Helical Covalent Polymers with Unidirectional Ion Channels as Single Lithium-Ion Conducting Electrolytes

Open AccessCCS ChemistryCOMMUNICATION1 Dec 2021Helical Covalent Polymers with Unidirectional Ion Channels as Single Lithium-Ion Conducting Electrolytes Yiming Hu, Nathan Dunlap, Hai Long, Hongxuan Chen, Lacey J. Wayment, Michael Ortiz, Yinghua Jin, Abdulrahiman Nijamudheen, Jose L. Mendoza-Cortes, Se-hee Lee and Wei Zhang Hu Department of Chemistry, University Colorado Boulder, CO 80309 Google Scholar More articles by this author , Dunlap Mechanical Engineering, Long National Renewable Energy Laboratory, Golden, 80401 Chen Wayment Ortiz Jin Nijamudheen Chemical Engineering Materials Science, Michigan State University, East Lansing, MI 48824 Mendoza-Cortes *Corresponding authors: E-mail Address: [email protected] https://doi.org/10.31635/ccschem.021.202101257 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Single-ion conducting polymer electrolytes have attracted great attention safe alternatives liquid in high energy density lithium-ion batteries. Herein, we report the first example a crystalline anionic helical single solid electrolyte (SPE). Single-crystal X-ray analysis shows that folds into densely packed double helices, bundles unidirectional negatively charged channels formed can facilitate transportation. Such covalent ( HCP) exhibits excellent room temperature conductivity (1.2 × 10−3 S·cm−1) absence external lithium salts, transference number (0.84), low activation (0.14 eV), wide electrochemical stability window (0.2–5 V). We found nonflammable, nonvolatile ionic serve solvating medium enhancer (>1000 times increase). These ion-conducting properties are comparable best polyethylene oxide-based mixed salts. Finally, show solvated HCP SPE enables reversible cycling an all-solid-state cell prepared high-voltage NMC 811 cathode. Our study opens up new possibilities for developing next-generation high-performance solid-state electrolytes. Download figure PowerPoint Introduction Lithium-ion batteries power majority world’s portable electronics our daily life, from phones laptops. However, current flammable used raise potential safety concerns due problems overheating leakage. Solid-state overcome most issues associated Recently, (SPEs) composed salts matrix their structural tunability, mechanical strength, light weight, flexibility.1 So far, SPEs doped Li neutral [e.g., oxide (PEO)], which both cations anions migrate contribute measured conductivity.2 In such dual-ion systems, Li-ion (Li-ion conductivity/overall 100%) is generally below 50%, limiting charge discharge rates output battery.3–5 One way immobilize only allow cation mobility covalently attach backbones. (SICPEs) immobilized provide (>0.7) reduce buildup ion concentration gradients dendrites growth, thus greatly enhancing efficiency lifetime.6–9 SICPEs mostly been attaching side groups backbone polymers.10 Most amorphous, diffusion migration assisted segmental motion at above Tg. Although presence domains some (e.g., PEO6:LiXF6) has reported transport improve conductivity,11,12 there very few examples SICPEs, synthetic challenge obtaining materials.13–16 linear efficient SICPE. Similar PEO-based electrolytes, contains coordinating centers along structure. unlike PEO, forming columnar channels, efficiently cations. 1.2 S·cm−1, value eV atom−1), Importantly, it good chemical compatibility metal ultimately enabled cathode [NMC = Lithium Nickel Manganese Cobalt Oxide (LiNi0.8Co0.1Mn0.1O2)]. The additional advantages HCP-based include stability, well-defined pore structures. study, time, reveals formation polymer, provides interesting direction future design highly SICPEs. Results Discussion Spiroborates unique be reversibly through condensation diols boronic acids yet resistant hydrolysis stable water, methanol, even alkaline solutions.17,18 Owing nature, spiroborate linkages applied dynamic assembly multianionic discrete structures, macrocycles cages,17,19–21 shown applications electrolytes,22 sensors,23,24 catalysts,25 hosts molecules or ions.26–28 Previously, developed method prepare alkyl borate-linked organic frameworks (ICOFs) (Scheme 1).16 It delocalization borate performance stabilities.29 Gaussian 1630 perform functional theory (DFT) geometry optimization two structures Scheme 1 B3LYP method,31 6-311++G(2d,p) basis set, polarizable continuum model (PCM) solvation model32 acetonitrile solvents. Li+ binding obtained comparing energies between Li+-complex structure individual complex Li+. calculated “previous work” “this 12.1 6.2 kcal/mol, respectively, validating assumption better conjugation would weaken interaction BO4− Therefore, work, selected 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) large conjugated aromatic system multi-diol monomer 1). envisioned if negative charges delocalized surrounding conjugate tight pairs suppressed, enhance conductivity. HHTP B(OMe)3 LiOH provided (Figures 1a 1b). structure, conformation, packing mode were unambiguously determined single-crystal diffraction discrepancy factor R 10.71%.33 | Alkyl aryl clearly conformation tubular channels. Each wall square-shaped channel consists linearly aligned axis every 15.2 Å, providing located center rigid note each reacted, unreacted diol multiple hydrogen bonds neighboring strand, array helices bonding interactions, crystal showed various solvents water. crude was washed open air amount benchtop solvents, methylene chloride, acetone, tetrahydrofuran (THF). product also survive heated conditions long time (Soxhlet extraction THF 2 days). Unlike polymers linked esters prone hydrolysis, showing similar powder (PXRD) measurements after soaking water 48 h.33 thermal <5% weight loss 300 °C according thermogravimetric (TGA) results Supporting Information Figure S1). PXRD patterns as-synthesized bulk materials match simulation well based on S2), indicating sample same crystal. scanning electron microscopy (SEM) image cuboid-shaped crystals shape S3). Synthesis its structure: Top view (a) (b) internal cavity HCP. Two chains colored green brown, blue. one-dimensional (1D) dense packing, suggest excel lightweight single-ion electrolyte. examined. Prior testing, vacuum-dried overnight 120 °C. Electrochemical performed pellets pressed within custom 13 mm diameter dies While dry modest conductor, increased several orders magnitude upon PYR13FSI (IL) bis(fluorosulfonyl)imide (FSI−) N-propyl-N-methylpyrrolidinium (PYR13+) salt/PYR13FSI mixture capable interfaces (SEIs) variety electrode batteries.34 never medium. Before testing HCP, one drop deposited onto pellet allowed soak approximately h. impedance spectroscopy (EIS) measure Nyquist plots 2a steep spike characteristic frequency capacitive nature conformal blocking electrodes. A room-temperature S·cm−1 measured, reported35 nearly order higher than materials.36 should noted significantly ICOF (3.05 10−5 S cm−1) consisting spiroborates,16 supporting notion aryl-spiroborate anion interactions weakened system, leading enhanced Due semicircles, typical plots, could not captured under range experiment. contributions ohmic, grain boundary, resistance differentiated. all included determining overall IL: EIS over temperatures. Arrhenius plot function temperature. (c) using BVE technique. (d) Impedance before measurement. framework (COF) microcrystalline powders mass fractions (>30%) polymeric binders freestanding cast films.37 these composites mechanically robust, uneven distribution COF impacts movement ions films. Thick coatings resistive act like roadblocks diffusing ions, restricting By pressing binder-free sample, ensure conduction pathways 1D intrinsic remain unimpeded ions. When polyvinylidene fluoride (PVDF) binder, HCP/PVDF composite 10% identical S7). To knowledge, demonstrates enhancement pure IL. no dissolved therefore expected directly crystals. Instead, dielectric constant promote dissociation loosely bound backbone, allowing them quickly direction. IL, constituting 20 wt % mass, enough achieve maximum This much lower loading studies conductors more heavily researched commonly call solvent loadings exceeding 90 %.3,4,35,38 Large additions additives integrity lead electrochemical, thermal, instabilities. just retain crystallinity S2) S5. inflammability, volatility, negligible vapor pressure, represent significant further demonstrate effect IL electrolyte, tested propylene carbonate (PC) PYR14TFSI plasticizers. test when PC added, 5.6 cm−1, whereas 1.0 cm−1 obtained, observed PYR13FSI-soaked Figures S6 S8). support boosting conductivity, likely general. 2b displays (Arrhenius) relationship, indicates decoupled skeleton. uncommon attributed uniquely ordered included, display nonlinear elevated temperatures, phenomenon closely approximated well-known Vogel–Tammann–Fulcher (VTF) equation. 5,39 suggests mechanism hopping lattice sites inorganic rather simply dissolving remarkably 0.14 atom−1 best-performing previously electrolytes.40 conventional polar solvent, mobile anions. poor average numbers cause polarization permanently wall; prohibited. 0.84 Bruce–Vincent–Evans (BVE) 2c 2d). close unity represents improvement compared ILs typically 0.2 0.5.3–5 evidence added primary source conduction. Rather, solvates reducing energy, loosening faster HCP’s atomically precise cyclic voltammogram (Figure 3a) stability. No flow corresponding decomposition 5 V. Only cathodic anodic currents deposition (Li+ + e− → Li) stripping (Li e−) near 0 V versus Li, capability surface morphology investigated ex situ SEM S4). smooth 10 cycles plating, ability enable uniform, dendrite-free plating. Linear sweep voltammograms remaining S9) they fairly ∼5 sloping profile 6 powders. Above V, observed, breakdown lithium, reported.41 high-voltage, high-power materials. 3 Cyclic Ti/HCP/Li cell. Cycling symmetric Li/HCP/Li cycled 0.1 mA cm−2. data LiIn/HCP/NMC battery. Corresponding voltage (solid line: charge; dash discharge). effective Li/ HCP/Li >150 galvanostatic deposition/stripping 150 h 3b). cell’s confirms metallic lithium. estimated direct (DC) measurements. material prove useful next generation Li-metal batteries, promises densities beyond theoretical achievable todays cells. electrolyte’s 3c). battery assembled fashion 60 rate C 50 cycles. Upon charge, achieved active specific capacity >260 mAh/g, limit (200 mAh/g). 3d) extra originates (∼2.6 V) charging event usually layered unexpected assembly, momentarily short-circuited, resulting self-discharge overlithiation cathode’s overlithiated plateau accounts ∼50 mAh/g (NMC 811) cell, outlined literature.42,43 discharging, 57.8% initial reversible, but irreversible excluded, Coulombic approach 75%. With continued cycling, stabilized ∼120 efficiencies >98% four preliminary indicate fact modern nickel-rich materials, although work needed optimize particular system. facile prolonged Despite irreversibility capacity, achieves Further construction composition widening ∼4.5 will certainly improved first-cycle respectively. Nonetheless, present Conclusion counter cations, conducing For introduce charges, form loose assist Solvation small quantity allows Li-conductivity (room while robust electrochemically Li+/Li. superior mainly pathway aryl-spiroborate/lithium pairs. demonstrating use polymer. outstanding combined electrolyte–IL demonstrated extended, plating/stripping accompanied ex-situ electrode. practical conclusively Ni-rich designing fabricating lightweight, stable, ion-conductive lithium-metal applications. available includes experimental methods, characterization (TGA, PXRD, SEM), figures, results. Conflict Interest There conflict interest report. Funding supported Boulder. 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