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Figure 4. Energy density (Wh kg−1) and capacity retention (%) for the three main types of cathode materials for the most common phases used in NIBs. The size of the dot represents number of cycles while the color indicates the type of metal. densities.161,162 It should be noted that the electrochemical per- formance of a material does not depend solely on one kind of ion substitution, it depends greatly on the presence of other cations in the structure and the mutual interaction between them. In general, P2-NaxMO2 can potentially enable higher rate capability due to the facile sodium ion mobility through the adjacent trigo- nal prismatic environment.24,25,163–165 This feature is unique to P2 sodium materials as a superior advantage compared to LIB cathodes. Similar analysis on O3-type oxide cathode materials shows that most materials reported in the literature contained an Mn-, Co-, or Ni- content with less than 0.5 ratios while Fe-content was usually in the range of 0.25–0.75. High Mn- and Co-content usu- ally leads to higher energy density and capacity retention166,167 while high Fe- and Ni-content tends to result in lower energy density but higher capacity retention.168–173 In order to achieve a sustainable supply, Mn-based compositions should be the main focus for layered oxides, where their physical/electrochemical properties can be modulated through the incorporation of other metal ions. The choice of the metal substitution depends on the requirement of the applications, such as voltage, specific capac- ity, or cycle life. The second category of the cathodes is polyanions. The crys- tal structure of polyanions is quite rich and depends strongly on the nature and the interconnection between the polyhedral constituting the framework. The main space groups encoun- tered in this class of materials are C2, P1, P21/c, P42, Pn, and R-3c (Fig. 4). For NASICON-based materials, R-3c is the dominant space group; nevertheless, Na+ ordering can also occur with a symmetry reduction to monoclinic systems.174 Strong covalent bonds between polyhedral units enable this type of material to support long-term cycling with minimal 8 MRS ENERGY & SUSTAINABILITY // VOLUME XX // www.mrs.org/energy-sustainability-journalPDF Image | cathode materials for sustainable sodium‐ion batteries
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