Lyotropic liquid crystalline mesophases from acid-salt-surfactant systems: synthesis and characterization of mesoporous LiMPO4 (M=Mn(II),Fe(II),Co(II) AND Ni(II))

This study presents the synthesis and characterization of mesoporous lithium metal phosphates (LMPs) of Mn(II), Fe(II), Co(II), and Ni(II). The LMPs were synthesized using a modified molten salt self-assembly (MASA) method. Clear and homogeneous solutions of lithium nitrate (LiNO3), transition metal nitrate (M(H2O)62, phosphoric acid (H3PO4, PA), and surfactant (pluronic P123, EO20PO70EO20, where EO is ethylene oxide and PO is propylene oxide) in water were spread on a microscope slide by drop-cast coating method to from a lyotropic liquid crystalline (LLC) mesophase. The mesophases were characterized using polarized optic microscope (POM) and x-ray diffractrometer (XRD) techniques. In the mesophase, the mole ratio of the inorganic components was kept constant (1:1:1, Li(I):M(II):PA) but the inorganic ingredient (lithium salt, transition metal salt, and PA) to surfactant mole ratios were varied from 10 to 90. The mesophases are ordered and diffract at small angles in all compositions. However, the mesophases slowly undergo transformation from LLC mesophase to semisolid mesostructured particles by the hydrolysis of PA and LMP formation over time. The drop-cast coated samples were calcined to produce mesoporous LMPs. The samples were characterized using N2 adsorption-desorption, XRD, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Attenuated total reflectance - fourier-transform infrared spectroscopy (ATR-FTIR) techniques. The LMPs are amorphous up to 400 oC but become crystalline above this temperature. The amorphous mesoporous LMPs have large Brunauer, Emmett and Teller (BET) surface area, around 30-100 m2/g but drops down to a few m2/g upon annealing at 500 oC. The SEM images show that the particle morphology depends on the inorganic/surfactant ratio in the initial mesophase. Both Mn(II) and Co(II) produce the olivine phase of LiMnPO4 (LMnP) and LiCoPO4 (LCoP), respectively, under our reaction conditions. However, Ni(II) samples need either excess lithium source or adjustment of pH of the clear solutions to form olivine phase of LiNiPO4 (LNiP). This adjustment can be done by using LiH2PO4 as the Li(I) and phosphate source in place of LiNO3 and PA. Unlike iron compound, the olivine phases of LMPs of Mn(II), Co(II) and Ni(II) were successfully obtained. In the iron case, it is difficult to keep iron in 2+ oxidation state under our reaction conditions. It undergoes an oxidation to form Fe3+ species. Therefore, mesoporous FePO4 and Li3Fe2(PO4)3 materials were synthesized, where the iron has 3+ oxidation state. Most synthesis has been carried out over glass slides that simply contain 16% of sodium. We found that our samples undergo Na+ ion-exchange reaction with the glass substrates above 300 oC. Therefore, the samples were first calcined at 300 oC over glass substrates and further annealed at higher temperatures in alumina sample holder to produce mesoporous forms. However, if the annealing step is carried over the glass slides, sodium metal phosphates (NaMPs) form in maricite phase. These samples were also characterized by XRD, SEM, TEM, and ATR-FTIR techniques. To eliminate the ion-exchange reactions, other substrates like quartz, pyrex or fluorine doped tin oxide (FTO) were used. However, notice that ion-exchange can also be performed to synthesize mesoporous maricite NaMPs as another synthesis method.