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Nowadays, our lives have become completely dependent on energy. That is the reason why special attention was focused to the development of clean sustainable energy sources due to the depletion of fossil fuel and its negative impact on the environment. In this regard, many electrochemical storage systems were explored. However, lithium ion batteries are the most effective systems dominating the battery market and used in several applications like cellphones, laptops, digital cameras, etc. The performance of such electrochemical energy storage system strongly depends on the used electrode material. Here we will present our recently obtained results on phosphates as safe and cost-efficient electrode materials for the battery technology.

Natrium super ionic conductor (NASICON) materials providing attractive properties such as high ionic conductivity and good structural stability are considered as very promising materials for use as electrodes for lithium- and sodium-ion batteries. Herein, a new high-performance electrode material, Li0.5Ni0.5Ti1.5Fe0.5(PO4)3/C, was synthesized via the sol-gel method and was electrochemically tested as an anode for lithium ion batteries, providing enhanced electrochemical performance as a result of nickel substitution into the lithium site in the LiTi2(PO4)3 family of materials. The synthesized material showed good ionic conductivity, excellent structural stability, stable long-term cycling performance, and improved high rate cycling performance compared to LiTi2(PO4)3. The Li0.5Ni0.5Ti1.5Fe0.5(PO4)3/C electrode delivered reversible capacities of about 93 and 68% of its theoretical one at current rates of 0.1 C (6.42 mA·g-1) after 100 cycles and 5 C (320.93 mA·g-1) after 1000 cycles, respectively. Theoretically, three Li+ ions can be inserted into the vacancies of the Li0.5Ni0.5Ti1.5Fe0.5(PO4)3/C structure. However, when the electrode is discharged to 0.5 V, more than three Li+ ions are inserted into the NASICON structure, leading to its structural transformation, and thus to an irreversible electrochemical behavior after the first discharge process.

Lithium-metal batteries offer substantial advantages over lithium-ion batteries in terms of gravimetric and volumetric energy densities. However, their widespread practical use is hindered by safety concerns, often attributed to the poor stability of the metallic lithium interface, where electrochemical impedance spectroscopy (EIS) can provide crucial information. The EIS spectra of metallic lithium electrodes proved to be more complex than expected, especially when studying thin lithium metal foils. Here, it is identified that charge-transfer impedance becomes one of the main components of the EIS spectra, the magnitude of which is found to be strongly dependent on the native passivation layer of metallic lithium and on the nature of electrolyte. "Asymmetricity" of the EIS spectra in symmetric cells when separated the working and counter electrode contributions to the total impedance using three-electrode cells is also identified.

Ni0.5 Ti2 (PO4 )3 /C NASICON-type phosphate is introduced as a new anode material for lithium-ion batteries (LIBs). Ni0.5 Ti2 (PO4 )3 /C was synthesized through the sol-gel route and delivered some remarkable electrochemical performances. Specifically, the Ni0.5 Ti2 (PO4 )3 /C electrode demonstrates a high rate capability performance and delivers high reversible capacities ranging from 130 mAh g-1 to about 111 mAh g-1 at current rates ranging from 0.1 C to 5 C in the voltage window of 1.85-3 V (vs. Li+ /Li). In the same voltage range, the material reaches an initial capacity of 105 mAh g-1 with a capacity retention of about 82 % after 1000 cycles at the high current rate of 10 C. The electrodes are also tested in the wider voltage range of 0.5-3 V (vs. Li+ /Li) and show good reversibility and rate capability performance. Moreover, the Ni0.5 Ti2 (PO4 )3 /C electrodes enable fast Li+ diffusion (in the order of 10-13 cm2 s-1 ) compared with other NASICON-type materials. As a result, a first discharge capacity of 480 mAh g-1 is reached.

Natrium super ionic conductor (NASICON) materials providing attractive properties such as high ionic conductivity and good structural stability are considered as very promising materials for use as electrodes for lithium- and sodium-ion batteries. Herein, a new high-performance electrode material, Li

A correlation between the crystal structure, the ionic conductivity and the electrochemical performance in Lithium-ion batteries was established for a series of NASICON-type phosphates Li0.5M0.5Ti1.5Fe0.5(PO4)3 (M = Mn, Co, Mg). These electrode materials, where the M1 site contains both lithium and the divalent cation M, were prepared using a simple sol-gel process while controlling the pH and the final synthesis temperature. The three phosphates crystallize in the rhombohedral system (S.G. R-3c) with comparable unit cell parameters but with slight difference in the local distortion of the PO4 tetrahedra as confirmed by the Raman study. The ionic conductivities of the Li0.5M0.5Ti1.5Fe0.5(PO4)3 materials were measured at different temperatures using a wide range of frequencies. Mn-based phosphate shows the best features for application as electrode material for Li-ion batteries in term of the conductivity at room temperature and the activation energy of Li+ conduction process. The initial discharge capacity of 100 mAh.g − 1 was obtained for the Mg-based phosphate, 104.3 mAh.g − 1 for the Co-based material while the Mn-based material delivers the best first discharge capacity of 125.3 mAh.g − 1 with the lowest polarization in relation with its better conduction properties. This result was also confirmed by the rate capability tests where Mn-based phosphate shows enhanced electrochemical performance even at fast rate of 5C.

Ni

Partial lithium substitution with nickel (0.25 of Ni2+ ion) in the previously reported Li1.5Fe0.5Ti1.5(PO4)3/C (LFTP@C) was performed to improve its structural and electrochemical properties. The new LiNi0.25Fe0.5Ti1.5(PO4)3/C (LNFTP@C) material was then tested as electrode for lithium ion batteries. In the voltage window 1.85V–3.0 V vs. Li+/Li, attractive electrochemical performances were obtained, mostly in terms of rate capability performance. At a current rate of 0.1C (6.6 mAg−1), the material delivered a capacity of around 120 mAhg−1, while at 5C, we observed a slight drop of the specific capacity reaching a value of 108 mAhg−1. Long-term cycling performance stability was also tested demonstrating a remarkable capacity decrease during the last 500 cycles. The capacity retention decreased from 94% to 91% after 500 cycles to about 77% and 74% after 1000 cycles at fast current rates of 5C (329.8 mAg−1) and 10C (659.6 mAg−1), respectively. In the wider voltage window, an average specific capacity of around 380 mAhg−1 was attained at a slow current rate of 0.1C.

Being considered as a high Li-ion mobility material, Nasicon structured Li 1.5 Fe 0.5 Ti 1.5 (PO 4 ) 3 phosphate material was synthesized via sol-gel route and electrochemically tested as electrode material for lithium-ion batteries. The material was tested in half-lithium electrochemical cells, within two voltage windows, 1.5–3.0 V and 0.5–3.0 V, and delivered first discharge capacities of 129 mAh/g and 567 mAh/g, respectively. Raman spectroscopy was used to confirm the material's structure before and during cycling. In addition, a comparative study of the electrochemical performance by the use of two different binders (PVDF and CMC), was conducted and showed a significant change in the electrochemical performance due to the change of the binder. Electrochemical impedance spectroscopy was used to evidence the electrodes' interface changes during cycling.