Review—Solid and Polymer Electrolyte Materials and Related Processing Methods Suitable for Three-Dimensional Battery Architectures

Currently, electrolytes used in lithium-ion batteries are flammable and leaky, causing safety problems when used under high temperatures or extreme conditions. Solid electrolytes can fundamentally avoid the occurrence of such issues, at the same time, it can significantly increase the energy density of solid state lithium batteries. Solid electrolytes are classified into inorganic solid electrolytes and solid polymer electrolytes. Although inorganic solid electrolytes have the high mechanical strength and room temperature ionic conductivity, it has poor flexibility and complicated preparation process. In contrast, solid polymer electrolyte has good elasticity and good interface contact, which can overcome many disadvantages of the inorganic solid electrolyte. Among them, polyethylene oxide (PEO) is first proposed as a polymer electrolyte. Due to its excellent mechanical properties, electrochemical stability and thermal stability, it has been a hot topic for polymer solid electrolytes for decades. However, its low room temperature ionic conductivity limits practical application. Given the problems existing in PEO-based polymer electrolytes, several methods for improving ionic conductivity have been proposed. The primary methods include plasticization, the organic-inorganic composite, and polymer blending. Comparing these methods, it can be seen that adding plasticizers to the polymer can effectively increase the conductivity of the electrolyte, but at the same time it will cause a decrease in the mechanical properties, and the safety issues limit its application in lithium-ion batteries. Inorganic fillers can balance the problems of ionic conductivity and mechanical properties, but the construction of a good filler-polymer dispersion system is complicated in preparing such composite electrolytes, design a new type of multi-dimensional the ion transport network also face tremendous challenges. Undoubtedly, in the future research, inorganic fillers will be the dominant means in the modification of composite electrolytes. Compared with the former two modification methods, polymer blending is easy to operate and friendly to industry, but low ionic conductivity at room temperature still exist. To give full play to the advantages of polymer blending, using it as an auxiliary means to improve the performance of composite electrolytes will be the primary development direction of such modification methods. PEO is the most widely studied polymer electrolyte. Even though a large number of modification methods have emerged in its development history, the ionic conductivity at room temperature is still limited to a relatively low level. To meet the needs of the application in lithium-ion batteries, a high operating temperature (50−70℃) is still needed, the biggest problem remains exist. To solve the problems in polymer solid electrolytes, the research directions in the future may mainly focus on: Expanding the modification method of PEO to other polymer electrolyte host materials, broadening the scope of research, and finding the available polymer electrolytes at room temperature. Concerned about the preparation of ultra-thin polymer electrolytes, reducing the ion transmission path to increase the transmission efficiency of lithium ions between positive and negative electrodes. Effectively combines inorganic solid electrolytes and solid polymer electrolytes to give full play to their advantages. In addition, exploring the effect of inorganic filler morphology on the conductivity of the composite electrolyte will also deserve attention. Many one-dimensional, two-dimensional materials can build ion transport networks so that lithium ions can travel rapidly along the path. With the deepening of research, it is expected that PEO-based polymer electrolytes may replace liquid electrolytes and become an essential cornerstone for building the next generation of safe and reliable lithium-ion batteries.

<p indent="0mm">Since the commercialization of lithium-ion batteries in the 1990s, lithium-ion batteries have been successfully applied in portable electronics, electric vehicles, and grid energy storage. Although current organic liquid electrolytes have high ionic conductivities, they are inherently flammable, volatile, and prone to leakage. Moreover, severe side reactions and dendrite growth on the surface of the lithium anode during the charge-discharge process can cause safety hazards, which greatly impede their applications in lithium metal batteries. Solid electrolytes, including inorganic solid electrolytes and polymer electrolytes, are regarded as effective alternatives to organic liquid electrolytes for the construction of lithium metal batteries with high energy density and safety. Among them, solid polymer electrolytes offer excellent flexibility, processability, and interfacial compatibility over inorganic solid electrolytes, and they are extraordinarily promising for lithium metal batteries with high energy density and safety. Ideal solid polymer electrolytes should have following features: (1) High ionic conductivity (&gt; <sc>10 ^–4 S cm ^–1) </sc> at room temperature; (2) high lithium ion transference number (~1) to reduce the concentration polarization and improve the rate performance of batteries; (3) intimate contact at the electrode/electrolyte interfaces; (4) wide electrochemical window <sc>(&gt;4.5 V</sc> vs. Li/Li ⁺) to match high-voltage cathodes and improve the energy density of batteries; (5) good mechanical stability to resist processing, buffer electrode volume change and inhibit dendrite growth; (6) good thermal stability to withstand environmental changes. Generally, the ionic conductivity of pure solid polymer electrolytes at room temperature is low <sc>(~10 ^–6 S cm ^–1). </sc> Researchers have tried to improve the ionic conductivities by adjusting the lithium salt concentration, such as developing “polymer-in-salt” solid electrolytes. However, increasing the concentration of lithium salt leads to the deterioration of the mechanical strength. Strategies such as developing novel lithium salts, modifying polymer matrix, and incorporating inorganic fillers into solid polymer electrolytes are proposed to promote ionic conductivities of solid polymer electrolytes. In particular, composite polymer electrolytes, fabricated by dispersing a certain amount of inorganic fillers into solid polymer electrolytes, have improved ionic conductivities without sacrificing their mechanical performances. Poor interfacial property between electrodes and electrolytes is also a critical issue for solid polymer electrolytes. On one hand, poor and uneven solid/solid contacts at the electrode/electrolyte interfaces lead to high resistance and sluggish ionic transport kinetics. Furthermore, the volume change of the positive and negative electrodes in the charge/discharge process deteriorates the interfacial contacts, blocks the ion and electron transport through the interfaces, and greatly reduces the electrochemical reaction kinetics. On the other hand, the electrochemical windows of solid polymer electrolytes are usually narrow <sc>(＜4.5 V).</sc> During cycling, redox reactions are prone to occur at the electrode/electrolyte interfaces, causing battery failure. Solid polymer electrolytes have also poor thermal and mechanical stabilities. Therefore, design and synthesis of polymer-based solid electrolytes with excellent comprehensive performances and construction of fast and stable ion transport channels at the electrolyte/electrode interfaces are of great significance for the successful development of solid-state lithium metal batteries. This paper presents a brief review of the research progress in solid polymer electrolytes from two aspects: Improving the ionic conductivities of solid polymer electrolytes and enhancing the interfacial performance at electrolyte/electrode interfaces. First, targeted optimization strategies on ionic conductivities of solid polymer electrolytes, including constructing continuously aligned ionic transport paths and shortening the ionic transport distance, are summarized. Second, interface optimization strategies, including constructing wetting interfaces and synthesizing asymmetric electrolytes, are presented to reduce the interface resistance and improve the interfacial contact. Finally, perspectives on the development of solid polymer electrolytes and high-performance solid-state lithium metal batteries are discussed, and key research directions and advanced test methods are proposed. This review may provide a comprehensive understanding and further guidance for not only the material design of solid polymer electrolytes, but also the structural design of lithium metal batteries with favorable electrochemical and interfacial performances.

Solid polymer electrolytes (SPEs) have garnered extensive attention as potential alternatives to traditional liquid electrolytes, primarily due to their prowess in curbing lithium dendrite formation and preventing electrolyte leaks. The quest for SPEs that are both mechanically robust and exhibit superior ionic conductivity has been vigorous. However, achieving a harmonious balance between these two attributes remains a significant challenge. In this study, we introduce a novel quasi-solid electrolyte, ingeniously crafted from a poly(urethane-urea) network, enriched with lithium salts and plasticizers. This innovative composition not only boasts remarkable toughness but also ensures commendable ionic conductivity. Our post-gelation method yields gel polymer electrolytes that undergo rigorous evaluation, leading to an optimized version that stands out with its exceptional room-temperature ionic conductivity (2.94×10-4 S cm-1) and outstanding toughness (11.9 MJ m-3). Moreover, it demonstrates a broad electrochemical window (4.73 V), remarkable stability across a 600-hour cycle test, a high capacity retention exceeding 80 % after 100 cycles at 0.2 C, and a noteworthy self-healing capability. This quasi-solid polymer electrolyte emerges as a promising contender to replace current liquid electrolyte solutions.

Polymer electrolytes are promising materials for electrochemical device applications, namely, high energy density rechargeable batteries, fuel cells, supercapacitors, electrochromic displays, etc. The area of polymer electrolytes has gone through various developmental stages, i.e. from dry solid polymer electrolyte (SPE) systems to plasticized, gels, rubbery to micro/nano-composite polymer electrolytes. The polymer gel electrolytes, incorporating organic solvents, exhibit room temperature conductivity as high as ∼10−3 S cm−1, while dry SPEs still suffer from poor ionic conductivity lower than 10−5 S cm−1. Several approaches have been adopted to enhance the room temperature conductivity in the vicinity of 10−4 S cm−1 as well as to improve the mechanical stability and interfacial activity of SPEs. In this review, the criteria of an ideal polymer electrolyte for electrochemical device applications have been discussed in brief along with presenting an overall glimpse of the progress made in polymer electrolyte materials designing, their broad classification and the recent advancements made in this branch of materials science. The characteristic advantages of employing polymer electrolyte membranes in all-solid-state battery applications have also been discussed.

Solvent-free in-situ polymerized plastic crystal electrolytes for long-cycling lithium metal batteries

Cellulose acetate-based gel electrolytes grafted with surface-functionalized SiO2 nanofiber for green energy storing applications

A simple low-cost method to prepare gel electrolytes incorporating graphene oxide with increased ionic conductivity and electrochemical stability

Solid-state batteries have attracted much attention due to their safety and energy density. Polyvinylidene fluoride (PVDF)-based solid polymer electrolyte (SPE) shows great application potential due to its excellent flexibility, mechanical properties, and processing performance. However, limited ionic conductivity restricts its application. In addition, suppressing the growth of lithium dendrites is another key issue to be solved in solid-state batteries. Adding ionic conductive fillers (e.g., Li7La3Zr2O12) to increase ionic conductivity is the main method. In previous work, we found that surface modification of Li7La3Zr2O12 with gallium-based liquid metal can improve interfacial compatibility and inhibit the growth of lithium dendrites, thereby improving the battery's performance. In this study, we combined LM-modified Li7La3Zr2O12 with PVPF-HFP and used the phase separation method to fabricate composite films with a porous network. After absorbing the electrolyte, gel electrolytes (GPEs) were obtained. With the modification of the filler and optimization of pore size and connectivity, the gel electrolyte achieved an ionic conductivity of 3.8 × 10-3 S·cm-1 at room temperature. The half-cell equipped with the modified gel electrolyte can cycle 400 times at 1C with a retention rate of 96.24%, showing promising cycling stability. This research provides insight into the design and application of gel electrolytes.

Solid polymer electrolyte (SPE) have been expected as high safety and reliable materials compared with conventional organic liquid electrolytes. In order to apply polymer electrolytes to all-solid-state Lithium Ion Battery (LIB), it is essential to improve their lithium ion conductivity and membrane stability. In this study, we focused on polymer nanofibers to overcome these issues on SPEs for LIB applications. Polymer nanofibers have unique characteristics such as high surface area, good mechanical property, and great material transport property [1]. We have reported fabrication, characterizations, and applications of various functional polymer nanofibers prepared by an electrospinning method [2]. Recently, we developed proton or anion conductive polymer nanofibers and revealed their outstanding ion conductive properties [3]. The nanofiber framework (NfF) composite membranes consisting of the ion conductive nanofibers and polymer electrolyte matrix showed remarkable fuel cell properties due to their improved ion conductivity, gas barrier property, and membrane stability [4]. Here presents our recent work on lithium ion conductive polymer nanofibers and their application to all-solid-state LIBs. The electrospinning method was attempted to fabricate lithium ion conductive NfFs composed of lithium salt and polymers bearing ethylene oxide units in their main or side chains. The lithium ion conductive NfF composite membranes were prepared by filling polymer electrolyte matrices into the voids of the NfFs. Electrochemical, thermal, and mechanical properties of the NfFs and NfF composite membranes were evaluated to demonstrate improved electrolyte characteristics. Fabrication and evaluation of all-solid-state LIBs based on the NfF composite membranes will also be reported. Acknowledgements This work is partially supported by JSPS KAKENHI (26410225), and a grant (Platform for Technology and Industry) from Tokyo Metropolitan Government, Japan.

A polysaccharide extracted from guar beans-based gel polymer electrolytes for efficient dye-sensitized solar cells

Electrolyte plays a pivotal role in Li-ion battery (LIB). Generally, it has been considered as a liquid phase material that allows for reasonable dissolution ability of inorganic salt and ion transportability across the electrodes. Since conventional liquid electrolytes faced limitations to improve battery performance, the solid-state electrolyte has raised rapidly to replace the liquid electrolyte. Solid polymer electrolyte (SPE) is one of the most promising solid-state electrolytes, it has attracted attention due to its strength as an electrolyte such as high accessibility, tolerance against volume change of electrodes, and reasonable chemical/thermal stability. Especially poly(ethylene oxide) (PEO) or PEO-based electrolytes have been widely developed, because of their outstanding Li salt dissolution ability. PEO forms a unique helical complex structure with Li salt, the complex is highly stable. It allows PEO to dissolve Li salt much easier than other polyethers, such as poly(propylene oxide) or poly(oxymethylene). However, the high stability of the complex could disturb fast ionic conduction in electrolyte medium, it is the reason why PEO electrolyte has poor ionic conductivity at ambient temperature (10-7 to 10-6S/cm at room temperature). Crown ethers, the macrocycles composed of ethylene oxide, also attract attention for SPEs. Even though the monomer is the same (ethylene oxide) for both PEO and Crown ethers, the properties of each complex are different. Crown ether electrolyte shows higher ionic conductivity than PEO electrolyte at ambient temperature, it is assumed that the crown ether electrolyte is an amorphous phase while PEO electrolyte has high crystallinity below the melting point (60~80%). Crown ether is also promising for Li metal batteries. Crown ether is the hosting material that has a preorganized acceptor structure (also well-known as macrocyclic effect), therefore it can adjust kinetics of reduction on the surface of Li metal anode. Even though promising abilities of crown ether electrolytes have been reported, their ion conduction mechanisms are yet understood well. Therefore, it is worth studying about complex structure and ion conduction mechanism of crown ether electrolyte for a better understanding of SPE, and further, it can be a milestone to design new SPEs. To understand the complex structure and ion conduction mechanism in crown ether electrolytes, we performed both experimental and theoretical analysis. We synthesized the complexes of different sizes of crown ethers (12-crown-4, 15-crown-5, and 18-crown-6) and Li salts (LiTFSI, LiClO4, LiBF4, and LiI). The complexes are characterized by Fourier transformed infrared (FTIR), X-ray diffraction (XRD), nuclear magnetic resonance (NMR), thermal gravimetric analysis (TGA), and AC impedance analysis. DFT calculation and molecular dynamics for each complex were performed to obtain an atomistic description of the complexes.

In-situ polymerized acrylate-based polymers are very appealing as solid polymer electrolytes (SPEs) in lithium (Li) batteries due to the drop-in compatibility of such in-situ polymerization with conventional battery production, the ease of acrylate polymerization and their inexpensive, facile SPE chemistry. We identified, however, that such SPEs suffer from either a low cationic transference number with dual ion conducting salts (0.12-0.2) or a low ionic conductivity with single Li-ion conducting (SLIC) salts (6·10-6 S cm-1). In this project we overcame these limitations and developed significantly improved SPE with ionic conductivity of up to 2·10-4 Scm-1 and a relatively high Li-ion transference number of 0.4. With a significantly reduced fraction of mobile anions in the hybrid SPE, in-situ polymerized SPE cells with an LiFePO4 (LFP) cathode achieve a stable performance for over 100 cycles at temperatures as high as 100 °C, which is unattainable with conventional Li salts or electrolytes. Furthermore, the motional narrowing observed in the line-shapes of solid-state nuclear magnetic resonance (SS-NMR) spectra provided additional insights of the differences in Li nucleus environments and revealed a reduced activation energy for the hybrid salt SPEs due to their more open structure. This study opens the path for the fabrication of high-performance solid polymer lithium batteries capable of operating at high temperatures using commercial battery fabrication equipment. We expect that further tuning of the acrylate based SPE composition may allow further increases in its conductivity without sacrifices in its electrochemical stability or mechanical properties.

Low room temperature ionic conductivity and interfacial incompatibility are the key factors that hinder the practical application of solid polymer electrolyte (SPEs) in lithium metal batteries. Increasing the ability of the SPEs to dissolve and dissociate lithium salt is helpful to enhance ion transport capacity of the SPEs. Herein, ketone groups with high solubility and dissociation ability of lithium salt are introduced into the structural design of SPE, an aliphatic ketone solid polymer electrolyte (KT@SPE) with crosslinking structure is prepared by ultraviolet (UV) polymerization. The prepared KT@SPE shows excellent viscoelastic and possess room temperature ionic conductivity of 10 −4 S cm −1 with 200 wt% lithium bis((trifluoromethyl)sulfonyl)azanide (LiTFSI). Thanks to the contribution of high ion transport capacity, construction of multi‐hydrogen bonds network structure of KT@SPE and a wettability of controlling residual dimethyl sulfoxide (DMSO) solvent to the interface, the assembled symmetrical Li cell realizes stable cycling for over 2000 h at 0.15 mA cm −2 . Moreover, LiFePO 4 cell achieves stable long cycle at 5C and enable Li/KT@SPE 3 /LiFe 0.6 Mn 0.4 PO 4 cell operates at 4.4 V. This work not only provides a design strategy for preparing novel solid polymer electrolytes, but also exhibits the excellent application potential of aliphatic ketone‐based polymer electrolyte in solid‐state lithium batteries at high current density and high voltage.

Playing with ionic liquids to uncover novel polymer electrolytes

Jeffamine® based polymers as highly conductive polymer electrolytes and cathode binder materials for battery application