YFE0111600)Haihe Laboratory of Sustainable Chemical Transformations for financial supportpartially supported by the Graduate Top-notch Innovation Award Plan in Liberal Arts and Science of Tianjin University for the Year of 2023 (B2-2023-012)
文摘Li_(6)PS_(5)Cl is a highly wanted sulfide-solid-electrolyte(SSE)for developing all-solid-state lithium batteries,due to its high ionic conductivity,good processability and abundant compositional elements.However,its cyclability is poor because of harmful side reactions at the Li_(6)PS_(5)Cl/Li interface and growth of lithium dendrites inside Li_(6)PS_(5)Cl phase.Herein,we report a simple interface-engineering remedy to boost the electrochemical performance of Li_(6)PS_(5)Cl,by coating its surface with a Li-compatible electrolyte Li3OCl having low electronic conductivity.The obtainedLi_(6)PS_(5)Cl@Li_(3)OCl core@shell structure exhibits a synergistic effect.Consequently,compared with the bare Li_(6)PS_(5)Cl,this composite electrolyte exhibits great performance improvements:1)In Li|electrolyte|Li symmetric cells,the critical current density at 30℃gets increased from 0.6 mA cm^(-2)to 1.6 mA cm^(-2),and the lifetime gets prolonged from 320 h to 1400 h at the cycling current of 0.2 mA cm^(-2)or from 10 h to 900 h at the cycling current of 0.5 mA cm^(-2);2)In Li|electrolyte|NCM721 full cells running at 30℃,the cycling capacity at 0.2 C(or 0.5 C)gets enhanced by 20%(or from unfeasible to be feasible)for 100 cycles and the rate capability reaches up to 2 C from 0.2 C;and in full cells running at 60℃,the cycling capacity is increased by 7%at 0.2 C and the rate capability is enhanced to 3.0 C from 0.5 C.The experimental studies and theoretical computations show that the performance enhancements are due to the confined electron penetration and suppressed lithium dendrites growth at theLi_(6)PS_(5)Cl@Li_(3)OCl interface.
基金financially supported by National Key R&D Program for International Cooperation(No.2021YFE0115100)the project of the National Natural Science Foundation of China(Nos.51872240,51972270 and 52172101)+4 种基金Key Research and Development Program of Shaanxi Province(No.2021ZDLGY14-08 and 2022KWZ-04)Natural Science Foundation of Shaanxi Province(2020JZ-07)the Research Fund of the State Key Laboratory of Solidification Processing(NPU),China(2021-TS-03)the Fundamental Research Funds for the Central Universities(No.3102019JC005 and G2022KY0604)the Research Fund of the State Key Laboratory of Solid Lubrication(CAS),China(LSL-2007)。
文摘Composite solid electrolytes(CSEs)with poly(ethylene oxide)(PEO)have become fairly prevalent for fabricating high-performance solid-state lithium metal batteries due to their high Li~+solvating capability,flexible processability and low cost.However,unsatisfactory room-temperature ionic conductivity,weak interfacial compatibility and uncontrollable Li dendrite growth seriously hinder their progress.Enormous efforts have been devoted to combining PEO with ceramics either as fillers or major matrix with the rational design of two-phase architecture,spatial distribution and content,which is anticipated to hold the key to increasing ionic conductivity and resolving interfacial compatibility within CSEs and between CSEs/electrodes.Unfortunately,a comprehensive review exclusively discussing the design,preparation and application of PEO/ceramic-based CSEs is largely lacking,in spite of tremendous reviews dealing with a broad spectrum of polymers and ceramics.Consequently,this review targets recent advances in PEO/ceramicbased CSEs,starting with a brief introduction,followed by their ionic conduction mechanism,preparation methods,and then an emphasis on resolving ionic conductivity and interfacial compatibility.Afterward,their applications in solid-state lithium metal batteries with transition metal oxides and sulfur cathodes are summarized.Finally,a summary and outlook on existing challenges and future research directions are proposed.
基金supported by the Innovative and Entrepreneurial Talent Plan(Jiangsu Province,China)。
文摘In comparison with lithium-ion batteries(LIBs)with liquid electrolytes,all-solid-state lithium batteries(ASSLBs)have been considered as promising systems for future energy storage due to their safety and high energy density.As the pivotal component used in ASSLBs,composite solid polymer electrolytes(CSPEs),derived from the incorporation of inorganic fillers into solid polymer electrolytes(SPEs),exhibit higher ionic conductivity,better mechanical strength,and superior thermal/electrochemical stability compared to the single-component SPEs,which can significantly promote the electrochemical performance of ASSLBs.Herein,the recent advances of CSPEs applied in ASSLBs are presented.The effects of the category,morphology and concentration of inorganic fillers on the ionic conductivity,mechanical strength,electrochemical window,interfacial stability and possible Li+transfer mechanism of CSPEs will be systematically discussed.Finally,the challenges and perspectives are proposed for the future development of high-performance CSPEs and ASSLBs.
基金the National Natural Science Foundation of China(Grant No.21673051)the Department of Science and Technology of Guangdong Province,China(No.2019A050510043).
文摘Compared with commercial lithium batteries with liquid electrolytes,all-solidstate lithium batteries(ASSLBs)possess the advantages of higher safety,better electrochemical stability,higher energy density,and longer cycle life;therefore,ASSLBs have been identified as promising candidates for next-generation safe and stable high-energy-storage devices.The design and fabrication of solid-state electrolytes(SSEs)are vital for the future commercialization of ASSLBs.Among various SSEs,solid polymer composite electrolytes(SPCEs)consisting of inorganic nanofillers and polymer matrix have shown great application prospects in the practice of ASSLBs.The incorporation of inorganic nanofillers into the polymer matrix has been considered as a crucial method to achieve high ionic conductivity for SPCE.In this review,the mechanisms of Li+transport variation caused by incorporating inorganic nanofillers into the polymer matrix are discussed in detail.On the basis of the recent progress,the respective contributions of polymer chains,passive ceramic nanofillers,and active ceramic nanofillers in affecting the Li+transport process of SPCE are reviewed systematically.The inherent relationship between the morphological characteristics of inorganic nanofillers and the ionic conductivity of the resultant SPCE is discussed.Finally,the challenges and future perspectives for developing high-performance SPCE are put forward.This review aims to provide possible strategies for the further improvement of ionic conductivity in inorganic nanoscale filler-reinforced SPCE and highlight their inspiration for future research directions.
基金financially supported by the National Key R&D Program of China(Grant no.2016YFB0100100)Strategic Priority Research Program of the Chinese Academy of Sciences(Grant no.XDA17020404)+2 种基金Strategic Priority Research Program of the Chinese Academy of Sciences(Grant no.XDA09010203)R&D Projects in Key Areas of Guangdong Province(Grant no.2019B090908001)DICP&QIBEBT(Grant no.DICP&QIBEBT UN201702)。
文摘Single-ion conducting solid polymer electrolytes are expected to play a vital role in the realization of solid-state Li metal batteries.In this work,a lithiated Nafion(Li-Nafion)-garnet ceramic Li6.25La3 Zr2 Al0.25O12(LLZAO)composite solid electrolyte(CSE)membrane with 30μm thickness was prepared for the first time.By employing X-ray photoelectron spectroscopy and transmission electron microscope,the interaction between LLZAO and Li-Nafion was investigated.It is found that the LLZAO interacts with the Li-Nafion to form a space charge layer at the interface between LLZAO and Li-Nafion.The space charge layer reduces the migration barrier of Li-ions and improves the ionic conductivity of the CSE membrane.The CSE membrane containing 10 wt%LLZAO exhibits the highest ionic conductivity of2.26×10-4 S cm-1 at 30℃among the pristine Li-Nafion membrane,the membrane containing 5 wt%,20 wt%,and 30 wt%LLZAO,respectively.It also exhibits a high Li-ion transference number of 0.92,and a broader electrochemical window of 0-+4.8 V vs.Li+/Li than that of 0-+4.0 V vs.Li+/Li for the pristine Li-Nafion membrane.It is observed that the CSE membrane not only inhibits the growth of Li dendrites but also keeps excellent electrochemical stability with the Li electrode.Benefitting from the above merits,the solid-state LiFePO4/Li cell fabricated with the CSE membrane was practically charged and discharged at 30℃.The cell exhibits an initial reversible discharge specific capacity of 160 mAh g-1 with 97%capacity retention after 100 cycles at 0.2 C,and maintains discharge specific capacity of 126 mAh g-1 after500 cycles at 1 C.The CSE membrane prepared with Li-Nafion and LLZAO is proved to be a promising solid electrolyte for advanced solid-state Li metal batteries.
基金the support of the Zhejiang Provincial Natural Science Foundation of China (LR20E020002, LD22E020006)the National Natural Science Foundation of China (NSFC) (U20A20253, 21972127, 22279116)。
文摘The rapid development of new energy vehicles and 5G communication technologies has led to higher demands for the safety,energy density,and cycle performance of lithium-ion batteries as power sources.However,the currently used liquid carbonate compounds in commercial lithium-ion battery electrolytes pose potential safety hazards such as leakage,swelling,corrosion,and flammability.Solid electrolytes can be used to mitigate these risks and create a safer lithium battery.Furthermore,high-energy density can be achieved by using solid electrolytes along with high-voltage cathode and metal lithium anode.Two types of solid electrolytes are generally used:inorganic solid electrolytes and polymer solid electrolytes.Inorganic solid electrolytes have high ionic conductivity,electrochemical stability window,and mechanical strength,but suffer from large solid/solid contact resistance between the electrode and electrolyte.Polymer solid electrolytes have good flexibility,processability,and contact interface properties,but low room temperature ionic conductivity,necessitating operation at elevated temperatures.Composite solid electrolytes(CSEs) are a promising alternative because they offer light weight and flexibility,like polymers,as well as the strength and stability of inorganic electrolytes.This paper presents a comprehensive review of recent advances in CSEs to help researchers optimize CSE composition and interactions for practical applications.It covers the development history of solid-state electrolytes,CSE properties with respect to nanofillers,morphology,and polymer types,and also discusses the lithium-ion transport mechanism of the composite electrolyte,and the methods of engineering interfaces with the positive and negative electrodes.Overall,the paper aims to provide an outlook on the potential applications of CSEs in solid-state lithium batteries,and to inspire further research aimed at the development of more systematic optimization strategies for CSEs.
基金supported by the National Natural Science Foundation of China(51872027)the Fundamental Research Funds for the Central Universities(FRF-TP-20-014A2)。
文摘All-solid-state lithium batteries(ASSLBs) employing sulfide electrolyte and lithium(Li) anode have received increasing attention due to the intrinsic safety and high energy density.However,the thick electrolyte layer and lithium dendrites formed at the electrolyte/Li anode interface hinder the realization of high-performance ASSLBs.Herein,a novel membrane consisting of Li_(6)PS_(5) Cl(LPSCl),poly(ethylene oxide)(PEO) and Li-salt(LiTFSI) was prepared as sulfide-based composite solid electrolyte(LPSCl-PEO3-LiTFSI)(LPSCl:PEO=97:3 wt/wt;EO:Li=8:1 mol/mol),which delivers high ionic conductivity(1.1 × 10^(-3) S cm^(-1)) and wide electrochemical window(4.9 V vs.Li^(+)/Li) at 25 ℃.In addition,an ex-situ artificial solid electrolyte interphase(SEI) film enriched with LiF and Li3 N was designed as a protective layer on Li anode(Li(SEI)) to suppress the growth of lithium dendrites.Benefiting from the synergy of sulfide-based composite solid electrolyte and ex-situ artificial SEI,cells of S-CNTs/LPSCI-PEO3-LiTFSI/Li(SEI) and Al_(2)O_(3)@LiNi_(0.5)Co_(0.3)Mn_(0.2)O_(2)/LPSCl-PEO3-LiTFSI/Li(SEI) are assembled and both exhibit high initial discharge capacity of 1221.1 mAh g^(-1)(135.8 mAh g^(-1)) and enhanced cycling stability with 81.6% capacity retention over 200 cycles at 0.05 C(89.2% over 100 cycles at 0.1 C).This work provides a new insight into the synergy of composite solid electrolyte and artificial SEI for achieving high-performance ASSLBs.
基金The authors would like to acknowledge the financial support from National Nat-ural Science Foundation of China (U2004199)Excellent Youth Foundation of Henan Province (202300410373)+2 种基金China Postdoctoral Science Foundation (2021T140615 and 2020M672281)Natural Science Foundation of Henan Province (212300410285)Young Talent Support Project of Henan Province(2021HYTP028).
文摘Developing laminar composite solid electrolyte with ultrathin thickness and continuous conduction channels in vertical direction holds great promise for all-solid-state lithium batteries.Herein,a thin,laminar solid electrolyte is synthesized by filtrating–NH 2 functionalized metal-organic framework nanosheets and then being threaded with poly(ethylene oxide)chains induced by the hydrogen-bonding interaction from–NH_(2) groups.It is demonstrated that the threaded poly(ethylene oxide)chains lock the adjacent metal-organic framework nanosheets,giving highly enhanced structural stability(Young’s modulus,1.3 GPa)to 7.5-μm-thick laminar composite solid electrolyte.Importantly,these poly(ethylene oxide)chains with stretching structure serve as continuous conduction pathways along the chains in pores.It makes the non-conduction laminar metal-organic framework electrolyte highly conductive:3.97×10^(−5) S cm^(−1) at 25℃,which is even over 25 times higher than that of pure poly(ethylene oxide)electrolyte.The assembled lithium cell,thus,acquires superior cycling stability,initial discharge capacity(148 mAh g^(−1) at 0.5 C and 60℃),and retention(94% after 150 cycles).Besides,the pore size of nanosheet is tailored(24.5–40.9˚A)to evaluate the mechanisms of chain conformation and ion transport in confined space.It shows that the confined pore only with proper size could facilitate the stretching of poly(ethylene oxide)chains,and meanwhile inhibit their disorder degree.Specifically,the pore size of 33.8˚A shows optimized confinement effect with trans-poly(ethylene oxide)and cis-poly(ethylene oxide)conformation,which offers great significance in ion conduction.Our design of poly(ethylene oxide)-threaded architecture provides a platform and paves a way to the rational design of next-generation high-performance porous electrolytes.
基金supported by the National Research Foundation of Korea (NRF) grant funded by the MSIT,Korea (No. 2018R1A5A1025224 and No. 2019R1A2C1084020)this research received funding support from a grant from the Korea Planning&Evaluation Institute of Industrial Technology (KEIT),funded by the MOTIE of Korea (No. 10077287)。
文摘Composite solid electrolytes(CSEs)have emerged as promising candidates for safe and high-energy–density solid-state lithium metal batteries(SSLMBs).However,concurrently achieving exceptional ionic conductivity and interface compatibility between the electrolyte and electrode presents a significant challenge in the development of high-performance CSEs for SSLMBs.To overcome these challenges,we present a method involving the in-situ polymerization of a monomer within a self-supported porous Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZT)to produce the CSE.The synergy of the continuous conductive LLZT network,well-organized polymer,and their interface can enhance the ionic conductivity of the CSE at room temperature.Furthermore,the in-situ polymerization process can also con-struct the integration and compatibility of the solid electrolyte–solid electrode interface.The synthesized CSE exhibited a high ionic conductivity of 1.117 mS cm^(-1),a significant lithium transference number of 0.627,and exhibited electrochemical stability up to 5.06 V vs.Li/Li+at 30℃.Moreover,the Li|CSE|LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) cell delivered a discharge capacity of 105.1 mAh g^(-1) after 400 cycles at 0.5 C and 30℃,corresponding to a capacity retention of 61%.This methodology could be extended to a variety of ceramic,polymer electrolytes,or battery systems,thereby offering a viable strategy to improve the electrochemical properties of CSEs for high-energy–density SSLMBs.
基金This work was supported by the National Natural Science Foundation of China(Grant No.22075064,No.21673065,No.21611130177).
文摘Solid electrolytes have received widespread attention due to their higher safety than liquid electrolytes in the past decades.In particular,organic-inorganic composite solid electro-lytes(CSEs)in which inorganic fllers dispersed in polymer solid electrolytes are consid-ered to be one of the most promising candidate electrolytes for high-performance solid-state lithium batteries.Understanding the local environments and the conduction pathway/dynamics of Lit is essential for the design of high-performance CSEs.Nuclear magnetic resonance(NMR)is a non-invasive quantitative technique that has unique ca-pabilities in providing molecular structure information,morphological evolution,and measuring the movement of ions at different time scales.Therefore,for battery re-searchers,an accurate and comprehensive under standing of the basic principles and experimental design of solid-state NMR(SSNMR)is of great significance for investigating the abundant molecular structure and dynamics information in CSEs.The specific appli-cations of the SSNMR technique in CSEs are briefly introduced in this present review.
基金supported by the 2024 Capital Construction Funds within the Provincial Budget of Jilin Provincial Development and Reform Commission[2024C018-2].
文摘Traditional lithium-ion batteries(LIBs)employing liquid electrolytes face inherent safety risks,motivating the development of solid polymer electrolytes(SPEs)like polyethylene oxide(PEO).However,pure PEO suffers from low room-temperature ionic conductivity and poor mechanical strength.Composite solid electrolytes(CSEs)incorporating inorganic filler offer promise but are hindered by poor interfacial compatibility.This study addresses this critical issue through surface engineering.Mercaptopropyl trimethoxysilane(MPTMS)is used to modify garnet-type Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)particles,introducing thiol groups(-SH)onto their surface.Subsequently,thiol-functionalized LLZTO(LLZTO@MPTMS)participate in the insitu copolymerization of polyethylene glycol methyl methacrylate(PEGMEMA)and crosslinker polyethylene glycol dimethacrylate(PEGDMA),yielding a novel PEO-based CSE(PCSE).The effects of PEGMEMA molecular weight,PEGMEMA/PEGDMA ratio,and LLZTO@MPTMS content have been systematically examined to optimize the electrolyte.The resulting PCSE exhibits an ionic conductivity of 1.20×10^(-4)S·cm^(-1)at 30℃,a lithium-ion transference number of 0.36,and a wide electrochemical stability window up to 5.1 V(vs.Li^(+)/Li).Li/PCSE/Li symmetric cells demonstrate stable cycling for nearly 240 h at 0.05 mA·cm^(-2),indicating enhanced interface compatibility with lithium metal and effective dendrite suppression.Furthermore,LiFePO_(4)/PCSE/Li full cells deliver a high initial discharge capacity of 155.0 mAh·g^(-1)at 0.1 C and retain 76.0%capacity after 100 cycles,alongside excellent rate capability.These results confirm that the combined strategy of LLZTO surface modification with MPTMS and in-situ copolymerization effectively mitigates interfacial issues,presenting a promising material system for high-performance solid-state LIBs.
基金financially supported by the National Natural Science Foundation of China (Nos.51971146,51971147,52171218 and 52271222)Shanghai Municipal Science and Technology Commission (No.21010503100)+3 种基金the Major Program for the Scientific Research Innovation Plan of Shanghai Education Commission (No.2019-01-07-00-07-E00015)Shanghai Outstanding Academic Leaders Plan,Guangxi Key Laboratory of Information Materials (Guilin University of Electronic Technology,201017-K)Shanghai Rising-Star Program (No.20QA1407100)General Program of Natural Science Foundation of Shanghai (No.20ZR1438400)。
文摘Composite solid electrolytes(CSEs) containing polymer matrices and inorganic fillers hold promise for the next generation of solid-state batteries.However,the role of residual solvents in CSEs remains controversial.This study investigated the evolution and function of the residual solvent in a polymer-Li_2B_(12)H_(12) CSE.A partial reaction occurred between Li_2B_(12)H_(12) and solvent N,N-dimethylformamide(DMF),which produced dimethylaminomethanol(DMAM) in the CSE.Density functional theory calculations have revealed that DMA M forms stronger hydrogen bonds with polyvinylidene fluoride chains than DMF,which can have a plasticizing effect on the polymer matrix,leading to lower crystallinity and quicker segment motion.Therefore,this CSE exhibited improved Li-ion conducting properties,enabling the stable cycling of Li‖LiFePO_(4) solid-state batteries.This study provided insights into the role of residual solvents in CSEs.
