This review is devoted to different types of novel polymer electrolytes for lithium power sources developed during the last decade. In the first part, the compositions and conductivity of various polymer electrolytes are considered. The second part contains NMR applications to the ion transport mechanism. Polymer electrolytes prevail over liquid electrolytes because of their exploitation safety and wider working temperature ranges. The gel electrolytes are mainly attractive. The systems based on polyethylene oxide, poly(vinylidene fluoride-co-hexafluoropropylene), poly(ethylene glycol) diacrylate, etc., modified by nanoparticle (TiO₂, SiO₂, etc.) additives and ionic liquids are considered in detail. NMR techniques such as high-resolution NMR, solid-state NMR, magic angle spinning (MAS) NMR, NMR relaxation, and pulsed-field gradient NMR applications are discussed. ¹H, ⁷Li, and ¹⁹F NMR methods applied to polymer electrolytes are considered. Primary attention is given to the revelation of the ion transport mechanism. A nanochannel structure, compositions of ion complexes, and mobilities of cations and anions studied by NMR, quantum-chemical, and ionic conductivity methods are discussed.

Elementary processes of electro mass transfer in the nanocomposite polymer electrolyte system by pulse field gradient, spin echo NMR spectroscopy and the high-resolution NMR method together with electrochemical impedance spectroscopy are examined. The new nanocomposite polymer gel electrolytes consisted of polyethylene glycol diacrylate (PEGDA), salt LiBF₄ and 1—ethyl—3—methylimidazolium tetrafluoroborate (EMIBF₄) and SiO₂ nanoparticles. Kinetics of the PEGDA matrix formation was studied by isothermal calorimetry. The flexible polymer–ionic liquid films were studied by IRFT spectroscopy, differential scanning calorimetry and temperature gravimetric analysis. The total conductivity in these systems was about 10⁻⁴ S cm⁻¹ (−40 °C), 10⁻³ S cm⁻¹ (25 °C) and 10⁻² S cm⁻¹ (100 °C). The method of quantum-chemical modeling of the interaction of SiO₂ nanoparticles with ions showed the advantage of the mixed adsorption process, in which a negatively charged surface layer is formed from Li⁺ BF₄^— ions on silicon dioxide particles and then from ions of the ionic liquid EMI⁺ BF₄⁻. These electrolytes are promising for use both in lithium power sources and in supercapacitors. The paper shows preliminary tests of a lithium cell with an organic electrode based on a pentaazapentacene derivative for 110 charge–discharge cycles.

Polyurethanes based on the aminoethers of ortho-phosphoric acid and polyisocyanates of an aliphatic nature were studied as a substrate for the preparation of new polymer electrolyte. The conductivity of polyurethane ionomer samples obtained using the optimal amount of aliphatic polyisocyanates and after keeping them in a 1 M LiBF₄ solution in γ-butyrolactone reaches 0.62 mS cm⁻¹. It has been established that the transport of positively charged ions through the polymer matrix is due to the formation of clusters of phosphate ions and their association into the conducting channels. The introduction of carboxylate ions into the conducting channels by modifying the aminoethers of ortho-phosphoric acid with phthalic anhydride leads to an increase in their size and rise in the mobility of cations. As a result, the conductivity of polyurethane gel electrolytes increased to 2.1 mS cm⁻¹.

Causes of the double maximum conductivity of nanocomposite net electrolytes in the presence of SiO₂ nanoparticles (7 nm) were revealed by differential scanning calorimetry and quantum-chemical modeling. The first maximum results from increasing the dissociation of lithium salt, whereas the second one is due to the formation of conductive paths involving SiO₂ nanoparticles.

The effect of the composition of liquid electrolytes in the bulk and at the interface with the LiFePO₄ cathode on the operation of a solid-state lithium battery with a nanocomposite polymer gel electrolyte based on polyethylene glycol diacrylate and SiO₂ was studied. The self-diffusion coefficients on the 7Li, 1H, and 19F nuclei in electrolytes based on LiBF₄ and LiTFSI salts in solvents (gamma-butyrolactone, dioxolane, dimethoxyethane) were measured by nuclear magnetic resonance (NMR) with a magnetic field gradient. Four compositions of the complex electrolyte system were studied by high-resolution NMR. The experimentally obtained ¹H chemical shifts are compared with those theoretically calculated by quantum chemical modeling. This made it possible to suggest the solvate shell compositions that facilitate the rapid transfer of the Li⁺ cation at the nanocomposite electrolyte/LiFePO₄ interface and ensure the stable operation of a solid-state lithium battery.