The use of substitutional p‐doping as a means to enhance the insertion energies of multivalent metals in transition metal oxides, and therefore the resulting voltages in an electrochemical cell, due to band structure modulation is investigated using first principles calculations. The investigations reveal the formation of n‐hole polarons (with n > 1) in the form of oxygen dimers in p‐doped charge‐transfer insulating transition metal oxides, caused by localized p holes on oxide ions in agreement with previous findings. It is found that the oxygen dimer formation has an adverse effect on adsorption energetics compared to the single‐hole case without dimerization. On the other hand, strained systems or Mott insulators with qualitatively different valence band composition do not exhibit oxygen dimerization with multihole doping. The results demonstrate the advantages and limitations of transition metal oxide electrode p‐doping and show a path to possible strategies to overcome detrimental effects.

中文翻译：

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过渡金属氧化物阴极材料的掺杂能否提高多价金属可达到的电压？

使用第一性原理计算研究了使用取代p掺杂作为增强过渡金属氧化物中多价金属插入能的手段，以及由于带结构调制而在电化学电池中产生的电压的方法。研究揭示了n孔极化子的形成（其中n > 1）以p掺杂的电荷转移绝缘过渡金属氧化物中的氧二聚体形式，这是由氧化物离子上的局部p孔引起的，与先前的发现一致。已发现，与没有二聚作用的单孔情况相比，形成二聚体的氧对吸附能有不利影响。另一方面，具有价态带组成定性不同的应变系统或Mott绝缘子在多孔掺杂下不会表现出氧二聚作用。结果证明了过渡金属氧化物电极p掺杂的优势和局限性，并显示了克服有害影响的可能策略的途径。