Incorporation of Ionic Conductive Polymers into Sulfide Electrolyte-Based Solid-State Batteries to Enhance Electrochemical Stability and Cycle Life

Sulfide-based inorganic solid electrolytes are promising materials for high-performance safe solid-state batteries.The high ion conductivity,mechanical characteristics,and good processability of sulfide-based inorganic solid electrolytes are desirable properties for realizing high-performance safe solid-state batteries by replacing conventional liquid electrolytes.However,the low chemical and electrochemical stability of sulfide-based inorganic solid electrolytes hinder the commercialization of sulfide-based safe solid-state batteries.Particularly,the instability of sulfide-based inorganic solid electrolytes is intensified in the cathode,comprising various materials.In this study,carbonate-based ionic conductive polymers are introduced to the cathode to protect cathode materials and suppress the reactivity of sulfide electrolytes.Several instruments,including electrochemical spectroscopy,X-ray photoelectron spectroscopy,and scanning electron microscopy,confirm the chemical and electrochemical stability of the polymer electrolytes in contact with sulfide-based inorganic solid electrolytes.Sulfide-based solid-state cells show stable electrochemical performance over 100 cycles when the ionic conductive polymers were applied to the cathode.

A Modification of LiMn2O4 by Ionic Conductive Agent and Electronic Conductive Agent Coating

Carbon was used as electronic conductive agent, and metasilicic acid lithium (Li2SiO3) as ionic conductive agent, the two factors were investigated cooperatively. We evaluated their effect by using spherical spinel LiMn2O4 which prepared ourselves as cathode material. Then Li2SiO3/carbon surface coating on LiMn2O4 (LMO/C/LSO) which Li2SiO3 inside and carbon/Li2SiO3 coated LiMn2O4 (LMO/LSO/C) were prepared, All of materials were characterized by X-ray diffraction (XRD) and electrochemical test;spherical LiMn2O4 was characterized by scanning electron microscopy (SEM);and coated materials were characterized by transmission electron microscopy (TEM). While uncoated spinel LiMn2O4 maintained 72% of capacity in 60 cycles by the rate of 0.2C, and LMO/LSO/C showed the best electrochemical performance, 89% of the initial capacity remained after 75 cycles at 0.2C. Furthermore, the rate performance of LMO/LSO/C also improved obviously, about 30 mAh·g-1 of capacity attained at the rate of 5C, higher than LMO/C/LSO and bare LiMn2O4.

A Stretchable Ionic Conductive Elastomer for High-Areal-Capacity Lithium-Metal Batteries

Developing high-areal-capacity and dendrite-free lithium(Li)anodes is of significant importance for the practical applications of the Li-metal secondary batteries.Herein,an effective strategy to stabilize the high-arealcapacity Li electrodeposition by modifying the Li metal with a stretchable ionic conductive elastomer(ICE)is demonstrated.The ICE layer prepared via an instant photocuring process shows a promising Li^(+)-ion conductivity at room temperature.When being used in Li-metal batteries,the thin ICE coating(~0.27μm)acts as both a stretchable constraint to minimize the Li loss and a protective layer to facilitate the uniform flux of Li ions.With this ICE-modifying strategy,the reversibility and cyclability of the Li anodes under high-areal-capacity condition in carbonate electrolyte are significantly improved,leading to a stable Li stripping/plating for 500 h at an ultrahigh areal capacity of 20 mAh cm^(-2)in commercial carbonate electrolyte.When coupled with industry-level thick LiFePO;electrodes(20.0 mg cm^(-2)),the cells with ICE-Li anodes show significantly enhanced rate and cycling capability.

Enabling high-performance all-solid-state lithium batteries with high ionic conductive sulfide-based composite solid electrolyte and ex-situ artificial SEI film

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.

A healable, mechanically robust and ultrastretchable ionic conductive elastomer for durably wearable sensor

The ionic conductive elastomers show great promise in multifunctional wearable electronics,but they currently suffer from liquid leakage/evaporation or mechanical compliance.Developing ionic conductive elastomers integrating non-volatility,mechanical robustness,superior ionic conductivity,and ultra-stretchability remains urgent and challenging.Here,we developed a healable,robust,and conductive elastomer via impregnating free ionic liquids(ILs)into the ILs-multigrafted poly(urethane-urea)(PUU)elastomer networks.A crucial strategy in the molecular design is that imidazolium cations are largely introduced by double-modification of PUU and centipede-like structures are obtained,which can lock the impregnated ILs through strong ionic interactions.In this system,the PUU matrix contributes outstanding mechanical properties,while the hydrogen bonds and ionic interactions endow the elastomer with self-healing ability,conductivity,as well as non-volatility and transparency.The fabricated ionic conductive elastomers show good conductivity(3.8×10^(-6) S·cm^(-1)),high mechanical properties,including tensile stress(4.64 MPa),elongation(1470%),and excellent healing ability(repairing efficiency of 90%after healing at room temperature for 12 h).Significantly,the conductive elastomers have excellent antifatigue properties,and demonstrate a highly reproducible response after 1000 uninterrupted extension-release cycles.This work provides a promising strategy to prepare ionic conductive elastomers with excellent mechanical properties and stable sensing capacity,and further promote the development of mechanically adaptable intelligent sensors.

Electrically Detaching Behavior and Mechanism of Ionic Conductive Adhesives

Design of rapidly detachable adhesives with high initial bonding strength is of great significance but it is full of great challenge. Here, we report the fast electrically detaching behavior (100% detaching efficiency in just 1 min under dozens of DC voltage) and high initial bonding strength (>12 MPa) of epoxy-based ionic conductive adhesives (ICAs). The epoxy-based ICAs are fabricated by introducing polyethylene glycol dimethyl ether (PEGDE) and 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([EMIM]OTF) into epoxy. The combination of PEGDE and [EMIM]OTF enables the free ions to migrate directively in electric field, and the anchoring of PEG chains onto epoxy chains ensures the long-term reliability of ICAs. The investigation on the electrically detaching mechanism suggests that the enrichment and following rapid interfacial electrochemical reactions of [EMIM]OTF lead to formation of metal hydroxide (Me(OH)n) nanoparticles at the bonding interfaces, thus the strong interactions containing interlocked forces, van de Waals’ forces and hydrogen bonding interactions between ICAs and bonding substrates are destroyed. This work provides a promising direction for detachable adhesives with both high initial bonding strength and high detaching efficiency in short time.

High ionic conductive protection layer on Zn metal anode for enhanced aqueous zinc-ion batteries

Aqueous zinc-ion batteries(ZIBs)has been regarded as a promising energy storage system for large-scale application due to the advantages of low cost and high safety.However,the growth of Zn dendrite,hydrogen evolution and passivation issues induce the poor electrochemical performance of ZIBs.Herein,a Na_(3)Zr_(2)Si_(2)PO_(12)(NZSP)protection layer with high ionic conductivity of 2.94 m S/cm on Zn metal anode was fabricated by drop casting approach.The protection layer prevents Zn dendrites formation,hydrogen evolution as well as passivation,and facilitates a fast Zn~(2+)transport.As a result,the symmetric cells based on NZSP-coated Zn show a stable cycling over 1360 h at 0.5 m A/cm^(2)with 0.5 m Ah/cm^(2) and 1000 h even at a high current density of 5 m A/cm^(2) with 2 m Ah/cm^(2).Moreover,the full cells combined with V_(2)O_(5)-based cathode displays high capacities and high rate capability.This work offers a facile and effective approach to stabilizing Zn metal anode for enhanced ZIBs.

Bacterial Cellulose/Zwitterionic Dual-network Porous Gel Polymer Electrolytes with High Ionic Conductivity

Bacterial cellulose(BC)was innovatively combined with zwitterionic copolymer acrylamide and sulfobetaine methacrylic acid ester[P(AM-co-SBMA)]to build a dual-network porous structure gel polymer electrolytes(GPEs)with high ionic conductivity.The dual network structure BC/P(AM-co-SBMA)gels were formed by a simple one-step polymerization method.The results show that ionic conductivity of BC/P(AM-co-SBMA)GPEs at the room temperature are 3.2×10^(-2) S/cm@1 M H_(2)SO_(4),4.5×10^(-2) S/cm@4 M KOH,and 3.6×10^(-2) S/cm@1 M NaCl,respectively.Using active carbon(AC)as the electrodes,BC/P(AM-co-SBMA)GPEs as both separator and electrolyte matrix,and 4 M KOH as the electrolyte,a symmetric solid supercapacitors(SSC)(AC-GPE-KOH)was assembled and testified.The specific capacitance of AC electrode is 173 F/g and remains 95.0%of the initial value after 5000 cycles and 86.2%after 10,000 cycles.

Improvement of ionic conductivity of solid polymer electrolyte based on Cu-Al bimetallic metal-organic framework fabricated through molecular grafting

A composite solid electrolyte comprising a Cu-Al bimetallic metal-organic framework(CAB),lithium salt(LiTFSI)and polyethylene oxide(PEO)was fabricated through molecular grafting to enhance the ionic conductivity of the PEO-based electrolytes.Experimental and molecular dynamics simulation results indicated that the electrolyte with 10 wt.%CAB(PL-CAB-10%)exhibits high ionic conductivity(8.42×10~(-4)S/cm at 60℃),high Li+transference number(0.46),wide electrochemical window(4.91 V),good thermal stability,and outstanding mechanical properties.Furthermore,PL-CAB-10%exhibits excellent cycle stability in both Li-Li symmetric battery and Li/PL-CAB-10%/LiFePO4 asymmetric battery setups.These enhanced performances are primarily attributable to the introduction of the versatile CAB.The abundant metal sites in CAB can react with TFSI~-and PEO through Lewis acid-base interactions,promoting LiTFSI dissociation and improving ionic conductivity.Additionally,regular pores in CAB provide uniformly distributed sites for cation plating during cycling.

Ionic conductive hydrogels toughened by latex particles for strain sensors

Conductive hydrogels have attracted tremendous attention due to their excellent softness and stretchability as wearable strain sensing devices.However,most of hydrogel-based strain sensors suffered from poor self-recoverability and fatigue resistance,resulting in significant decrease of strain sensitivity after recycling.Here,a soft and flexible wearable strain sensor is prepared by using an ionic conductive hydrogel with latex particles as physical cross-linking centers.The dynamic physical cross-linking structure can effectively dissipate energy through disruption and reconstruction of molecular segments,thereby imparting excellent stretchability,self-recoverability and fatigue resistance.In addition,the hydrogel exhibits excellent strain-sensitive resistance changes,which enables it to be assembled as a wearable sensor to monitor human motions.As a result,the hydrogel strain sensor can provide precise feedback for a wide range of human activities,including large-scale joint bending and tiny phonating.Therefore,the tough ionic conductive hydrogel would be widely applied in electronic skin,medical monitoring and artificial intelligence.

Intrinsically ionic conductive nanofibrils for ultra-thin bio-memristor with low operating voltage

Memristors integrated with low operating voltage,good stability,and environmental benignity play an important role in data storage and logical circuit technology,but their fabrication still faces challenges.This study reports an ultra-thin bio-memristor based on pristine environmentfriendly silk nanofibrils(SNFs).The intrinsic ionic conductivity,combined with high dielectric performance and nanoscale thickness,lowers the operation voltage down to0.1-0.2 V,and enables stable switching and retention time over 180 times and 10^(5)s,respectively.Furthermore,the SNFbased memristor device in a crossbar array achieves stable memristive performance,and thus realizes the functions of memorizing image and logic operation.By carrying out variable-temperature electrical experiments and Kelvin probe force microscopy,the space charge-limited conduction mechanism is revealed.Integrating with low operating voltage,good stability,and ultra-thin thickness makes the SNF-based memristors excellent candidates in bioelectronics.

Ionic liquid electrolytes for sodium-ion batteries to control thermal runaway

Sodium-ion batteries are expected to be more affordable for stationary applications than lithium-ion batteries,while still offering sufficient energy density and operational capacity to power a significant segment of the battery market.Despite this,thermal runaway explosions associated with organic electrolytes have led to concerns regarding the safety of sodium-ion batteries.Among electrolytes,ionic liquids are promising because they have negligible vapor pressure and show high thermal and electrochemical stability.This review discusses the safety contributions of these electrolyte properties for high-temperature applications.The ionic liquids provide thermal stability while at the same time promoting high-voltage window battery operations.Moreover,apart from cycle stability,there is an additional safety feature attributed to modified ultra-concentrated ionic liquid electrolytes.Concerning these contributions,the following have been discussed,heat sources and thermal runaway mechanisms,thermal stability,the electrochemical decomposition mechanism of stable cations,and the ionic transport mechanism of ultra-concentrated ionic liquid electrolytes.In addition,the contributions of hybrid electrolyte systems consisting of ionic liquids with either organic carbonate or polymers are also discussed.The thermal stability of ionic liquids is found to be the main contributor to cell safety and cycle stability.For high-temperature applications where electrolyte safety,capacity,and cycle stability are important,highly concentrated ionic liquid electrolyte systems are potential solutions for sodium-ion battery applications.

Ion–Electron Coupling Enables Ionic Thermoelectric Material with New Operation Mode and High Energy Density

Ionic thermoelectrics(i-TE) possesses great potential in powering distributed electronics because it can generate thermopower up to tens of millivolts per Kelvin. However,as ions cannot enter external circuit, the utilization of i-TE is currently based on capacitive charge/discharge, which results in discontinuous working mode and low energy density. Here,we introduce an ion–electron thermoelectric synergistic(IETS)effect by utilizing an ion–electron conductor. Electrons/holes can drift under the electric field generated by thermodiffusion of ions, thus converting the ionic current into electrical current that can pass through the external circuit. Due to the IETS effect, i-TE is able to operate continuously for over 3000 min.Moreover, our i-TE exhibits a thermopower of 32.7 mV K^(-1) and an energy density of 553.9 J m^(-2), which is more than 6.9 times of the highest reported value. Consequently, direct powering of electronics is achieved with i-TE. This work provides a novel strategy for the design of high-performance i-TE materials.

Polymer dispersed ionic liquid electrolytes with high ionic conductivity for ultrastable solid-state lithium batteries

Solid polymer electrolytes(SPEs)have emerged as one of the most promising candidates for building solid-state lithium batteries due to their excellent flexibility,scalability,and interfacial compatibility with electrodes.However,the low ionic conductivity and poor cyclic stability of SPEs do not meet the requirements for practical applications of lithium batteries.Here,a novel polymer dispersed ionic liquid-based solid polymer electrolyte(PDIL-SPE)is fabricated using the in situ polymerization-induced phase separation(PIPS)method.The as-prepared PDIL-SPE possesses both outstanding ionic conductivity(0.74 mS cm^(-1) at 25℃)and a wide electrochemical window(up to 4.86 V),and the formed unique three-dimensional(3D)co-continuous structure of polymer matrix and ionic liquid in PDIL-SPE can promote the transport of lithium ions.Also,the 3D co-continuous structure of PDIL-SPE effectively accommodates the severe volume expansion for prolonged lithium plating and stripping processes over 1000 h at 0.5 mA cm^(-2) under 25℃.Moreover,the LiFePO_(4)//Li coin cell can work stably over 150 cycles at a 1 C rate under room temperature with a capacity retention of 90.6%from 111.1 to 100.7 mAh g^(-1).The PDIL-SPE composite is a promising material system for enabling the ultrastable operation of solid-state lithium-metal batteries.

A highly ionic conductive succinonitrile-based composite solid electrolyte for lithium metal batteries

Solid-state Li metal batteries with solid electrolytes have built a potential way to solve the safety and low energy density problems of current commercial Li-ion batteries with liquid electrolyte.As a key component of solid-state Li metal batteries,solid electrolytes require high ionic conductivities and good mechanical properties.We have designed a composite solid electrolyte(CSE)consisting of poly(vinylidene fluoride-hexafluoropropylene)(PVDF-HFP)-Li_(6.5)La_(3)Zr_(1.5)Ta_(0.5)O_(12)(LLZTO)-succinonitrile(SN)and Li bis(trifluoromethylsulphonyl)imide(LiTFSI).The PVDF-HFP-based porous matrix made by electrospinning ensures good mechanical properties of the electrolyte membrane,and the large proportion of SN filling material makes the electrolyte membrane have an ionic conductivity of 1.11 mS·cm^(–1)without the addition of liquid electrolyte.The symmetric battery assembled with CSE can be cycled stably for more than 600 h,and the LiFePO4|CSE|Li full battery can also be cycled stably for more than 200 cycles.In addition to Li metal batteries,Li-O_(2)and Li-CO_(2)batteries that use CSE as electrolytes also have good performances,reflecting the universality of CSE.CSE does not only guarantee good mechanical properties but also obtain a high ionic conductivity.This design provides a new idea for the commercial application of polymer-based solid batteries.

Organic fast ion-conductor with ordered Li-ion conductive nano-pathways and high ionic conductivity for electrochemical energy storage

Solid electrolyte(SE)is the most crucial factor to fabricate safe and high-performance all-solid-state lithium-ion batteries.However,the most commonly reported SE,including solid polymer electrolyte(SPE)and inorganic oxides and sulfides,suffer problems of low ionic conductivity at room temperature for SPE and large interfacial impedance with electrodes for inorganic electrolytes.Here we for the first time demonstrate a novel ionic plastic crystal lithium salt solid electrolyte(OLiSSE)fast ion-conductor dilithium(1,3-diethyl-4,5-dicarboxylate)imidazole bromide with ordered Li-ion conductive nanopathways and an exceptional ionic conductivity of 4.4×10^(−3)Scm^(−1)at 30℃.The prepared OLiSSE exhibits apparent characters of typical ionic plastic crystals in the temperature range of−20 to 70℃,and shows remarkable thermal stability and electrochemical stability below 150℃ and 4.7 V,respectively.No lithium dendrite or short circuit behavior is detected for the Li|OLiSSE|Li cell after the galvanostatic charge-discharge test for 500 h.The fabricated Li|OLiSSE|LiFePO_(4) all-solid-state cell without using any separator and liquid plasticizer directly delivers an initial discharge capacity of 151.4 mAh g^(−1) at the discharge rate of 0.1 C,and shows excellent charge-discharge cycle stability,implying large potential application in the next generation of safe and flexible all-solid-state lithium batteries.

High-capacity,high-rate,and dendrite-free lithium metal anodes based on a 3D mixed electronic-ionic conductive and lithiophilic scaffold

Lithium metal anode possesses a high theoretical capacity and the lowest redox potential,while the severe growth of Li dendrite prevents its practical application.Herein,we prepared a structure of Li_(3)P nanosheets and Ni nanoparticles decorated on Ni foam(NF)as a three-dimensional(3 D)scaffold for dendrite-free Li metal anodes(Li-Li_(3)P/Ni@Ni foam anodes,shortened as L-LPNNF)using a facile melting method.The LiP nanosheets exhibit excellent Li-ion conductivity as well as superior lithiophilicity,and the 3 D nickel scaffold provides sufficient electron conductivity and ensures structure stability.Therefore,symmetric cells assembled by L-LPNNF possess lowered voltage hysteresis and improved long cycle stability(a voltage hysteresis of 104.2 mV after 500 cycles at a high current density of 20 mA cm^(-2) with a high capacity of 10 mA h cm^(-2)),compared with the cells assembled with Li foil or Li-NF anodes.Furthermore,the full cells with paired L-LPNNF anodes and commercial LiFePOcathodes suggest a specific capacity of 124.6 mA h gand capacity retention of 90.8%after 180 cycles with the Coulombic efficiency(CE)of~100%at a current rate of 1 C.This work provides a potentially scalable option for preparing a mixed electronic-ionic conductive and lithiophilic scaffold for dendrite-free Li anodes at high current densities.

Deep dive into anionic metal-organic frameworks based quasi-solid-state electrolytes

The development and application of high-capacity energy storage has been crucial to the global transition from fossil fuels to green energy.In this context,metal-organic frameworks(MOFs),with their unique 3D porous structure and tunable chemical functionality,have shown enormous potential as energy storage materials for accommodating or transporting electrochemically active ions.In this perspective,we specifically focus on the current status and prospects of anionic MOF-based quasi-solid-state-electrolytes(anionic MOF-QSSEs)for lithium metal batteries(LMBs).An overview of the definition,design,and properties of anionic MOF-QSSEs is provided,including recent advances in the understanding of their ion transport mechanism.To illustrate the advantages of using anionic MOF-QSSEs as electrolytes for LMBs,a thorough comparison between anionic MOF-QSSEs and other well-studied electrolyte systems is made.With these in-depth understandings,viable techniques for tuning the chemical and topological properties of anionic MOF-QSSEs to increase Li+conductivity are discussed.Beyond modulation of the MOFs matrix,we envisage that solvent and solid-electrolyte interphase design as well as emerging fabrication techniques will aid in the design and practical application of anionic MOF-QSSEs.

3D spiny AlF_(3)/Mullite heterostructure nanofiber as solid-state polymer electrolyte fillers with enhanced ionic conductivity and improved interfacial compatibility

Lithium metal batteries assembled with solid-state electrolyte can offer high safety and volumetric energy density compared to liquid electrolyte.The polymer solid-state electrolytes of poly(ethylene oxide)(PEO)are widely used in lithium metal solid-state batteries due to their unique properties.However,there are still some defects such as low ionic conductivity at room temperature and weak inhibition of lithium dendrite growth.Herein,the spiny inorganic nanofibers heterostructure with mullite whiskers grown on the surface of aluminum fluoride(AlF_(3))nanofibers are introduced into the PEOLi TFSI electrolytes for the first time to prepare composite solid-state electrolytes.The AlF_(3)as a strong Lewis acid can adsorb anions and promote the dissociation of Li salts.Besides,the specially threedimensional(3D)structure enlarges the effective contacting interface with the PEO polymer,which allows the lithium ions to be transported not only along the large aspect ratio of AlF3nanofibers,but also along the mullite phase in the transmembrane direction rapidly.Thereby,the transport channel of lithium ions at the spiny inorganic nanofibers-polymer interface is further improved.Benefiting from these advantages,the obtained composite solid-state electrolyte has a high ionic conductivity of 1.58×10^(-4)S cm^(-1)at 30℃and the lithium ions transfer number of 0.53.In addition,the AlF3has strong binding energy with anions,low electronic conductivity and wide electrochemical stability window,and reduced nucleation overpotential of lithium during cycling,which is positive for lithium dendrite suppression in solid-state electrolytes.Thus,the assembled symmetric Li/Li symmetric batteries exhibit stable cycling performance at different area capacities of 0.15,0.2,0.3 and 0.4 m A h cm^(-2).More importantly,the LiFePO_(4)(LFP)/Li battery still has 113.5 m A h g-1remaining after 400 cycles at 50℃and the Coulomb efficiency is nearly 100%during the long cycle.Overall,the interconnected structure of 3D spiny inorganic heterostructure nanofiber constitutes fast and uninterrupted lithium ions transport channels,maximizing the synergistic effect of interfacial transport of inorganic fillers and reducing PEO crystallinity,thus providing a novel approach to high performance solid-state electrolytes.

Alkali Ionic Conductivity in Inorganic Glassy Electrolytes

Glassy electrolytes could be a potential candidate for all-solid-state batteries that are considered new-generation energy storage devices. As glasses are one of the potential fast ion-conducting electrolytes, progressive advances in glassy electrolytes have been undergoing to get commercial attention. However, the challenges offered by ionic conductivity at room temperature (10−5 - 10−3 S∙cm−1) in comparison to those of organic liquid electrolytes (10−2 S∙cm−1) hindered the applicability of such electrolytes. To enhance the research development on ionic conductivity, the overall picture of the ionic conductivity of glassy electrolytes is reviewed in this article with a focus on alkali oxide and sulfide glasses. We portray here the techniques applied for alkali ion conductivity enhancement, such as methods of glass preparation, host optimization, doping, and salt addition for enhancing alkali ionic conductivity in the glasses.