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All-solid-state lithium batteries are a promising alternative to commercially available lithium-ion batteries due to their ability to achieve high energy density, safety, and compactness. Electrolytes are key components of all-solid-state batteries, as they are crucial in determining the batteries’ efficiency. Herein, the structure of LiM2(PO4)3 (M = Ti, Ge, Zr) and lithium-ion migration mechanisms are introduced as well as different synthetic routes and doping (co-doping), and their influence on conductivity is discussed. The effective methods of reducing electrolyte/electrode interface resistance and improving ion-conducting properties are summarized. In addition, different polymer/NASICON composites are considered. The challenges and prospects of practical applications of NASICON-type lithium phosphates as electrolytes for all-solid-state batteries are discussed.

Studies have been carried out to optimize the composition, formation technique and test conditions of membrane electrode assemblies (MEA) of hydrogen–oxygen anion-exchange membranes fuel cells (AEMFC), based on Fumatech anion-exchange membranes. A non-platinum catalytic system based on nitrogen-doped CNT (CNTN) was used in the cathode. PtMo/CNTN catalysts with a reduced content of platinum (10–12 wt.% Pt) were compared with 10 and 60 wt.% Pt/CNTN at the anode. According to the results of studies under model conditions, it was found that the PtMo/CNTN catalyst is significantly superior to the 10 and 60 wt.% Pt/CNTN catalyst in terms of activity in the hydrogen oxidation reaction based on the mass of platinum. The addition of the Fumion ionomer results in minor changes in the electrochemically active surface area and activity in the hydrogen oxidation reaction for each of the catalysts. In this case, the introduction of ionomer–Fumion leads to a partial blocking of the outer surface and the micropore surface, which is most pronounced in the case of the 60Pt/CNTN catalyst. This effect can cause a decrease in the characteristics of MEA AEMFC upon passing from 10PtMo/CNTN to 60Pt/CNTN in the anode active layer. The maximum power density of the optimized MEA based on 10PtMo/CNTN was 62 mW cm−2, which exceeds the literature data obtained under similar test conditions for MEA based on platinum cathode and anode catalysts and Fumatech membranes (41 mW cm−2). A new result of this work is the study of the effect of the ionomer (Fumion) on the characteristics of catalysts. It is shown that the synthesized 10PtMo/CNTN catalyst retains high activity in the presence of an ionomer under model conditions and in the MEA based on it.

The possibility of targeted change of the properties of ion exchange membranes by incorporation of various nanoparticles into the membranes is attracting the attention of many research groups. Here we studied for the first time the influence of cerium phosphate nanoparticles on the physicochemical and transport properties of commercial anion exchange membranes based on quaternary ammonium-functionalized polystyrenes, such as heterogeneous Ralex® AM and pseudo-homogeneous Neosepta® AMX. The incorporation of cerium phosphate on one side of the membrane was performed by precipitation from absorbed cerium ammonium nitrate (CAN) anionic complex with ammonium dihydrogen phosphate or phosphoric acid. The structures of the obtained hybrid membranes and separately synthesized cerium phosphate were investigated using FTIR, P31 MAS NMR, EDX mapping, and scanning electron microscopy. The modification increased the membrane selectivity to monovalent ions in the ED desalination of an equimolar mixture of NaCl and Na2SO4. The highest selectivities of Ralex® AM and Neosepta® AMX-based hybrid membranes were 4.9 and 7.7, respectively. In addition, the modification of Neosepta® membranes also increased the resistance to a typical anionic surfactant, sodium dodecylbenzenesulfonate.

A novel potentiometric multisensory system for the analysis of sulfamethoxazole and trimethoprim combination drugs was developed. The potentiometric sensors (Donnan potential (DP) was used as an analytical signal) with an inner reference solution were based on perfluorosulfonic acid (PFSA) membranes modified with polyaniline (PANI) by in situ oxidative polymerization. The order of the membrane treatment with precursor solutions and their concentrations was varied. Additionally, the PFSA/PANI composite membranes were hydrothermally treated at 120 °C. The influence of the preparation conditions and the composition of membranes on their sorption and transport properties was studied. We estimated the factors affecting the sensitivity of DP-sensors based on the PFSA/PANI composite membranes to ions of sulfamethoxazole and trimethoprim simultaneously presented in solutions. A developed multisensory system provided a simultaneous determination of two analytes in aqueous solutions without preliminary separation, derivatization, or probe treatment. The re-estimation of the calibration characteristics of the multisensory system did not show a statistically significant difference after a year of its use. The limits of detection of sulfamethoxazole and trimethoprim were 1.4 × 10−6 and 8.5 × 10−8 M, while the relative errors of their determination in the combination drug were 4 and 5% (at 5 and 6% relative standard deviation), respectively.

Replacing liquid electrolytes with solid-state conductors is one of the key challenges to increasing the safety and energy density of next-generation Li secondary batteries. In this work, the NASICON-type Li1+xAlxZryTi2−x−y(PO4)3 with 0 ≤ x, y ≤ 0.2 solid electrolytes were synthesized using solid-state and sol-gel techniques at various sintering temperatures (800, 900, and 1000 °C). Their morphology and conducting properties were studied to determine the optimal dopant content and synthesis method. Li1.2Al0.2Zr0.1Ti1.7(PO4)3 and Li1.1Al0.1Zr0.2Ti1.7(PO4)3 prepared at 900 °C using a solid-state reaction exhibit the highest total conductivity at 25 °C (7.9 × 10−4 and 5.4 × 10−4 S cm−1, respectively), which is due to the optimal size of lithium transport channels, as well as the high density of these samples. The potential profile of Li|Li1.2Al0.2Zr0.1Ti1.7(PO4)3|Li cells was retained during cycling at a current density of 0.05 mA cm−2 for 100 h, indicating a high interfacial Li metal/electrolyte stability.

Sulfamethoxazole and trimethoprim are synthetic bacteriostatic drugs. A potentiometric multisensory system for the analysis of sulfamethoxazole and trimethoprim combination drugs was developed. Perfluorosulfonic acid membranes containing functionalized CNTs were used as the sensor materials. The CNTs’ surface was modified by carboxyl, sulfonic acid, or (3-aminopropyl)trimethoxysilanol groups. The influence of the CNT concentration and the properties of their surface, as well as preliminary ultrasonic treatment of the polymer and CNT solution before the casting of hybrid membranes, on their ion-exchange capacity, water uptake, and transport properties was revealed. Cross-sensitivity of the sensors to the analytes was achieved due to ion exchange and hydrophobic interactions with hybrid membranes. An array of cross-sensitive sensors based on the membranes containing 1.0 wt% of CNTs with sulfonic acid or (3-aminopropyl)trimethoxysilanol groups enabled us to provide the simultaneous determination of sulfamethoxazole and trimethoprim in aqueous solutions with a concentration ranging from 1.0 × 10−5 to 1.0 × 10−3 M (pH 4.53–8.31). The detection limits of sulfamethoxazole and trimethoprim were 3.5 × 10−7 and 1.3 × 10−7 M. The relative errors of sulfamethoxazole and trimethoprim determination in the combination drug as compared with the content declared by the manufacturer were 4% (at 6% RSD) and 5% (at 7% RSD).

The effect of different nitrogen-doped carbon additives (carbon coating from polyaniline, N-doped carbon nanotubes, and N-doped carbon nanoparticles) on electrochemical performance of nanocomposites based on the olivine-type LiFePO4 was investigated. Prepared materials were characterized by XRD, SEM, TGA-MS, CHNS-analysis, IR-, Raman, and impedance spectroscopies. Polyaniline deposition on the LiFePO4 precursor with following annealing lead to the formation of a LiFePO4/C nanocomposite with a carbon coating doped with nitrogen. Due to nitrogen atoms presence in carbon coating, the LiFePO4/N-doped carbon nanocomposites showed enhanced conductivity and C-rate capability. The discharge capacities of the synthesized materials in LIBs were close to the theoretical value at 0.1 C and retained high values with increasing current density. At high C-rates, the best results were obtained for a more dispersed LiFePO4/C composite with carbon coating prepared from polyaniline previously in situ deposited on LiFePO4 precursor particles. Its discharge capacity reached 96, 84, 73, and 47 mAh g−1 at 5, 10, 20, and 60 C-rates, respectively.

The influence of different conductive additives (carbon nanofibers (CNFs), carbon nanoplatelets, and pyrolytic carbon from sucrose (Sucr) or polyvinylidene fluoride) on the morphology, electron conductivity, and electrochemical performance of LiFePO4-based cathodes was investigated to develop the most efficient strategy for the fabrication of high-rate cathodes. Pyrolytic carbon effectively prevents the growth of LiFePO4 grains and provides contact between them, CNFs provide fast long-range conductive pathways, while carbon nanoplatelets can be embedded in carbon coatings as high-conductive “points” which enhance the rate capability and decrease the capacity fading of LFP. The LiFePO4/CSucr/CNF showed better performance than the other cathodes due to the synergy of the high-conductive CNF network (the electronic conductivity was 1.3 × 10−2 S/cm) and the shorter Li+ ion path (the lithium-ion diffusion coefficient was 2.1 × 10−11 cm2/s). It is shown that the formation of composites based on LFP and carbon nanomaterials via mortar grinding is a more promising strategy for electrode material manufacturing than ball milling.

The Li4Ti5O12/C composites were prepared by a hydrothermal method with in situ carbon addition. The influence of the morphology and content of various carbon materials (conductive carbon black, mesoporous carbon G_157M, and carbon replicas) on the electrochemical performance of the Li4Ti5O12/C composites was investigated. The obtained composites were characterized using X-ray diffraction, scanning electron microsopy, high-resolution transmission electron microscopy, thermogravimetric analysis, Raman spectroscopy, and N2 sorption-desorption isotherms. Morphology of the Li4Ti5O12/C composites depends on the carbon matrix used, while both morphology and the amount of carbon material have a great impact on the rate capability and cycling stability of the obtained composites. At low current densities, the Li4Ti5O12/C composite with 5 wt.% G_157M exhibits the highest discharge capacity, while at high charge-discharge rates, the Li4Ti5O12/carbon black composites show the best electrochemical performance. Thus, at ~0.1C, 5C, and 18C rates, the discharge capacities of the obtained Li4Ti5O12/C composites are 175, 120, and 70 mAh/g for G_157M, 165, 126, and 78 mAh/g for carbon replicas, and 173, 128, and 93 mAh/g for carbon black. After 100 cycles, their capacity retention is no less than 95%, suggesting their promising application perspective.

The influence of incorporation of the dopants with proton-acceptor properties into perfluorosulfonic acid cation exchange membranes (MF-4SC and Nafion), and their treatment conditions on the characteristics of Donnan potential (DP)-sensors (analytical signal is the Donnan potential) in the aqueous solutions containing asparaginate and potassium ions in a wide pH range was investigated. A silica, surface modified by 3-aminopropyl and 3-(2-imidazolin-1-yl)-propyl groups, was used as the dopant. The membranes were subjected to mechanical deformation and thermal treatment at various relative humidities. The relationship between water uptake and diffusion permeability of membranes subjected to modification and treatment and the cross sensitivity of DP-sensors based on them to counter and co-ions was studied. The multisensory systems for the simultaneous determination of asparaginate and potassium ions in a concentration range from 1.0 × 10−4 to 1.0 × 10−2 M and pH range from 4 to 8 were developed. An array of cross-sensitive DP-sensors based on MF-4SC membranes containing 3 wt.% SiO2 modified by 10 mol.% 3-aminopropyl and 3-(2-imidazolin-1-yl)-propyl was used for the potassium asparaginate hemihydrate and magnesium asparaginate pentahydrate determination in Panangin® (with an error of 2 and 4%, respectively).

LiFe1-xVxPO4/C (x= 0.01, 0.03, 0.05, 0.1) composites had been obtained by sol-gel method and characterized with the use of the XRD-analysis, SEM and charge/discharge tests. The doping was shown to result in decrease of electrode polarization, and correspondingly in capacity increase at high C-rates.

The possibilities of manufacturing batteries with Nafion 117 membranes in the Na+-form intercalated by mixtures of non-aqueous organic solvents used both as an electrolyte, separator, and binder were investigated. Electrochemical stability of various organic solvent mixtures based on N,N-dimethylacetamide, ethylene carbonate, propylene carbonate, and tetrahydrofuran were characterized. It was shown that a sodium battery based on a Nafion-Na membrane intercalated by mixture of ethylene carbonate and propylene carbonate with a Na3V1.9Fe0.1(PO4)3/C positive electrode is characterized by a discharge capacity of ≈110 mAh·g−1 (current density of 10 mA·g−1) at room temperature and shows the ability to cycle without degradation during 20 cycles. Batteries with Nafion membrane electrolytes, containing N,N-dimethylacetamide, were characterized using capacity fading during cycling, which is due to the interaction of N,N-dimethylacetamide and a negative sodium electrode.