Lithium Ion Pathway within Li7La3Zr2O12‐Polyethylene Oxide Composite Electrolytes

A polyethylene oxide/metal-organic framework composite solid electrolyte with uniform Li deposition and stability for lithium anode by immobilizing anions

Polyethylene oxide (PEO) based-solid polymer electrolytes were prepared with low weight polymers bearing carboxylic acid groups added onto the polymer backbone, and the variation of the conductivity and performance of the resulting Li ion battery system was examined. The composite solid polymer electrolytes (CSPEs) were composed of PEO, LiClO4, PAA (polyacrylic acid), PMAA (polymethacrylic acid), and Al2O3. The addition of additives to the PEO matrix enhanced the ionic conductivities of the electrolyte. The composite electrolyte composed of PEO:LiClO4:PAA/PMAA/Li0.3 exhibited a low polarization resistance of 881.5 ohms in its impedance spectra, while the PEO:LiClO4 film showed a high value of 4,592 ohms. The highest ionic conductivity of 9.87 × 10−4 S cm−1 was attained for the electrolyte composed of PEO:LiClO4:PAA/PMAA/Li0.3 at 20 °C. The cyclic voltammogram of Li+ recorded for the cell consisting of the PEO:LiClO4:PAA/PMAA/Li0.3:Al2O3 composite electrolyte exhibited the same diffusion process as that obtained with an ultra-microelectrode. Based on this electrolyte, the applicability of the solid polymer electrolytes to lithium batteries was examined for an Li/SPE/LiNi0.5Co0.5O2 cell.

High energy density of solid-state batteries requires a thin solid electrolyte separator layer (<30 μm), that can sustain high currents and is easily processable. Polymer-ceramic composite electrolytes can potentially fulfill these requirements by combining the advantages of each type. Ceramic electrolytes have high room-temperature ionic conductivity, transference number of one, and mechanical strength to suppress lithium dendrites, whereas polymer electrolytes are easily processable and can form conformable interfaces with the electrodes. High interfacial-impedance between polymer and ceramic electrolytes make the composites with dispersed ceramic particles less attractive.1 A composite electrolyte architecture where a three-dimensionally interconnected porous ceramic is filled with polymer electrolyte, previously reported by our group, can avoid the interfacial impedance issue, although for thin composite membranes, the interfacial impedance between ceramic framework and excess polymer layer on top/bottom surface will still dominate the overall impedance.2 Here we will present fabrication and electrochemical evaluation of ~150 μm thick composite electrolytes with the above-described 3D-interconnected ceramic architecture. The 3-D framework is obtained by partially sintering Ohara ceramic particle tapes obtained via tape casting, which are filled with curable polymer electrolyte precursors. To obtain a thin (5 μm), uniform polymer electrolyte layer on both surfaces, spray coating was employed. The resulting composite membrane exhibited good dendritic resistance in symmetric cell cycling, improved transference number compared to the polymer electrolytes. We also found significantly improved flexibility of the composite electrolytes with plasticization, however, at the cost of reduction in ionic conductivity due to damage to the ceramic network caused by plasticizer-induced swelling of the cross-linked polymer electrolyte. This research was sponsored by the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy for the Vehicle Technologies Office’s Advanced Battery Materials Research Program (Tien Duong, Program Manager). This abstract has been authored by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan). References Chen, X. C.; Liu, X.; Samuthira Pandian, A.; Lou, K.; Delnick, F. M.; Dudney, N. J., Determining and Minimizing Resistance for Ion Transport at the Polymer/Ceramic Electrolyte Interface. ACS Energy Letters 2019, 4 (5), 1080-1085.Palmer, M. J.; Kalnaus, S.; Dixit, M. B.; Westover, A. S.; Hatzell, K. B.; Dudney, N. J.; Chen, X. C., A three-dimensional interconnected polymer/ceramic composite as a thin film solid electrolyte. Energy Storage Materials 2020, 26, 242-249.

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.

The large amount of waste chemical fiber textiles that exists has posed pressure on the sustainable development of the natural environment and of society. Therefore, it is of great importance to increase the added value of waste chemical fiber textiles and expand their applications in other fields. Herein, acrylic yarn from waste clothing is used as the raw material to construct a three-dimensional (3D) acrylic-based ceramic composite nanofiber solid electrolyte. The electrochemical properties of batteries based on this solid electrolyte are also investigated. We found that the fabricated composite electrolyte has good performance in lithium ion conduction and electrochemical stability because of its 3D acrylic-based ceramic composite fiber framework. The introduction of this composite electrolyte to a lithium symmetric battery enabled the battery to circulate stably for 2350 h at 50 °C without short-circuiting. In addition, all-solid-state batteries using a LiFePO4 cathode exhibited high reversible capacity. Lastly, a flexible lithium metal pouch battery was able to operate safely and stably under extreme conditions. This work demonstrates a strategy for upcycling waste textiles into ion-conducting polymers for energy storage applications.

The safety issues concerning conventional Li+ ion batteries (LIBs) are attributed to the use of flammable organic liquid electrolyte (LE), which could result in fire and explosion. To address the safety issues and increase the durability, All-solid-state Li+ ion batteries (ASLBs) using inorganic solid electrolyte (SE) are considered as an ideal alternative for developing safe LIBs. Their wide range of operating temperature, from room temperature to over 90°C, is also an important advantage with regards to energy storage systems.SE can be classified into two types: sulfide-based SEs and oxide-based SEs. First, in the case of sulfide-based SEs, thio-LISICON, and Li-argyrodite are present and these have high ionic conductivity that are comparable to LE . Furthermore, a sulfide-based SE with a polymer electrolyte has been extensively investigated as well. However, one of the major disadvantages of a sulfide-based SE is that it is chemically unstable in air as it reacts with moisture in the air to produce H2S gas, which is a hazardous.On the contrary, oxide- based SEs including garnet, NASICON type may be attractive because they not only have high ionic conductivity but also, are chemically stable in air. Given these aspects, many researchers are devoted to the combination of oxide-based SEs and polymer electrolytes by adding oxide-based SE powders in a polymer matrix, as polymer electrolytes exhibit more suitable mechanical properties than those of ceramics, but show low ionic conductivity at room temperature.The combination of oxide-based SEs and polymers have paved new ways to create better electrolytes which incorporate both the high ionic conductivity of the oxide-based SE and the stable mechanical properties of polymers. In the case of composite electrolytes, many researchers anticipated that the higher the oxide-based SE (herein, ceramic) content in a composite electrolyte, the higher the Li+ ion conduction contribution from the ceramic. To investigate the effect of Li+ ion conduction from ceramic powders, analytical research studies according to the ceramic content have been conducted. Unexpectedly, even if the ratio of ceramic powder is increased, the ceramic’s contribution to Li+ ion conductivity could not be confirmed as there is no path for the Li+ ions to percolate through the ceramic due to high interfacial resistance in the ceramic powders. Furthermore, this ceramic powder acts as a resistor due to high interfacial resistances between the ceramic powder and polymer electrolyte. In this work, scalable and flexible composite electrolyte film (SFCEF) was fabricated based on a fiber-shaped ceramic and polymer support. Ceramic fibers of Li1.3Ti1.7Al0.3(PO4)3 (LATP) were prepared by sintering the precursor-coated sacrificial template and then infiltrated with a polyethylene oxide (PEO) polymer to obtain the FSCEF. The LATP fibers induced continuous Li+ ion channels, allowing the FSCEF to show an ionic conductivity exceeding 10−4 S cm−1 at 60 °C. The synergistic action of the ceramic frameworks and supportive PEO resulted in enhanced mechanical flexibility. Furthermore, the possibility of using a FSCEF in all-solid-state batteries was confirmed by conducting electrochemical performance tests on a Li/FSCEF/LCO (LiCoO2) cell. We expect that the herein reported findings will contribute to the synthesis of thin and flexible solid-state electrolyte films with manufacturing scalability for promising high-voltage all-solid-state batteries.

A review of composite polymer-ceramic electrolytes for lithium batteries

Lithium ion batteries are a crucial technologies for electric vehicles and portable electronics due to their high energy density. However, flammable liquid electrolytes create a safety concern and transitioning to all solid state batteries allows for the potential of higher energy density by utilizing lithium metal anodes. Two classes of solid materials have been explored to replace liquid electrolytes: ceramic and polymer electrolytes. Composite electrolytes, typically in the form of dispersed ceramic particles or nanowires in polymer matrix, combine these two materials to have good ionic conductivity while maintaining the mechanical properties of the polymer. While they have achieved fairly high conductivity (typically 10-4 S/cm), the mechanism for such ion conduction is not well understood.The polymer likely plays a crucial role as the ceramic volume fractions are typically under 20%.1,2 Four possible ways that polymers could increase in conductivity in the composite have been identified: decreased crystallinity, increased free volume, disruption of polymer alignment, and increased lithium ion dissolution due to acidic surface groups on the ceramic.1,3,4 We have developed thin film model systems to probe the interface of the polymer with and ceramic surfaces. We found that when confined to thin films, the conductivity of the polymer electrolyte increased compared to the bulk. We utilized differential scanning calorimetry to identify the crystallinity and found that the small crystallinity variation could not account for the variation in conductivity. Subsequently, we utilized surface conductivity and transference number measurements to understand the effects of acidic surface groups. X-ray Absorption measurements will be similarly utilized to probe the variation in lithium ion environments within these materials to understand any variation in the lithium salt dissolution. It was found that the variation in conductivity based on this effect is small.In order to probe the possible variation in free volume, Small Angle Neutron Scattering will be utilized to quantify the free volume within thin films, bulk polymer, and composite electrolytes. This can quantify the volume associated with each monomer and therefore how much space is between polymer chains for lithium ion movement.5 Lastly, while the polymer chain alignment has not been extensively discussed composite literature, it has been identified that when polymer electrolytes are cast on a surface, polymer electrolytes typically show anisotropy with measurements parallel to the surface having higher conductivity due to the alignment of the chain.6 Therefore, ceramic fillers in the composites may disrupt this packing and allow for higher conductivity perpendicular to the cast surface, the direction in which they are most commonly measured. In order to probe this effect, we measure the anisotropy of both our thin film electrolytes as well as composite electrolytes to compare the significance of the anisotropy and utilize small angle x-ray scattering to measure any anisotropy in the structure.

Single-ion-conducting polymers are ideal electrolytes for rechargeable lithium batteries as they eliminate salt concentration gradients and concomitant concentration overpotentials during battery cycling. Here we study the ionic conductivity and morphology of poly(ethylene oxide)-b-poly(styrenesulfonyllithium(trifluoromethylsulfonyl)imide) (PEO-b-PSLiTFSI) block copolymers with no added salt using ac impedance spectroscopy and small-angle X-ray scattering. The PEO molecular weight was held fixed at 5.0 kg mol–1, and that of PSLiTFSI was varied from 2.0 to 7.5 kg mol–1. The lithium ion concentration and block copolymer composition are intimately coupled in this system. At low temperatures, copolymers with PSLiTFSI block molecular weights ≤4.0 kg mol–1 exhibited microphase separation with crystalline PEO-rich microphases and lithium ions trapped in the form of ionic clusters in the glassy PSLiTFSI-rich microphases. At temperatures above the melting temperature of the PEO microphase, the lithium ions were released from the clusters, and a homogeneous disordered morphology was obtained. The ionic conductivity increased abruptly by several orders of magnitude at this transition. Block copolymers with PSLiTFSI block molecular weights ≥5.4 kg mol–1 were disordered at all temperatures, and the ionic conductivity was a smooth function of temperature. The transference numbers of these copolymers varied from 0.87 to 0.99. The relationship between ion transport and molecular structure in single-ion-conducting block copolymer electrolytes is qualitatively different from the well-studied case of block copolymers with added salt.

Synergistically enhanced roles based on 1D ceramic nanowire and 3D nanostructured polymer frameworks for composite electrolytes

In solid-state lithium-ion batteries, composite polymer-ceramic electrolytes (CPEs) of poly(ethylene oxide) (PEO) and nanosized Li6.4La3Zr1.4Ta0.6O12 (LLZTO) particles combine polymer-like flexibility and processability with significantly enhanced ionic conductivity and electrochemical stability from the ceramic filler, forming a promising electrolyte system. However, the poor interfacial compatibility between LLZTO and PEO leads to inhomogeneous filler distribution during electrolyte preparation, compromising both interfacial stability and discharge capacity in solid-state batteries. To address this, we developed an effective modification approach involving PEG-functionalized LLZTO through ultrasonic-assisted solution processing, followed by composite electrolyte fabrication with PEO. This method significantly improves LLZTO dispersion homogeneity within the polymer matrix. The optimized CPEs demonstrate superior electrochemical performance, including high ionic conductivity (∼1.0 × 10–4 S cm–1 at 25 °C), exceptional electrochemical stability (up to 5.24 V vs Li+/Li), and excellent interfacial compatibility with lithium metal anodes. Consequently, the assembled Li//CPE//LiFePO4 all-solid-state batteries deliver a high initial discharge capacity of 147.1 mAh g–1 and outstanding cycling stability with 99.0% capacity retention after 100 cycles at 0.5C (55 °C).

The purpose of this study was to improve the ionic conductivity and physical properties of a polymer electrolyte by complexing it with ceramic particles. First, a polymer/ceramic composite solid electrolyte was prepared by synthesizing a super porous silica aerogel powder and adding it to a slurry containing a polyethylene oxide (PEO)-based polymer electrolyte; then, the electrochemical properties of electrolyte of different compositions were confirmed. PEO and polymethyl methacrylate (PMMA) were copolymerized, the optimum ratio of lithium salt, plasticizer, and silica aerogel was determined, and ion conductivity of the composite electrolyte was improved. When the EO:Li ratio was 10:1, the glass transition temperature was the lowest, and the room-temperature ion conductivity was improved to 3.0 × 10-5 S/cm. As a result of XRD and thermal analysis, it was confirmed that the stability and durability of the electrolyte interface can also be improved by complexation of the polymer electrolyte with ceramic particles.

Effect of NASICON-type LiSnZr(PO4)3 ceramic filler on the ionic conductivity and electrochemical behavior of PVDF based composite electrolyte

Solid-state polymer electrolytes are highly anticipated for next generation lithium ion batteries with enhanced safety and energy density. However, a major disadvantage of polymer electrolytes is their low ionic conductivity at room temperature. In order to enhance the ionic conductivity, here, graphene quantum dots (GQDs) are employed to improve the poly (ethylene oxide) (PEO) based electrolyte. Owing to the increased amorphous areas of PEO and mobility of Li+ , GQDs modified composite polymer electrolytes achieved high ionic conductivity and favorable lithium ion transference numbers. Significantly, the abundant hydroxyl groups and amino groups originated from GQDs can serve as Lewis base sites and interact with lithium ions, thus promoting the dissociation of lithium salts and providing more ion pathways. Moreover, lithium dendrite is suppressed, associated with high transference number, enhanced mechanical properties and steady interface stability. It is further observed that all solid-state lithium batteries assembled with GQDs modified composite polymer electrolytes display excellent rate performance and cycling stability.

The unclear Li+ local environment and Li+ conduction mechanism in solid polymer electrolytes, especially in a ceramic/polymer composite electrolyte, hinder the design and development of a new composite electrolyte. Moreover, both the low room-temperature Li+ conductivity and large interfacial resistance with a metallic lithium anode of a polymer membrane limit its application below a relatively high temperature. Here we have identified the Li+ distribution and Li+ transport mechanism in a composite polymer electrolyte by investigating a new solid poly(ethylene oxide) (PEO)-based NASICON-LiZr2(PO4)3 composite with 7Li relaxation time and 6Li → 7Li trace-exchange NMR measurements. The Li+ population of the two local environments in the composite electrolytes depends on the Li-salt concentration and the amount of ceramic filler. A composite electrolyte with a [EO]/[Li+] ratio n = 10 and 25 wt % LZP filler has a high Li+ conductivity of 1.2 × 10-4 S cm-1 at 30 °C and a low activation energy owing to the additional Li+ in the mobile A2 environment. Moreover, an in situ formed solid electrolyte interphase layer from the reaction between LiZr2(PO4)3 and a metallic lithium anode stabilized the Li/composite-electrolyte interface and reduced the interfacial resistance, which provided a symmetric Li/Li cell and all-solid-state Li/LiFePO4 and Li/LiNi0.8Co0.1Mn0.1O2 cells a good cycling performance at 40 °C.