Single Ion Conductivities Research Articles

A New (Trifluoromethane)Sulfonylimide Single-Ion Conductor with PEG Spacer for All-Solid-State Lithium-Based Batteries

A New (Trifluoromethane)Sulfonylimide Single-Ion Conductor with PEG Spacer for All-Solid-State Lithium-Based Batteries

Supramolecular Crystals based Fast Single Ion Conductor for Long-cycling Solid Zinc Batteries.

The solid polymer electrolytes (SPEs) used in Zn-ion batteries (ZIBs) have low ionic conductivity due to the sluggish dynamics of polymer segments. Thus, only short-range movement of cations is supported, leading to low ionic conductivity and Zn2+ transference (tZn2+). Zn-based supramolecular crystals (ZMCs) have considerable potential for supporting long-distance Zn2+ transport; however, their efficiency in ZIBs has not been explored. The present study developed a ZMC consisting of succinonitrile (SN) and zinc bis(trifluoromethylsulfonyl)imide (Zn(TFSI)2), with a structural formula identified as Zn(TFSI)2SN3. The ZMC has ordered three-dimensional tunnels in the crystalline lattices for ion conduction, providing high ionic conductivities (6.02 × 10-4 S cm-1 at 25 °C and 3.26 × 10-5 S cm-1 at -35 °C) and a high tZn2+ (0.97). We demonstrated that a Zn‖Zn symmetrical battery with ZMCs has long-term cycling stability (1200 h) and a dendrite-free Zn plating/stripping process, even at a high plating areal density of 3 mAh cm-2. The as-fabricated solid-state Zn battery exhibited excellent performance, including high discharge capacity (1.52 mAh cm-2), long-term cycling stability (83.6% capacity retention after 70000 cycles (7 months)), wide temperature adaptability (-30 to 50 °C) and fast charging ability.

Advanced Single-Ion Conducting Block Copolymer Electrolyte for Safer and Less Costly Lithium–Metal Batteries

Advanced Single-Ion Conducting Block Copolymer Electrolyte for Safer and Less Costly Lithium–Metal Batteries

Fabrication of Single-Ion Conductors Based on Liquid Crystal Polymer Network for Quasi-Solid-State Lithium Ion Batteries.

Single-ion conductive polymer electrolytes can improve the safety of lithium ion batteries (LIBs) by increasing the lithium transference number (tLi+) and avoiding the growth of lithium dendrites. Meanwhile, the self-assembled ordered structure of liquid crystal polymer networks (LCNs) can provide specific channels for the ordered transport of Li ions. Herein, single-ion conductive nematic and cholesteric LCN electrolyte membranes (denoted as NLCN-Li and CLCN-Li) were successfully prepared. NLCN-Li was then coated on commercial Celgard 2325 while CLCN-Li was coated on poly(vinylidene fluoride-hexafluoropropylene) film, coupled with plasticizer, to make NLCN-Li/Cel and CLCN-Li/Pv quasi-solid-state electrolyte membranes, respectively. Their electrochemical properties were evaluated, and it was found that they possessed benign thermal stability and electrolyte/electrode compatibility, high tLi+ up to 0.98 and high electrochemical stability window up to 5.2 V. A small amount (0.5M) of extra Li salt added to the plasticizer could improve the ion conductivity from 1.79 × 10-5 to 5.04 × 10-4 S cm-1, while the tLi+ remained 0.85. The assembled LFP|Li batteries also exhibited excellent cycling and rate performances. The orderliness of the LCN layer played an important role in the distribution and movement of Li ions, thereby affecting the Li deposition and growth of Li dendrites. As the first report of nematic and cholesteric LCN single-ion conductors, this work sheds light on the design and fabrication of ordered quasi-solid-state electrolytes for high-performance and safe LIBs.

A Solvent-Free Covalent Organic Framework Single-Ion Conductor Based on Ion–Dipole Interaction for All-Solid-State Lithium Organic Batteries

HighlightsA class of solvent-free covalent organic framework (COF) single-ion conductors (Li-COF@P) has been designed via ion–dipole interaction as opposed to traditional ion–ion interaction, promoting ion dissociation and Li+ migration through directional ionic channels.The Li-COF@P enabled long cycle life (88.3% after 2000 cycles) in all-solid-state Li organic batteries (ASSLOBs) under ambient operating conditions, which outperformed those of previously reported ASSOLBs.This Li-COF@P strategy holds promise as a viable alternative to the currently prevalent inorganic solid electrolytes.

Functional Protective Coatings Based on Polysaccharides and Single-Ion Conducting Polymers for Li Metal Batteries

This work aims to study a protective coating based on cellulose and P(LiMTFSI) single-ion conductor polymer and its effects on Li metal anode stability and reversibility. The strategy used involves the physical mixture of the aforementioned polymers to enhance the electrochemical performance through Li-ion flux homogenization at the Li metal surface, promoting the formation of a dense plating. Single-ion conducting polymers (SICPs) are incorporated due to their beneficial effects such as enhancing lithium ion transport, boosting lithium transference number (𝑡𝐿𝑖 +), and diminishing the effects of concentration polarization, avoiding the initiation and propagation of high surface area lithium (HSAL). Furthermore, a quasi-solid-state Li metal battery system is explored which brings additional advantages over the typically used organic electrolytes. In this sense, during this study we propose using the protective coating based on cellulose and P(LiMTFSI) to tailor an adequate interphase that creates a good adhesion, by taking advantage of the polymers film formation ability, and therefore improving the lifespan and safety of the battery. The coating effectiveness is tested by casting the solution on an activated lithium surface and performing lithium platting/stripping protocols in Li/Li and Li/Cu pouch cells under selected current densities (0.5, 1 and 2 mA/cm2). Complementary electrochemical tests are carried out to study transport, conductivity parameters, and its performance in full cell coupled with LFP cathode. Finally, we analyze the correlation with the physicochemical properties and electrochemical performed based on spectroscopic techniques and microscopy to study the most relevant parameters influencing a high Coulombic Efficiency. Acknowledgments This work has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska – Curie Grant Agreement N° 945357, and co-financing from the Slovenian Research and Innovation Agency (ARIS) is fully acknowledged.

(Invited) Innovating Sustainable, Cost-Effective, and Durable Redox Flow Battery Membranes

In the quest to integrate renewable energy sources like solar and wind into the electric grid efficiently, the development of long-duration energy storage (LDES) systems is paramount. The U.S. Department of Energy's Long Duration Storage Shot initiative is at the forefront of this endeavor, aiming to reduce the costs of grid-scale energy storage by 90% for systems with over 10 hours of operation. A key player in this mission is the non-aqueous redox flow battery (RFB), known for its use of earth-abundant materials and potential to meet these cost-reduction goals. However, the commercial viability of RFBs hinges on the development of high-performance, cost-effective membranes, which are crucial for their functionality and affordability. These membranes' ionic conductivity is vital for the power density of RFBs, while their ion selectivity and solvent uptake greatly influence the batteries' cycle life.Our team has made groundbreaking advancements in membrane technology for non-aqueous flow batteries. We've addressed the challenge of balancing ionic conductivity with mechanical strength in polymer electrolytes. Our findings reveal that enhanced solvent uptake while boosting membrane ionic conductivity, can compromise mechanical integrity. To counter this, we've employed two strategies: selective plasticization of the ion-conductive block in block copolymers and reinforcing the membrane's mechanical strength through hydrogen and ionic bonds with an inorganic scaffold. Significantly, we've also reduced the crossover of redox-active species in our membrane designs, notably decreasing polysulfide species crossover in a Na metal – polysulfide hybrid flow battery. This has led to improved capacity retention, Coulombic efficiency, and extended cycle life compared to traditional porous membranes.Our latest innovations include the development of hydrocarbon single-ion conductors, demonstrating enhanced conductivity and stability. We've also introduced crosslinking chemistry to control solvent uptake more effectively, thus improving ionic conductivity while preserving mechanical strength. Lastly, our pioneering tape casting method for producing ceramic-polymer composite membranes represents a major leap in scalable membrane production, paving the way for the practical application of non-aqueous redox flow batteries in long-duration energy storage. Acknowledgment This research was conducted at Oak Ridge National Laboratory, managed by UT Battelle, LLC, for the U.S. Department of Energy (DOE) and is sponsored by the U.S. Department of Energy through the Energy Storage Program in the Office of Electricity. We acknowledge Dr. Jagjit Nanda SLAC National Accelerator Laboratory for the fruitful discussions.

Lithium Borate Polycarbonates for High-Capacity Solid-State Composite Cathodes.

Improving composite cathode function is key to the success of the solid-state battery. Maximizing attainable cathode capacity and retention requires integrating suitable polymeric binders that retain a sufficiently high ionic conductivity and long-term chemo-mechanical stability of the cathode active material-solid-electrolyte-carbon mixture. Herein, we report block copolymer networks composed of lithium borate polycarbonates and poly(ethylene oxide) that improved the capacity (200 mAh g-1 at 1.75 mA cm-2) and capacity retention (94 % over 300 cycles) of all-solid-state composite cathodes with nickel-rich LiNi0.8Co0.1Mn0.1O2 cathode active material, Li6PS5Cl solid electrolyte, and carbon. Tetrahedral B(OR)2(OH)2 - anions immobilized on the polycarbonate segments provide hydrogen-bonding chain crosslinking and selective Li-counterion conductivity, parameterized by Li-ion transference numbers close to unity (tLi+~0.94). With 90 wt % polycarbonate content and a flexible low glass transition temperature backbone, the single-ion conductors achieved high Li-ion conductivities of 0.2 mS cm-1 at 30 °C. The work should inform future binder design for improving the processability of cathode composites towards commercializing solid-state batteries, and allow use in other cell configurations, such as lithium-sulphur cathode designs.

Fabrication of single-ion conductive quasi-solid-state electrolyte membrane for high-performance lithium-ion batteries

The aim of this work is to develop new quasi-solid-state electrolyte materials for lithium-ion batteries (LIBs) to improve their safety and comprehensive electrochemical performance. Herein, helical mesoporous silica nanofibers were synthesized by a sol–gel method. After grafting lithium salt onto their surfaces, a single-ion conductor (SL) was obtained. Then, using poly(vinylidene fluoride-co-hexafluoropropylene) as the polymer matrix, SL as the filler, a porous composite film was prepared by solution casting method. After soaking organic electrolyte with low concentration Li salt till saturation, one quasi-solid-state electrolyte membrane (PSLE) was achieved. It showed high electrolyte adsorption rate of 660 % and good thermal stability. A high lithium-ion transfer number of 0.85 indicated typical single-ion conductivity. Moreover, a high electrochemical stability window of up to 5.5 V and an ionic conductivity of 2.5 × 10−3 S·cm−1 at 25 °C were gained. The assembled LFP|PSLE|Li battery exhibited excellent rate performance and cycle stability, indicating that the PSLE has great application prospect in solid-state LIBs.

Local charge redistribution enables single ionic conductor for fast charge solid Li battery

Solid polymer electrolytes (SPEs) have been regarded as hopeful candidate electrolyte for solid-state lithium battery. However, the low Li+ transference number and poor interface stability pose great challenges for the high rate capability of SPE. Herein, inspired from the density functional theory (DFT) calculations that local positive charge distribution can be regulated by introducing strong electron-withdrawing groups, which can selectively anchor TFSI−, largely enhance the Li+ transference number. As predicted, the obtained CPE-NO2 deliver a remarkable Li+ transference number of 0.91, equal to a single-ion conductor for Li+, largely high than that of the SPE (0.31), according well with the molecular dynamics (MD) simulations and pyridine complexation experiments. Furthermore, the PEO||Li interfacial stability, flame retardant ability, and mass transfer of Li+ in interface can also be largely enhanced by interfacial by-product, which are fast Li+ conductors according to TOF-SIMS results. Impressively, the Li|CPE-NO2|Li cell exhibit superior cyclability for 2200 h at 0.1 mA cm−2, and the solid LFP|CPE-NO2|Li battery delivers prominent capacity of 127.4 mAh g−1 at a high rate 5 C (12 mins). This work breaks the fast charge limitation of solid lithium battery, and provides a feasible approach for the construction of advanced solid electrolyte.

Analysis of polyanion single ion conductor based on preparation of gel electrolyte for lithium ion battery

Abstract This study achieved efficient preparation of polyanionic single ion conductors by selecting appropriate raw materials and controlling preparation conditions. The results show that the window stability of electrolytic gel with a wide ionic electrochemical conductor is 2-4.5 V and 0.74 lithium ion migration. Lithium iron phosphate battery (LFP) is the positive electrode, lithium metal is the negative electrode, and PVDF-HFP Pampsli ion is the electrolyte. When lithium salt is not added, the rated power of the battery is 125 mah·g-1, and the current density is 2 C. The battery has a range of more than 500 times. In the current high-density 5 C situation, it has a specific capacity of 100 mAh·g-1 and a stable cycling ability of over 300 cycles, while maintaining nearly 100% stable Colomb efficiency.

Kinetic theory of weakly ionized plasma and electrolyte mixtures including Onsager matrix and frequency dispersion effects

AbstractWe summarize the method of hydrodynamic approximation for weakly ionized plasmas developed with Klimontovich in 1962 and give a generalization to many—component systems using Onsagers matrix theory and including dispersion effects. We develop the conductivity theory of complex plasma and electrolyte mixtures based on the model of charged hard spheres with given non‐additive contact distances, including frequency‐dependent electric fields. These generalizations are made with the aim to allow applications to complex natural systems as atmospheric plasmas and seawater. Finally, we give as an example a numerical calculation of the single ion conductivities of a six‐component seawater model.

Ion transport in composites of binary electrolyte and single ion conductor—A chronoamperometry study

Composite electrolytes for lithium batteries typically combine materials with very different mechanical properties and ionic transport mechanisms and the degree to which these two phases affect each other is not well understood. In this work we used numerical simulations and experiments to investigate the transport in composite electrolytes consisting of polyethylene oxide (PEO) with lithium bis-trifluoromethanesulfonimide (LiTFSI) and Li1.3Al0.3Ti1.7(PO4)3 (LATP) lithium ion conducting glass-ceramic particles. In particular we are interested in how the introduction of a single ion conductor (SIC) changes the salt concentration gradients in the polymer electrolyte (PE) under applied potential. To study this, we performed numerical simulations and chronoamperometry experiments in electrolytes with different arrangements of the SIC and PE phases, i.e. layers and particulate composites. The results show that the particulate composites have the highest concentration gradients and take the longest time to reach steady state current. The best arrangement appears to have a layer of SIC impenetrable to anions in the polymer phase within the electrolyte membrane.

Failure mechanisms at the Li anode/solid electrolyte interface during Li stripping

A precipitous increase in the resistance of the Li metal/solid electrolyte interface can occur during the stripping of Li from the electrode. This electrical failure has been typically attributed to the loss of contact associated with the growth of voids in the Li anode at the electrode/electrolyte interface. We first analyse the growth of voids at the electrode/electrolyte interface using a framework that couples the power-law creep deformation of the Li electrode and the flux of Li+ through a single-ion conductor solid electrolyte. We show that a modified Butler-Volmer kinetics where the local interfacial resistance decreases due to dislocations within the creeping Li predicts that voids indeed grow around interfacial sub-micron impurity particles. Consistent with observations that the increase in resistance of interface occurs earlier for thinner electrodes, we predict that the propensity of void growth increases with decreasing electrode thickness, and this is associated with the mechanical constraint imposed by the current collector. However, in contrast to the observations and rather counterintuitively, this analysis predicts that the cell voltage decreases with void growth. Consequently, we investigate an alternative mechanism of contact loss due to the deposition of insulating solute atoms within the Li electrode onto the interface. Predictions of the rising cell voltage using this analysis are in broad agreement with measurements. This leads us to hypothesize that although void growth occurs at the interface it is not the primary mechanism leading to the increase in interface resistance during stripping.

Retarding anion migration for alleviating concentration polarization towards stable polymer lithium-metal batteries

Traditional dual-ion lithium salts have been widely used in solid polymer lithium-metal batteries (LMBs). Nevertheless, concentration polarization caused by uncontrolled migration of free anions has severely caused the growth of lithium dendrites. Although single-ion conductor polymers (SICP) have been developed to reduce concentration polarization, the poor ionic conductivity caused by low carrier concentration limits their application. Herein, a dual-salt quasi-solid polymer electrolyte (QSPE), containing the SICP network as a salt and traditional dual-ion lithium salt, is designed for retarding the movement of free anions and simultaneously providing sufficient effective carriers to alleviate concentration polarization. The dual salt network of this designed QSPE is prepared through in-situ crosslinking copolymerization of SICP monomer, regular ionic conductor, crosslinker with the presence of the dual-ion lithium salt, delivering a high lithium-ion transference number (0.75) and satisfactory ionic conductivity (1.16 × 10−3 S cm−1 at 30 °C). Comprehensive characterizations combined with theoretical calculation demonstrate that polyanions from SICP exerts a potential repulsive effect on the transport of free anions to reduce concentration polarization inhibiting lithium dendrites. As a consequence, the Li||LiFePO4 cell achieves a long-cycle stability for 2000 cycles and a 90% capacity retention at 30 °C. This work provides a new perspective for reducing concentration polarization and simultaneously enabling enough lithium-ions migration for high-performance polymer LMBs.

3D cross-linked POSS-containing borate single ion conductor organic-inorganic hybrid gel electrolytes for dendrite-free lithium metal batteries

At present, lithium (Li) metal has become the most promising anode for the next generation of batteries due to its excellent theoretical capacity and low electrochemical potential. Nevertheless, low lithium-ion transference numbers and poor stability between conventional electrolytes and electrodes limit its development. In this work, a novel three-dimensional cross-linked hybrid borate single ion conductor polymer electrolyte (POSS-BSICP) was constructed by coupling of novel synthesized lithium bis-allylmalonate borate (LiBAMB), poly (ethylene glycol) diacrylate (PEGDA) and vinyl-containing caged poly(sesquisiloxane) (MAPOSS) in the presence of pentaerythritol tetrakis(mercaptoacetate) (PETMP) as cross-linker and PVDF-HFP as support materials through UV-thermal Dual-Curing procedures. As expected, the lithium-ion transference number and electrochemical stability of the hybrid electrolyte membranes improve with the incorporation of MAPOSS. The tLi+ is up to 0.82 and the electrochemical window reaches 5.50 V. The Li/Li cell assembled with the POSS-containing single ion conductor gel polymer electrolytes can be subjected to stripping/plating cycles without short circuit over 2700 h at 0.1 mA cm−2, the peak of the SiO bond at 102.3 eV in the Si 2p spectrum confirms that the POSS participate in the formation of SEI, indicating that the incorporation of MAPOSS could increase the compatibility between the electrolytes and electrode. The Li|POSS-BSICP|LiFePO4 cell exhibits excellent cycle performance with a capacity retention over 90 % after 170 cycles and 82.0 % after 290 cycles at 0.1 C.

Enhanced Ion Conductivity in a Poly(ionic liquid)-Grafted Nanoparticle-Based Single-Ion Conductor

Enhanced Ion Conductivity in a Poly(ionic liquid)-Grafted Nanoparticle-Based Single-Ion Conductor

NaSn2F5 nanocluster composed of nanoparticles with matched lattices induced by dislocations: Accelerated sodium-ion transport via in situ oxidation in solid-state sodium metal battery

Na metal batteries using inorganic solid-state electrolytes (SSEs) have attracted extensive attention due to their superior safety and high energy density. However, their development is plagued by the unclear structural/volumetric evolution of SSEs and the corresponding Na+ migration mechanisms. In this work, NaSn2F5 (NSF) clusters are composed of nanoparticles (NPs) with matched lattices induced by dislocations, which can mitigate the volume swelling/shrinkage of the NPs. NSF behaves like a single ion conductor with a high Na+ transference number (tNa+) of 0.79. Specially, the ionic conductivity (σ) of NSF is increased from 7.64 × 10-6 to 5.42 × 10-5 S cm−1 after partial irreversible oxidation of Sn2+ (0.118 Å) → Sn4+ (0.069 Å) with the shrunk ionic radius during the charge process, giving more spaces for Na+ migration. Furthermore, a poly(acrylonitrile)-NaSn2F5-NaPF6 composite polymer electrolyte (NSF CPE) was fabricated with a σ of 4.13 × 10-4 S cm−1 and a tNa+ of 0.60. The NSF CPE-based symmetric cell can operate over 3000 h due to the couplings between the different components in NSF CPE, which is beneficial for ion transfer and the construction of stable solid electrolyte interface. And the quasi-solid-state Na|NSF CPE|Na3V2(PO4)3 full cell displays excellent electrochemical performance.

In-situ Crosslinked Gel Polymer Electrolytes Based on Ionic Monomers as Charge Carriers for Lithium-Ion Batteries

Abstract In-situ polymerization is a method for fabricating lithium-ion batteries to contain solid or gel electrolytes without major manufacturing changes. Gel polymer electrolytes (GPEs) wherein some polymer in incorporated, decreasing the volume of liquid electrolyte, have been pursued as they may be safer. One challenge with GPEs is reduced ion transport properties. In this work, macromonomers with different chain chemistry and ionic monomers are crosslinked on electrospun polyvinylidene difluoride (PVDF) in the presence of solvents, without conventional salt, to in-situ fabricate GPEs with elevated transference number within coin cells. These GPEs would be single-ion conductors in the case of complete ionic monomer polymerization to the crosslinked network. The effect of chain chemistry and the percentage of macromonomers and ionic monomers in the GPEs on conductivity are investigated. It is found that poly(siloxane) diacrylate (PDMSDA)- and perfluoropolyether tetra-acrylate (PFPETA)-based GPEs outperform the poly(propylene glycol) diacrylate (PPGDA)- and poly(tetrahydrofuran) diacrylate (PTHFDA)-based GPEs in terms of ionic conductivity. The highest ionic conductivity was achieved for a PDMSDA-based GPE at 4.2 × 10-4 S/cm at 23°C. Graphite/NMC-811 full cells prepared with the in-situ polymerized PDMSDA-based GPEs show capacity retention of 82.6% after 100 cycles, albeit with limited electrode utilization due to ion transport limitations.

Solid-State, Single-Ion Conducting, Polymer Blend Electrolytes with Enhanced Li+ Conduction, Electrochemical Stability, and Limiting Current Density

Solid-State, Single-Ion Conducting, Polymer Blend Electrolytes with Enhanced Li⁺ Conduction, Electrochemical Stability, and Limiting Current Density