2.1. Metal Oxides
Transition metal oxides (TMOs) have emerged as the most significant anodes for SIBs attributed by their high abundance, easy synthesis, chemical stability, and cost-effectiveness, all contributing to their huge potential for commercialization. Since the most attractive conventional graphite anode is less active in Na cells, insertion/intercalation reaction anodes in TMOs have been intensively studied to replace the graphite. Especially, TMOs with early TM groups including Ti- and V-oxides have drawn considerable attention based on their high sodiation activity and excellent cycle stability.
Ti-based oxides can be typically regarded as insertion/intercalation-type electrodes and attractive anodes for SIBs in light of their advantages, such as the light molar weight of Ti, non-toxicity, high chemical stability, facile synthesis procedure, and cycle stability. In addition, the modest insertion potential of Na
+ ions at about 0.6 V (vs. Na/Na
+) helps prevent Na metal plating issues [
43]. The most common anodes studied in Ti-based oxides can be divided into three types: TiO
2, Li
4Ti
5O
12, and Na
2Ti
3O
7 phases (
Figure 5a) [
30,
44].
TiO
2 phases have several polymorphs in crystalline form such as anatase, brookite, rutile, and bronze phases, whereas only anatase, rutile, and bronze phases exhibit electrochemical activity for SIBs [
45]. The TiO
2 polymorphs are composed of TiO
6 octahedra and three-dimensional (3D) arrangement variations of the TiO
6 octahedra build different crystal structures and the corresponding electronic structures. In the case of the anatase structure, it has a space group of I4
1/amd with a tetragonal crystal system in which the TiO
6 octahedra share four edges organized in zig-zag chains as shown in
Figure 5a. The rutile TiO
2 structure, with the same tetragonal crystal system as anatase but a different space group of P4
2/mmm, shares only two edges of TiO
6 octahedra and forms linear chains parallel to the (001) planes. In contrast, bronze TiO
2 phase exhibits a monoclinic structure, featuring wrinkled sheets composed of edge- and corner-sharing TiO
6 octahedra (
Figure 5a).
Systematic studies on electrochemical reaction behavior of anatase TiO
2 exhibit that 0.25 mole of Na
+ ions can be intercalated into TiO
2 at 0.3 V vs. Na/Na
+ and 0.69 mole of Na
+ ion can be further inserted with an amorphization reaction during the first sodiation process (
Figure 5b) [
46]. However, an irreversible plateau at about 0.2 V vs. Na/Na
+ appears, where Na
+ ions are inserted into interstitial sites of anatase and form rhombohedral active phases [
30]. This irreversible reaction results in only 0.41 mole of Na
+ ions inserted into each TiO
2 reversibly during the following process, which causes a low reversible capacity of ~140 mAh g
−1 [
46].
In the case of rutile, it is the most chemically stable polymorph in TiO
2 and has a good cyclability. However, due to its poor electronic conductivity caused by its large band gap structure (about 3.0 eV) [
30], inferior rate capability was observed. Additionally, DFT calculation indicates that rutile TiO
2 has a relatively elevated energy barrier showing 20.65 eV for Na
+ ion diffusion compared to that of anatase TiO
2 (11.1 eV), and the Na
+ ion has a solitary diffusion path along the c-axis. Conversely, anatase TiO
2 has two-dimensional pathways along the a- and b-axes, which mean theoretically easier Na
+ ion diffusions in the anatase structure compared to that of rutile TiO
2 [
45].
Bronze TiO
2 has a C2/m space group and three distinct intercalation sites with an open structure by edge-sharing oxygen of neighboring layers. Liu et al. compared the Na
+ ion storage mechanism of anatase and bronze TiO
2 through X-ray absorption spectroscopy (XAS). Since bronze TiO
2 has lower crystallinity and density compared to those of the anatase structure, the sodiation process can be made easier by facilitating Na
+ ion diffusion. That means stability of bronze TiO is much better than that of anatase. However, the still unknown mechanism of irreversible phase transformation to Na
xTi
yO
z phase in bronze TiO
2 needs to be further studied to clarify the exact sodiation/desodiation process [
30,
44,
47,
48].
Recently, binary phase of anatase/bronze TiO
2 was studied for its application as a superior Na
+ ion storage electrode in SIBs [
45,
49,
50]. One-dimensional nanostructured nanofibers and binary phase heterojunctions of TiO
2 with a phosphated surface were introduced to improve ionic transportation kinetics and electronic conductivities. Meanwhile, charge/discharge, well-crystallized internal structure, and disordered amorphous surface structure were formed by phosphorylation resulting ionic/electronic fields and improved Na
+ ion conductivity. Simultaneously, the 1D nanofiber structure increased the contact area between the anode/electrolyte and thus reduced Na
+ ion diffusion distance (
Figure 5c) [
50]. As a result, anatase/bronze TiO
2 nanofiber showed a reversible capacity of 224.7 mAh g
−1 tested at 0.2 A g
−1 and prolonged cycle performance with a reversible capacity of 108.9 mAh g
−1 tested at 2 A g
−1 after 1000 cycles (
Figure 5d) [
50].
Figure 5.
(
a) Crystal structures of Ti-based oxides for SIB anode materials. Reproduced with permission [
30]. Copyright 2017, WILEY-VCH. (
b) Voltage profiles of anatase TiO
2 anode for SIBs tested at 3.35 mA g
−1. Reproduced with permission [
46]. Copyright 2014, WILEY-VCH. (
c) Schematic illustration of working mechanism of surface phosphorylation of TiO
2 anode for SIBs. (
d) Cycle performance of anatase/bronze TiO
2 nanofiber tested at 0.2 and 2.0 A g
−1, respectively. Reproduced with permission [
50]. Copyright 2020, Elsevier B.V.
Figure 5.
(
a) Crystal structures of Ti-based oxides for SIB anode materials. Reproduced with permission [
30]. Copyright 2017, WILEY-VCH. (
b) Voltage profiles of anatase TiO
2 anode for SIBs tested at 3.35 mA g
−1. Reproduced with permission [
46]. Copyright 2014, WILEY-VCH. (
c) Schematic illustration of working mechanism of surface phosphorylation of TiO
2 anode for SIBs. (
d) Cycle performance of anatase/bronze TiO
2 nanofiber tested at 0.2 and 2.0 A g
−1, respectively. Reproduced with permission [
50]. Copyright 2020, Elsevier B.V.
As a “zero strain” anode in SIBs, Li
4Ti
5O
12 (LTO) was applied for reversible sodium storage behavior, accommodating three Na
+ ions per LTO with a reversible capacity of 145 mAh g
−1 and an operating potential at around 0.9 V vs. Na/Na
+ [
30]. The electrochemical reaction mechanism of LTO observed in SIBs is three-phase transformation, which is different from the two-phase reaction mechanism observed in LIBs. As for the reaction equation, it is expressed as 2[Li
3]
8aV
16c[Ti
5Li]
16dO
12 + 6 Na
+ + 6 e
−1 ↔ V
8a[Li
6]
16c[Ti
5Li]
16dO
12 (Li7) + V
8a[Na
6]
16c[Ti
5Li]
16dO
12 (Na6Li) (V = vacancy) (
Figure 6a) [
44,
50]. The final product after the discharge process is a mixture of Na6Li and Li7. Through an annular-bright-field (ABF) image (
Figure 6b), interphases between Li
7/Li
4 and Li
7/Na
6Li were confirmed after the discharge. During the long-term cycle process, the changed lattice parameters were negligible, implying that LTO can exhibit an excellent electrochemical reversibility for long-term cyclability. However, Na
+ ion diffusivity of LTO (10
−16 cm
2 s
−1) is not as high as that of observed in LIBs (10
−11 cm
2 s
−1) [
45]. Therefore, it is necessary to introduce different strategies including nanostructure engineering, heteroion or material do** or coating methods, surface modifications, etc. [
44,
48]. Chen et al. synthesized porous nanofibers of LTO interconnected with conductive 3D graphene structures and it raised interfacial sites and decreased Na
+ ion diffusion distance (
Figure 6c). This resulted in a reversible capacity of 195 mAh g
−1 at a 0.2 C rate (35 mA g
−1) for 115 cycles, coupled with long-term cycling durability, maintaining a capacity of 120 mAh g
−1 at a 3 C rate (525 mA g
−1) over 12,000 cycles (
Figure 6d) [
51].
Na
2Ti
3O
7 (NTO) is a layered structure comprising three TiO
6 octahedra, which share two edges and corners, forming (Ti
3O
7)
2− zigzag layers. NTO is a monoclinic crystal system with a P2
1/m space group. The two Na
+ ions can reversibly intercalate into layered structure of stable NTO and the reaction equation is Na
2Ti
3O
7 + 2 Na
+ + 2 e
− ↔ Na
4Ti
3O
7 [
45]. NTO is one of the most encouraging insertion-type anodes with a theoretical capacity reaching 177 mAh g
−1 on account of its innovative lowest working potential at 0.3 V vs. Na/Na
+ [
44,
45,
52,
53]. However, NTO has a high band gap energy of 2.75 eV, indicating poor ionic and electronic conductivities and cycling stability [
45]. In addition, since the calculated activation energy for Na
+ ion migration through TiO
6 octahedral layers is too high, Na
+ ions cannot diffuse through interlayers but just along layers [
44,
45]. Therefore, various strategies have been applied such as morphological modification, heteroatom do** or coating, and formation of layered NTO and tunnel Na
2Ti
6O
13 hybrid material (NNTO). The tunnel-type structure of Na
2Ti
6O
13, which has a bigger channel than the radius of Na
+ ions, exhibits high ionic conductivity and long-term cycling stability but a lower specific capacity. As a hybrid structure formation of NNTO, solid solution reactions occurred in the tunnel-type Na
2Ti
6O
13 and phase transformation occurred in the layered-type NTO, where the synergies of two phases increase reaction kinetics, reversible capacity, and consistent cycle performance. NNTO delivered a higher 1st discharge capacity of 212.5 mAh g
−1 tested at 20 mA g
−1, surpassing the theoretical capacity of NTO (177 mAh g
−1). While the long-term cycle test exhibited an excellent cycle retention during 4000 cycles even examined at 2 A g
−1, the reversible capacity was only ~20 mAh g
−1, which requires further improvements in rate capabilities (
Figure 6e) [
27,
54]. So far, Ti-based TMOs have been broadly applied as stable anode materials with the insertion mechanism, exhibiting superior long-term cycle performance compared to other types of anodes. Even though these types of insertion mechanism have benefits of less volumetric change and structural stability during cycling, the improvements in ion diffusion kinetics and specific capacity still need to be improved [
7].
Figure 6.
(
a) Phase transformation mechanism of Li
4Ti
5O
12 (LTO) anodes during sodiation and desodiation process in SIBs. (
b) ABF image for the sodiated LTO particle. Reproduced with permission [
44]. Copyright 2019, WILEY-VCH. (
c) Graphical illustration of the structural advantages and merits in Na
+ ion diffusion kinetics of 3D graphene interconnected porous LTO (G-PLTO) electrode. (
d) Cycle performance of G-PLTO anode for SIBs tested at 0.2 C and 3 C rates, respectively. Reproduced with permission [
51]. Copyright 2016, WILEY-VCH. (
e) Long-term cycle performance of NNTO anodes for SIBs tested at 2.0 A g
−1. Reproduced with permission [
54]. Copyright 2018, WILEY-VCH.
Figure 6.
(
a) Phase transformation mechanism of Li
4Ti
5O
12 (LTO) anodes during sodiation and desodiation process in SIBs. (
b) ABF image for the sodiated LTO particle. Reproduced with permission [
44]. Copyright 2019, WILEY-VCH. (
c) Graphical illustration of the structural advantages and merits in Na
+ ion diffusion kinetics of 3D graphene interconnected porous LTO (G-PLTO) electrode. (
d) Cycle performance of G-PLTO anode for SIBs tested at 0.2 C and 3 C rates, respectively. Reproduced with permission [
51]. Copyright 2016, WILEY-VCH. (
e) Long-term cycle performance of NNTO anodes for SIBs tested at 2.0 A g
−1. Reproduced with permission [
54]. Copyright 2018, WILEY-VCH.
Beyond the insertion reaction anodes with excellent cyclabilities, conversion-reaction-type anodes have been extensively studied for SIBs with later TM oxides (Fe-O, Co-O, Ni-O, etc.) due to their high theoretical capacities. Specifically, iron oxide anodes have received huge attention as cost-effective anode materials due to the abundance of resources and easy synthesis methods. Both hematite (α-Fe
2O
3) and maghemite (γ-Fe
2O
3) exhibit a substantial theoretical capacity of 1005 mAh g
−1, though magnetite (Fe
3O
4) shows a significant theoretical capacity of 926 mAh g
−1 based on the reaction equations of Fe
2O
3 + 6 Na
+ + 6 e
− → 2 Fe + 3 Na
2O and Fe
3O
4 + 8 Na
+ + 8 e
− → 3 Fe + 4 Na
2O. Basically, later TMs including Fe, Co, Ni, Cu, etc. in oxides are inactive with Na
+ ions, so they undergo the one-step conversion reaction [
36]. Despite the high theoretical and practical capacities of Fe-based oxides, they suffer from their poor electronic conductivities, large volume changes, and severe agglomerations occurring during the cycling process. Fabricating nanocomposites with iron oxide particles and conductive carbon-based materials can be a facile and effective strategy to form conformal carbon coating or carbon matrix with iron oxide anodes [
55].
Chen et al., for instance, synthesized a porous 3D structure of γ-Fe
2O
3@C nanocomposite using an aerosol-assisted method (
Figure 7a) [
56]. The TEM image of the nanocomposite shows that spherical γ-Fe
2O
3, with a mean particle diameter of 5 nm, is evenly distributed within the carbon matrix (
Figure 7b). This composite shows reversible capacity of 740 mAh g
−1 after 200 cycles tested at 0.2 A g
−1 (
Figure 7c) and 358 mAh g
−1 is maintained even after 1400 cycles tested at 2 A g
−1. Additionally, it has superior rate capability with a capacity of 317 mAh g
−1 even tested at 8A g
−1 [
56]. With a more stable and conductive α-Fe
2O
3 phase compared to γ-Fe
2O
3, **a et al. reported the peapod-like structure of α-Fe
2O
3@N-PCNF composites, consisting of Fe
2O
3 nanoparticles encapsulated in uniformly N-doped porous carbon fibers to ensure structural stability and high electrical conductivity. α-Fe
2O
3@N-PCNFs demonstrate a remarkable discharge capacity of 1434 mAh g
−1 tested at 0.1 A g
−1 (
Figure 7d) and maintain 396 mAh g
−1 tested at 2 A g
−1, maintaining 90% of their capacity after 1500 cycles [
55,
57].
In the case of Fe
3O
4, it indicates a theoretical capacity of 926 mAh g
−1 by reacting with 8 Na
+ ions and electrons and also suffers from reaction irreversibility, poor electric conductivity, and fast capacity fading. Recently, Liu’s group synthesized Fe
3O
4/3D graphene hybrid materials where graphene matrix alleviates aggregation of nanosized Fe
3O
4 particles and improves cycling stabilities. After 200 cycles, a high discharge capacity of 518.7 mAh g
−1 was maintained when tested at 0.1 C (92.6 mA g
−1) with coulombic efficiencies (CEs) higher than 99% (
Figure 7e) [
55,
58]. Qin et al. developed chain-like Fe
3O
4/C/red P by employing magnetic fields, which shows an adequate cycle life with a discharge capacity of 1390 mAh g
−1 up to 200 cycles tested at 0.2 A g
−1 and superior rate capability with a capacity of 692 mAh g
−1 tested at 2A g
−1 [
8,
59].
Besides iron oxides, other conversion reaction types of later TM oxides for SIBs have also been widely studied such as MnO
2, Mn
3O
4, Co
3O
4, NiO, CuO, etc. Among them, MnO
2 in SIBs has attracted a lot of attention due to its low price, polarization, reaction potential, and a significant theoretical capacity of 1232 mAh g
−1 [
60]. Weng et al. synthesized ultrafine MnO
2 nanoparticles (~4 nm), surrounded by heterogenous interfacial mesoporous SiO
2 bonds, and it displays high rate capability and stable cyclability, exhibiting a notable discharge capacity of 1000 mAh g
−1 tested at 37.5 mA g
−1. It delivers an increased initial reversible capacity of 567 mAh g
−1 compared to that of pure MnO
2 particles (19 mAh g
−1), while maintaining 70% of its capacity following 500 cycles tested at 0.15 A g
−1 [
61]. To sum up, different engineering strategies have been applied to various compositions of TM oxides as insertion- or conversion-reaction-type anodes for SIBs. Moreover, greater attention needs to be paid to achieve reversible capacities close to their theoretical capacities with a high ICE regarding stable solid electrolyte interphase (SEI) layers covering the electrode surface [
62].
2.2. Metal Sulfides
Transition metal sulfides (TMSs) are representative chalcogenides, which have high theoretical capacities as anode materials for SIBs with the conversion reaction mechanism and higher reaction potentials compared to those of TMOs (
Figure 4b). TMSs have attracted great attention not only as anode materials for SIBs but also for other energy storage applications of supercapacitors or energy conversion applications with electrocatalysts and photocatalysts [
63,
64]. TMSs, S-containing compounds, generally exhibit lower specific capacities than those of TMOs because they also react with two Na
+ ions at the end of the discharge process by forming Na
2S or Na
2O phases, while the molar weight of S (32 g mol
−1) is higher than that of O (16 g mol
−1). However, TMSs are classified into two groups according to their composition as metal-rich sulfides (TM
xS
y, x > y) or S-rich sulfides (x < y), and some S-rich sulfides can show higher specific capacity than TMOs due to the high contents of S in the compounds. For example, the Fe-S binary system has various stoichiometric compounds from metal-rich to S-rich phases such as Fe
3S, FeS, Fe
3S
4, Fe
7S
8, and FeS
2 with theoretical capacity ranging from 269 to 894 mAh g
−1 [
55]. There are additional advantages of TMSs such as the strength of M-S bonds in TMSs being lower than that of M-O bonds in TMOs, meaning kinetic favorability of conversion reactions in TMSs [
7]. Some studies have also depicted that TMSs have better electrical conductivity and higher electrochemical activity than their corresponding TMO counterparts. Taking NiCo
2S
4 as an example, it shows much lower band gap energy of 2.4 eV (vs. 3.6 eV) and a higher sweep coefficient of I-V curves compared to those of NiCo
2O
4 [
65,
66].
TM disulfides (TMS
2), known as 2D layered materials (TM = Ti, V, Mo, W, etc.), have high contents of S in the structure with TM planes sandwiched by two-hexagonal S planes per unit of layer and exhibit high specific capacities (
Figure 8a) [
67,
68]. During the sodiation process, the reaction mechanism is expressed as TMS
2 + x Na
+ + x e
− → Na
xTMS
2 (x < 1.0) and Na
xTMS
2 + (4 − x) Na
+ + (4 − x) e
− → TM
0 + 2 Na
2S. At the initial stage of discharge, the insertion of Na
+ ions into the layered structure occurs followed by the conversion reaction with phase separation (
Figure 8b) [
69]. Since TMSs have relatively higher reaction potentials than anodes for SIBs, most TMSs undergo a conversion reaction at the end of the discharge process when the potential reaches close to the redox potential of Na/Na
+. Previous studies on exploring electrochemical properties of anodes for SIBs have mainly been performed on early TMS
2 of TiS
2 and VS
2, which have the lightest molar weight of TMs and are the most common 2D layered materials of MoS
2 phase. As an example, the MoS
2 structure undergoes an initial intercalation of Na
+ ions followed by a conversion reaction, sharing an analogous structure of graphite with covalently bonded layers separated by weak van der Waals bonding with common interlayer spacing of 0.62 nm. This facilitates the faster ion diffusion and sustains reversible capacities and volumetric changes during cycles [
67]. Specifically, structural changes in MoS
2 during the sodiation process can be classified into three groups: those with a two-layer stacked hexagonal structure (2H-MoS
2), one-layer stacked trigonal structure (1T-MoS
2), and three-layer stacked rhombohedral structure (3R-MoS
2) (
Figure 8c) [
70]. The total reaction equations are expressed as 2H-MoS
2 + 0.5 Na
+ + 0.5 e
− → 2H-Na
0.5MoS
2 (at 0.85 V vs. Na/Na
+), 2H-Na
0.5MoS
2 + (x − 0.5) Na
+ + (x − 0.5) e
− → 1T-Na
xMoS
2 (at 0.75 V vs. Na/Na
+, x < 1.5), and 1T-Na
xMoS
2 + (4 − x) Na
+ + (4 − x) e
− → Mo
0 + Na
2S (<0.2 V vs. Na/Na
+) [
69]. Based on the above reaction mechanisms, MoS
2 exhibits an inferior cyclability and significant voltage hysteresis arising from irreversible phase transformation and the shuttle effect in polysulfides.
The 2D layered structure of MoS
2 also shows intrinsically low electronic conductivity, resulting a high interfacial charge transfer impedance during cycling [
71]. Normally, nanostructured particles in the form as nanosheets, nanotubes, or nanoflowers are combined with conductive carbonaceous materials, including amorphous carbon particles, carbon nanotubes (CNTs), or reduced graphene oxide (rGO), to facilitate Na
+ ion diffusion and electron transport [
72,
73,
74]. While the 2D layered structure of MoS
2 has a high theoretical capacity of 670 mAh g
−1, the reported monolayer MoS
2/graphene in SIBs suffered from a low reversible capacity of 230 mAh g
−1 when tested at 25 mA g
−1, along with a poor cyclability [
75,
76]. Therefore, to enhance an electrochemical performance of MoS
2, advanced nanostructure fabrication is essential. Shi et al. synthesized 2D MoS
2-carbon hybrid sandwiched nanosheets into 3D hierarchical hollow nanotubes. The carbon hybrid structure enlarges the space of the 2H-MoS
2 (002) interlayer from 0.615 to 0.986 nm for fast Na
+ ion insertion/extraction kinetics. Simultaneously, the 3D hollow structure can alleviate aggregation of particles and cope with volume change for electrode structure integrity. They showed an initial discharge capacity of 620 mAh g
−1 with an accompanying ICE of 84% tested at 0.2 A g
−1 and maintained 477 mAh g
−1 after 200 cycles (
Figure 8d). Furthermore, a high reversible capacity of 415 mAh g
−1 could be kept through 200 cycles tested at 1 A g
−1 and 187 mAh g
−1 is attained at a higher current density of 20 A g
−1 [
75].
Figure 8.
(
a) Crystal structure illustration of TMS
2 structure (TM = Mo or W). Reproduced with permission [
68]. Copyright 2014, Elsevier Ltd. (
b) Crystal structures of MoS
2 structure with 2H, 1T, and 3R structures. Reproduced with permission [
69]. Copyright 2017, WILEY-VCH. (
c) Voltage profiles and phase transformation sequences of MoS
2 structure during sodiation and desodiation processes. Reproduced with permission [
70]. Copyright 2022, Elsevier B.V. (
d) Voltage profiles of MoS
2/C nanotube electrode tested at 0.2 A g
−1. Reproduced with permission [
75]. Copyright 2016, Elsevier Ltd.
Figure 8.
(
a) Crystal structure illustration of TMS
2 structure (TM = Mo or W). Reproduced with permission [
68]. Copyright 2014, Elsevier Ltd. (
b) Crystal structures of MoS
2 structure with 2H, 1T, and 3R structures. Reproduced with permission [
69]. Copyright 2017, WILEY-VCH. (
c) Voltage profiles and phase transformation sequences of MoS
2 structure during sodiation and desodiation processes. Reproduced with permission [
70]. Copyright 2022, Elsevier B.V. (
d) Voltage profiles of MoS
2/C nanotube electrode tested at 0.2 A g
−1. Reproduced with permission [
75]. Copyright 2016, Elsevier Ltd.
In the case of FeS
2 with a non-layered cubic structure, it features a high theoretical capacity of 894 mAh g
−1 and several advantages of cost-effectiveness, natural abundance, and environmental friendliness [
69]. Nevertheless, in terms of sodium storage, it also shows an inferior cycle performance stemming from the large volume changes occurring during conversion reactions below 0.8 V vs. Na/Na
+ after irreversible intercalation reactions [
77]. Several studies exhibited better cycle retentions by using a higher discharge cut-off potential at ~0.5 V vs. Na/Na
+ to avoid severe structural changes by conversion reactions, while this approach is not an ideal solution due to the substantially decreased reversible capacities [
55].
2.3. Metal Selenides
One of the representative materials in chalcogenides commonly studied as anodes for SIBs is transition metal selenide (TMSe). TMSes have been applied in numerous applications of electrochemical capacitors, optoelectronics, photodetectors, and secondary batteries of LIBs, SIBs, and magnesium ion batteries (MIBs) [
78,
79]. Obviously, selenium (Se), belonging to group 16 with S, can store two Na
+ ions and then form Na
2Se phase after the sodiation process. Compared to TMSs, it is hard to achieve higher specific capacities in TMSes due to the 2.5 times higher molar weight of Se than S. Additionally, Se has received less attention as anodes for SIBs compared to S because S is more Earth abundant and cheaper in cost [
80]. Nonetheless, the much higher electronic conductivity (~10
−3 S m
−1) of Se than S has led many studies on TMSes as anodes for SIBs to explore their own advantages [
77,
78,
81,
82]. The TM di-selenide (TMSe
2, where TM = Sn, Mo, W, V, Bi, Ti) structure is the same layered structure as TMS
2 with sandwiched Se-TM-Se layers with covalent bonds connected by weak van der Waals bonds to the c-axis. Considering a Se atom has a larger atomic radius and stronger metallicity, TMSes can have a larger interlayer distance and a higher intrinsic ionic conductivity [
78].
As shown in
Figure 9a, since Morales et al. first discovered MoSe
2 as an anode for SIBs in 1996s, diverse compositions have been researched [
78]. MoSe
2 has merits of higher electronic conductivity and broader interlayer spacing (0.64–0.65 nm) relative to those of MoS
2 (0.62 nm), whereas MoSe
2 initiates a conversion reaction at ~0.56 V vs. Na/Na
+, surpassing the potential of 0.4 V observed in MoS
2 phase. In order to further improve electronic conductivity while withstanding large volume changes (up to 300%) [
80], Liu et al. synthesized MoSe
2 nanosheets encapsulated by hollow carbon nanospheres (MoSe
2@HCNs) via a hydrothermal method. They showed an enlarged interlayer spacing of 1.02 nm and excellent CEs higher than 98.3%, while maintaining high discharge and charge capacities of 502 and 471 mAh g
−1 following 1000 cycles tested at 1 A g
−1 and 3 A g
−1, respectively. Additionally, a reversible capacity of 382 mAh g
−1 can be attained even when tested at a high current density of 10 A g
−1 [
83].
Chen et al. synthesized a hybrid mixture of 1T and 2H phases of MoS
2/MoSe
2 with the 2D structure of rGO (MoSSe@rGO) as a conductive matrix to create 3D pathways for electron transport through a high-temperature hydrothermal method (
Figure 9b) [
84]. Based on the improvements of its electrical conductivity and reactivity through metallic 1T phase, MoSSe features the high energy density of MoS
2 and stable stability of MoSe
2, with improved Na
+ ion storage kinetics by achieving a high pseudocapacitance of MoSSe@rGO. It has a few-layered structure (<6 layers) and an interlayer spacing of 0.8 nm, which can alleviate lattice strain and enhance Na
+ ion migration. The MoSSe@rGO electrode showed an initial capacity of 634.1 mAh g
−1 with an improved ICE of 73.6%, originated by its low Na
+ ion diffusion barrier of 0.087 eV and its high electrical conductivity of 5.6 × 10
−4 S cm
−1 (
Figure 9c). With increasing the current density, the applied polarization is 0.7 V even when tested at 6.4 A g
−1 and cycle retention is excellent at 90% during 600 cycles tested at 1 A g
−1 (
Figure 9d). In addition, the MoSSe@rGO electrode exhibited fast reaction kinetics at the discharge capacity 533.9 mAh g
−1 even at a low temperature of around 0 °C, which is 87.8% of the capacity obtained at room temperature [
84]. Beyond MoSe
2 phase, layered and non-layered TMSe phases have been studied in early and later TMSes, specifically including cost-effective Fe-containing FeSe, Fe
3Se
4, and FeSe
2 phases (
Figure 9a).
2.4. Metal Phosphides
Transition metal phosphides (TMPs) have gained considerable attention owing to the highest theoretical capacity of P anodes for SIBs. Since Si anodes in group 15 can only form the NaSi alloy phase, not a Na-rich phase akin to the Li
4.4Si phase formed in LIBs, P in group 16 is able to deliver the highest theoretical capacity reaching 2596 mAh g
−1 through generating Na-rich Na
3P alloy phase [
33]. However, red P, the most commonly applied anode material for SIBs among the P polymorphs, is flammable and has a limited electronic conductivity (~10
−14 S cm
−1). TMPs have been proven to address the flammability and low electronic conductivity issues by reacting with TM cations and P. Basically, TMPs have high degree of electron delocalization and high-lying mixed anion–TM bands, resulting in an overall lower reaction potential as anodes for SIBs compared to that of the above-mentioned compounds [
85]. These lower reaction potentials of TMPs can provide diversity in electrochemical energy storage mechanisms of anodes for SIBs with insertion, alloying, and conversion reactions depending on compositions of TMPs.
The covalent bond character of the TM-P bonding increases across the periodic table [
86] and early TM-containing phosphides (i.e., V-P) can exhibit insertion reaction mechanisms without conversion reactions occurred even at the end of discharge, close to Na/Na
+. In addition, a strong consistency in elemental compositions and structural trends in TMPs was observed with interesting structural and compositional diversity including different electronic properties from electrical conducting metallic phase to semiconducting and insulating phases of TMPs [
87]. In this regard, TMPs can be candidates for the most attractive anode materials for SIBs based on their considerable specific and volumetric capacities, low reaction potentials (0.3–0.7 V vs. Na/Na
+), and diverse electrochemical reaction mechanisms and properties [
33].
As an early-TM-containing binary V-P system, various phases are known from TM-rich to P-rich phases such as V
3P, V
2P, V
12P
7, V
4P
3, VP, V
4P
7, VP
2, and VP
4 and the latter four compounds have been researched as anode materials in LIBs [
85,
88,
89,
90]. Among them, VP showed a topotactic intercalation reaction with Li
+ ions with excellent cycle retentions and favorably low insertion potentials as anodes (
Figure 10a) [
91]. Unfortunately, this attractive material is not electrochemically active in Na cells, exhibiting a meaningless capacity. However, Kim et al. explored a novel anode material of V
4P
7 phase, exhibiting topotactic insertion/extraction reactions with Na
+ ions and an excellent cycle stability [
92]. V
4P
7 does not undergo conversion reactions even when completely discharged to 0.01 V vs. Na/Na
+ but shows insertion reaction mechanisms with the reaction equation of V
4P
7 + xNa
+ + xe
- ↔ Na
xV
4P
7 (x
0.95) (
Figure 10b). Topotactic Na
+ ion insertion/extraction reactions of V
4P
7 were confirmed by transmission electron microscopy (TEM), ex situ X-ray diffraction (XRD), X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) of V K edges (
Figure 10c–e). The V
4P
7 electrode exhibits a reversible capacity of 234 mAh g
−1 tested at 0.1 A g
−1 during 100 cycles alongside an imperceptible capacity decay (cycle retention of 99.99%) (
Figure 10f). When V
4P
7 is compared to the representative oxide anode of VO
2(B), which has a similar insertion reaction mechanism, the reversible capacities between the two phases are comparable, while V
4P
7 shows much lower reaction potential, leading to its higher energy density (
Figure 10g,h). Although this insertion type of TMPs can compensate for the drawback of insertion-type oxides with too high reaction potential, exploring other candidates beyond V
4P
7 has been limited to date [
92].
Additionally, the conversion reaction type of TMPs has been studied in P-rich compounds due to their high theoretical capacities. As shown in
Table 2, various compositions of P-rich phosphides have been studied as anodes for SIBs and they exhibit reversible capacities ranging from 250~1100 mAh g
−1 depending on their compositions (
Table 2) [
93,
94,
95,
96,
97,
98,
99,
100,
101,
102,
103,
104,
105,
106,
107].
Specifically, TM tetraphosphides (TMP
4s) contain four P elements and exhibit a high theoretical capacity over 1500 mAh g
−1. TMP
4s consisting of Earth-abundant elements of Mn or Fe can be promising candidates for economically efficient and high-performing anode materials for SIBs. Kim et al. reported a triclinic structure of 6-MnP
4 phase, which is one of the MnP
4 polymorphs and classified according to the arrangement of MnP
6 octahedra. This phase features high capacity for an anode material for SIBs, showing an initial reversible storage capacity of 1028 mAh g
−1 tested at 50 mA g
−1 (
Figure 11a) [
100]. The reaction mechanism of MnP
4 for SIBs was examined through ex situ XRD, TEM, and XANES spectra exhibiting a direct conversion reaction as MnP
4 + 12 Na
+ + 12 e
− → Mn
0 + 4 Na
3P, which is different to the two-step reactions of alloying and conversion observed in LIBs as MnP
4 + 7 Li
+ + 7 e
− → Li
7MnP
4 + 5 Li
+ + 5 e
− → Mn
0 + 4 Li
3P (
Figure 11b,c). The MnP
4 phase was combined with 20 wt.% graphene nanosheets (G20) to form MnP
4/G20 nanocomposite and it showed reversible capacity of 446 mAh g
−1 tested at 0.5 A g
−1 after 250 cycles, maintaining 78% of its initial capacity (
Figure 11d) [
100].
In addition to the Mn-P system, the most abundant element in TMs as Fe-containing TMPs have been applied to anode materials with FeP, FeP
2, and FeP
4 phases for SIBs. FeP has an orthorhombic crystal system with FeP
6 sharing edges and faces in the structure, holding a theoretical capacity of 926 mAh g
−1. Since FeP undergoes conversion reactions as FeP + 3 Na
+ + 3 e
− → Fe
0 + Na
3P accompanying large volume changes and structural instability, fabricating a composite with conductive carbon materials can be a simple approach. The hybrid 3D composite structure of FeP and P-doped graphitic N-rich graphene (FeP/NPG) was synthesized with higher ionic conductivity and structural stability of FeP particles [
108]. It demonstrated high reversible capacities of 613 mAh g
−1 tested at 50 mA g
−1 and 349 mAh g
−1 tested at a high current density of 3 A g
−1. Additionally, a good long-term cyclability was achievable with a reversible capacity of 378 mAh g
−1 and 90% capacity retention after 700 cycles tested at 1 A g
−1 [
108]. While orthorhombic FeP
2 phase is a high-capacity anode for LIBs [
109], possessing a theoretical capacity of 1365 mAh g
−1, this phase has been found to be electrochemically inactive in Na cells. Monoclinic FeP
4 phase, another P-rich phosphide in the Fe-P system, undergoes a direct conversion reaction, the same as that observed in MnP
4 electrodes. The FeP
4 electrode indicates a reversible capacity of 1137 mAh g
−1 tested at 89 mA g
−1 with an ICE of 84% and the high capacity is maintained for 30 cycles (
Figure 11e) [
98].
Recently, the monoclinic structure of CrP
4 phase with the space group C2/c, identical to that of the metallic phase of VP
4, was introduced as a high-capacity anode for SIBs. Its narrower direct band gap, in contrast to the aforementioned 6-MnP
4 and FeP
4 phases, is a distinguishing feature [
95]. The electrochemical reaction mechanism of CrP
4 was confirmed as a two-step process including insertion and conversion reactions: CrP
4 + xNa
+ + xe
− → Na
xCrP
4 + (12 − x)Na
+ + (12 − x)e
− → Cr
0 + 4 Na
3P. The CrP
4 electrode shows a first discharge capacity of 1125 mAh g
−1 tested at 50 mA g
−1, accompanied by an ICE of 78.3%. For high-rate cycle retention, CrP
4 nanoparticles were mixed with 15 wt.% of acetylene black carbon to achieve a higher reversible capacity of 369 mAh g
−1 over 100 cycles tested at 500 mA g
−1 compared to CrP
4 electrodes (
Figure 11f) [
95].
In addition to TMPs, binary phosphide phases including electrochemically active metals or non-metals of Sn, Si, and antimony (Sb) reacting with Na
+ ions have also been introduced as anode materials for SIBs. In particular, Sn-containing phosphide anodes have been most widely studied in compositions of Sn
4P
3, SnP, Sn
3P
4, and SnP
3 phases [
105,
110,
111]. Binary Sn-P phases exhibit high theoretical capacity ranging from 1133 to 1616 mAh g
−1 since both elements in the binary phases are electrochemically active with Na
+ ions. As an example, SnP
3 undergoes both conversion and alloying reactions and the reaction mechanism can be expressed as SnP
3 + 12.75 Na
+ + 12.75 e
− → Na
3.75Sn + 3 Na
3P with a theoretical capacity of 1616 mAh g
−1 [
105]. The SnP
3/C electrode delivers a reversible capacity close to 800 mAh g
−1 during 150 cycles without noticeable capacity decay tested at 150 mA g
−1 [
105]. The high electrochemical performance of Sn-P anodes can be attributed to the dispersed Na
3P phases providing a buffer matrix preventing the aggregation of Na
15Sn
4 nanoparticles and ensuring the structural stability of the electrode during reversible sodiation/desodiation processes [
110].
So far, it can be inferred that a variety of TM-rich and P-rich phosphides have been studied as anodes for SIBs, and the electrochemical reaction mechanisms of some of them are still unclear. In addition, the electrochemical reaction mechanisms and properties for anode candidates have not been fully explored for all of the compositions and polymorphs of TMPs. Above all, the drawbacks that can possibly occur in high-capacity TMP anodes such as severe volume changes during cycling, sluggish ionic and electronic conductivities caused by a conversion reaction, and unstable SEI layers by mechanical fractures call for solutions for high-performance anode applications for SIBs.
2.5. Metal Nitrides
Transition metal nitrides (TMNs) have received relatively little attention compared to the aforementioned compounds, however, they may be promising candidates as next-generation anode materials for SIBs owing to their superior ion diffusion kinetics and lower conversion reaction potentials, which have been observed in various TMNs [
112,
113]. The N-do** strategy has been widely applied in multiple types of carbonaceous materials including graphene, CNTs, carbon matrix, carbodiimide, MXene, etc. The beneficial effect of N do** has been proved for alkali ion storage performance as well as electronic conductivity enhancement [
114,
115]. Utilizing N as an anionic redox center in anode materials for LIBs can yield a notable specific capacity, based on the relatively low molecular weight of N, but a large number of Li
+ ions are accompanied by a conversion reaction forming the Li
3N phase. Li
3N phase is known to have an unprecedentedly high ionic conductivity (~10
−3 S cm
−1) [
116] with robust mechanical stability as a promising component of solid electrolyte interface (SEI) phase [
117,
118,
119,
120]. In this regard, TMNs can generate a mechanically stable SEI layer on the surface of TMNs with a high ionic conductivity. Compared to oxygen-centered counterparts such as TMOs, the N anionic centers show structural stability and high electrochemical reactivity, exhibiting fast alkali ion diffusion kinetics [
121,
122,
123,
124]. Hence, TMNs are expected to be highly advantageous for next-generation anodes, and various compounds including TiN, VN, Mo
2N, MnN, Fe
2N, and Fe
3N have been recently introduced for SIBs.
TMNs have three representative forms, face-centered cubic (fcc), hexagonal closed packed (hcp), and simple hexagonal structures, with unusual combinations of metallic, covalent, and ionic bonding properties [
123]. As for early TMNs, several candidates are TiN, VN, NbN, MoN, Mo
2N, and WN, where the N atoms are integrated into numerous interstitial sites of the parent TMs and generate a rearranged electronic structure.
The intercalation type of cubic structure TiN can bring open channels for Na
+ ion intercalation reactions based on its low volumetric density of 5.4 g cm
−3 and has several advantages such as high chemical stability, electrical conductivity (3.7 × 10
6 S m
−1), and Young’s modulus (420 GPa) [
125]. However, this material has a bottleneck of finding cost-effective and eco-friendly synthesis methods. The traditional synthesis process of TiN uses a direct reaction between Ti-based powders and N
2 or NH
3 gases under high temperature (600~1200 °C) [
124], which is not desirable for safe and mass productive processes. Meanwhile, Liu et al. synthesized TiN@C composite by using MXene as the Ti source and the sacrificial templates [
126]. MXenes are a class of 2D inorganic compounds such as TM carbides, nitrides, or carbonitrides. A simple method to prepare TiN was proposed as 2D layered MXene of Ti
3C
2T
x (T = F or O) which was synthesized first and converted to TiN by using an intercalation agent of hexamethylenetetramine (HMT) with heating at 800 °C under Ar conditions. The quantum-dot-sized TiN can provide shorter ionic diffusion distances, while 2D ultrathin carbon nanosheets can reinforce structural stability and enhance electron transport rate. As-synthesized TiN@C delivers a discharge capacity of 414 mAh g
−1 with a current density of 0.5 A g
−1 and high reversible capacities of 170 mAh g
−1 and 149 mAh g
−1 after 5000 cycles at 0.5 A g
−1 and 1 A g
−1, respectively [
126].
One of the other early TMNs, VN, which has a significant theoretical capacity of 1238 mAh g
−1 and electrical conductivity of 1.49 × 10
6 S m
−1 [
125,
127], was introduced as an anode for SIBs. Cheng et al. applied a cost-effective synthesis process involving hard carbon (HC) composites by coating 8.6 wt.% of VN on the HC surface (VN-HC). The synthesis process includes the reaction of VOCl
3 with cellulose followed by heating under N
2 at 1400 °C. The as-synthesized VN-HC exhibited a first discharge capacity of 354 mAh g
−1 tested at 50 mA g
−1 and a reversible capacity of 294 mAh g
−1 following 50 cycles. When the total capacity of VN-HC composite is divided by the mass of VN alone, it reaches the highest specific capacity of 605 mAh g
−1 in VN phases [
127]. Zeng et al. synthesized ultrafine VN quantum dots encapsulated in yolk–shell N-doped carbon nanospheres (VN QDs/N-C) that can shorten ion diffusion distances, relieve volume expansions, and improve conversion reaction rates. VN QDs/N-C shows a high first discharge capacity of 1167.7 mAh g
−1 while a low charge capacity of 486 mAh g
−1 tested at 50 mA g
−1 with an ICE of 41.6%. However, it showed moderate reversible capacity of 275.4 mAh g
−1 even with a very high current density of 20 A g
−1 after 30,000 cycles [
128].
Wei et al. presented a novel strategy to control the electrochemical reaction mechanism of a layered VN structure pillared by Al atoms, showing an intercalation reaction with Na
+ ions rather than a conventional conversion reaction (
Figure 12a) [
129]. Al atoms can act like a pillar to stabilize the inside channels of layered VN and improve ion transport in the interlayers by hindering the occurrence of conversion reactions. The results showed a high reversible specific capacity of 372 mAh g
−1 tested at a current density of 50 mA g
−1 and long cycle stability with a reversible capacity of 115 mAh g
−1 after 7500 cycles tested at 0.5 A g
−1 (
Figure 12b). The as-prepared VN was combined with rGO and it indicated a higher capacity of 400 mAh g
−1 tested at 50 mA g
−1 and a longer cyclability with a capacity of 155 mAh g
−1 during 10,000 cycles at a high current density of 1 A g
−1. However, the ICEs of VN and VN@rGO are extremely low, about 12%, which might be due to the mismatch of electrolyte and should be further improved in the future [
129].
To date, various later TMNs such as MnN, FeN, Fe
2N, Fe
3N, CrN, and Cu
2N have also been applied in energy storage applications of supercapacitors and LIBs. MnN is one of the attractive candidates for anode materials based on the Earth-abundant Mn resources and its high theoretical capacity, while there have been limited studies on this material for SIB applications. A 3D nanostructured MnN@rGO composite has been applied in anodes for SIBs to accommodate severe volumetric changes of MnN during sodiation/desodiation [
130]. When the electrode was tested at a current density of 0.25 A g
−1, MnN@rGO composite exhibits an ICE of 52.1%, accompanied by discharge and charge capacities of 1635 and 850 mAh g
−1, respectively (
Figure 12c) [
130]. The electrochemical reaction mechanism of MnN has not been investigated in this study, while it could exhibit a theoretical capacity of 1166 mAh g
−1 if MnN undergoes the reaction of conversion to form Na
3N phase. It is expected that improvements in the ICE of this material will achieve high specific capacity.
Fe-based TMNs are one of the promising candidates for cost-effective anode materials and Fe
2N showed relatively higher electrochemical performance. Recently, Li et al. developed 1D self-supporting Fe
2N nanocubes as hollow core–shell hybrid fibers (CSHN) coated by N-doped carbon matrix. The hierarchical carbon matrix can contribute to the fast electronic conductivity and protect active materials from side reactions, simultaneously leading to fast charge/discharge capability. Moreover, its porous nature can buffer the volume expansion and retain reversible capacities with a high cycle retention. This composite electrode delivers a high capacity around 400 mAh g
−1, maintaining 95.6% of the initial capacity after 2000 cycles tested at 2 A g
−1 (
Figure 12d). The achieved performance is superior to those of state-of-the-art anodes of TMNs for SIBs such as Fe
3N, Sn
3N
4, VN, Mo
2N, and Ni
3N [
131].
The above-mentioned TMNs present rather high energy densities due to the high specific capacities and low reaction potentials of TMNs, while a significantly high capacity has not been achieved yet. One of the bottlenecks of TMNs for realizing high-performance anodes is mainly originated by the inferior ICEs observed in most TMNs. There are several factors that influence the ICE of anode materials such as irreversible decomposition of electrolyte forming SEI layers, surface defects or functional groups, irreversible sodiation/desodiation processes, etc. [
132]. Further optimization of electrolyte compositions, binders, and compatibilities with TMNs should be studied to address these issues. Furthermore, the lack of research on N-rich TMNs may be another reason for the lack of attention on TMNs as potential next-generation anodes, thus a lot more studies on exploring new compositions of TMNs are required for further improvements in this material group.