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Review
. 2023 Oct 30;16(21):6970.
doi: 10.3390/ma16216970.

Review and New Perspectives on Non-Layered Manganese Compounds as Electrode Material for Sodium-Ion Batteries

Ricardo Alcántara  1 , Carlos Pérez-Vicente  1 , Pedro Lavela  1 , José L Tirado  1 , Alejandro Medina  1 , Radostina Stoyanova  2
Affiliations
Review

Review and New Perspectives on Non-Layered Manganese Compounds as Electrode Material for Sodium-Ion Batteries

Ricardo Alcántara et al. Materials (Basel). .

Abstract

After more than 30 years of delay compared to lithium-ion batteries, sodium analogs are now emerging in the market. This is a result of the concerns regarding sustainability and production costs of the former, as well as issues related to safety and toxicity. Electrode materials for the new sodium-ion batteries may contain available and sustainable elements such as sodium itself, as well as iron or manganese, while eliminating the common cobalt cathode compounds and copper anode current collectors for lithium-ion batteries. The multiple oxidation states, abundance, and availability of manganese favor its use, as it was shown early on for primary batteries. Regarding structural considerations, an extraordinarily successful group of cathode materials are layered oxides of sodium, and transition metals, with manganese being the major component. However, other technologies point towards Prussian blue analogs, NASICON-related phosphates, and fluorophosphates. The role of manganese in these structural families and other oxide or halide compounds has until now not been fully explored. In this direction, the present review paper deals with the different Mn-containing solids with a non-layered structure already evaluated. The study aims to systematize the current knowledge on this topic and highlight new possibilities for further study, such as the concept of entatic state applied to electrodes.

Keywords: manganese compounds; multianion; phosphate; post-lithium batteries; sodium-ion batteries; spinel.

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Conflict of interest statement

The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to publish the results.

Figures

Figure 3
Figure 3
Structures of several Mn-containing electrode materials. (a) Cubic spinel Li0.03Mn2O4 [16]. (b) Tetragonal spinel NaMnO2 [13]. (c) NaMn2O4 [17]. (d) Tunnel-type, Na0.44MnO2 [18].
Figure 1
Figure 1
Element abundances of the upper continental crust [1,2].
Figure 2
Figure 2
Schematic overview of the main types of Mn-based materials for SIB.
Figure 4
Figure 4
Calculated and experimental voltage profile of tunnel-type NaxMnO2 in sodium cell. Reprinted (adapted) with permission from Ref. [25]. Copyright (2012) ACS.
Figure 5
Figure 5
Electrochemical properties of multiangular rod-shaped Na0.44MnO2 in a sodium cell. Reprinted (adapted) with permission from Ref. [36]. Copyright (2017) ACS.
Figure 6
Figure 6
Structures of selected manganese compounds for sodium batteries. (a) Tetragonal α-MnO2 (I4/m) [57]. (b) Cubic spinel NiMn2O4 [58]. (c) Cation-disordered rock salt-type NaMnO2 [59]. (d) Perovskite-type NaMnF3 [60].
Figure 7
Figure 7
Electrochemical properties of spinel-type MgMn1.6Fe0.4O4 in sodium cell. Reprinted (adapted) with permission from Ref. [15]. License Number 5560700952879 (Elsevier).
Figure 8
Figure 8
Structures of selected manganese compounds for sodium batteries based on polyanions. (a) Maricite-type NaMnPO4. (b) Olivine-type NaMnPO4. (c) NASICON-type Na3Mn2(PO4)3.
Figure 9
Figure 9
Structures of (a) Na3MnPO4CO3 and (b) Na3MnPO4CS3 [102].
Figure 10
Figure 10
Schematic diagram for a one-step process of two types of electrode materials [102]. Continue blue line: normal process. Dotted red line: entatic state path. The strain energy is X.
Figure 11
Figure 11
Electrochemical properties of NASICON-type Na3MnTi(PO4)3 in sodium cell. Reprinted (adapted) with permission from Ref. [112]. Copyright (2016) ACS.
Figure 12
Figure 12
Structure of Na2MnSiO4.
Figure 13
Figure 13
Structure of Na2MnII[MnII(CN)6]·2H2O [126].
Figure 14
Figure 14
Electrochemical properties of MnFe2O4@C in sodium cell. Reprinted (adapted) with permission from Ref. [159]. Copyright (2016) ACS.
Figure 15
Figure 15
Advantages and challenges of the SIB batteries with manganese compounds.
Figure 16
Figure 16
Strategies for improvement of the SIB batteries with manganese compounds.
See this image and copyright information in PMC

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