Summary The effects of solvent absorption on the electrochemical and mechanical properties of polymer electrolytes for use in solid-state batteries have been measured by researchers since the 1980s. These studies have shown that small amounts of absorbed solvent may increase ion mobility and decrease crystallinity in these materials. Even though many polymers and lithium salts are hygroscopic, the solvent content of these materials is rarely reported. As ppm-level solvent content may have important consequences for the lithium conductivity and crystallinity of these electrolytes, more widespread reporting is recommended. Here we illustrate that ppm-level solvent content can significantly increase ion mobility, and therefore the reported performance, in solid polymer electrolytes. Additionally, the impact of absorbed solvents on other battery components has not been widely investigated in all-solid-state battery systems. Therefore, comparisons will be made with systems that use liquid electrolytes to better understand the consequences of absorbed solvents on electrode performance.
With the ever-growing energy storage notably due to the electric vehicle market expansion and stationary applications, one of the challenges of lithium batteries lies in the cost and environmental impacts of their manufacture. The main process employed is the solvent-casting method, based on a slurry casted onto a current collector. The disadvantages of this technique include the use of toxic and costly solvents as well as significant quantity of energy required for solvent evaporation and recycling. A solvent-free manufacturing method would represent significant progress in the development of cost-effective and environmentally friendly lithium-ion and lithium metal batteries. This review provides an overview of solvent-free processes used to make solid polymer electrolytes and composite electrodes. Two methods can be described: heat-based (hot-pressing, melt processing, dissolution into melted polymer, the incorporation of melted polymer into particles) and spray-based (electrospray deposition or high-pressure deposition). Heat-based processes are used for solid electrolyte and electrode manufacturing, while spray-based processes are only used for electrode processing. Amongst these techniques, hot-pressing and melt processing were revealed to be the most used alternatives for both polymer-based electrolytes and electrodes. These two techniques are versatile and can be used in the processing of fillers with a wide range of morphologies and loadings.
Solid-state NMR spectroscopy is an established experimental technique which is used for the characterization of structural and dynamic properties of materials in their native state. Many types of solid-state NMR experiments have been used to characterize both lithium-based and sodium-based solid polymer and polymer–ceramic hybrid electrolyte materials. This review describes several solid-state NMR experiments that are commonly employed in the analysis of these systems: pulse field gradient NMR, electrophoretic NMR, variable temperature T1 relaxation, T2 relaxation and linewidth analysis, exchange spectroscopy, cross polarization, Rotational Echo Double Resonance, and isotope enrichment. In this review, each technique is introduced with a short description of the pulse sequence, and examples of experiments that have been performed in real solid-state polymer and/or hybrid electrolyte systems are provided. The results and conclusions of these experiments are discussed to inform readers of the strengths and weaknesses of each technique when applied to polymer and hybrid electrolyte systems. It is anticipated that this review may be used to aid in the selection of solid-state NMR experiments for the analysis of these systems.
Silicone polymers possess very unusual properties when compared to organic polymers. The addition of grafted boronic acid groups allows for elastomeric film formation through self-association and enhances compatibility with biological systems by increasing elastomer miscibility with aqueous systems, pH tunability, and the ability to bind to saccharides. Boronic acid dimerization was reported to be the origin of cross-linking in silicone boronic acids, but the boron environments involved in this process remain poorly understood. Solid state 11B NMR was used to investigate the boron coordination environments in these materials. 11B quadrupolar line shape fitting, a method previously used to characterize minerals and amorphous glasses, revealed structural information, including coordination number and coordination sphere symmetry. Chain extension in these materials was attributed to hydrogen bonding between boronic acids and could be identified by the presence of three-coordinate boron sites. Cross-linking between boronic acid sites through four-coordinate, dative bonded boron centers was found to be the origin of elastomer formation; the oxygen Lewis bases on the silicone backbone do not appear to play a role. The proportion of boronic acid in the material and location of the boronic acid sitestelechelic versus pendantboth impacted cross-linking in these materials.
Polymer blends have emerged as promising candidates for solid polymer electrolytes (SPEs) in lithium batteries as dry blending polymers allow the benefits of each polymer to be easily combined. However, mixing polymers with different ionic transport properties can complicate the understanding of ion transport mechanisms in the blended material. Indeed, in polymer blends, the contribution of each component to ionic transport differs considerably. This paper presents a systematic study of the salt dissociation ability of polar functional groups in various polymer blends. The blends presented here were obtained through dry processing, which allows the effect of solvents on salt/polymer interactions to be neglected. The studied polymers, which are commonly used to produce SPEs, were selected based on their polar functional groups: PEO (ether), PCL (ester), PPC (carbonate), PVA (alcohol), HNBR (nitrile), and PVP (amide). Given the combined EDX, 7 Li NMR, and FTIR results, a ranking of the lithium salt solvating ability of these polymers as a function of their polar functional groups has been made. This study also provides valuable information that contributes to increase comprehension of ionic transport in SPEs.
Solid-state magic angle spinning (MAS) NMR was used to investigate changes in proton dynamics in phosphate solid acids that exhibited increased proton conductivity between room temperature and 110 °C. Double quantum dipolar recoupling methods were used to quantify site-specific changes in proton−proton dipolar coupling as a function of temperature. The static dipolar coupling and motionally induced changes to it were compared. This was accomplished by calculating (from crystal structures) and measuring (from the initial parts of the DQ recoupling curves) the root-sum-square of the dipolar coupling, a geometry-independent measure of dipolar coupling strength referred to as the "apparent dipolar coupling", D app . The analysis of KH 2 PO 4 and RbH 2 PO 4 showed that the experimentally determined apparent dipolar couplings were reduced from the calculated values at increased temperatures in dynamic systems. Higher proton conductivity was associated with greater reduction of the apparent dipolar coupling as measured by dipolar recoupling NMR methods. Most interestingly, in its monoclinic phase, RbH 2 PO 4 has two chemically distinct proton environments, one disordered and one ordered, which are resolved by 1 H MAS NMR. These sites exhibit different dipolar coupling responses as a function of temperature, revealing that proton conduction in this temperature range arises from motions involving only one of the sites. This site-specific dynamics is measured directly for the first time, using a combination of MAS to resolve the 1 H sites and dipolar recoupling experiments to probe the temperature dependence of the 1 H− 1 H dipolar interactions.
Despite their high conductivity, factors such as being fragile enough to face processing issues and interfacial incompatibility with lithium electrodes are some of the main drawbacks hindering the commercialization of inorganic (mainly oxide-based) solid electrolytes for use in all-solid-state lithium batteries. To this end, strategies such as the addition of solid polymer electrolytes have been proposed to improve the electrode−electrolyte interface. Hybrid electrolytes, which are usually composed of ceramic particles dispersed in a polymer, generally have a better affinity with electrodes and higher ionic conductivity than pure inorganic electrolytes. However, a significant downside of this strategy is that differences in lithium transportability between electrolyte layers can result in the formation of a high interfacial energy barrier across the cell. One strategy to ensure sufficient "wetting" of ceramics is to incorporate a liquid electrolyte directly into the solid inorganic electrolyte resulting in the formation of a hybrid liquid−ceramic electrolyte. To this end, liquid−ceramic hybrid electrolytes were prepared by adding LiG 4 TFSI, a solvate ionic liquid (SIL), to garnet, NASICON, and perovskite-type ceramic electrolytes. Although SIL addition resulted in increased ionic conductivity, comparisons between the pure SIL and the hybrid systems revealed that improvements were due to the SIL alone. A thorough investigation of the hybrid systems by solid-state nuclear magnetic resonance (NMR) revealed little to no lithium exchange between the ceramic and the SIL. This confirms that lithium conductivity preferentially occurs through the SIL in these hybrid systems. The primary role of the ceramic is to provide mechanical strength.
Solid polymer electrolytes have been widely proposed for use in all solid-state lithium batteries. Advantages of polymer electrolytes over liquid and ceramic electrolytes include their flexibility, tunability and easy processability. An additional benefit of using some types of polymers for electrolytes is that they can be processed without the use of solvents. An example of polymers that are compatible with solvent-free processing is epoxide-containing precursors that can form films via the lithium salt-catalyzed epoxide ring opening polymerization reaction. Many polymers with epoxide functional groups are liquid under ambient conditions and can be used to directly dissolve lithium salts, allowing the reaction to be performed in a single reaction vessel under mild conditions. The existence of a variety of epoxide-containing polymers opens the possibility for significant customization of the resultant films. This review discusses several varieties of epoxide-based polymer electrolytes (polyethylene, silicone-based, amine and plasticizer-containing) and to compare them based on their thermal and electrochemical properties.
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