《Table 1 Structure parameters of LiCrxNiyMn2-x-yO4 (0≤x≤0.3, 0≤y≤0.3) samples》

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《Cr~(3+)和Ni~(2+)复合掺杂的尖晶石氧化物用于提高钻孔热电池放电性能（英文）》

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Fig.1 shows the XRD patterns of the spinel LiCrxNiyMn2-x-yO4（0≤x≤0.3，0≤y≤0.3）samples.As can be seen from Fig.1 that the diffraction peaks of spinel samples with different doping amounts were well consistent with the characteristic peaks of LiMn2O4（PDF No.70-3120）with an Fd3m space group.No additional diffraction peaks were observed except for lithium manganate，indicating a good purity of the spinel samples.It can be clearly observed that the diffraction peaks of the doped derivative were shifted to a large angle compared to LiMn2O4according to the partial enlargement of the（400）plane diffraction peak，which was caused by the decrease of lattice parameters due to doping.As we know，the average oxidation states of manganese ions in LiMn2O4is+3.5，that is，the amount of Mn3+and Mn4+ions exist in a ratio of 1∶1.X-ray photoelectron spectrometry（XPS）analysis show that the oxidation states of Cr and Ni in lithium manganate are+3 and+2，respectively[17]，and the two ions have a radius of 0.061 5 and 0.070 nm，respectively.Both of Cr3+and Ni2+ions substitute the Mn3+ions in lithium manganate，thus the Mn3+ions（0.064 5 nm）shift to the smaller radius of the Mn4+ions（0.053 nm）with the addition of Ni2+ions in order to maintain electrical neutrality.The lattice parameters of the spinel sample calculated based on the XRD diffraction data are listed in Table 1，and this result is consistent with the above discussion.However，the sample with the most doped amount of Ni2+ions did not have the smallest interplanar spacing，which may be related to the loss of oxygen in the sample.