Hyperfine fields at the Li site in LiFePO(4)-type olivine materials for lithium rechargeable batteries: a (7)Li MAS NMR and SQUID study

The (7)Li NMR isotropic shift for olivine LiMPO(4) (M = Fe, Mn, Co, Ni) is assigned to hyperfine coupling between the (7)Li nucleus and the transition metal unpaired electrons on the basis of the Curie-Weiss temperature dependence of the shift. The hyperfine shift arises from a linear combination of Li-O-M through-bond interactions wherein the unpaired A' electrons contribute a negative shift and the unpaired A' ' electrons contribute a positive shift. The hyperfine coupling constant is determined for each composition.     

Review on synthesis methods to obtain LiMn2O4-based cathode materials for Li-ion batteries

Journal of Solid State Electrochemistry - Lithium manganese spinel (LiMn2O4) is considered a promising cathode material for lithium-ion batteries (LIBs). Its structure, morphology, and...     

A facile method to prepare bi-phase lithium vanadate as cathode materials for Li-ion batteries

Bi-crystal lithium vanadate is synthesized with starting materials of V₂O₅ and LiF by one-step solid-state reaction. Since fluorine reacts with crucible made of silica, Li_0.3V₂O₅-liked and LiV₃O₈-liked phases without F coexist in the produces. The stoichiometric proportion of two phases depends on the amount of dopant LiF. These are confirmed by X-ray diffraction (XRD), Fourier transform infrared (FTIR), and transmission electron microscopy (TEM). Charge and discharge curves of bi-crystal materials present better reversibility of voltage plateaus than that of pure V₂O₅. The initial discharge capacity of Li_0.3V₂O₅-liked phase dominated bi-crystal material is higher than pure V₂O₅. LiV₃O₈-liked phase dominated bi-crystal material has lower initial discharge capacity but delivers better cycling performance. Electrochemical impedance spectroscopy (EIS) measurements are performed to evaluate electrochemical kinetics of the bi-crystal materials. The results indicate that bi-crystal phase benefit the transfer resistance, interior diffusion resistance, and structure stability. Cathodes with different bi-phase structures have variable charge transfer resistance and lithium-ion diffusion speed due to this special structure.     

Synthesis and electrochemical characterizations of nano-crystalline LiFePO4 and Mg-doped LiFePO4 cathode materials for rechargeable lithium-ion batteries

Nano-crystalline LiFePO₄ and LiMg_0.05Fe_0.95PO₄ cathode materials were synthesized by sol–gel method in argon atmosphere using succinic acid as a chelating agent. Physico-chemical characterizations were done by thermogravimetric and differential thermal analysis, X-ray diffraction, scanning electron microscopy, transmittance electron microscopy, and Raman spectroscopy. Electrochemical behavior of the cathode materials were analyzed using cyclic voltammetry, and galvanostatic charge/discharge cycling studies were employed to characterize the reaction of lithium-ion insertion into and extraction from virginal and magnesium-doped LiFePO₄, in the voltage range 2.5 to 4.5 V (Vs Li/Li⁺) using 1 M LiPF₆ with 1:1 ratio of ethylene carbonate and dimethyl carbonate as electrolytes. LiMg_0.05Fe_0.95PO₄ exhibits initial charge and discharge capacities of 159 and 141 mAh/g at 0.2 C rate respectively, as compared to 121 and 107 mAh/g of pristine LiFePO₄. Furthermore, LiMg_0.05Fe_0.95PO₄ has retained more than 89% of the capacity even after 60 cycles. Hence, LiMg_0.05Fe_0.95PO₄ is a promising cathode material for rechargeable lithium-ion batteries.     

Structure and lithium transport pathways in Li2FeSiO4 cathodes for lithium batteries

The importance of exploring new low-cost and safe cathodes for large-scale lithium batteries has led to increasing interest in Li(2)FeSiO(4). The structure of Li(2)FeSiO(4) undergoes significant change on cycling, from the as-prepared γ(s) form to an inverse β(II) polymorph; therefore it is important to establish the structure of the cycled material. In γ(s) half the LiO(4), FeO(4), and SiO(4) tetrahedra point in opposite directions in an ordered manner and exhibit extensive edge sharing. Transformation to the inverse β(II) polymorph on cycling involves inversion of half the SiO(4), FeO(4), and LiO(4) tetrahedra, such that they all now point in the same direction, eliminating edge sharing between cation sites and flattening the oxygen layers. As a result of the structural changes, Li(+) transport paths and corresponding Li-Li separations in the cycled structure are quite different from the as-prepared material, as revealed here by computer modeling, and involve distinct zigzag paths between both Li sites and through intervening unoccupied octahedral sites that share faces with the LiO(4) tetrahedra.     

Direct reuse of LiFePO4 cathode materials from spent lithium-ion batteries: Extracting Li from brine

Due to the serious imbalance between demand and supply of lithium, lithium extraction from brine has become a research hotspot. With the demand for power lithium-ion batteries (LIBs) increased rapidly, a large number of spent LiFePO₄ power batteries have been scrapped and entered the recycling stage. Herein, a novel and efficient strategy is proposed to extract lithium from brine by directly reusing spent LiFePO₄ powder without any treatment. Various electrochemical test results show that spent LiFePO₄ electrode has appropriate lithium capacity (14.62 mg_Li/g_LiFePO4), excellent separation performance (α_Li-Na = 210.5) and low energy consumption (0.768 Wh/g_Li) in electrochemical lithium extraction from simulated brine. This work not only provides a novel idea for lithium extraction from brine, but also develops an effective strategy for recycling spent LIBs. The concept of from waste to wealth is of great significance to the development of recycling the spent batteries.     

Review and prospect of layered lithium nickel manganese oxide as cathode materials for Li-ion batteries

Layered structural lithium metal oxides with rhombohedral α-NaFeO₂ crystal structure have been proven to be particularly suitable for application as cathode materials in lithium-ion batteries. Compared with LiCoO₂, lithium nickel manganese oxides are promising, inexpensive, nontoxic, and have high thermal stability; thus, they are extensively studied as alternative cathode electrode materials to the commercial LiCoO₂ electrode. However, a lot of work needs to be done to reduce cost and extend the effective lifetime. In this paper, the development of the layered lithium nickel manganese oxide cathode materials is reviewed from synthesis method, coating, doping to modification, lithium-rich materials, nanostructured materials, and so on, which can make electrochemical performance better. The prospects of lithium nickel manganese oxides as cathode materials for lithium-ion batteries are also looked forward to.     

Li-ion batteries from LiFePO4 cathode and anatase/graphene composite anode for stationary energy storage

Li-ion batteries made from LiFePO₄ cathode and anatase TiO₂/graphene composite anode were investigated for potential application in stationary energy storage. Fine-structured LiFePO₄ was synthesized by a novel molten surfactant approach whereas anatase TiO₂/graphene nanocomposite was prepared via self-assembly method. The full cell that operated at 1.6 V demonstrated negligible fade even after more than 700 cycles at measured 1 C rate. While with relative lower energy density than traditional Li-ion chemistries interested for vehicle applications, the Li-ion batteries based on LiFePO₄/TiO₂ combination potentially offers long life and low cost, along with safety, all which are critical to the stationary applications.     

Thermal explosion synthesis of LiFePO4 as a cathode material for lithium ion batteries

Research on Chemical Intermediates - Olivine-type LiFePO4 cathode material was successfully synthesized by a simple method of thermal explosion (TE) using hexamethylenetetramine (C6H12N4) as fuel....     

One-dimensional (1D) nanostructured and nanocomposited LiFePO4: its perspective advantages for cathode materials of lithium ion batteries

Nanostructured materials have attracted recent research interest as battery materials due to their expected enhancement of properties. The characteristic nanoscale dimension and its structuring guarantees improved charge and mass transfer during charge/discharge processes. Among the potential cathode materials investigated as a substitute to LiCoO(2), one of the most promising materials is LiFePO(4) with olivine structure (LFP). In this perspective article, the current research and development in the synthesis and electrochemical studies of nanostructured LFP are reviewed with a special emphasis on one-dimensional (1D) nanostructures and nanocompositing with 1D conductive materials. In addition to various examples of 1D LFP with detailed synthetic methods, why 1D nanostructures could be meaningful is discussed in terms of a geometric point of view and the anisotropic lithiation/de-lithiation mechanism of LFP.     

High-temperature carbon-coated aluminum current collector for enhanced power performance of LiFePO4 electrode of Li-ion batteries

The charge/discharge capacity and cycle stability at high C-rate of LiFePo₄ (LFPO) electrodes using three types of Al current collectors, including smooth un-etched Al foil, anodization-etched Al foil, and the etched Al foil covered with a conformal C coating grown at 600 °C in CH₄, were investigated. The results unequivocally demonstrate the strong effects exerted by the surface structure and composition of the Al current collectors on the power performance. In particular, the use of the C-coated current collector not only remarkably increases the power-delivering capability, by 3–7-fold based on different comparison criteria, of the LFPO electrode, but also greatly enhances its cycle stability under high C-rate (5C). The rate enhancement exceeds that of a low-temperature organic-bound C-coating reported in the literature. The enhancements are consistent with observed reduction in overall charge-transfer resistance, which can be attributed to the removal of the native insulating oxide surface layer of the current collector and to the improved adhesion at the active layer/current collector interface. This current collector is also applicable to other cathode and anode (e.g., Li₄Ti₅O₁₂) materials of Li-ion batteries for the same beneficial effects.     

Effect of carbon sources on the electrochemical performance of Li2FeSiO4 cathode materials for lithium ion batteries

Li₂FeSiO₄ cathode materials have been prepared by sol-gel method. The effects of carbon sources on the structural, morphological and electrochemical behaviors of Li₂FeSiO₄ were investigated. The scanning electronic microscope (SEM) and X-ray diffraction powder analysis (XRD) indicate that the obtained samples using different carbon sources possess some difference in the morphology and in the particle size. The sample using the mixture of citric acid and oxalic acid as carbon source has a maximum discharge capacity of 118 mA h g^?1 at 0.1 C between 1.8 and 4.5 V. The resulting cyclic voltammograms and electrochemical impedance spectra suggest that the sample using mixed acid as carbon source has smaller polarization and smaller charge transfer impedance.     

Structural and electrochemical investigation of Li2MgSnO4 anode for lithium batteries

Hexagonal Li₂MgSnO₄ compound was synthesized at 800 °C using Urea Assisted Combustion (UAC) method and the same has been exploited as an anode material for lithium battery applications. Structural investigations through X-ray diffraction, Fourier Transform Infra Red spectroscopy and ⁷Li NMR (Nuclear Magnetic Resonance spectroscopy) studies demonstrated the existence of hexagonal crystallite structure with a = 6.10 and c = 9.75. An average crystallite size of ∼400 nm has been calculated from PXRD pattern, which was further evidenced by SEM images. An initial discharge capacity of ∼794 mA h/g has been delivered by Li₂MgSnO₄ anode with an excellent capacity retention (85%) and an enhanced coulombic efficiency (97–99%). Further, the Li₂MgSnO₄ anode material has exhibited a steady state reversible capacity of ∼590 mA h/g even after 30 cycles, thus qualifying the same for use in futuristic lithium battery applications.     

Structural characterization of the lithium silicides Li15Si4, Li13Si4, and Li7Si3 using solid state NMR

Local environments and lithium ion dynamics in the binary lithium silicides Li(15)Si(4), Li(13)Si(4), and Li(7)Si(3) have been characterized by detailed variable temperature static and magic-angle spinning (MAS) NMR spectroscopic experiments. In the (6)Li MAS-NMR spectra, individual lithium sites are generally well-resolved at temperatures below 200 K, whereas at higher temperatures partial or complete site averaging is observed on the ms timescale. The NMR spectra also serve to monitor the phase transitions occurring in Li(7)Si(3) and Li(13)Si(4) at 235 K and 146 K, respectively. The observed lithium isotropic shift ranges of up to approximately 50 ppm indicate a significant amount of electronic charge stored on the lithium species, consistent with the expectation of the extended Zintl-Klemm-Busmann concept for the electronic structure of these materials. The (29)Si MAS-NMR spectra obtained on isotopically enriched samples, aided by double-quantum spectroscopy, are well suited for differentiating between the individual types of silicon sites within the silicon frameworks, and in Li(13)Si(4) their identification aids in the assignment of individual lithium sites via(29)Si{(7)Li} cross-polarization/heteronuclear correlation NMR. Variable temperature static (7)Li NMR spectra reveal motional narrowing effects, illustrating high lithium ionic mobilities in all of these compounds. Differences in the mobilities of individual lithium sites can be resolved by temperature dependent (6)Li MAS-NMR as well as (6)Li{(7)Li} rotational echo double resonance (REDOR) spectroscopy. For the compound Li(15)Si(4) the lithium mobility appears to be strongly geometrically restricted, which may result in a significant impediment for the use of Li-Si anodes for high-performance batteries. A comparison of all the (6)Li and (7)Li NMR spectroscopic data obtained for the three different lithium silicides and of Li(12)Si(7) previously studied suggests that lithium ions in the vicinity of silicon clusters or dimers have generally higher mobilities than those interacting with monomeric silicon atoms.     

7Li and 13C solid-state NMR spectra of lithium cuprates

7Li and 13C solid-state MAS NMR spectra of three lithium cuprates with known X-ray structures--lithium([12]crown-4)2 dimethyl and diphenyl cuprate (1,2) and lithium(thf)4-[tris(trimethylsilyl) methyl]2 cuprate (3)--have been measured and analysed with respect to the quadrupolar coupling constants of lithium-7, chi(7Li), and the asymmetry parameters of the quadrupolar interactions, eta(7Li), as well as the 6, 7Li and 13C chemical shifts. The chi(7Li) values of 23, 30, and 18 kHz for 1, 2 and 3, respectively, are in line with the high symmetry around the lithium nucleus in the solvent-separated structures and may be used as reference data for this structural motif. Calculations based on charges derived from ab initio 6-31 G* HF computations using the point charge model (PCM) and the program GAMESS support the experimental findings.     

Electrochemical performances of lithium ion batteries from hydrothermally synthesized LiFePO4 and carbon spherules

Hydrothermally synthesized LiFePO₄ cathode and carbon spherules anode materials were investigated by full-cells for the first time. The assembled half-cells suggest that electrode materials prepared hydrothermally have excellent electrochemical properties. Despite having a capacity loss during the formation process, the assembled LiFePO₄/CS full-cells still exhibit an excellent cycling performance with stable coulombic efficiency at 100% and less than 9% capacity fading after 260 cycles, which suggest that hydrothermally fabricated electrode materials have a potential application in EVs and stationary energy storage.     

High-pressure investigation of Li2MnSiO4 and Li2CoSiO4 electrode materials for lithium-ion batteries

In this work, the high-pressure behavior of Pmn2(1)-Li(2)MnSiO(4) and Pbn2(1)-Li(2)CoSiO(4) is followed by in situ X-ray diffraction at room temperature. Bulk moduli are 81 and 95 GPa for Pmn2(1)-Li(2)MnSiO(4) and Pbn2(1)-Li(2)CoSiO(4), respectively. Regardless of the moderate values of the bulk moduli, there is no evidence of any phase transformation up to a pressure of 15 GPa. Pmn2(1)-Li(2)MnSiO(4) shows an unusual expansion of the a lattice parameter upon compression. A density functional theory investigation yields lattice parameter variations and bulk moduli in good agreement with experiments. The calculated data indicate that expansion of the a lattice parameter is inherent to the crystal structure and independent of the nature of the transition-metal atom (M). The absence of pressure-driven phase transformation is likely associated with the incapability of the Li(2)MSiO(4) composition to adopt denser structures while avoiding large electrostatic repulsions.     

锂离子电池有机电解液材料研究进展

综述了锂离子电池有机电解液材料的研究现状。锂离子电池有机电解液主要由电解质锂盐、有机溶剂和添加剂三个部分组成,新型电解质锂盐的研究开发可分为三个方面：（1）LiTFSI及其类似物;（2）络合硼酸锂化合物;（3）络合磷酸锂化合物。有机溶剂的研究工作主要集中在新型有机溶剂的开发上。最重要的添加剂主要有三类：（1）主要用以改善碳负极SEI膜性能的添加剂;（2）过充电保护添加剂;（3）配体添加剂。     

Investigation of the gas evolution in lithium ion batteries: effect of free lithium compounds in cathode materials

The evolution of gas in lithium ion batteries (LIBs) was investigated. The large amount of gas emission related to a charged cathode has been a critical issue because it causes deformation and performance degradation of LIBs. This study examined the effect of free lithium compounds such as Li₂CO₃ or LiOH on gas generation, which revealed several different features comparing with gas generation related to the cathode active materials themselves: CO₂ was the main gas generated, chain-structured carbonate solvents such as dimethyl carbonate or ethyl methyl carbonate generated more gas than cyclic-structured ethylene carbonate, and the gas generation did not occur without LiPF₆ in the electrolyte solution. These were found to be the main reason for the different gas-generating behaviors between LiCoO₂ (LCO) and LiNi_0.85Co_0.12Al_0.03O₂ (NCA) cathodes. For LCO, which has a very small amount of free lithium compounds on the surface, the gas was generated mainly by a reaction between delithiated LCO itself and the electrolyte solution, whereas a considerable amount of gas was generated by surface free lithium for NCA. Therefore, the removal of free lithium compounds is essential, particularly for NCA, to prevent the swelling of LIBs.