Attempts to introduce vanadium doping into the olivine-structured LiMnPO₄ cathode material for the Li-ion batteries resulted in the (y + z)PO₄³⁻ → yVO₄³⁻ + 4zOH⁻ (y < 0.17, z ≤ 0.1) co-substitution and the formation of the hydrotriphylite-type Li_1−xMn_1+x(PO₄)_1−y−z(VO₄)_y(OH)_4z solid solutions. Their crystal structure and chemical composition were studied with Rietveld structure refinement from synchrotron X-ray powder diffraction data, energy-dispersive X-ray analysis, infrared and Raman spectroscopy, electron energy loss analysis and mass spectrometry. Li_0.96Mn_1.04(PO₄)_0.74(VO₄)_0.16(OH)_0.4 crystallizes in the space group Pnma and a = 10.5150(2) Å, b = 6.11773(9) Å and c = 4.78555(9) Å with up to 5% of Mn in the Li position. Charge compensation is achieved through partial oxidation of the Mn cations to the oxidation state above +2. The heterovalent substitution in anionic sublattice and defectiveness of the cationic one cause blocking of Li-ion diffusion channels that drastically impede the electrochemical performance resulting in electrochemical capacity not exceeding 35 mAh g⁻¹.

试图引入钒掺杂到橄榄石结构的LiMnPO ₄的正极材料用于锂离子电池导致（Ý  +  Ž）PO ₄ ^3- → ý VO ₄ ^3-  + 4 ž OH ^- （Ý  <0.17，ž  ≤ 0.1）共取代并形成水滑石型Li ₁ - _x Mn _{1+ x}（PO ₄）_{1 -yz}（VO ₄）_y（OH）_4z固溶体。通过同步加速器X射线粉末衍射数据，能量色散X射线分析，红外和拉曼光谱，电子能量损失分析和质谱，通过Rietveld结构改进研究了它们的晶体结构和化学组成。Li _0.96 Mn _1.04（PO ₄）_0.74（VO ₄）_0.16（OH）_0.4在空间群Pnma中结晶，a  = 10.5150（2）Å，b  = 6.11773（9）Å和c = 4.78555（9）Å，在Li位置含5％的Mn。通过将Mn阳离子部分氧化至+2以上的氧化态来实现电荷补偿。阴离子亚晶格中的异价取代和阳离子亚晶格的缺陷导致锂离子扩散通道的阻塞，从而极大地阻碍了电化学性能，导致电化学容量不超过35 mAh g ^-1。