Cation Transfer Research Articles

Optimizing surface contact area and electrolyte type to develop a more effective rechargeable battery

Rechargeable batteries are playing an increasingly prominent role in our lives due to the ongoing transition from fossil energy sources to green energy. The purpose of this study was to investigate variables that impact the effectiveness of rechargeable batteries. Alkaline (non-rechargeable) and rechargeable batteries share common features that are critical for the operation of a battery. The positive and negative electrodes, also known as the cathode and anode, are where the energy of the battery is stored. The electrolyte is what facilitates the transfer of cations and anions in a battery to generate electricity. Due to the importance of these components, we felt that a systematic investigation examining the surface area of the cathode and anode as well the impact of electrolytes with different properties on battery performance was justified. Utilizing a copper cathode and aluminum anode coupled with a water in salt electrolyte, a model rechargeable battery system was developed to test two hypotheses: a) increasing the contact area between the electrodes and electrolyte would improve battery capacity, and b) more soluble salt-based electrolytes would improve battery capacity. After soaking in an electrolyte solution, the battery was charged and the capacity, starting voltage, and ending voltage of each battery were measured. The results of this study supported our hypothesis that larger anode/cathodes surface areas and more ionic electrolytes such as sodium chloride, potassium chloride and potassium sulfate resulted in superior battery capacity. Incorporating these findings can help maximize the efficiency of commercial rechargeable batteries.

In silico strategy to design an efficient organic photoswitch based on excited-state cation transfer.

A new class of photoswitches and the corresponding elementary photoinduced reaction, the so-called Excited-State Cation Transfer (ESCT), are investigated. This reaction relies on an intramolecular photo-release/photo-complexation of cation: after irradiation, the cation is translocated from a complexation site 1 to a site 2 during the excited state lifetime. Our purpose is thus to develop a computational strategy based on Density Functional theory (DFT) and its time-dependent counterpart (TD-DFT) to improve the different properties of the ESCT photoswitches, namely (i) the ground state complexation constant K, (ii) the excited state complexation constant K*, (iii) the photoejection properties and (iv) the population of the triplet states from a singlet state via intersystem crossing to increase the lifetime of the excited state. In this work, we are interested in optimizing the ESCT properties of a betaine pyridinium chromophore substituted by a 15-aza-5-crown, that was previously shown to efficiently photoeject a Ca2+ cation from the site 1 but no photo-recapture was observed in the site 2 [Aloïse et al., Phys. Chem. Chem. Phys., 2016, 22, 15384]. To this purpose, we have investigated the impact of the modification of the site 1 on the ESCT properties by introducing different substituents (EDG groups, halogen atoms) at different positions. So far, promising systems have been identified but a simultaneous improvement of all the ESCT photoswitches properties has yet not been achieved.

Electrochemical investigations of PVdF-HFP-NaTFSI-[BMPYr][TFSI] polymer-salt-IL electrolyte for Na-rechargeable battery

Sodium-ion batteries (SIBs) are being aggressively pursued for potential use in energy storage systems due to the natural abundance and low cost of sodium. In the present investigation, structural, thermal and electrochemical properties of a ionic liquid based Na-ion conducting polymer-salt-IL electrolytes (IL-NCPEs) formed using copolymer poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP), sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) salt along with IL; 1-butyl-1-methypyrrolidinium bis(trifluoromethanesulfonyl)imide ([BMPYr] [TFSI]) is being reported. The samples were characterized using ionic conductivity, transference number measurement, thermal & electrochemical studies as a function of wt% IL. Incorporated [BMPYr][TFSI]-IL in the NCPE (i.e., PVdF-HFP + 10 wt% NaTFSI) modifies the different physicochemical properties such as complex formation, thermal, transport and electrochemical properties. The ionic conductivity of prepared IL-NCPEs has been found to increase with increasing the content of [BMPYr][TFSI]-IL and reaches to a maximum value of ∼0.85 mS/cm (at 30 °C). Also, the temperature dependent ionic conductivity obeys Arrhenius type thermally activated behaviour. For the optimized [BMPYr][TFSI]-IL, compatibility of IL-NCPEs with Na-metal electrode, high total ionic transference number (tionic ∼ 0.98), cationic transference number (tNa+ ∼ 0.31) and wide electrochemical stability (ESW ∼ 4.0 V) have been obtained. The above obtained properties of the prepared IL-NCPEs are promising for application in Na-rechargeable battery.

Effective Ion Charges in Ion Exchangers and Electrolyte Solutions

Structures, effective numbers of charges and molecular orbitals of ion pairs and representative fragments of a sulfocation exchanger in various ionic forms were calculated by the non-empirical quantum chemical method of LCAO MO. The effective charges of ions in accordance with the principles of the molecular orbital method were fractional values. For contact ion pairs, where the effective ion charges were experimentally measured by X-ray absorption spectroscopy, we obtained full agreement with the calculated values. The charge numbers of cations and anions differed in both hydrate-separated and ion-exchange systems due to the fact that the oxygen atoms of hydrated water molecules influenced the formation of molecular orbitals. According to the obtained values of the numbers of charges and interionic distances, the energies of the electrostatic interaction of ions were calculated using the integral form of Coulomb's law. Experimental values of the energies of chemical bonds of counterions and fixed ions were obtained using the conductometric contact-difference method when measuring the specific electrical conductivity of MK-40 cation exchange membranes in the range of 20-50oC and according to the Arrhenius equation. The coordination of experimental and calculated chemical bond energies in the ion exchanger was achieved after the addition of hydrogen bond energy to the electrostatic interaction energy. In order to be able to completely nonempirically calculate the energies of chemical bonds in an ion exchanger, we took the value of the hydrogen bond energy as the excitation energy of the first energy level of deformation vibrations of water molecules having a value of 19.4 kJ/mol. A comparison of the contribution of the electrostatic interaction to the total binding energy of alkali metal cations with a fixed ion showed its small role in ion exchange and membrane transport, so that in the first approximation we can say that the transfer of alkali metal cations is determined by the breaking of the hydrogen bond. For cations of a larger charge (calcium), the electrostatic energy already makes a significant contribution, and for trivalent ions, the energies of the Coulomb interaction and hydrogen bonding are close to each other. The soliton mechanism of translation of the energy of deformation vibrations along a chain of water molecules is considered, which allows explaining the decrease in energy when several hydrogen bonds are broken.

Artificial SEI Layer Combined with Single-Ion Polymer Electrolytes to Prevent Dendrite Growth in Lithium Metal Batteries

Li-metal batteries have the potential to become the next generation of batteries since they can provide an increased energy density vs. Li-ion batteries. However, the safety issue caused by the inhomogeneous Li deposition and Li dendrite growth greatly limits their commercial application. Several methods have been proposed to address this issue. On the one hand, when Li ions are released from one electrode and consumed at the other electrode, it causes a salt concentration gradient. Besides, the electrical migration of anions in the opposite direction aggravates the concentration of gradient since anions do not react at the electrodes. Fast dendritic growth then occurs when the current is high enough to fully deplete the Li+ ion at the anode during charge. Thus, suppressing concentration gradient by immobilizing the anions would in principle solve the fast dendritic growth issue. On the other hand, the Solid Electrolyte Interphase (SEI) plays a crucial role in the operation of Li metal batteries since it prevents further reduction and continuous electrolyte reaction. SEI derives from the passivation layer formed onto the surface of Li metal under dry air during lithium foil extrusion and then evolves further in contact with the electrolytes and during subsequent electrochemical Li stripping/plating. The SEI is inhomogeneous and since it contains lower resistance pathways for Li+ transport, it favors inhomogeneous deposition at any current. Thus, SEI engineering, in order to favor the homogeneity of current density and enhanced mechanical properties to confine lithium could, in principle, improve the performance of Li metal batteries.Thus, we studied the use of single-ion conducting polymers with high cationic transference numbers (tLi+ close to 1) as artificial SEIs (art-SEIs) since they include immobile anions and thus prevent Li+ depletion during charge and, at the same time, improve lithium metal confinement and the homogeneity of current density. Our results show much improved homogeneity of Li deposition and cycling stability after single-ion art-SEI coating using an ether-based liquid electrolyte combined with a separator. Nevertheless, it could not enable long-term cycling as the separator does not enable homogeneous pressure and current density onto the lithium anode. Thus, the use of a single-ion conducting solid polymer electrolyte was combined with a single-ion conducting art-SEI (as illustrated in Figure 1). This strategy allows the suppression of salt concentration gradients, inhomogeneous pressure and current density, thus enables homogeneous Li deposition and long-term cycling of Li metal anode. Figure 1

Revealing the Anion-Solvent Interaction for Ultralow Temperature Lithium Metal Batteries.

Anion solvation in electrolytes can largely change the electrochemical performance of the electrolytes, yet has been rarely investigated. Herein, three anions of bis(trifluoromethanesulfonyl)imide (TFSI), bis(fluorosulfonyl)imide (FSI), and derived asymmetric (fluorosulfonyl)(trifluoro-methanesulfonyl)imide (FTFSI) are systematically examined in a weakly Li+ cation solvating solvent of bis(3-fluoropropyl)ether (BFPE). In-situ liquid secondary ion mass spectrometry demonstrates that FTFSI- and FSI- anions are associated with BFPE solvent, while weak TFSI- /BFPE cluster signals are detected. Molecular modeling further reveals that the anion-solvent interaction is accompanied by the formation of H-bonding-like interactions. Anion solvation enhances the Li+ cation transfer number and reduces the organic component in solid electrolyte interphase, which enhances the Li plating/stripping Coulombic efficiency at a low temperature of -30°C from 42.4% in TFSI-based electrolytes to 98.7% in 1.5m LiFTFSI and 97.9% in LiFSI-BFPE electrolytes. The anion-solvent interactions, especially asymmetric anion solvation also accelerate the Li+ desolvation kinetics. The 1.5m LiFTFSI-BFPE electrolyte with strong anion-solvent interaction enables LiNi0.8 Mn0.1 Co0.1 O2 (NMC811)||Li (20µm) full cell with stable cyclability even under -40°C, retaining over 92% of initial capacity (115 mAhg-1 , after 100 cycles). The anion-solvent interactions insights allow to rational design the electrolyte for lithium metal batteries and beyond to achieve high performance.

Comparing Experimentally-Measured Sand’s Times with Concentrated Solution Theory Predictions in a Polymer Electrolyte

We compare the electrochemically measured Sand’s time, the time required for the cell potential to diverge when the applied current density exceeds the limiting current, with theoretical predictions for a 0.47 M poly(ethylene oxide) (5 kg mol−1)/LiTFSI electrolyte. The theoretical predictions are made using concentrated solution theory which accounts for both concentration polarization and polymer motion, using independently measured parameters that depend on concentration, c: conductivity (κ), salt diffusion coefficient (D), cationic transference number with respect to the solvent velocity (), thermodynamic factor and partial molar volume of the salt (); is the mean molar activity coefficient of the salt. We find quantitative agreement between experimental data and theoretical predictions. We derive a generalized analytical expression for Sand’s time for electrolytes based on dilute solution theory. This expression correctly predicts the divergence of the Sand’s time at the limiting current, in agreement with experimental data and concentrated solution theory predictions. When the applied current is large compared to the limiting current, the analytical expression approaches the standard expression for Sand’s time used in the literature.

The effect of different halogen atoms on the rigid and energy transfer of organic cations

Low-dimensional organic-inorganic hybrid metal halides (OIMHs) have become an emerging class of light-emitting materials. Two zero-dimensional (0D) lead-free organic (EnrofloH2)4Mn3X12 (X = Cl, Br) has been reported in this work. Upon 338 and 340 nm excitation, (EnrofloH2)4Mn3Cl12·2Cl and (EnrofloH2)4Mn3Br12·2Br exhibit emission peaking at 460, 514 nm and 460, 520 nm respectively. It was noticed that the choice of the halide could profoundly govern the luminescent subjects (ENR or Mn2+) through the altered energy transfer. Different halogens could influence the rigidity of ENR organic cations by changing their stacking patterns and band gaps, thus manipulating their luminescent properties. The bandgap behaviors have been revealed by density functional theory calculations. Based on the results, the emission of both compounds come from organic cations (EnrofloH22+) and 4D-6A1 transition of Mn2+ ions. The spectral interplay of these emission bands is governed by the temperature and the possibility of exchanging mechanisms between two emission centers.

Lipophilic tetramethylpiperidine N-oxyl (TEMPO) as a phase-transfer redox mediator in thin films for anion and cation sensing

This study successfully demonstrates the use of a lipophilic derivative of TEMPO, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl stearate, as a redox mediator for ion transfer processes at the interface between two immiscible electrolyte solutions. The results prove that TEMPO exhibits outstanding performance for mediating anion and cation transfer across polymeric ion-selective membranes doped with lipophilic ion-exchangers. The redox reaction at the inner interface of the electrode was controlled by cyclic voltammetry and allowed to modulate the flux of different ions according to the Hofmeister selectivity series. The behavior of this system was shown to agree well with the theory combining redox and phase-boundary potentials by comparing experimental and calculated cyclic voltammograms. Model ions were used to show the ideal Nernstian shift of the peak position while changing the phase-boundary potential at the outer interface when ion activity is varied in the aqueous phase. We also showcase that limitations from electrochemical instabilities in anion transfer observed using other redox probes are now overcome.

A “Polymer‐in‐Salt” Solid Electrolyte Enabled by Fast Phase Transition Route for Stable Zn Batteries

AbstractSolid polymer electrolyte‐based batteries show great promise because of their safe operating properties, wide voltage window and suitable flexibility. However, low ionic conductivity, low cation transfer number, weak oxidation/reduction resistance and low mechanical strength limit their implementation in Zn ion batteries. Here, w e developed a “polymer‐in‐salt” Zn2+‐conductive solid electrolyte (denoted as 70% salt‐SPE) constructed by a simple and fast phase transition method. The room‐temperature ionic conductivity and the transfer number of the 70% salt‐SPE reaches 1.6 mS cm−1 and 0.78, respectively. Meanwhile, the ZnF2‐rich inorganic/organic hybrid solid electrolyte interface is formed, and the stable voltage window reaches 9.35 V. In consequence, the Zn||Zn symmetric cell continuously cycles over 700 hours at current density of 2 mA cm−2 and the Zn||Cu symmetric battery runs with Coulombic efficiency of >99%. The Zn||MnPBA full battery delivers a discharge specific capacity of 109 mAh g−1 at room temperature and 190 mAh g−1 at 60 °C. Meanwhile, impressive cyclic stability of 6000 cycles with capacity retention of 80% is achieved, which originates from the effectively optimized ion transport action and dendrite‐free Zn plating/stripping.

Comparing Theoretical Salt Concentration Profiles in a Polymer Electrolyte with Experimental Measurements using Operando Raman Spectroscopy

Concentrated solution theory has furthered our understanding of ion transport in electrolytes. This theory can be used to predict salt concentration profiles under an applied current if the transport properties of the electrolyte (conductivity (κ), restricted diffusion coefficient (D), and the cation transference number with respect to the solvent velocity ()), and the thermodynamic factor (T f ) are known. In this work, we provide the first study comparing the predicted salt concentration profiles with measurements based on operando Raman spectroscopy. Concentration polarization is asymmetrical; the increase in salt concentration near the positive electrode is a factor of two greater than the decrease in salt concentration near the negative electrode. We find qualitative agreement between theory and experiment. Further work is needed to resolve the quantitative differences.

Developing Single‐Ion Conductive Polymer Electrolytes for High‐Energy‐Density Solid State Batteries

AbstractSingle‐ion conductive polymer electrolytes (SICPEs) with a cationic transference number (tLi+) close to unity exhibit specific advantages in solid‐state batteries (SSBs), including mitigating the ion concentration gradient and derived problems, suppressing the growth of lithium dendrites, and improving the utilization of cathode materials and the rate performance of SSBs. However, the application of SICPEs remains major challenges, i.e., the ionic conductivity is inferior at room temperature. Therefore, the recent accomplishments in improving the ambient ionic conductivity to be compatible SICPEs with a high transference number are discussed in this review. In particular, some strategies of delocalizing charges in polyanions, designing a highly conductive polymer matrix, and utilizing synergistic effects in SICPEs are focused to shed light on the further development of solid polymer electrolytes for SSBs. Finally, multifunctional species of SICPEs are discussed in view of the mechanical contact and/or charge transfer problems at the solid–solid interface in SSBs.

Environmentally-Friendly Electroplating Process Using Solid Electrolyte Membranes

The automobile is a very broad industry, and consists of tens of thousands of parts. Many parts of automobile employ surface treatment to provide several functions such as electronic and anti-corrosion properties. Among several surface treatment process, plating is an important elemental technology for automobile industry. For the industrial perspective, interest in SDGs significantly increases, and efforts to reduce environmental impact are highly urgent. Recently, we have developed novel electroplating process, solid electrodeposition (SED), which is based on ion transfer through solid electrolyte membrane1). This process has unique deposition characteristics that the metal film can be deposited only on the contact area between cathode and the membrane, in a fashion similar to stamping deposition. The SED process has an advantage for reducing amounts of waste effluent and CO2 gas. Moreover, this process has a potential of high deposition rate due to utilization of thin electrolyte membrane, providing lower electrical resistance between electrodes1), 2). Therefore, in the environmental and economical perspective, we believe that SED is promising process to metallize the substrate surface as an alternative to the conventional electroplating, especially in the field of electronics manufacturing. In this study, we report on SED system in details and characterization of deposited copper and nickel films. We also introduce copper fine patterning technique combined with SED using hard mask. Figure 1 shows schematic of the present SED system. The head part composed of anode plate, electrolyte solution and membrane are placed on substrate under controlled temperature and pressure. The membrane mainly plays a role of selective cation transfer from electrolyte solution to the substrate, although a small amounts of electrolyte solution can also be transferred due to pressure difference between internal head part and atmosphere. This solution uniformly spread to the interface between membrane and substrate so that uniform metal deposition is continuously proceeded without adhering the membrane with the substrate. Additionally, the SED system allows one to shorten the distance between electrodes because membrane can act as a diaphragm. Therefore, the power consumption is smaller than that of conventional electroplating, owing to decrease in an internal electrical resistance, providing the decrease of exhaust CO2 gas. The deposited film has relatively uniform thickness as shown in Figure 2, the result of which is due to the short distance between electrodes as well as uniform current feeding to deposit metal films through the back side of the cathode. The deposited copper and nickel films are crystalline and highly conductive, the quality of which are being enough for application of the SED process in the current electronics device manufacturing. By combining the SED process with the conventional screen printing technique, copper circuit patterns with line width of below 50 μm could also be successfully fabricated.1) Akamatsu, S. Nakano, K. Kimura, Y Takashima, T. Tsuruoka, H. Nawafune, Y. Sato, J. Murai, H. Yanagimoto, ACS Appl. Mater. Interfaces, 13, 13896-13906 (2021)2) Narui, Y. Hoshi, I. Shitanda, M. Itagaki, H. Yanagimoto, M. Hiraoka and H. Iisaka, E01-920, 232nd ECS Meeting. Figure 1

Studies of monomer–dimer equilibria of methylene blue as a probe to investigate the solute–solvent and hydrophobic interactions in aqueous solutions of polyethylene glycols at 298 K

Electronic absorption spectrums of methylene blue (MB) in the concentration range wherein monomer–dimer equilibria exist have been systematically investigated in aqueous solutions of polyethylene glycols (PEG's) having molar mass 400, 1000 and 4000 g∙mol–1, at 298 K. The data on the absorption spectrums (550–700 nm) of MB are resolved to obtain monomer and dimer spectrums as well the geometrical details of the species (such as oscillatory strength, dipole moment etc.) are calculated. The molar absorption extinction coefficients for monomer and dimer cations of MB, the dimer dissociation constant values are calculated as a function of PEG concentrations. It has been noted that, absorption maximum occurs at 664 ± 1 and 605 ± 1 nm, respectively, for monomer and dimers which do not get affected much by presence of polymeric molecules and the data show perfect obedience of Beer–Lambert's law. The changes in dimer geometry from sandwich type to end–on–end type have been studied by applying exciton theory of Kasha et al. The dimer dissociation constant values at finite as well for infinitely dilute concentration of PEG's exhibit orderly amendment with respect to molar mass of PEG's and alteration in chain length of molecules. We report the free energy changes of transfer of dimeric cations of different concentrations from water to aqueous solutions of PEG's of fixed concentration, that is, to probe the interactions of water and PEG molecules with a hope of getting information about salting–in/salting–out effects, as well of binding of dye molecules with PEG's. We have suggested complexation of end hydroxylic groups of PEG's with dimer cations. The results are further interpreted as salting–in of PEG complex with MB–dimers only in the limit of infinite dilution (solute–solvent interactions) while salting–out of these complexed species is observed as a function of MB–dimer concentration.

In-situ generated solid-state electrolytes with intimate interface affinity enable conductivity and high performances for lithium-ion batteries

The issues of interfacial compatibility derived from electrolyte/electrodes and unsatisfied ionic conductivity still hinder the practical application of lithium-ion batteries. In the present study, the crosslinked solid polymer electrolytes (SPEs) based on dual epoxy group were prepared through in-situ thermal polymerization method. FSO2NH2 was employed as additive for high reactivity to adapt the kinetic reaction and improve the conductivities of electrolytes. The as-prepared SPEs exhibit a high degree of amorphous structure, lower transmission glass temperature, considerable ionic conductivity (>1.0 mS cm−1) at 25 °C, wider electrochemical stability window, and excellent Li cation transference number. Moreover, the battery performance of the as-prepared PBDE−1 electrolyte-based half-cell means that it delivers a high initial specific capacity (ca. 161.2 mAh g−1), and achieves remarkable Coulombic efficiency of 99.8% after 200 cycles at 0.1 C. X-ray photoelectron spectra further revealed the formation of a solid electrolyte interphase (SEI) layer, which can alleviate Li dendrite growth and facilitate the lifespan stability of Li/graphite anode during cycling. These findings may provide a reference for the development of solid-state lithium batteries.

Dynamic Zn/Electrolyte Interphase and Enhanced Cation Transfer of Sol Electrolyte for All-Climate Aqueous Zinc Metal Batteries.

Zn metal as one of the promising anodes of aqueous batteries possesses notable advantages, but it faces severe challenges from severe side reactions and notorious dendrite growth. Here, ultrathin nanosheets of α-zirconium phosphate (ZrP) are explored as an electrolyte additive. The nanosheets not only create a dynamic and reversible interphase on Zn but also promote the Zn2+ transportation in the electrolyte, especially in the outer Helmholtz plane near ZrP. Benefited from the enhanced kinetics and dynamic interphase, the pouch cells of Zn||LiMn2 O4 using this electrolyte remarkably improve electrochemical performance under harsh conditions, i.e. Zn powders as the Zn anode, high mass loading, and wide temperatures. The results expand the materials available for this dynamic interphase, provide an insightful understanding of the enhanced charge transfer in the electrolyte, and realize the combination of dynamic interphase and enhanced kinetics for all-climate performance.

Transfer-Imprinting-Assisted Growth of 2D/3D Perovskite Heterojunction for Efficient and Stable Flexible Inverted Perovskite Solar Cells.

2D/3D perovskite heterostructures show great potential to boost efficiency and stability of perovskite solar cells (PSCs). Here, a solvent-free transfer-imprinting-assisted growth (TIAG) method is employed to in situ grow 2D/3D perovskite heterojunctions. The solid-state transfer of spacer cation by the TIAG process enables a spatially confined growth of the 2D perovskite interlayer with uniform morphology between the 3D perovskites and charge transport layer. Meanwhile, the pressure associated with the TIAG process promotes the crystalline orientation, which is beneficial to carrier transport. As a result, the inverted PSC achieved a PCE of 23.09% (with certified 22.93%) and maintained 90% of their initial PCE after aging at 85 °C for 1200 h or operating for 1100 h under continuous AM 1.5 illumination. Flexible inverted PSCs achieved a PCE of 21.14% with mechanical robustness by maintaining above 80% of their initial PCE after 10000 bending cycles under a 3 mm bending radius.

Fundamental investigations on the ionic transport and thermodynamic properties of non-aqueous potassium-ion electrolytes

Non-aqueous potassium-ion batteries (KIBs) represent a promising complementary technology to lithium-ion batteries due to the availability and low cost of potassium. Moreover, the lower charge density of K+ compared to Li+ favours the ion-transport properties in liquid electrolyte solutions, thus, making KIBs potentially capable of improved rate capability and low-temperature performance. However, a comprehensive study of the ionic transport and thermodynamic properties of non-aqueous K-ion electrolyte solutions is not available. Here we report the full characterisation of the ionic transport and thermodynamic properties of a model non-aqueous K-ion electrolyte solution system comprising potassium bis(fluorosulfonyl)imide (KFSI) salt and 1,2-dimethoxyethane (DME) solvent and compare it with its Li-ion equivalent (i.e., LiFSI:DME), over the concentration range 0.25–2 molal. Using tailored K metal electrodes, we demonstrate that KFSI:DME electrolyte solutions show higher salt diffusion coefficients and cation transference numbers than LiFSI:DME solutions. Finally, via Doyle-Fuller-Newman (DFN) simulations, we investigate the K-ion and Li-ion storage properties for K∣∣graphite and Li∣∣graphite cells.

Ionic transport in solid-state composite poly(trimethylene carbonate)–Li6.7Al0.3La3Zr2O12 electrolytes: The interplay between surface chemistry and ceramic particle loading

The ionic transport in solid-state composite electrolytes based on poly(trimethylene carbonate) (PTMC) with LiTFSI salt and garnet-type ion-conducting Li6.7Al0.3La3Zr2O12 (LLZO) ceramic particles is here investigated for a range of different compositions. Positive effects on ionic conductivity have previously been reported for LLZO incorporated into poly(ethylene oxide) (PEO), but the origin of these effects is unclear since the inclusion of particles also affects polymer crystallinity. PTMC is, in contrast to PEO, a fully amorphous polymer, and therefore here chosen for the design of a more straight-forward composite electrolyte (CPE) system to study ionic transport. With LLZO loadings ranging from 5 to 70 wt%, the CPE with 30 wt% of LLZO exhibits the highest ionic conductivity with a cationic transference number of 0.94 at 60 °C. This is significantly higher than for the pristine PTMC polymer electrolyte. Generally, low to moderate LLZO loadings display a gradual increase of the ionic conductivity, transference number and also of the polymer-cation coordination number. The combined contributions of ionic transport along polymer-ceramic interfaces and Lewis acid-base interaction between the LLZO particles and the LiTFSI salt can explain this enhancement. With loadings of LLZO above 50 wt%, a detrimental effect on the ionic conductivity was however observed. This could be explained by agglomeration of ceramic particles, and by a partial coverage of LLZO particles with a Li2CO3 layer. Consequently, inner polymer-particle interfaces become more resistive, and Li+conduction is prevented along interfacial pathways. The presence of Li2CO3 has more detrimental impact at higher LLZO loadings, since inter-particle connectivity will be hampered, and this is vital for efficient ionic transport. This suggests that there is an interplay between the LLZO particle surface chemistry with its loading, which ultimately controls the Li-ion transport.

Uptake and Micronutrient Cations Transfer in Acid Alfisol as Influenced by Four Decadal Continuous Use of Amendments and Chemical Fertilizers in Maize-Wheat Cropping System

Uptake and Micronutrient Cations Transfer in Acid Alfisol as Influenced by Four Decadal Continuous Use of Amendments and Chemical Fertilizers in Maize-Wheat Cropping System