The chemistry of thorium phosphate reported in the literature has been found to be erroneous. It was reconsidered in terms of careful chemical preparations and specific analytical methods. Special attention has been paid to the atom ratio value referred to r = thorium/phosphorus, which was experimentally fixed in order to obtain the correct composition of the final compound. A new compound with the chemical formula Th4(PO4)4P2O7, derived from the crystal structure determination, has been obtained. The unit cell parameters were obtained from powder and single-crystal X-ray diffraction data. It is orthorhombic (space group Pcam, Z = 2) with the cell dimensions a = 12.8646(9) Å, b = 10.4374(8) Å, c = 7.0676(5) Å, and V = 949.00(9) Å3. The atomic positions were derived from Patterson and Fourier methods and the structure was refined to an R value of 0.039. The structure consists of layers parallel to (010) containing both PO4 and P2O7 groups. These layers alternate with planes of Th atoms. The coordination sphere of the two independent heavy atoms is formed by eight O atoms from five PO4 and one P2O7 groups. The formula of thorium phosphate Th4(PO4)4P2O7 is in good agreement with the elementary composition derived from electron microprobe analysis, which gave a ratio r = 2/3. Any other value of r (1/2 < r < 3/4) induces the formation of polyphase systems:  Th4P6O23 and ThO2 for r > 2/3; Th4P6O23 and ThP2O7 for r < 2/3. The characterization of thorium phosphate diphosphate by means of infrared spectroscopy confirmed the presence of diphosphate groups in the compound.

Lithium intercalation into ␤-VOPO 4 has been performed, both chemically and electrochemically, with X-ray diffraction characterization of the resulting phases at various levels of intercalation-deintercalation. It is shown that intercalation occurs through a first-order transition at 3.98 V vs. Li ϩ /Li 0 , which leads to a ␤-LiVOPO 4 -like structure but with lithium ordering which doubles the a and b unit cell parameters. Starting from chemically intercalated ␤-Li 0.92 VOPO 4 , the reversible process involves 0.55 electron per transition metal, i.e., 90 mAh/g, at a C/50 rate which owing to the 3.95 V potential plateau, gives an attractive specific energy of 355 Wh/kg. Fundamentally, it is shown herein that the redox energy of V 5ϩ /V 4ϩ couple in an octahedral coordination involving (V ϭ O) mϩ unit is included between those observed in oxides and in M 2 (PO 4 ) 3 compounds with (PO 4 ) 3Ϫ oxo-anions.