Advanced Composites and Hybrid Materials (2022) 5:2651–2674 https://doi.org/10.1007/s42114-021-00412-z REVIEW Composite polymer electrolytes: progress, challenges, and future outlook for sodium‑ion batteries Dheeraj K. Maurya1 · Ragupathy Dhanusuraman2 · Zhanhu Guo3 · Subramania Angaiah1 Received: 26 October 2021 / Revised: 17 December 2021 / Accepted: 26 December 2021 / Published online: 28 February 2022 © The Author(s), under exclusive licence to Springer Nature Switzerland AG 2022 Abstract Sodium-ion battery (SIB) arises as propitious energy sources complementing the energy supply demands amidst of proliferating energy crises and environmental trauma due to fossil fuel consumption. Higher earth abundance, similar electrochemistry as lithium, and cost-effectiveness have driven the research focused on building better SIBs. Solid inorganic and polymer electrolytes (PEs) are prevailing electrolyte candidates for SIBs. The bottleneck of both the electrolytes, such as low ionic conductivity, poor mechanical and thermal stability, and high interfacial charge resistance, has retarded the rate of their commercial acceptance for futuristic energy devices. To tackle these burning issues, strategies to couple inorganic and polymer electrolytes as composite polymer electrolytes (CPEs) are drawing immense interest in academia and industry. The present review discusses the state-of-the-art composite polymer electrolytes for SIBs. It comprises three parts. The first part briefs about the introduction and performance index of CPEs to assess the importance of CPEs over existing electrolytes. In the second part, various synthesis methods for CPEs preparations are encapsulated. The third part is focused on the role of extrinsic fillers (active and passive) and the corresponding mechanism involved in ionic transport in CPEs by recently reported works. The role of filler engineering in addressing the remedies of CPEs is also intensely scrutinized. Finally, this review is concluded with the perspective of CPEs toward the future of SIB development. This review is aiming to understand the insight of fillers within CPEs and their impact on the performance of SIBs. Keywords Sodium-ion batteries (SIBs) · Inorganic ceramic electrolyte (ICE) · Composite polymer electrolyte (CPE) · Fillers · Ion transport Abbreviations SIBSodium-ion battery LIBLithium-ion battery ICEInorganic ceramic electrolyte PEGPolyethylene glycol PEGDMEPoly(ethylene glycol) dimethyl ether SNSuccinonitrile PEOPolyethylene oxide * Subramania Angaiah a.subramania@gmail.com 1 Electro‑Materials Research Laboratory, Centre for Nanoscience and Technology, Pondicherry University, Puducherry 605014, India 2 Nano‑Electrochemistry Lab (NEL), Department of Chemistry, National Institute of Technology Puducherry, Karaikal 609‑609, India 3 Integrated Composites Laboratory (ICL), Department of Chemical and Biomolecular Engineering, University of Tennessee, Knoxville, TN 37996, USA PVDFPoly(vinylidene fluoride) PVDF-HFPPoly(vinylidene fluoride-co-hexafluoropropylene) PVPPolyvinylpyrrolidone PMMAPoly(methyl methacrylate) NaClO4Sodium perchlorate NaTFSISodium bis(trifluoromethylsulfonyl)imide NaFSISodium (I) bis(fluorosulfonyl)imide QDQuantum dot SiO2Silicon dioxide LCLiquid crystal ZrO2Zirconium dioxide Al2O3Aluminum oxide CaOCalcium oxide Zn2Fe2O4Zinc ferrite Si3N4Silicon nitride NaPO3Sodium triphosphate NaIO4Sodium periodate NaTFSodium triflate NaCF3SO3Sodium trifluoromethanesulfonate 13 Vol.:(0123456789) 2652 NaPF6Sodium hexafluorophosphate TEGDMETetraethylene glycol dimethyl ether AFMAtomic force microscopy PEPolymer electrolyte CPEComposite polymer electrolyte DMFDimethylformamide DMAcDimethylacetamide 1 Introduction Renewable energy-driven energy storage devices have been recognized as a powerful solution to minimize the depletion of fossil fuels, solely responsible for severe environmental threats such as global warming and air pollution [1–5]. Electrochemical energy research attracts enormous attention as a component of practical applications like batteries, fuel cells, and supercapacitors, utilizing conversion and storage of renewable energy into electrochemical energy [5–11]. The rapid evolution of electric vehicles, grid energy storage, and portable electronics has raised soaring demands to develop more energy-efficient energy storage devices. Over the past three decades, rechargeable lithium-ion batteries (LIBs), owing to the merits such as high voltage, high energy density, low self-discharge rate, and long cycle life, have been deemed as a potential alternative meeting intermittent demands of portable energy storage [12–17]. Nowadays, the colossal production of LIBs is suffering from the economic sustainability crisis of lithium sources. Consequently, the limited lithium Fig. 1 Comparison of performance of current LIB and SIB technologies. (Ref. [24] reproduced with the permission of Elsevier) 13 Advanced Composites and Hybrid Materials (2022) 5:2651–2674 reserves and increased price of lithium salts have motivated researchers to develop alternatives for LIB technologies based on abundant materials. In recent years, SIBs have been paid immense attention due to their higher natural earth abundance than lithium in the earth’s crust. SIBs have been considered to replace LIBs due to their similar electrochemical charge storage mechanism as LIBs. A good number of companies currently adapted SIB technologies (e.g., HiNa battery (China), Faradion, and Tiamat) and conducting research and development for advanced SIBs [2, 18, 19]. The electrolyte is the critical component of high-performance rechargeable SIBs, which mainly transport ­Na+ and block electrons’ diffusion. In the present situation, major conventional SIBs are employing organic liquid electrolytes comprising flammable carbonates. Operating SIBs with the Na metal anode and liquid electrolyte cause leakage and fire risks during overcharge or abused operations in electrical vehicles applications. Additionally, SIBs encounter inevitable dendrite growth due to the side reactions between highly reactive liquid electrolytes with the Na anode causing capacity fade and low cycling ability in SIBs [20–23]. Rejuvenating highperformance electrolyte materials is focused on safety assurance and long-term cycling improvement SIBs (Fig. 1). In the same way, as LIBs, the development of all-solid-state batteries aims to address the safety concerns of SIBs. The strategy of replacing liquid electrolytes with solid-state electrolytes has significantly been pursued in the current energy storage scenario. Advanced Composites and Hybrid Materials (2022) 5:2651–2674 2653 Fig. 2 Schematic of different electrolytes for current SIBs All-solid-state electrolytes are generally classified into ­ a+ conductive solid polymer electrolytes (SPEs), inorganic N ceramic electrolytes (ICEs), and solid ceramic-polymer composite electrolytes (CPEs) (Fig. 2). ICEs and SPEs are the prevailing solid electrolytes that have been exploited for the last two decades for all-solid-state SIBs [25–30]. SPEs mainly comprise the polymer matrix solvated in a sodium salt to form a macromolecular architecture that inherits good flexibility, easy processability, low flammability, and better compatibility with the electrodes. These superior characteristics of SPEs stabilize them as an appealing electrolyte material for flexible and wearable energy storage devices [17, 31, 32]. However, the practical applicability of SPEs is hampered due to severe drawbacks such as low ionic conductivity, narrow electrochemical stability windows, and poor thermal stability. On the other hand, ICEs offer a great zeal toward their use in all-solid-state SIBs owing to their advantages such as high ionic conductivity, high electrochemical stability, superior thermal stability, and robust mechanical properties [14, 21, 29, 33–39]. Their intrinsic rigidity and inevitable poor interfacial compatibility with the electrodes led to a tremendous challenge for more efficient high-density allsolid-state SIB. In the past decade, the researchers introduced numerous solutions and promising approaches to eradicate the disadvantages of SPEs and ICEs. Various strategies like cross-linking and blending of polymers, addition of liquid plasticizers in the polymer matrix, and developing polymerionic liquid electrolytes have been practiced for SIB development. As prepared electrolyes succeed in uplifting the ionic conductivity but on the expensive cost in the form of reduced long-term cyclic stability and poor mechanical strength [40, 41]. A new class of solid polymer-ceramic composite utilizes the advantages of both ICEs and SPEs and overcomes the disadvantages to develop high energy-efficient SIBs. Synergistically coupling the ICEs with an organic polymer have demonstrated smart stratagem technology to harness the favorable properties of existing inorganic–organic entities [35, 42–46]. This particular class of electrolytes is extremely successful in fulfilling the aim of achieving high ionic conductivity, robust mechanical strength, wide electrochemical potential stability window, improved lithium-ion transference number, low interfacial resistance, and dendrite suppression capability (Fig. 3). Tremendous research has been done to Fig. 3 Performance characteristics of inorganic ceramic electrolytes (ICE), solid polymer electrolytes (SPE), and composite polymer electrolytes (CPE) 13 2654 develop CPE for LIBs and a good number of reviews regarding composite electrolytes for LIBs are reported [4, 14, 24, 35, 42–44, 47–55]. But there is no review emphasizing the development of composite polymer electrolytes for SIBs. The present review discusses the state-of-the-art of composite polymer electrolytes for SIBs. This article does not intend to review solid and gel polymer electrolytes but focuses on the composite polymer-ceramic-based composite polymer electrolytes (CPEs). A basic understanding and performance index to assess the importance of CPEs over existing classes of electrolytes is discussed. Various synthesis methods for CPEs fabrications are introduced and a detailed overview of ongoing research on CPEs regarding SIBs is also intensely scrutinized. The role of extrinsic fillers (active and passive) and the mechanism involved in ionic transport in CPEs following recently reported works are also discussed in correlation with the filler engineering in addressing the remedies of CPEs. Finally, this review is concluded with the perspective of CPEs toward the future of SIB development. This review aims to understand the insight of fillers within CPEs and their impact on the performance of SIBs. 2 Requirement for composite polymer electrolyte Solid polymer electrolytes generally contain a polymer matrix with sodium salt without any involvement of liquid solvent in it. Host polymer plays a vital role in shaping the electrolyte with better flexibility, cost-effective process ability, high compatibility toward electrodes, and high electrochemical performance. Unfortunately, the acceptance of solid polymer electrolytes victimizes owing to the low ionic conductivity and poor electrochemical stability window. Fig. 4 Physical properties of ingredients for CPEs in SIBs 13 Advanced Composites and Hybrid Materials (2022) 5:2651–2674 Quest of achieving more superiority develops promising strategies for solid polymer electrolyte revival such as dropping liquid plasticizer [32, 46], the introduction of ionic liquids, enthusiastic solvents [16, 56], and finally adding inorganic fillers [17, 44, 45]. Physical characteristics of ingredients for existing all classes of composite polymer electrolytes are shown in Fig. 4. These practices have revived solid polymer electrolytes with an inevitable sacrifice of mechanical strength, thermal, and chemical instability. But the addition of fillers led the researchers in achieving their standards of SIBs in a commercial application. Polymer electrolytes with salt in a plasticized solvent are termed as solid polymer electrolytes, polymer electrolytes with salt and inheriting ionic liquids are categorized as gel polymer electrolytes, and polymer electrolytes incorporating inorganic ceramics are commonly named as composite polymer electrolytes. The best negotiable solution for overcoming the challenges of ICEs and SPEs is to couple both types of electrolytes to develop CPEs. Synergistic coupling of inorganic–organic moieties is a fruitful approach among the practices to harness the maximum advantage of current electrolytes. Here, we are focusing only on ceramic fillers embedded composite polymer electrolytes. 3 Synthesis methods 3.1 In situ polymerization In situ polymerization is a widely accepted technique for the preparation of nanocomposites demanding uniform dispersion and direct integration of filler nanoparticles in a bulk polymer matrix. This process simply involves the filler dispersion in the precursor monomer solution and further proceeds through the polymerization of monomer via standard Advanced Composites and Hybrid Materials (2022) 5:2651–2674 polymerization reactions to give nanocomposite. To avoid the agglomeration of nanofillers, the grafting technique allows the direct covalent linking of fillers over the polymer matrix. Regarding SIB applications, Chen et al. prepared a 3D-CPE via in situ polymerization of PEGMA monomer and anion-trapping boron containing crosslinker (B-HEMA) inside a mechanically supporting PVDF-HFP polymer matrix containing NaTF and TEGDME as plasticizer [57]. Initially, mechanical supporting PVDF-HFP matrix was prepared using phase transfer method with mass ratio of 1:10 for PVDF-HFP-acetone and water (6% mass fraction). Subsequently, boron-containing CPE was prepare by soaking the porous PVDF-HFP polymer in the monomer solution containing mixture of PEGMA (2.5 g), B-HEMA (0.2 g), NaTF (0.48 g), TEGDME (1.05 mL), and AIBN (0.01 g) solution for 0.5 h in ambient conditions. As-prepared 3D-CPE was subjected to heat treatment of 70 °C for 12 h in vacuum. Presence of numerous polar C–C–O– groups on host polymer chains causes rapid dissociation of NaTF. Additionally, [–B–O–] crosslinking bonds in CPE act as a trapping center for anions due to the Lewis acid nature of boron moieties. Since, boron accepts electronegative anions from NaTF salt due to its ­sp2 hybridization with an unoccupied orbital. The synthesized electrolyte shows an appreciable ionic conductivity, high transference number, and wide electrochemical window of 0.26 mS ­cm−1 @40 °C, 0.66, and 5.1 V, respectively. Improved electrochemical performance is accredited to the structural versatility and availability of boron moieties in 3D-CPE for SIBs. In another reported work, poly(methacrylate) (PMA)/poly(ethylene glycol) (weight ratio of 65:35) based hybrid polymer electrolyte using in situ polymerization with 5 wt.% nano-α-Al2O3 as filler and ­NaClO4 salt was reported for all solid-state SIBs. As-prepared CPE exhibited a high ionic conductivity of 1.46 × ­10−4 S c­ m−1 at 70 °C with a wide electrochemical stability window (4.5 V vs. N ­ a+/Na) [58]. Similarly, a polyvinyl carbonate (PVC)-based CPE comprising PVDF-HFP mechanically supported matrix coupled with the organic plasticizing agent was reported using in situ polymerization technique. As-prepared PVC-based CPE exhibited appreciable room temperature ionic conductivity of 0.12 mS c­ m−1 with electrochemical window of 5.3 V [59]. CPE also exhibited a maximum transference number of 0.60 which is due to the high polarity of PVC and TEGDME that restrains the migration of T ­ f− anions and thus facilitated high N ­ a+ transference value. Yi et al. adopted a versatile approach by intertwining electrospinning technique with the in situ polymerization technique. They reported a PMMA polymer-based CPE in which PMMA polymer was filled into electrospinning derived ­Na3Zr2SiPO12-PVDF-HFP composite membrane using in situ polymerization. Initially, ­Na3Zr2SiPO12-PVDF-HFP composite was prepared using electrospinning technique and then a CPE was obtained 2655 using mixture of PMMA, dibenzoyl peroxide, and 1 M of liquid electrolyte (1 M of N ­ aPF6 in EC/PC, 1:1) via in situ polymerization. As-developed CPE exhibited an excellent ionic conductivity, wide electrochemical window, and high transference number of 2.78 × ­10−3 S ­cm−1, ⁓4.9 V, and ⁓0.63, respectively [60]. 3.2 Doctor blade/solution casting Solution casting is a conventional technique to prepare polymer electrolyte membranes having a thickness ranging from 50 to 300 μm. A wide range of CPEs is developed using this method with various concentrations of fillers, sodium salt, and plasticizers. The steps involved during this synthesis of CPEs are as follows: ➢ Preparation of homogenous and transport solution of polymer in the desired solvent. ➢ Subsequent addition of salts in a polymer solution. ➢ Addition of filler nanoparticles. ➢ A properly dispersed solution with desired viscosity is cast on a glass/Teflon plate using doctor blade. ➢ Slow evaporation of solvent for few days. Very recently, Devi et al. reported a PEO/PVP-based CPE employing InAs nanowires as fillers using solution casting technique. Initially, a homogeneous solution of PEO (0.4 g), PVP (0.1 g), and ­NaPF6 salt with 8:1 molar ratios of O/ Na in methanol was prepared. Further, the filler was added in stoichiometric proportion (0.5–3.0 wt.%) to the solution. Solution was then casted into polypropylene petri dishes and further dried in vacuum for the complete removal of solvent [61]. Similarly, Yu et al. reported PEO/carbon quantum dots (CQDs)-based CPE using solution casting technique. PEO and ­NaClO4 were dissolved in acetonitrile and kept stirring for 12 h to acquire homogeneity. Further, the solution was casted on polytetrafluoroethylene (PTFE) plate and dried for 24 h at 70 °C in vacuum atmosphere to get CPE [62]. Kim et al. prepared a NASICON/PVDF-HFP-based CPE via solution casting using a doctor blade (Fig. 5a) [48]. Initially, as-prepared NASICON filler was mixed with PVDF-HFP polymer using planetary ball mill in solvent (DMAc:acetone, 1:2) for 30 h. Post milling obtained viscous solution was casted using doctor blade on a Teflon mold substrate. As-casted membrane was immersed in water for 10 min followed by drying in an oven at 60 °C/12 h and 70 °C/6 h in a vacuum to get a solid polymer membrane. These membranes were hot-pressed and further soaked in a standard liquid electrolyte to get CPE. The CPE was again pressed under 6.3 kPa pressure to remove excess liquid electrolyte (Fig. 5b). Several research works involving the solution casting technique have been reported to synthesize the flexible quasi-solid state CPEs for SIBs [42, 63–67]. 13 2656 Fig. 5 a Composite solid electrolyte prepared via doctor blade method employing filler NASICON powder, host PVDF-HFP polymer and sodium salt (1 M N ­ aCF3SO3/TEGDME). Reproduced with permission from ref. [48]. Copyright 2014 RSC. b Schematic of flexible all-solid-state sodium battery employing quasi solid electrolyte. 3.3 Phase inversion method The phase inversion method is the commonly used technique to prepare polymer electrolyte membranes with different functionalities. It is a demixing process in which a homogeneous polymer solution is transformed from a liquid state to a solid state in a controlled manner. The structure, properties, and chemical interaction of CPEs prepared by the phase inversion method solely rely on the choice of polymer and additives added in the casting solution. The steps for the phase inversion methods are as follows: ➢ Initially, polymer solution in a suitable solvent is casted on a glass sheet or Teflon substrate with the required thickness. ➢ The casted membrane is immersed in a non-solvent precipitation bath (e.g., water). ➢ An asymmetric surface structure appears on the immersed polymer membrane which precipitates rapidly due to the exchange of solvent and nonsolvent across the interface. 13 Advanced Composites and Hybrid Materials (2022) 5:2651–2674 Reproduced with permission from ref. [70]. Copyright 2018 Wiley– VCH. c Schematic diagram of PEO-NASICON composite polymer electrolytes by filling PEO (NaTFSI) solution inside the porous NASICON-NZSP frameworks. Reproduced with permission from ref. [69]. Copyright 2016 American Chemical Society ➢ Numerous phase transition occurs during the exchange between solvent (polymer membrane) and nonsolvent (water) which depends on the choice of casting solution and additives. Verma et al. prepared CPEs based on PVDF-HFP/xTiO2 (x = 0, 0.25, 0.50, 0.75, 1.0, 1.25, and 1.50 wt.%) via phase inversion technique [68]. Initially, the transparent solution of PVDF-HFP + DMF + ­TiO2 was prepared via the addition of PVDF-HFP in the homogeneous suspension of DMF-TiO2. The obtained solution was poured into a glass petri dish and kept in a steam chamber at 100 °C. A thick, whitish, highly porous PVDF-HFP/TiO2 CPE membrane has been obtained after 2-h exposure. The high porosity of CPE is credited to the two simultaneous processes during phase inversion, one the evaporation of DMF at an elevated temperature and the other one is the diffusion of steam into the pores of PVDFHFP created due to evaporation of DMF from PVDF-HFP polymer membrane. Further soaking the membrane into the standard liquid electrolyte (0.5 M ­NaPF6 in EC: PC, 1:1 wt./ wt. ratio) produces a transparent CPE. Advanced Composites and Hybrid Materials (2022) 5:2651–2674 Porous NASICON-Na3Zr2Si2PO12 ceramic frameworks with controlled porosity synthesized via sol–gel method were reported by Wang et al. [69]. PEO polymer along with NaTFSI sodium salt was then filled into the continuous pores of NASICON-Na3Zr2Si2PO12 ceramic frameworks (10 wt.%, 25 wt.%, and 32 wt.%). In this way, they developed a threedimensional interconnected ceramic-polymer interface with the CPEs (Fig. 5c). 3.4 Hot pressing method The hot press technique is a facile, rapid, economically cheaper, and solvent-free synthesis method to fabricate polymer electrolyte membranes with good uniformity and density. Initially, precursor materials such as polymer, salt, plasticizers, and fillers are finely grounded for a certain duration. As-obtained mixture is heated to a temperature close to the melting temperature of the host polymer to produce a homogeneous and dense slurry. This slurry is further sandwiched between two stainless steels and subjected to high pressure in a controlled manner to give CPEs. Serra Moreno et al. developed a PEO:NaTFSI-SiO2-based CPE using solvent-free hot pressing technique [71]. Starting materials like PEO, NaTFSI, and ­SiO2 nanoparticles were initially dried under vacuum for the respective duration. Ramp-wise pressure was applied to the finely grounded mixtures obtained after ball milling (17.7 kg ­cm−2/15 min, 141.5 kg ­cm−2/45 min at 90.2 °C) to get various PEO-based CPEs. In other work, Dalvi et al. reported the PEO-NASICON-based CPE (63PEO-37[PEO1−yNaIy], y = 0.03–0.013) using hot press method. NASICON nanoparticle synthesized by solid state reaction with particle size ⁓30 nm was dispersed into homogeneous solution containing PEO blended with NaI to obtain a viscous slurry. This slurry was further vacuum dried and subjected to hot press with pressure of 2 tons ­cm−2. As-prepared CPE exhibited a homogeneous distribution of NASICON nanoparticles in PEO matrix free from any phase segregation (PEO-NZSP) [72]. Chandra et al. reported a CPE containing host polymer (PEO), sodium salt ­(NaHCO3), and nanofiller ­(SiO2) for SIB using isostatic hot pressing method. Fully dried polymer blended with sodium salt (70PEO:30NaHCO3) was homogeneously mixed with various concentration of S ­ iO2 nanofillers, with heating treatment at ∼70 °C to obtain slurry. This slurry was further hotpressed between stainless steel blocks to form a mechanically stable membrane [73]. Chandra et al. have also reported a PEO-based CPE [(1 − x)(75 PEO:25 N ­ aPO 3):xSiO 2] (x = 0–15 wt.%) via hot pressing technique [74]. 3.5 Electrospinning Electrospinning is a facile and cost-effective technique to produce one-dimensional nanostructures and three-dimensional 2657 interconnected nanofibrous networks in the form of nonwoven membranes. It is a versatile technique to synthesize one-dimensional nanostructures, three-dimensional polymer membranes, inorganic and inorganic–organic hybrid materials. Unlike conventional nanomaterials, uni-dimensional nanofibers have admirable length, impressive mechanical strength, and efficient electron migration. These hierarchical nanostructures in the form of nanofibers and nanofibrous membranes with high surface area, high porosity, tunable morphology, multi composition, good isotropy, and rich active sites serve them as a prevalent candidate for electrode and electrolyte materials for electrochemical energy storage devices such as electrochemical supercapacitors [6, 75–80]. The performance of SIBs relies on the compatibility of the electrolyte material. An extensive chemical interaction is demanded between the electrolyte and the electrode materials to boost electrochemical performance. Owing to this reason, the electrospinning technique is widely used to prepare the polymer membrane. Electrospun polymer membranes have a large porosity and high electrolyte uptake, which increases the viability of the electrolyte material. Electrospun nanofiber-based separators are promising materials for SIB applications due to their exceptional chemical stability, high porosity, appreciable affinity toward organic electrolyte, and superior electrochemical performance [78–80]. 4 Performance index and characterization of composite polymer electrolytes The concept of CPE is introduced to overcome the demerits of existing polymer electrolytes. Nevertheless, an ideal CPE must have the following characteristics for SIBs (Fig. 6). The performance index of an electrolyte can be assessed based on the following traits: ➢ CPEs should exhibit a high ionic conductivity (up to order ­10−3 S ­cm−1) in temperatures ranging from ambient to high to execute high cycle and rate performance for SIBs. ➢ CPEs must have a wide electrochemical potential stability window (0 − 5 V) to prevent sluggish reactions with the electrodes in Na-insertion and de-insertion during the charge–discharge process of SIBs. ➢ CPEs should inherit superior thermal stability (−40 to 150 °C) and high dimensional stability to avoid deformation while operating at an elevated temperature. In general, the thermal stability of polymer electrolytes causes severe hazards like short circuits and thermal runway due to the deformation of polymer electrolytes in SIBs. ➢ CPEs should have a high N ­ a+ transference number (≈ 1) for preventing ionic concentration polarization and contributing to high power performance. 13 2658 Advanced Composites and Hybrid Materials (2022) 5:2651–2674 Fig. 6 Performance index of composite polymer electrolytes ➢ CPEs should also have a high mechanical strength to suppress the intrusion of sodium dendrites. The mechanical stiffness of a CPE is crucial for its application in wearable and flexible energy storage devices. ➢ CPEs should be cost-effective for a wide range of commercial applications in SIBs. ➢ CPEs should be low toxicity and composed of earthabundant elements to procure long-term availability of energy-driven SIBs. 4.1 Characterization of composite polymer electrolytes CPEs are considered as one of the promising electrolyte alternatives to the rapidly growing SIB market. The electrochemical performance and physical characteristics of an electrolyte solely rely on the quality of CPEs membranes. The way separator cum electrolytes will perform under the electrochemical process parameters like cyclic stability, rate capability, and voltage profiles and delivered ionic conductivity is dependent on the structural and functional properties of CPEs [14, 22, 66]. Assessment of structural features of CPEs includes microcrystalline nature, thickness, wettability, porosity, and electrolyte uptake. The evaluation of chemical properties of CPEs includes Raman, FTIR, and NMR spectroscopy (Fig. 7). 13 The functional properties crucial for electrochemical performance include the ionic conductivity, electrochemical stability window, and transport number measurement. An ideal CPE must have to characterize in terms of its structural, chemical, and functional characteristics to bridge electrolyte characteristics with the performance of SIBs [40, 81]. Essential characterization techniques for the primary evaluation of CPEs for SIB application are summarized in Table 1. This table does not include the ex-situ and in-situ studies for post-mortem analysis of SIBs. 5 Composite polymer electrolytes with passive fillers Passive fillers refer to the N ­ a + free ceramics which are implicitly capable in contributing the ­Na + through the electrolytes. The addition of passive fillers is a promising approach to strengthen the polymer electrolytes in terms of their physical and electrochemical performance for SIBs [31, 43, 44]. In SIBs, passive fillers have been extensively harvested to alter the chemical physics of the polymer electrolytes at the cost of their reduced crystallinity and glass transition temperature. In this section, we have summarized the ongoing developments on composite electrolytes for SIBs based on the passive fillers (Table 2). Advanced Composites and Hybrid Materials (2022) 5:2651–2674 2659 Fig. 7 Summary for research methods of electrolytes (liquid, polymer, and solid) and interfaces for SIBs. Adapted with permission from ref. [22]. Copyright© 2019 Wiley–VCH The mechanism for the ion transport of such electrolytes is discussed separately. Different exotic materials such as boron [57], ­TiO2 [68], ­SiO2 [71, 82–84], E8 liquid crystal [66], ­ZnFe2O3 [85], ­Si3N4 [86], ­Al2O3 [70], CaO [87], and carbon quantum dot [88] are used as fillers for SIBs. Implementation of these conventional fillers is gaining attention for the CPE development in practical SIBs. Villaluenga et al. developed a novel PEO-SiO2 nanohybrid electrolyte with a high N ­ a+ transference number [82]. The hurdle of ambipolar conductivity in CPEs is jumped by covalently grafting ­SiO2 nanoparticles with sodium salt and oligo-PEG chains. ­SiO2-anion and ­SiO2-PEG-anion were dissolved into a binary mixture of PEO and PEGDME with a weight ratio 1:1. EO/Na ratio was varied to different values (40, 20, 10, and 6.5) for further investigation. ­SiO2-anion (EO/Na ≈ 10) and S ­ iO2-PEG-anion (EO/Na ≈ 20) based ion-conducting electrolytes exhibit similar ionic conductivity 2 × ­10−5 S ­cm−1. This is due to the reason that S ­ iO2 grafted PEG chains do not contribute to solvation owing to conformal constraints. ­SiO2-anion (EO/Na ≈ 10) electrolyte Table 1 Different characterization techniques and their capabilities in the assessment of CPEs Parameter Technique Capability Morphology Field emission scanning electron microscopy (FESEM) X-ray diffraction (XRD) •Surface morphology, nanofiber diameter determination •Average crystal structure •Crystallinity variation of polymer •High spatial resolution down to atomic scale in structure and morphology •Variation of weight loss with the temperature •Determination of crystallinity •Electrolyte uptake capability •Mechanical stability testing •Determination of ion association and dissociation, free anion, ion pair, and ion aggregates in the CPEs •Bonding information •Local structure, electronic structure, and ion-dynamics information •Cation number information •Ionic conductivity, bulk resistance, grain boundary, activation energy, and interfacial resistance information •Electrochemical voltage stability window determination of CPEs Crystallinity Transmission electron microscopy (TEM) Thermal stability Wettability Mechanical stability Functional group Thermo-gravimetric analysis (TGA) Differential scanning calorimetry (DSC) Contact angle measurement Stress–strain measurement Fourier transform infrared spectroscopy (FTIR) Ion pathway Raman Nuclear magnetic resonance (NMR) Transference number Ionic conductivity Chronoamperometry Complex impedance spectrometry Electrochemical stability window Linear sweep voltammogram (LSV) 13 2660 Advanced Composites and Hybrid Materials (2022) 5:2651–2674 Table 2 Recent reported work on CPEs with passive fillers Polymer Sodium salt Synthesis method Ionic conductivity (S ­cm−1) ESW Ref PVDF-HFP-boron (0.5 wt.%) PVDF-HFP-TiO2 (0.5 wt.%) PVDF-HFP-Al2O3 PEO-SiO2 (5 wt.%) PEO-E8 LC PEO-SiO2-anion PEO-SiO2-PEG-anion PVDF-SiO2 PMMA-SiO2 (4 wt.%) PEO-ZnFe2O4 (0.5 wt.%) PVDF-Si3N4 PEO-CaO (5 wt.%) PEO-carbon QD PVP-ZrO2 (0.5 wt.%) PVDF-HFP-glass fiber PVDF-HFP-glass fiber-dopamine NaTF NaPF6 NaPF6 NaTFSI NaIO4 RSO2N(−)SO3CF3 RSO2N(−)SO3CF3 NaCF3SO3 NaClO4 NaCF3SO3 NaClO4 NaClO4 NaClO4 NaPO3 NaClO4 NaClO4 In situ polymerization Phase inversion Doctor blade Solvent-free hot press Solution casting Solvent drying Solvent drying Solution casting Solvent drying Solution casting Electrospinning Solution casting Solution casting Solution casting Coating and drying Coating and drying 0.257 at 40 °C 1.3 1.3 at 25 °C 1.1 at 80 °C (EO/Na ≈ 20) – ˂10−5 (EO/Na ≈ 10) ˂10−5 (EO/Na ≈ 10) 0.06 at 25 °C 3.5 at 25 °C 0.06 at 25 °C 4.1 at 25 °C 0.049 at 25 °C 0.0717 1.02 at 25 °C 4.6 at 80 °C 5.4 at 80 °C 5.1 3.5 4.3 4.9 – 4.4 3.8 4.1 3.3 4 5.4 5 4.5 2.0 4.8 4.8 [57] [68] [70] [71] [66] [82] [82] [83] [84] [85] [86] [87] [88] [92] [93] [93] shows an electrochemical stability window of 4.4 V wider than the S ­ iO2-PEG-anion (EO/Na ≈ 20) having a value of 3.8 V owing to higher sodium concentration. Ma et al. attempted to resolve the problematic aggregation of nanoparticles used as fillers in the polymer matrices by introducing the well-dispersed carbon QDs of size 2–3 nm diameter in the PEO matrix [88]. The strategy of using nanoscale fillers of a smaller size such as QDs successfully overcame the hindrance in ionic conductivity. Meanwhile, carbon QDs offer various Lewis sites to increase the dissociation degree of sodium salts. PEO-CQD-based CPE exhibits an improved ionic conductivity of 7.71 × ­10−5 S ­cm−1. Liquid crystals (LC) are preferred over conventional nanofillers due to their intrinsic features like anisotropy, self-healing, spontaneous alignment, and good process ability. Koduru et al. used a nematic liquid crystal as a filler to fabricate novel polymer/liquid crystal composite electrolytes [66]. In the nematic phase of the LC system, linear isotropy of liquid crystal favors the formation of a high density of ion-conductive paths. PEO/E8 LC system with 10 wt.% ­NaIO4 salt exhibits the minimum crystallinity and highest ionic conductivity of 1.05 × ­10−7 S ­cm−1. This enhanced ionic conductivity was accounted based on the dynamic percolation model following the Lewis acid–base mechanism. Dielectric measurement studies of the samples witnessed that the strong interactions among the sodium salt ions (­ Na+ and I­ O4−), ether oxygen of host polymer PEO, and functional groups associated with E8 LC (cyanobiphenyl and cyanoterphenyl) increased the amorphosity of PEO/E8 LC nanocomposite electrolyte. 13 Chen et al. developed an innovative composite electrolyte comprising PVDF-HFP polymer modified with anion trapping boron moiety (B-CPE) via in situ polymerization method [57]. As-synthesized electrolyte exhibits an ionic conductivity of 2.57 × ­10−4 S ­cm−1 with a high transference number (0.66) and improved interfacial stability with the sodium metal anode. Boron atom inherits Lewis acid character and accepts the electronegative ions obtained from the dissociation of sodium salts (NaTF), thus increased the N ­ a+ transference number of composite electrolyte. To smoothen the ion transport at the electrolyte/ electrode interface as well as inside electrodes, a strategy of preparing NFM cathode via in situ solidification of polymer electrolyte inside NFM through heat polymerization reaction was adopted. Consequently, c-NFM/B-CPE/Na cell exhibits a high discharge capacity of 113.8 mA h ­g−1 with 80.1% capacity retention at 0.2 C (Fig. 8a–f). Wang et al. reported a full cell comprising N ­ a3V2(PO4)3 (NVP) electrode and PVDF-based composite solid electrolyte in which ­SiO2 nanoparticles were added as fillers along with N ­ aCF3SO3 salt via conventional solution casting technique (Fig. 8g–k). The highest ionic conductivity for as-developed CPE was calculated as 6.0 × ­10−5 S ­cm−1 at 25 °C. Full cell assembled using CPE has demonstrated a specific capacity and specific energy density of 76 mA h ­g−1 and 126 W h ­kg−1 at 0.5 C rate, respectively. After 100 charge–discharge cycles, the Na cell still retained 70% of its initial specific capacitance [69]. Xu et al. intruded CaO filler derived from waste egg shell to develop a PEO/CaO CPE [87]. The strong alkaline character of CaO enhanced the ionic conductivity 4.5 times Advanced Composites and Hybrid Materials (2022) 5:2651–2674 2661 Fig. 8 a SEM images of original porous supporting matrix (P-support) B and b B-PC with an inset image of P-support and B-CPE. c Magnified SEM image of B-PE. d Cross-sectional SEM image of B-CPE. e Original NFM cathode deposited on Al foil current collector and f Cross-section image of c-NFM/B-CPE/Na full cell. a–f are reproduced with permission from ref. [57]. Copyright 2014 Elsevier. g, h FESEM image of PVDF-SiO2-based CPE surface. i Digital image of circular CPE film. j, l SEM image of the cross-sectional view of CPE and k photograph of as-prepared CPE. g–k are reproduced with permission from ref. [83]. Copyright 2014 Elsevier. l SEM and m cross-sectional SEM image of P/SN@PBNi electrolyte. l and m are reproduced with permission from ref. [86]. Copyright 2014 Elsevier higher than the pristine polymer electrolyte. Additionally, this filler contributes high mechanical stability and a wide electrochemical stability window up to 5 V. As-fabricated Na/PEO-CaO/Na3V2(PO4)3 full cell battery gives an appreciable reversible capacity of 101.2 mA h ­g−1 at 0.5 C after 100 cycles. Ma et al. perform the electrochemical and SIB characteristics by twining the separator and the electrode [86]. Considering the aspect that PVDF is used as a binder for the electrode, it is possible to couple the PVDF-based electrode and the separator (Fig. 8l and m). Inspiring from this, ­Si3N4 embedded PVDF (P/SN) electrospun separator was fabricated with superior characteristics like high-temperature resistance, good chemical stability, and high dielectric properties. As-developed separator is deposited on the Prussian blue ­Na2Ni[Fe(CN)6] (PBNi) electrode using electrospinning technique to get a P/SN@PBNi separator-electrode combination. Crosslinking of –CH2–CF2– with the β-PVDF chains significantly improves the thermal stability, tensile strength, and ionic conductivity and decreases interfacial impedance. P/SN@PBNi-based battery exhibits high initial Coulomb efficiency (96.8%), appreciable cyclic stability (92.2% after 503 cycles), and superior rate performance (78 mA h ­g−1 at 5 C). Passive fillers or N ­ a + free ceramics are effectively enhanced the physical and electrochemical performance. Ion transport is the major characteristic of CPEs for their applications in SIBs. Passive fillers are mainly metal oxides whereas some other nanostructures such as carbon QDs, ­Si3N4, boron, and E8 liquid crystal also lie in this category. The mechanism for the ionic conduction in such fillers is the same as the prominent metal oxides. The addition of passive fillers influences the host polymer-sodium salt system in two ways. ➢ The segmental motion of host polymer chains The inclusion of fillers in the polymer matrix suppresses the recrystallization process of the polymer molecular chains and increases the amorphous regions in polymer electrolytes. These amorphous regions are solely responsible for the ionic conduction in solid polymer electrolytes [77, 89–91]. The ionic conductivity of CPEs increases with a rise in temperature with gradual inhibition of crystallinity of the polymer. ➢ Polymer-passive filler interface Ion transport of CPEs with passive fillers is also encouraged via Lewis acid-base interactions. Host polymer chains act as ion transport medium via dipole-dipole interaction. Passive filters act as a Lewis acid whereas anions of added sodium salt act a Lewis base. These two entities compete with each other to form a complex with the host polymer. In this way, fillers act as a crosslinking center for the poly- 13 2662 Advanced Composites and Hybrid Materials (2022) 5:2651–2674 Aggregation of filler beyond a certain threshold concentration is a severe problem observed in CPEs. To overcome this, carbon QDs were used as a filler in PEO-NaClO 4 polymer electrolyte. As-prepared PEO-NaClO4-CQD (3 wt.%) based CPE exhibited a substantial enhancement in ionic conductivity and higher ­Na+ transference number (0.42) as compared to pristine PEO-NaClO4 polymer electrolyte. Dissociation of sodium salt in PEO was investigated using FTIR analysis. The dissociation ratio for PEONaClO4-CQD (3 wt.%) is found to be 97.9% higher than the PEO-NaClO4 polymer electrolyte (86.1%). The working mechanism of prepared CPEs is schematically shown (Fig. 9b). It is obvious from figure that PEO-NaClO4 polymer electrolyte consists of a good crystallinity with minimal amorphous regions which provides flexural and lengthy ion transport pathway for N ­ a+ conduction causing low ionic conductivity. In contrast, PEO-NaClO 4-CQD (3 wt.%) based CPE is having a strong Lewis acid–base interaction among CQD fillers, sodium salt, and host polymer. These interactions felicitated the segmental motion and large free volume for ionic transport and also enhanced the dissociation of sodium salt results into high ionic conductivity. Pristine PEO-NaClO4 system was synergistically coupled with CaO filler derived from waste egg shell [87]. CaO is a ceramic filler material that is more alkaline and sodiophillic as compared to other remaining metal oxides reported so far. Successive addition of CaO filler (0.25 wt.%, 0.5 wt.%, 1 wt.%, 3 wt.%, 0.25 wt.%, 5 wt.%, and 7 wt.%) significantly raises the ionic conductivity which was found to be higher than the commercially purchased CaO filler. Further increasing the filler concentration beyond 5 wt.% reduces the ionic conductivity values due to the segregation of fillers. The addition of CaO fillers influences Fig. 9 a Schematic illustration of the mechanism of PVDF-HFPAl2O3-based CPE exhibiting synergistic Lewis acid–base intermolecular bonding host polymer and filler nanoparticles. a is adapted with permission from ref. [70]. ­Copyright© 2019 Wiley–VCH. b Schematic diagram of ion transport mechanism in pristine PEO SPE and PEO/CQDs CPE. b is adapted with permission from ref. [88]. ­Copyright© 2018 Wiley–VCH. c Schematic of the mechanism for ionic transport in PEO-CaO-based CPE. Reproduced with permission from ref. [87]. ­Copyright© 2020 Royal Society of Chemistry and the Chinese Chemical Society. d Schematic illustration of ion transport in B-CPE and C-CPE during charge–discharge process. Reproduced with permission from ref. [57]. ­Copyright© 2020 Elsevier mer and the anion. At the filler-polymer interface, the crystallinity of the polymer gets perturbed due to the formation of a hydrogen bond between the filler and host polymer (Fig. 9a). This led to the appearance of free volume for ion conduction. In addition to this, surface groups of the passive fillers act as Lewis acid-base interaction centers with the alkali salt (Lewis base) and host polymer (O atoms as Lewis base) felicitating more salt dissociation which synergistically increased the concentration of N ­ a+ and hence ionic conductivity [35, 43, 44, 46]. 13 Advanced Composites and Hybrid Materials (2022) 5:2651–2674 the PEO/NaClO4 polymer electrolyte in two ways. Firstly, the crystallinity of PEO disrupted upon the intrusion of fillers facilitating the segmental motion of polymer chains. Secondly, adsorption/desorption of ­Na+ filler surface promotes rapid ion transport (Fig. 9c). Chen et al. developed an innovative composite electrolyte comprising PVDF-HFP polymer modified with anion trapping boron moiety (B-CPE) via the in situ polymerization method [57]. The two full cells with the configuration of c-NFM/B-CPE/Na and c-NFM/C-CPE/Na were tested in terms of their electrochemical performance in SIBs. As tested, c-NFM/B-CPE/Na cell exhibited a high first discharge capacity of 113.8 mA h ­g−1 with capacity retention of 80.4% of its initial capacity even after 700 cycles at a current rate of 0.2 C compared to the c-NFM/C-CPE/ Na cell which exhibits a first discharge capacity of only 103.2 mA h ­g −1 with capacity retention of 43.3%. This improved rate capability is a credit to the existence of low electrode polarization due to high ionic conductivity and high ­Na+ transference number. The proposed mechanism for the improved electrochemical performance is shown in Fig. 9d. The c-NFM/C-CPE/Na owing lower N ­ a+ ion transference, resulting in concentration gradients of the salt and cell polarization during the cycling process, ended with the deterioration of rate capability. In contrast, the c-NFM/B-CPE/Na inherits a single N ­ a+ conducting nature. The presence of anion trapping boron hinders the migration of anions (­ Tf−) and stabilizes the mobility of cations ­(Na+) during the insertion/de-insertion process. This, in turn, alleviates concentration polarization of electrolytes during cycling, thus remarkably enhances ­Na+ transport, Table 3 Recently reported work on CPE with active fillers Polymer 2663 leading to the improvement of rate capability, cycling stability, and discharge capacities of SIBs. 6 Composite polymer electrolytes with active fillers Unlike passive fillers, active fillers refer to the N ­ a+-containing ceramics which explicitly supplies the N ­ a+ through the electrolytes. These active filers are having superior characteristics like high ionic conductivity, good chemical stability, wide electrochemical stability window, and high rigidity [42, 94, 95]. Active fillers have low activation energies due to the presence of defects and ionic conductivity is facilitated by mutual hopping of ions from one site to another site during ­Na+ transport [2, 10, 18]. Importantly, these fillers are capable to supply N ­ a+ for ion transport in SIBs. In LIBs, active fillers have been adopted extensively exploited to strengthen the viability of polymer electrolytes. Regarding SIBs, prevailing ionic conductors such as NASICONs are used as a filler in various polymers to fabricate CPEs [47, 49, 63, 72, 96]. In this section, we have given an overview of current strategies on CPEs for SIBs based on the active fillers. The mechanism for the ion transport of such electrolytes is discussed separately. ­Na3Zr2Si2PO12 [62], ­Na3Zr1.8Mg0.2Si2PO12 [63], and ­Na2Zn2TeO6 [65] have been tried as an active fillers for the CPE development (Table 3). This strategy is gaining enormous attention due to the improved physical and electrochemical performance of pristine polymer electrolytes. Kim et al. developed a high-performance CPE inheriting high ionic conductivity, wide electrochemical Sodium salt PEO-Na3Zr2Si2PO12 (40 wt.%) NaFSI (EO/Na ≈ 20) PEO-Na3Zr1.8Mg0.2Si2PO12 (40 wt.%) NaFSI (EO/Na ≈ 20) Epoxy-Na3Zr2Si2PO12 (30 wt.%) – NaTF PVDF-HFP-Na3Zr2Si2PO12 NaClO4 PVDF-HFP-Na3Zr2Si2PO12 NaTFSI Na3Zr2Si2PO12-PEO (10 wt.%) PEO-Na3Zr1.8Mg0.2Si2PO12 (50 wt.%) NaTFSI (EO/Na ≈ 14) PEO-PAN-Na3Zr2Si2PO12 NaClO4 NaTFSA Polyether-Na3Zr2Si2PO12 PEO-Na3Zr2Si2PO12 (25 wt.%) PMMA-PVDF-HFP-Na3Zr2Si2PO12 NaClO4 NaPF6 Synthesis method Ionic conductivity (S ­cm−1) ESW Ref Solution casting 0.022 at 25 °C – [42] Solution casting 0.044 at 25 °C 4.4 [42] Polymer filling Solution casting Solution casting Polymer filling Solution casting 0.145 at 25 °C 0.12 2.25 at 25 °C 0.14 at 25 °C 2.8 at 80 °C 7 6 – – 4.3 [47] [48] [49] [69] [63] Solution casting Solution casting with UV irradiation Solvent drying Electrospinning and in situ polymerization 0.136 at 25 °C 0.010 at 25 °C 4.8 – [62] [67] 0.021 at 30 °C 2.78 at 30 °C – 4.9 [64] [60] 13 2664 stability window, and exceptional thermal stability [48]. ­Na 3Zr 2Si 2PO 12 nanoparticles were uniformly dispersed in PVDF-HFP polymer by using a binary mixture of solvents, i.e., DMAc:acetone, 1:2. This solution was casted as a membrane by the doctor blade method and further immersed in water for 10 min. As-developed CPE was further activated by the addition of 1 M of NaTF/TEGDME liquid electrolyte. The final weight proportion of the CPE is found at 70:15:15 for NASICON filler:PVDFHFP:ether-based electrolyte. Electrochemical stability of ether-based electrolyte uplifts to 5 V from 3 V upon addition of NASICON fillers. NASICON/PVDF-HFP CPE shows lower bulk resistance than the NASICON/PVDFHFP composite film with activation with liquid electrolyte. Small inclusion of liquid improves the ceramic-ceramic, ceramic-polymer, and electrolyte–electrode interfacial stabilities. A full cell of hard carbon/NASICON/PVDFHFP/NaFePO4 exhibits 98% Coulombic efficiency with a discharge capacity of 120 mA h ­g −1 at 0.2 C rate. The enhancement in flexibility and bendability of the prepared CPEs has been demonstrated by illuminating LED under normal static and bent conditions. Zhang et al. achieved a high ionic conductivity of 2.4 × ­10−3 S ­cm−1 at 80 °C and low interfacial resistance by embedding NASICON fillers (­Na 3 Zr 2 Si 2 PO 12 and ­Na3Zr1.8Mg0.2Si2PO12 (40 wt.%)) into PEO matrix [42]. The temperature dependence of ionic conductivity values for both the electrolytes reaches its apex at 40–50 °C owing to the crystalline amorphous transition of the host polymer. ­Na3Zr1.8Mg0.2Si2PO12 (40 wt.%)-PEO-NaFSI shows much higher ionic conductivity than pristine PEO-NaFSI. ­Na3V2(PO4)3/PEO-Na 3Zr1.8Mg0.2Si2PO12-NaFSI/Na cell delivers the highest reversible capacity of 106.1 mA h ­g−1 with an initial Coulombic efficiency of 94%. Yi et al. prepared a PMMA polymer-filled ­Na3Zr2Si2PO12 (40 wt.%)-PVDF-HFP CPE via in situ polymerization [60]. As-prepared electrolyte exhibits a high ionic conductivity of 2.78 × ­10−3 S c­ m−1, an electrochemical stability window of 4.9 V, and a high cationic transference number of 0.63. Asprepared electrolyte exhibits maximum stress of 6.2 MPa. The addition of ­Na3Zr2Si2PO12 powder into the PVDF-HFP nanofibers not only enhanced the mechanical strength but also reduced the strain of the prepared CPE. Yu et al. introduced a CPE based on PEO/NaClO4/Na3Zr2Si2PO12 via solution casting technique [64]. As-prepared solid-state CPE showed an excellent ionic conductivity of 1.45 × ­10−4 S c­ m−1 at 60 °C. Cyclic stability of symmetrical cell-based Na/PEO-NaClO44-Na3Zr2Si2PO12/Na improves due to the inclusion of active filler capable of suppressing sodium dendrites. Full cell Na/PEO-NaClO4-Na3Zr2Si2PO12/N0a2MnFe(CN)6 exhibits a discharge capacity of 124 mA h ­g−1 at a current rate of C/10. As-fabricated SIB shows a stable cycling performance with cyclic stability of 13 Advanced Composites and Hybrid Materials (2022) 5:2651–2674 83% and Coulombic efficiency of 97–99% after being cycled 300 times (Fig. 10h–k). Wang et al. developed a NASICON/PEO-based ceramicpolymer composite in which the semi-crystalline PEO polymer was used as a filler in the NASICON framework [69]. To avoid the segregation of microsized fillers and to increase the availability of ceramic-polymer filler interfaces, ceramic framework-polymer filler strategies have been adopted instead of the conventional ceramic filler polymer matrix. Sol–gel derived ­Na3Zr2Si2PO12 framework was synergistically couple with PEO:NaTFSI filler (10 wt.%, 25 wt.%, and 32 wt.%) to develop CPE. Among these, 10 wt.% polymer embedded CPE shows a thin coating of polymer whereas the higher concentration of fillers develops the thick coating on NASICON framework. As-developed CPE with 10 wt.% of polymer filler exhibited an ionic conductivity of 1.4 × ­10−4 S ­cm−1 at room temperature. Scanning probe microscopy (SPM) was used to investigate the ­Na+ diffusion at the interface into two modes. The first one is bimodal-AFM that measures sample hardness and the second is ESM which detects the surface deformation caused by ion transportation. Cheng et al. reported a ceramic in polymer hybrid solid electrolyte (HSE) comprising synergistically coupled polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) polymer with ­Na3Zr2Si2PO12 (NASICON) ceramic fillers. As-synthesized HSE exhibits good flexibility, remarkable high ionic conductivity of 2.25 × ­10−3 S c­ m−1 at ambient temperature, and good interfacial stability. N ­ a3V2(PO4)3/C/ CPE/Na-based full cell exhibits an interfacial resistance of 152 Ω [49]. As-fabricated ­Na3V2(PO4)3/C/CPE/Na-based battery shows a reversible capacity of 98 mA h ­g−1 with a capacity retention of 85% even after 175 cycles. Till now, most of the researchers have developed the CPE with low content of N ­ a+ filler in the host polymer electrolytes. In this regard, Hiraoka et al. synthesized a new polyether/Na3Zr2Si2PO12 CPE with filler content varying from 0 to 300 wt.% into the host polymer matrix [67]. The sole aim of this study is to harvest the utility of host polyether and ­Na3Zr2Si2PO12 filler to its maximum extent as an electrolyte. CPE with 30 wt.% of filler concentration in polyether/NaTFSA exhibited the highest ionic conductivity of 1.03 × ­10−5 S ­cm−1 at room temperature. This is due to the facilitated segmental motion of polymer chains and promotion of dissociation of sodium salt upon addition of lower concentration of active fillers. The positive influence of higher content of filler concentration has a profound effect in interfacial characteristics. Polyether/NaTFSA-Na3Zr2Si2PO12 (200 wt.%) exhibited the lowest interfacial resistance and activation energy among prepared CPEs. This superiority is accredited to the presence of ­Na3Zr2Si2PO12 accelerating ­Na+ transport at the electrolyte–electrode (Na metal) interface. In order to ensure the safety, Na-ion and Na-sulfur with the respected cells Na/polyether/NaTFSA-(200 wt.%Na3Zr2Si2PO12)/NaCoO2 and Na/ Advanced Composites and Hybrid Materials (2022) 5:2651–2674 2665 Fig. 10 a Interfacial morphology between NMTO ceramic electrode and all-solid-state CE after 200 galvanostatic cycles, with a low and b high magnification. c Galvanostatic cycling of Na|electrolyte|Na symmetric cells using PEO (NaTFSI) and NASICON/PEO CE as electrolytes, under constant current of 1 μA cm. a–c are reproduced with permission from ref. [69]. ­Copyright© 2020 Elsevier. d Illustration of the NASICON structure of the N ­ a3Zr2Si2PO12 material. e Scanning electron microscopy (SEM) image of the ­Na3Zr2Si2PO12 powder. f SEM image of the PEO-NaClO4-Na3Zr2Si2PO12 membrane. g X-ray diffraction (XRD) patterns of the ­Na3Zr2Si2PO12 powder, PEO membrane, and PEO-NaClO4-Na3Zr2Si2PO12 composite membrane, as well as the reference pattern of the N ­ a3Zr2Si2PO12 compound. d–g were reproduced with permission from ref. [64]. ­Copyright© 2019 American Chemical Society. h–j Photographs of composite polymer electrolytes with 0 wt.%, 30 wt.%, and 300 wt.% of NZSP fillers. k Variation of ionic conductivities with the temperature exhibited by composite polymer electrolytes (0–300 wt.% of NZSP). h–k are reproduced with permission from ref. [67]. ­Copyright© 2020 American Chemical Society. l XRD pattern of filler N ­ a2Zn2Te2O6 nanoparticles. m SEM image of NZTO powder. n Photograph of composite polymer membrane. o Ionic conductivity of PEO-NaTFSI-Na2Zn2Te2O6 (0–60 wt.%) composite polymer electrolytes. l–o were reproduced with permission from ref. [65]. ­Copyright© 2019 Elsevier polyether/NaTFSA-(200 wt.% N ­ a3Zr2Si2PO12)/sulfur modified polyacrylonitrile (SPAN) cells were operated at 333 K (Fig. 10d–g). Wu et al. developed a CPE based on PEO embedded with novel sodium-ion-conducting filler, i.e., Ga-doped ­Na2Zn2TeO6, via solution casting technique [65]. CPEs with different concentration of filler (0%, 10%, 20%, 30%, 40%, 50%, and 60%) have been prepared. The PEO-NaTFSI/NZTO (50 wt.%) CPE exhibits a remarkable ionic conductivity of 4 × ­10−5 S ­cm−1 at an ambient temperature which was further elevated to 1 × ­10−3 S ­cm−1 at 80 °C with an electrochemical stability window of 4 V (Fig. 10l–o). The tensile strength is uplifted from 0.15 to 0.54 MPa (PEO/NaTFSI) whereas the tensile moduli raised from 1.3 to 14.2 MPa for CPE. N ­ a2V3(PO4)3-based cathode was fabricated using PEO:NaTFSI as a binder and ion-conducting network formed at the electrolyte–electrode interface. Three batteries were fabricated using three different types of cathodes with CPE 13 2666 against sodium metal anode (1) nanostructured ­Na2V3(PO4)3 with CPE, (2) microcrystalline N ­ a2V3(PO4)3 with CPE, and (3) PEO:NaTFSI solid electrolyte with microcrystalline ­Na2V3(PO4)3. Among the three prototypes, the first battery shows a minimal internal resistance of 250 Ω while the third one exhibits the highest value of internal resistance, i.e., 550 Ω. The discharge capacities of the batteries were found to be 105, 95, and 72 mA h ­g−1, respectively. Depending on concentration of active fillers in host polymer, CPEs may be “inorganic rich” (˂50 vol%) or “polymer rich” (inorganic content > 50 vol%) [14]. In case of inorganicrich CPEs, ion conduction is expected through the 3D percolation network that critically relies on particle size and dispersion. The overall ­Na+ conductivity is dependent on their volume fraction and possible ion-conduction pathways. In case of polymer-rich CPEs, the maximum contribution in ionic transport is expected from polymer network; the probability of migrating through inorganic fillers is less. Overall the ionic conductivity, the ionic conduction could be facilitated through (a) combined polymer electrolyte–ceramic particles pathways, (b) interface region between polymer and inorganic particles, (c) the polymer electrolyte phase (polymer-rich CPEs), and (d) inorganic electrolyte bulk phase (inorganicrich CPEs) [27, 28, 46]. Lim et al. suggested a substantial solution for facilitating ceramic contribution through the induction of ion transport channels in the oxide-based solid electrolyte using a top-down method [47]. They filled the epoxy-resin polymer within the internal pores of oxide-based NASICON electrolyte resulting in the improvement in physical properties and electrochemical performance of the electrolyte. Using this method, the physical properties of the CPE is expected to increase due to use of epoxy-resin, while the ionic conduction of NASICON is well due to formation of separate ion transport channel. Bare NASICON pellet was filled with epoxy-resin polymer material followed by 5-min curing under UV illumination. Consequently, the high ionic conductivity of 1.45 × ­10−4 S ­cm−1 was achieved with exceptional electrochemical stability of 7 V and thermal stability up to 400 °C. As-fabricated NVP/NASICON/Na exhibited a specific capacity of 120 mA h ­g−1 at 0.1 C rate. Yu et al. adopted a dual-layer approach to prepare the CPE for ambient temperature SIBs [62]. The dual-layer strategy took the benefit of anode compatible layer from one side whereas the other side is cathode friendly. A novel laminated electrolyte was developed using PAN-SN-Na3Zr2Si2PO12/PAN-Na3Zr2Si2PO12-NaClO4 that exhibited an excellent ionic conductivity of 1.36 × ­10−4 S ­cm−1 with an electrochemical stability window of 0–4.8 V. A full cell was fabricated using Na-metal anode and N ­ a2MnFe(CN)6 cathode which exhibited high capacity and appreciable cyclic stability. 13 Advanced Composites and Hybrid Materials (2022) 5:2651–2674 6.1 Ion transport mechanism Active fillers refer to the ­Na+-containing ceramics having the potential to strengthen the physical and electrochemical performance of the host polymer. Highly targeted solidstate sodium-ion conducting ICEs are actively employed as an active filler for the CPE preparation. Pure and alkali metal/alkaline earth metal doped ­Na 3Zr 2Si 2PO 12- and ­Na2Zn2TeO6-based ICEs are exploited as active fillers owing to their high ionic conductivity, high rigidity, and wide electrochemical stability window. Intrinsic bulk ionic conductivity is due to the presence of continuous defects causing low activation energy for multiple ions hopping rather than single ion movement. The role of these fillers is more enthusiastic than the passive filler as they provide more pathways for the ions to migrate and facilitate conductivity in CPEs. Usually, in active filler-based CPEs, the ­Na+ conduction is through the polymer-ceramic interface and the segmental motion of polymer chains but in contrast, active filler-based CPEs provide a new intrinsic path through their filler’s surface. In this way, they contributed implicitly to the enhancement in ionic conductivity of CPEs. Kim et al. in 2015 reported the active filler-based CPEs for the first time in SIBs. They reported a N ­ a3Zr2Si2PO12 embedded PVDF-HFP electrolyte containing ether-based liquid electrolyte [48]. ­Na+-containing CPE exhibited a maximum ionic conductivity of 1.4 × ­10−3 S ­cm−1 at an elevated temperature of 90 °C. This ionic conductivity value is larger than the comprising liquid, inorganic filler, and host polymer-based electrolytes. They recommended three possible migration paths for N ­ a+ conduction (1) hopping of ions through the ceramic surface, (2) plasticizer transport of liquid electrolytes, and (3) cross ion hopping through a polymer-ceramic and ceramic-liquid interface. Doped NASICON filler-based CPEs are reported using the same strategy and with different solvents and polymers. Wu et al. used a Ga-doped N ­ a2Zn2TeO6 filler filled PEO CPEs for SIB development. Different weight percentages of filler (0%, 10%, 20%, 30%, 40%, 50%, and 60%) were dispersed in PEO:NaTFSI-based solid polymer electrolyte system [65]. CPE prepared with 50 wt.% ­Na2Zn2TeO6-PEO/ NaTFSI exhibited maximum ionic conductivity 3 × ­10−3 S ­cm−1 at a temperature of 80 °C which is highest among all the reported PEO-based CPEs for SIBs. This ionic conductivity for the higher concentration of NZTO (40 wt.%) CPEs is due to the above melting temperature of PEO, the crystallinity of host polymer vanishes, and the ion transport due to connected NZTO fillers is dominant. On the other hand, the raised ionic conductivity for lower concentration is due to suppression in crystallization of PEO polymer. Lim et al. reported an interesting work using a top-down approach to prepare a polymer in ceramic electrolyte rather Advanced Composites and Hybrid Materials (2022) 5:2651–2674 2667 than the trending ceramic in polymer-based CPE where the contribution of ceramic fillers is negligible and maximum ionic conductivity is due to host polymer chains [47]. Initially, NASICON solid electrolyte was sintered to introduce ion transport channels and further as-sintered electrolyte was filled with epoxy polymer to develop epoxy-NASICON CPE. The physical strength of the CPE was doubled; however, the thermal and electrochemical performances have been retained (Fig. 11a). Cheng et al. in 2020 reported the reason for ionic conductivity enhancement in ceramic in polymer hybrid solid electrolyte comprising NASICON nanoparticles embedded PVDF-HFP polymer matrix [49]. As-prepared hybrid solid composite electrolyte facilitated a migration pathway for sodium-ion conduction during its charging and discharging. They suggested four possible pathways for the sodium-ion conduction particularly termed as intrachain hopping of sodium ions, interchain hopping of sodium ions, and through Fig. 11 a Comparison of the ionic conductivity effect in different ceramic ratios in a ceramic-polymer composite state. Reproduced with permission from ref. [47]. ­Copyright© 2020 from the Royal Society of Chemistry. b and c Schematic diagram of ionic transport in host PVDF-HFP polymer and CPE. Reproduced with permission from ref. [49]. ­Copyright© 2020 Springer Nature 13 2668 Advanced Composites and Hybrid Materials (2022) 5:2651–2674 polymer and polymer-NASICON interface, respectively (Fig. 11b–c). The ionic-conductivity enhancement in the reported electrolyte is accredited to the following four aspects: ➢ NASICON fillers in the electrolyte perturbed the crystallinity of the host PVDF-HFP polymer which in turn facilitates the segmental motion of the polymer. This provides the more expanded region for characteristic sodiumion conduction through the electrolyte. ➢ NASICON-PVDF-HFP interface causes the permeation effect which creates an interconnected transmission channel on the surface of the fillers, playing a vital role in sodium-ion conduction. The difference in sodium-ion concentration between NASICON fillers and host PVDF-HFP polymer induces a concentration gradient in an electrolyte which enthusiastically contributes polymer electrolytes to absorb more sodium ions. Owing to this, there is an increase in Na-ion vacancy promoting ionic transport. ➢ The presence of highly Na-ion conductive NASICON implicitly contributes to the ionic conductivity improvement. 7 Electrolyte–electrode interfacial characteristics The major obstacle in building high-performance CPEbased SIBs is the poor interaction between CPEs with the electrodes which increases the interfacial resistance. A high mechanical, chemical, thermal, and electrochemical stability is crucial to suppress sluggish charge transfer reaction that occurs at the electrode–electrolyte interface [14, 20, 22, 23]. The fundamental concept of formation of solid electrolyte interface is deliberately shown in Fig. 12. Accordingly, the solid electrolyte interface is formed when the redox potential of the electrode materials exceeds the electrochemical potential window of the electrolyte. Constructing excellent interfaces between ceramic fillers and polymer chains in SCEs could effectively solve the intrinsic problems of SCE to achieve high-performance all-solid-state batteries. The stability of the electrolyte depends upon the LUMO (lowest unoccupied molecular orbital) and HOMO (highest occupied molecular orbital) gaps of the electrolyte and Fermi level of the electrodes. [14]. The electrolyte would be stable when the lowest unoccupied molecular orbital (LUMO) of the electrolyte is higher than that of the Fermi energy of anode. Similarly, when the highest occupied molecular orbital (HOMO) of the electrolyte is lower than that of Fermi energy level of cathode [15, 26, 34, 97]. Particularly, in the case of CPEs which contain both inorganic solids and polymer electrolytes, the rigid nature of inorganic ceramic electrolytes is having poor compatibility 13 Fig. 12 Schematic open circuit energy diagram of an electrolyte. The term μA and μC are the redox potential and ϕA and ϕC are the work function of anode and cathode, respectively. ­Eg is the electrochemical potential stability window of the electrolyte with the electrodes and suffers from a large interfacial resistance. On the other hand, polymer electrolytes are more adaptable toward interfacial stability. During operations of SIBs, they formed a stable solid electrolyte interface which is steadily conductive to ­Na+ but exhibits insulating behavior for electron migration [18, 20, 33, 36, 96, 98]. This capability of polymer electrolytes plays a vital role in improving cycle life, capacity loss, rate capability, and safety concerns among SIBs [31, 40, 99, 100]. A tailored solution for minimizing the challenge of high interfacial resistance is to couple both the electrolytes rationally in terms of forming electrode–electrolyte interface layers [14, 26, 34, 49]. Tremendous research work has been reported for improving electrode–electrolyte interfacial characteristics in SIBs. Xie et al. reported a SIB comprising a quasi-solid-state electrolyte and graphite along with graphite and Sn foil as cathode and anode, respectively (Fig. 13a and b). The use of Sn foil as both anode and current collector replaced the anode active materials different strategy to enhance the energy density of as-developed SIB compared to conventional SIBs [70]. Regarding CPEs in SIBs, a strategy of introducing thin film coating on the CPE is a promising approach for extending improved electrochemical performance. Gao et al. enhanced the mechanical strength of PVDF-HFP polymer electrolyte by providing commercial glass fiber as mechanical support [93]. But, the hydrophobic nature of PVDF-HFP impedes the flow of liquid electrolytes causing poor battery performance at high charge–discharge densities. This problem was overcome by a thin coating of hydrophilic polydopamine over PVDF-HFP electrolyte. The retention of discharge capacity for glass fiber/PVDF-HFP/polydopamine Advanced Composites and Hybrid Materials (2022) 5:2651–2674 2669 separator is found to be 89.4% higher than that of glass fiber/ PVDF-HFP separator which shows 84.1% discharge capacity after 100 cycles. Glass fiber/PVDF-HFP/polydopamine separators show a stable Coulombic efficiency of 99.7% after 100 cycles compared to glass fiber/PVDF-HFP separators (99.4%). This might be due to strong adhesion between electrode and electrolyte. The presence of catechol moieties on the polydopamine backbone provides strong adhesion to the substrates. Additionally, this mussel-powered adhesive is capable of buffering the volume changes of electrode materials during repeated charge–discharge processes. Yi et al. used a Na/C cloth as an anode material instead of Na metal. They developed a PMMA polymer-filled NZSP/ PVDF-HFP electrospun nanocomposite membrane via in situ polymerization [60]. Full cell ­Na0.67Ni0.23Mg0.1Mn0.67O2/ PMMA-NZSP/PVDF-HFP/Na/C exhibited remarkable rate capability with an initial discharge capacity of 96 mA h ­g−1 and excellent cyclability of 95% after 600 cycles. The internal resistance of Na/C symmetrical cell exhibited a value of 130 Ω, 160 Ω, and 270 Ω after 1st, 20th, and 40th cycles, respectively, which is lower than the corresponding Nabased symmetrical cell exhibiting an internal resistance of 120 Ω, 520 Ω, and 800 Ω after 1st, 20th, and 40th cycles, respectively. A higher value of internal resistance after discharge is due to activation of Na/C electrode after the first discharge process. To smoothen the ion transport at the electrolyte/electrode interface as well as inside the electrodes, a strategy of preparing a composite NFM cathode via in situ solidification of PE inside NFM through heat polymerization reaction was adopted. A higher concentration of polymer in ceramic also contributes to improving electrolyte–electrode interfacial characteristics. Hiraoka et al. found that polyether/NZSP (˂200 wt.%) based CPE exhibited low interfacial resistance with Fig. 13 a Schematic illustration of the configuration and working mechanism SIB during its charging process. a is adapted with permission from ref. [70]. ­Copyright© 2019 Wiley–VCH. b Impedance spectra of SIBs with glass fiber, HSE, and NASICON ceramic elec- trolyte. c Schematic diagram of ionic transport in ceramic electrolyte. Reproduced with permission from ref. [49]. ­Copyright© 2020 Springer Nature 13 2670 Advanced Composites and Hybrid Materials (2022) 5:2651–2674 Fig. 14 Future enhancements of oxide ceramic-based composite electrolytes. Reproduced with permission from ref. [47]. ­Copyright© 2020 from the Royal Society of Chemistry Na metal compared to the NZSP free system due to high N ­ a+ transference number [67]. In a low concentration of NZSP (> 100 wt.%), the increase in N ­ a+ transference number is influenced by dissociation of NaTFSA salt upon addition of NZSP. At higher concentrations, the CPE accumulates a large number of NZSP particles and causes aggregation of NZSP near CPE/Na interface. Charge transfer energy is lower in high concentration CPE (˂200 wt.%) that is lower than the desolvation energy of the solvated ether oxygen of the polymer. This would enable higher concentration CPEs in SIBs with high charge–discharge rates owing to their rapid ion migration at CPE/Na interface. Cheng et al. reported a PVDF-HFP/NZSP CPE activated by a liquid electrolyte. N ­ a3V2(PO4)3/C/CPE/Na-based full cell exhibits an interfacial resistance of 152 Ω very much than smaller that of NASICON-based battery with interfacial resistance of 792 Ω [49]. As-fabricated N ­ a3V2(PO4)3/C/CPE/ Na-based battery shows a reversible capacity of 98 mA h ­g−1 with a capacity retention of 85% even after 175 cycles (Fig. 13b–c). In general, extraction of ­Na+ from the cathode is accomplished at the cost of unavoidable volume changes in the electrodes resulting in the formation of voids. These vicinities are hardly full-filled by NASICON nanoparticles causing high electrode–electrolyte interface resistance. Asfabricated CPEs provide compatibility and mechanical stiffness at the interface in the form of interconnected migration paths during battery operation. 8 Conclusion and future outlook In conclusion, we have reviewed the basic understanding and recent developments of composite polymer electrolytes (CPEs) for SIBs. Recent work undergoing electrolyte development for sodium-based energy storage is elucidated in this 13 review. The necessary aspect regarding synthesis, assessment, and mechanism of CPEs in SIB is describes correlating their performance indices. Still, scientists are facing the practical ability of CPEs in SIBs and new paradigms and efforts are still required to bridging the gap between experimental and commercial fulfillment. Major challenges still need to be confronted are as follows: (1) Low ionic conductivity is still barricading in meeting the performance comparable to the highly conductive liquid electrolytes. Novel polymer materials and respective fillers with high ionic conductivity should be explored. Regarding SIBs, the choice of fillers is restricted up to two or three prevailing inorganic electrolytes although a large number of ICEs for SIBs are available. (2) Host polymer for CPEs should be tuned with rational engineering techniques aiming to create more amorphous entities to improve the ionic conductivity. Functionalization recipes such as copolymerization, crosslinking, and grafting should be practiced with modified synthesis. (3) Diagnosing the interfacial compatibility to maximize electrochemical performance within CPEs as well as across CPEs and electrodes (cathodes/anodes) by introducing additives in electrolytes, laminated structure development, unifying electrode–electrolyte materials and novel interfacial architectures (Fig. 14). (4) Minimization of cost for the SIB development is a crucial demand for SIBs to be manufactured at a larger scale. Implementation of low-cost materials, bioinspired polymers, and sustainable precursors should be accelerated to reduce prices. (5) Design of novel electrolyte system for building flexible, transparent, and electrochromic SIBs. Advanced Composites and Hybrid Materials (2022) 5:2651–2674 Funding Dr. AS gratefully acknowledges the UGC, New Delhi, for their financial supports under the BSR Mid-Career award scheme (No. F.19–214/2018). Declarations 2671 16. 17. Conflict of interest The authors declare no competing interests. 18. References 1. Larcher D, Tarascon JM (2015) Towards greener and more sustainable batteries for electrical energy storage. Nat Chem 7(1):19–29. https://doi.org/10.1038/nchem.2085 2. Buonomenna MG, Bae J, (2017) Sodium-ion batteries: a realistic alternative to lithium-ion batteries? Nanosci Nanotechnol Asia 7(2):139– 154. https://doi.org/10.2174/2210681206666161019145001 3. 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Materials 13(16). https://d oi.o rg/1 0. 3390/ma13163453 13 2674 Advanced Composites and Hybrid Materials (2022) 5:2651–2674 99. Bocharova V, Sokolov AP (2020) Perspectives for polymer electrolytes: a view from fundamentals of ionic conductivity. Macromolecules 53(11):4141–4157. https://doi.org/10.1021/acs.macromol.9b02742 100. Torres FG, De-la-Torre GE, Gonzales KN, Troncoso OP (2020) Bacterial-polymer-based electrolytes: recent progress and applications. ACS Appl Energy Mater 3(12):11500–11515. https:// doi.org/10.1021/acsaem.0c02195 Publisher's Note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. Mr. Dheeraj K. Maurya is working as a research scholar at Centre for Nanoscience & Technology, Pondicherry University, Puducherry, India. He has received his M.Sc. (Applied Physics) and M.Phil. (Physics) in 2014 and 2016, respectively from BBA University, Lucknow. His research interest includes development of polymer nanocomposites for energy storage and sensors applications. D. Ragupathy received his master degree in 2005 from Bharathiar University, Coimbatore, India and Ph.D. degree from Kyungpook National University, Daegu, South Korea in 2010. He did postdoctoral work at Kyungpook National University and Pusan National University, South Korea. He is currently working as Assistant Professor in the Department of Chemistry, National Institute of Technology Puducherry, Karaikal, India. He is recently focusing his 13 research attention on interdisciplinary topics covering synthesis ofconducting polymers, nanostructuring of materials, electrochemistry and deviceapplications. Zhanhu Guo earned his Ph.D. degree in Chemical Engineeringfrom Louisiana State University in 2005. He received his three-yearpostdoctoral training in mechanical and aerospace engineering at the University of California Los Angeles. He is an Associate Professor in Chemical and Biomolecular Engineering and directs the Integrated Composites Laboratory at The University of Tennessee, Knoxville. His current research interests are inthe areas of optical, optoelectronic, electric, magnetic, and dielectric materials for energy conversion/storage, electromagnetic interference (EMI) shielding, catalysis, sensing, and electronics. Subramania Angaiah is currently working as a Professor at the Centre for Nanoscience and Technology, Pondicherry University, India. Heobtained his Ph.D. degree from Alagappa University & CSIR-CECRI (2001) and his postdoctoral training from the Korean Institute of Science and Technology(KIST), Seoul, South Korea. His current research interests include the development of nanostructured materials for metalion batteries, super capacitors, quantum dot sensitized solar cells, dyesensitized solar cells and perovskite solar cells.