Cellulose nanofiber-reinforced solid polymer electrolytes with high ionic conductivity for lithium batteries.

Lithium-metal electrodes are promising for developing next-generation lithium-based batteries with high energy densities. However, their implementation is severely limited by dendritic growth during battery cycling, which eventually short-circuits the battery. Replacing conventional liquid electrolytes with solid polymer electrolytes (SPEs) can suppress dendritic growth. Unfortunately, in SPEs the high stiffness required for suppressing dendrites comes at the expense of efficient lithium-ion transport. Some polymer-based composite electrolytes, however, enable the decoupling of stiffness and ionic conductivity. This study introduces a composite SPE comprised of a relatively soft poly(ethylene oxide-co-epichlorohydrin) (EO-co-EPI) statistical copolymer with high ionic conductivity and cellulose nanofibers (CNFs), a filler with extraordinary stiffness sourced from abundant cellulose. CNF-reinforcement of EO-co-EPI increases the storage modulus up to three orders of magnitude while essentially maintaining the SPE's high ionic conductivity. The composite SPE exhibits good cycling ability and electrochemical stability, demonstrating its utility in lithium metal batteries.

Task-Specific Phosphonium Iongels by Fast UV-Photopolymerization for Solid-State Sodium Metal Batteries.

Sodium metal batteries are an emerging technology that shows promise in terms of materials availability with respect to lithium batteries. Solid electrolytes are needed to tackle the safety issues related to sodium metal. In this work, a simple method to prepare a mechanically robust and efficient soft solid electrolyte for sodium batteries is demonstrated. A task-specific iongel electrolyte was prepared by combining in a simple process the excellent performance of sodium metal electrodes of an ionic liquid electrolyte and the mechanical properties of polymers. The iongel was synthesized by fast (<1 min) UV photopolymerization of poly(ethylene glycol) diacrylate (PEGDA) in the presence of a saturated 42%mol solution of sodium bis(fluorosulfonyl)imide (NaFSI) in trimethyl iso-butyl phosphonium bis(fluorosulfonyl)imide (P111i4FSI). The resulting soft solid electrolytes showed high ionic conductivity at room temperature (≥10−3 S cm−1) and tunable storage modulus (104−107 Pa). Iongel with the best ionic conductivity and good mechanical properties (Iongel10) showed excellent battery performance: Na/iongel/NaFePO4 full cells delivered a high specific capacity of 140 mAh g−1 at 0.1 C and 120 mAh g−1 at 1 C with good capacity retention after 30 cycles.

Polymer-templated mesoporous lithium titanate microspheres for high-performance lithium batteries.

The spinel Li4Ti5O12 (LTO) is a promising lithium ion battery anode material with the potential to supplement graphite as an industry standard, but its low electrical conductivity and Li-ion diffusivity need to be overcome. Here, mesoporous LTO microspheres with carbon-coatings were formed by phase separation of a homopolymer from microphase-separated block copolymers of varying molar masses containing sol-gel precursors. Upon heating the composite underwent a sol-gel condensation reaction followed by the eventual pyrolysis of the polymer templates. The optimised mesoporous LTO microspheres demonstrated an excellent electrochemical performance with an excellent specific discharge capacity of 164 mA h g-1, 95% of which was retained after 1000 cycles at a C-rate of 10.

Single-Ion Conducting Polymer Nanoparticles as Functional Fillers for Solid Electrolytes in Lithium Metal Batteries.

Composite solid electrolytes including inorganic nanoparticles or nanofibers which improve the performance of polymer electrolytes due to their superior mechanical, ionic conductivity, or lithium transference number are actively being researched for applications in lithium metal batteries. However, inorganic nanoparticles present limitations such as tedious surface functionalization and agglomeration issues and poor homogeneity at high concentrations in polymer matrixes. In this work, we report on polymer nanoparticles with a lithium sulfonamide surface functionality (LiPNP) for application as electrolytes in lithium metal batteries. The particles are prepared by semibatch emulsion polymerization, an easily up-scalable technique. LiPNPs are used to prepare two different families of particle-reinforced solid electrolytes. When mixed with poly(ethylene oxide) and lithium bis(trifluoromethane)sulfonimide (LiTFSI/PEO), the particles invoke a significant stiffening effect (E' > 106 Pa vs 105 Pa at 80 °C) while the membranes retain high ionic conductivity (σ = 6.6 × 10-4 S cm-1). Preliminary testing in LiFePO4 lithium metal cells showed promising performance of the PEO nanocomposite electrolytes. By mixing the particles with propylene carbonate without any additional salt, we obtain true single-ion conducting gel electrolytes, as the lithium sulfonamide surface functionalities are the only sources of lithium ions in the system. The gel electrolytes are mechanically robust (up to G' = 106 Pa) and show ionic conductivity up to 10-4 S cm-1. Finally, the PC nanocomposite electrolytes were tested in symmetrical lithium cells. Our findings suggest that all-polymer nanoparticles could represent a new building block material for solid-state lithium metal battery applications.

Tuning the Properties of a UV-Polymerized, Cross-Linked Solid Polymer Electrolyte for Lithium Batteries.

Lithium metal anodes have been pursued for decades as a way to significantly increase the energy density of lithium-ion batteries. However, safety risks caused by flammable liquid electrolytes and short circuits due to lithium dendrite formation during cell cycling have so far prevented the use of lithium metal in commercial batteries. Solid polymer electrolytes (SPEs) offer a potential solution if their mechanical properties and ionic conductivity can be simultaneously engineered. Here, we introduce a family of SPEs that are scalable and easy to prepare with a photopolymerization process, synthesized from amphiphilic acrylic polymer conetworks based on poly(ethylene glycol), 2-hydroxy-ethylacrylate, norbornyl acrylate, and either lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) or a single-ion polymethacrylate as lithium-ion source. Several conetworks were synthesized and cycled, and their ionic conductivity, mechanical properties, and lithium transference number were characterized. A single-ion-conducting polymer electrolyte shows the best compromise between the different properties and extends the calendar life of the cell.

Spatially Resolved Production of Platinum Nanoparticles in Metallosupramolecular Polymers.

Nanocomposites consisting of a polymer matrix and metallic nanoparticles can merge the functional, structural, and mechanical properties of the two components and are useful for applications that range from catalysis to soft electronics. Gaining spatial control over the nanoparticle incorporation is useful, for example to confine catalytic sites or create electrically conducting pathways. Here, we show that this is possible by the controlled disassembly of a metallosupramolecular polymer containing zerovalent platinum complexes to form nanoparticles in situ. To achieve this, a telechelic poly(ethylene-co-butylene) was end-functionalized with diphenylacetylene ligands and chain-extended through the formation of bis(η2-alkyne)Pt0 complexes. These complexes are stable at ambient conditions, but they can be dissociated upon heating or exposure to ultraviolet light, which allows producing Pt nanoparticles when and where needed and without auxiliary reagents or formation of byproducts. This approach was exploited to create objects with well-defined catalytically active areas.