Anode Material for Sodium Ion Battery

DOI: 10.1002/chem.201402511

Minireview

& Sodium-Ion Batteries

High-Capacity Anode Materials for Sodium-Ion Batteries Youngjin Kim,[b] Kwang-Ho Ha,[a] Seung M. Oh,*[b] and Kyu Tae Lee*[a]

Chem. Eur. J. 2014 J. 2014, 20 , 11980 – 11992

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 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Minireview Abstract: Na-ion batteries are an attractive alternative to Li-

ion batteries for large-scale energy storage systems because of their low cost and the abundant Na resources. This Review provides a comprehensive overview of selected anode materials with high reversible capacities that can in-

Introduction Thanks to their excellent electrochemical performance, for several decades, Li-ion batteries have been successfully utilized as a power source in hybrid electric vehicles and mobile electronic devices such as mobile phones and lap-top computers.[1] However, the present technology for Li-ion batteries is not expected to be able to meet the demands for power sources in future energy storage applications. In addition, lithium resources are expensive and too geographically constrained.[2] Accordingly, new rechargeable battery systems such as sodium ion, sodium metal, magnesium, metal–air, and metal–sulfur batteries are being considered as alternatives to replace Li-ion batteries. In particular, Na-ion batteries have attracted rapidly increasing attention owing not only to the low cost of sodium due to its abundant resources but also their better safety compared to sodium-metal batteries such as high-temperature Na– S batteries.[3] Because of their low cost, the main potential application of Na-ion batteries is considered to be large-scale energy storage systems (ESS). However, it should be stressed that it is not easy to decrease the cost of Na-ion batteries relative to that of Liion batteries, in spite of the inexpensive Na precursors. In particular, Na-ion batteries have slightly lower energy densities than Li-ion batteries, which means that the cost per energy ($/Wh) of Na-ion batteries cannot easily be decreased because the energy density limitations offset the cost savings due to the use of Na. Figure 1 shows the cost of each part of the cell in a Na-ion battery. Precursors for transition metals such as Co, Ni, and Mn are much more expensive than precursors for alkali metals such as Li and Na, and the cost of sodium carbonate is only about 10% of the total cost of the precursors for the cathode materials, although the cost of cathode materials is the dominant expense (36%) for these batteries. Thus, only a 3.6% cost reduction is expected to be possible by replacing cathode materials. However, unlike for Li-ion batteries, a cheap Al current collector can be used for the anode in Na-ion batter[a] K.-H. Ha, Prof. K. T. Lee School of Energy and Chemical Engineering Ulsan National Institute of Science and Technology 50 Unist-gil, Eonyang-eup, Ulju-gun, Ulsan (South Korea) Fax: ( + 82)52-217-2909 E-mail: [email protected]

[b] Y. Kim, Prof. S. M. Oh School of Chemical and Biological Engineering Seoul National University 599 Gwanangno, Gwanak-gu, Seoul (South Korea) Fax: ( + 82)2-882-5869 E-mail: [email protected] Chem. Eur. J. 2014, 20 , 11980 – 11992

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crease the energy density of Na-ion batteries. Moreover, we discuss the reaction and failure mechanisms of those anode materials with a view to suggesting promising strategies for improving their electrochemical performance.

ies instead of an expensive Cu current collector, because Al does not alloy with Na. This can lead to a cost reduction of about 8%. A slight cost reduction is also expected to be achieved by replacing Li salts with Na salts in the electrolytes. Therefore, Na-ion batteries are considered to be potentially about 10 % less expensive in total cost than commercialized Liion batteries, assuming they deliver the same energy density. However, most electrode materials that have been introduced for Na-ion batteries to date show similar or slightly lower specific capacities and redox potentials than those for Li-ion batteries, resulting in the lower energy density for the Na-ion batteries. This indicates that the cost reduction achieved by using Na-ion batteries may not be significant in terms of the cost per energy. Therefore, it is important to develop electrode materials with high energy densities for Na-ion batteries to reduce the cost per energy unit. The energy density can be improved by i) using electrode materials with high specific capacities, ii) using cathode materials with high redox potentials, and iii) using anode materials with low redox potentials. However, most cathode materials store Na ions by intercalation chemistry, which means that the number of storage sites is limited. This suggests that it will be difficult to greatly increase the specific capacity of the cathode materials. The use of cathode materials with high redox +

Figure 1. Comparison of the manufacturing costs for Li-ion batteries (LIB)

and Na-ion batteries (NIB).

potentials is also limited because of electrolyte decomposition at high potentials. Most commercialized electrolytes even for Li-ion batteries are unstable and decompose at over 4.8 V versus Li/Li . Therefore, the best approach is developing anode materials with high specific capacities and appropriately low redox potentials to improve the energy density of Na-ion batteries so that they can successfully replace Li-ion batteries. Figure 2 shows the specific and volumetric energy densities of full cells with various reported anode materials,[4] assuming P2Na2/3Fe1/2Mn1/2O2 is used as a cathode material. [5] This reveals +

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Minireview specific capacities and lower redox potentials. In addition, Ge and Sb are more expensive than Si and Sn. Furthermore, a lower redox potential of anode materials is beneficial for achieving higher energy densities of full cells, and thus Si and Sn have been considered more promising than Ge and Sb. However, for Na-ion batteries, the redox potentials of Si and Sn are too close to that of Na metal, because the redox potential of

Figure 2. Theoretical gravimetric and volumetric energy densities of full cells

with various reported anode materials for Na-ion batteries. Yellow ellipse region represents the energy density of commercialized Li-ion batteries.

that a similar energy density to those of commercialized Li-ion batteries (150–200 Whkg1, 400–650 WhL1) can be achieved by using only high-capacity anode materials such as alloy materials, metal oxides, metal sulfides and phosphorus-based materials for Na-ion batteries. Recently, many review papers about Na-ion batteries have been published, but they have mainly described the advancement of cathode materials.[3] Therefore, in this review, we instead focus on the recent major development in the area of anode materials. In particular, this review provides a comprehensive overview of selected anode materials with high reversible capacities for increasing the energy density of Na-ion batteries, and we also discuss the reaction and failure mechanisms of those anode materials to suggest promising strategies for improving their electrochemical performance.

Alloy Materials Alloy materials such as Si, Ge, Sn, and Sb have been widely examined for Li-ion battery applications because their specific capacities are higher than those of commercialized carbonaceous materials such as graphite. As is the case for Li-ion batteries, alloy materials are considered promising anode materials for Na-ion batteries owing to their high specific capacities, as shown in Figure 3. Si and Sn have attracted more attention than Ge and Sb in Li-ion batteries because of the better electrochemical performance of Si and Sn including their higher

Kwang-Ho Ha received his B.Sc. (2012)from the Interdisciplinary School of Green Energy at Ulsan National Institute of Science and Technology (UNIST) in Korea. He started a M.S. course at the School of Energy and Chemical Engineering at UNIST under the supervision of Prof. Kyu Tae Lee (2013). Currently his studies are focused on syntheses and analyses toward electrode materials for Na-ion batteries.

Youngjin Kim received his B.S. degree in chemical engineering (2010) from Seoul National University of Science and Technology , Korea. He started an integrated M.S. and Ph.D. in School of Chemical and Biological Engineering from Seoul National University (SNU) under the supervision of Prof. Seung M. Oh in 2010. Currently his studies are focused on various electrode materials for Na-ion batteries.

Kyu Tae Lee is Professor of the School of Energy and Chemical Engineering at Ulsan National Institute of Science & Technology (UNIST), Korea. He received his B.Sc. (2000) and Ph.D. (2006, advisor: Prof. Seung M. Oh) in Chemical Engineering from Seoul National University (Korea). In 2007 , he joined Prof. Linda F. Nazar s group at the University of Waterloo (Canada) as a post-doctoral fellow. His current research is focused on new electrode materials for Li-ion and Na-ion batteries and new electrochemical energy conversion/storage systems. ’

Seung M. Oh is Professor of the School of Chemical and Biological Engineering at Seoul National University (SNU), Korea. He received his Ph.D. (1986) in Chemical Sciences from University of Illinois, Urbana-Champaign. His current research is focused on the failure mechanism and interfacial chemistry of electrode materials for Li-ion and Na-ion batteries , and new electrochemical energy conversion and storage systems.

Figure 3. Theoretical gravimetric and volumetric specific capacities of vari-

ous anode materials for Na-ion batteries. Chem. Eur. J. 2014, 20 , 11980 – 11992

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Minireview Na metal is higher than that of Li metal by 0.3 V. In the other words, while the redox potentials of Si and Sn are appropriate for Li-ion batteries, their redox potentials are close to 0 V versus Na/Na , which is detrimental to Na-ion batteries because even a small amount of polarization imposes kinetics limitations on electrochemical insertion of Na ions, resulting in abrupt capacity fading. Moreover, no report has experimentally shown the electrochemical sodiation of Si-based materials yet, although it is known that Si can theoretically alloyed with Na to form a NaSi phase. Therefore, Sb and Ge have been considered more promising anode materials than Sn and Si for Naion batteries. +

1. Sb-Based Materials

Recently, many research groups demonstrated that Sb showed excellent electrochemical performance such as very stable capacity retention over 100 cycles and high reversible capacity of about 500–600 mA h g1.[6] In particular, despite the micronscale size of the bulk Sb particles used, Monconduit et al. [6a] demonstrated that Sb reversibly alloyed with Na forming Na3Sb (Figure 4), and they also showed the excellent cycle performance of Sb, and even better cycle performance of Sb for Na-ion batteries than for Li-ion batteries. They suggested that the better cycle performance of Sb for Na-ion batteries is caused by the smaller volume change exhibited by Sb during the insertion/de-insertion of Na ions compared to that during the insertion/de-insertion of Li ions. Reductions in the volume change improve the cycle performance because the large volume changes lead to cracking and pulverization of the alloy materials and deformation of the electrodes, resulting

in severe capacity fading. To arrive at this explanation, the volume changes were calculated based on the unit cell volumes of Sb, hexagonal Na 3Sb, and rock salt Li3Sb (181.1, 237, and 283.8 3, respectively). However, Baggetto et al. [6b] pointed out that the above calculation did not consider the formula unit ( Z ) in the unit cells ( Z = 2 and 4 for Na3Sb and Li3Sb, respectively), and therefore recalculated the volume change between Sb and Li3Sb/Na3Sb. The corrected volume changes of Sb to form Li 3Sb and Na3Sb are about 135% and 293%, respectively, and thus, it is not correct to say that the better cycle performance of Sb for Na-ion batteries is caused by its smaller volume change. Baggetto et al. suggested that the better cycle performance of Sb for Na-ion batteries can attributed to the reduced anisotropic mechanical stress due to the repeated formation of only one crystalline phase for Na (Na3Sb) as opposed to the repeated formation of three crystalline phases for Li (Sb, Li2Sb, Li3Sb), as shown by the reaction mechanism of Sb for Na and Li (Table 1). In particular, Sb transforms into hexagonal

Table 1. Typical alloying reaction of Sb with Li and Na in electrochemical

cells.[a]

Discharge Charge

Na

Li

c-Sb !a-Na x Sb a-Na x Sb !c-Na3Sb(hex) c-Na3Sb(hex)!a-Sb

c-Sb !c-Li2Sb c-Li2Sb !c-Li3Sb c-Li3Sb !c-Sb

[a] c : crystalline; a : amorphous.

+

+

Figure 4. Operando evolution of the XRD pattern recorded at a C/8 rate (top

left). The black and the red patterns are those recorded during the discharges and charge, respectively. The corresponding voltage profile (top right). A zoom illustrating the diffraction peaks from the cubic Na 3Sb (bottom). Reproduced from ref. [6a] with permission. Chem. Eur. J. 2014, 20 , 11980 – 11992

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Na3Sb through amorphous Na x Sb during sodiation, while it is changed into cubic Li3Sb through Li2Sb during lithiation. The improved cycle performance was also suggested to be caused by the formation of stable and thin NaF-like SEI layers due to the addition of the FEC additive. In addition, although bulk Sb materials showed good electrochemical performance, nanosized Sb (10–20 nm) exhibited better rate performance and cyclability at high C-rate (  4C) (Figure 5).[6c] Even at 20C-rate, 20 nm Sb nanocrystals delivered a reversible capacity of about 500 mAh g1. However, these nanomaterials have the critical disadvantage of poorer coulombic efficiencies than bulk Sb in the initial cycle, which is attributed to the larger amount of electrolyte decomposed to form the SEI layer because of the larger surface area of the nanomaterials. As has been shown for alloy materials such as Si and Sn for Li-ion batteries, Sb electrodes also suffer from detrimental volume changes (ca. 300%) during sodiation and desodiation, and this eventually results in degradation of the electrodes and capacity loss due to the loss of electrical contact between Sb particles, although Sb does show stable cycle performance over 100 cycles.[6] Therefore, to alleviate these volume changes, Sb-based binary (active/inactive) alloy compounds such as M x Sb y (M = Mo, Al, and Cu) have been exploited to improve the electrochemical performance.[7] In these materials, M is an electrochemically inactive component and acts as a buffering matrix to maintain the electrode microstructure by diminishing the

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Minireview ods, respectively. Both showed high reversible capacities (> 400 mAh g1) and stable cycle performance over 100 cycles. In addition, a ternary composite composed of Sb, SiC, and C was introduced, and shown to exhibit improved cycle performance.[9] It is notable that most of the above-mentioned studies on Sb-based materials have used electrolytes with the FEC additive, because the formation of stable SEI layers by electrochemical decomposition of FEC is extremely effective for improving the cycle performance of Sb-based materials, although a buffering matrix made of carbon or inactive metal elements is also effective in alleviating the volume changes of Sb.[6a–d,f] It is well known that the surfaces of alloy materials are newly formed in each cycle, because alloy materials show large volume changes Figure 5. Cycling performance of Sb electrodes in Na- and Li-ion half-cells. 1C-rate correduring charging and discharging. This means that sponds to the current density of 0.66 A g1. For 4C-rate tests in Li-ion cells (B), initial conthe new surface is exposed to electrolytes and new ditioning cycles were attempted (2 cycles at 0.1C + 8 cycles at 0.5C) to stabilize the perSEI layers are formed at each cycle, resulting in the formance. Reproduced from ref. [6c] with permission. formation of thicker and thicker SEI layers during cycling. This greatly increases the charge-transfer resistvolume changes and preventing aggregation or coarsening of ance, causing abrupt capacity fading. Therefore, various elecactive elements during repeated sodiation and desodiation. trolyte compositions and additives have been studied to form Baggetto et al. examined the electrochemical performance of stable SEI layers in Li-ion batteries. [10] For example, FEC was AlSb,[7a] Mo3Sb7,[7b] and Cu2Sb[7c] thin film electrodes fabricated found to improve the cycle performance of Si-based materials by magnetron sputtering. Amorphous AlSb and Mo3Sb7 with large volume changes for Li-ion batteries, because FEC showed similar electrochemical behavior. They delivered similar forms stable LiF-like SEI layers.[10a–d] The same phenomenon reversible capacities of about 400 mAhg 1, and no crystalline was also observed for Sb-based materials with large volume phase was observed during sodiation and desodiation. Unlike changes for Na-ion batteries. Therefore, it should be emphathe reaction mechanisms of amorphous AlSb and Mo 3Sb7, the sized that the electrochemical performance of an electrode reaction mechanism for Cu2Sb included the formation of nanomaterial with a large volume change critically depends upon crystalline Na3Sb with the exclusion of Cu by a conversion rethe species of electrolytes. In particular, it is important to use action after full sodiation of crystalline Cu2Sb. However, the re- an optimized electrolyte when a new electrode material is deversibility of the crystalline Cu2Sb formation depended on the veloped. morphology of the electrode films. A thin film electrode fabricated by magnetron sputtering showed irreversible behavior 2. Sn-Based Materials and changed into amorphous Cu2Sb (or Cu + Sb) after full desodiation. Meanwhile, a reversible reaction mechanism was ob- Another promising group of alloy materials is the Sn-based served for the porous Cu2Sb fabricated by electrodeposition, anode materials.[11] Pure Sn[11a] can theoretically deliver and the crystalline Cu2Sb phase was observed after desodia847 mAh g1, which corresponds to the formation of Na 15Sn4. tion. The redox potentials for the formation of Na–Sn alloys are As another approach to suppress the deformation of alloy a few hundred mV lower than those of Li–Sn alloys. Figure 6 material electrodes caused by volume changes during cycling, shows four anodic plateaus at 0.2, 0.3, 0.56, and 0.7 V, which alloy-carbon composites have been widely studied for Li-ion are related to the desodiation of Na 15Sn4 to form Sn through [8] batteries. The role of carbon is not limited to providing an Na9Sn4, NaSn, and NaSn5, respectively. These results agreed electrical conduction path, and carbon can reversibly store Li well with theoretical calculations using density functional 1 ions to a level of about 300 mAhg . This strategy has also theory.[12] been successfully adopted for Na-ion batteries. Qian et al.[6d] However, the above reaction mechanism is somewhat inshowed promising electrochemical performance of an Sb/C coincident with the binary phase diagram of Na–Sn or in situ composite synthesized by simple mechanical milling of a comTEM analysis results.[11b] In particular, binary intermediate mercial Sb powder and conductive carbon. The Sb/C compophases such as Na3Sn, NaSn3, and NaSn4 observed in the site comprised approximately 10 nm Sb nanocrystallite embedbinary phase diagram are absent in the voltage profile of Sn, ded in a carbon matrix. The composite delivered a reversible as shown in Figure 7. In addition, in situ sodiation/desodiation 1 capacity of about 640 mAh g , indicating the formation of TEM analysis of tin nanoparticles (80–400 nm) showed different Na3Sb, and showed negligible capacity fading over 100 cycles. phase transitions. Sn nanoparticles were first sodiated to from [6e] [6f] Furthermore, Sb/MWCNT and Sb/C fiber composites were amorphous NaSn2 and Na-rich amorphous phases such as aobtained by using the wet milling and electrospinning methNa9Sn4 and a-Na3Sn via a two-phase reaction and one-phase +

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Minireview reaction, respectively. Then, crystalline Na15Sn4 was finally obtained after full sodiation. The in situ TEM analysis also showed that Sn nanoparticles are expanded by about 420% after full sodiation, and this volume change is detrimental to the cycle performance of Sn, as discussed regarding the Sb-based materials. As an approach to overcoming the large volume change of Sn, the use of threedimensionally cross-linkable binders such as polyacrylic acid (PAA)[11c] and carboxymethyl cellulose (CMC)[11d] was examined to improve the cycle performance. These binders were effective in inhibiting the deformation of electrodes, and better

Figure 7. Three a -Na x Sn phases in the single-phase sodiation. a) EDP of the first a -Na x Sn phase, which was taken

when the reaction front just swept the entire Sn NPs. The simulated EDP indicated that the composition of the first a -Na x Sn phase was close to the NaSn2 phase. b) EDP of the second a -Na x Sn phase. The amorphous halos match the simulated a -Na9Sn4 phase. c) EDP of the third a -Na x Sn phase, which was identified as a -Na3Sn based on volumetric expansion. It is structurally close to the c -Na15Sn4 phase as tiny c -Na15Sn4 crystallites usually nucleate in this phase. d) Schematic illustration of the structural evolution of Sn NPs during the sodiation. Reproduced from ref. [11b] with permission.

Figure 6. Voltage curves of the first desodiation and second sodiation of

sputtered tin, superimposed on the predicted DFT voltage curve, and open circuit measurements taken at 120 C by Huggins. Reproduced from ref. [11a] with permission. 8

cycle performance was obtained than with the PVdF binder, as is well-known for Si-based materials in Li-ion batteries. Furthermore, the FEC additive improved the cycle performance of Sn owing to the formation of the stable SEI. [11c] Like the electrochemical performance of Sn for Li-ion batteries, the cycle performance of Sn for Na-ion batteries was dependent on the voltage cut-offs. As the upper voltage limit was changed from 1.5 V to 0.8 V, the capacity retention was greatly improved. [11c] As was the case for Sb-based materials, Sn/carbon composites show improved electrochemical performance compared to bare Sn.[11d–f] Wang and co-workers[11e] compared the electrochemical performance of bare Sn/Ni nanorods and carboncoated Sn/Ni nanorods composites. Self-aligned Ni nanorods were obtained via electroless plating using the virus template method with the tobacco mosaic virus. Then, Ni–Sn core-shell nanorods were synthesized by physical vapor deposition of Sn thin layers (20 nm) on vertically self-aligned Ni nanorods on Chem. Eur. J. 2014, 20 , 11980 – 11992

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Figure 8. a) Schematic illustration of the 3D C/Sn/Ni/TMV1cys anode arrays

and the cross-section of hierarchical structure of a single Sn nanorod. b) Cycling performance of 2D Sn thin film, 3D Sn/Ni/TMV1cys, and 3D C/Sn/Ni/ TMV1cys anodes. Reproduced from ref. [11e] with permission.

stainless steel substrates. A thin carbon layer (5 nm) was further coated on the Sn–Ni nanorods using radio-frequency magnetron sputtering deposition. Both bare Sn and carboncoated Sn nanorods delivered similar reversible capacities of about 730 mAhg1, but the carbon-coated Sn showed better cycle performance than bare Sn, as shown in Figure 8. In addi-

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Minireview tion, the electrochemical performance of the carbon-coated tin composites was compared for Li-ion and Na-ion batteries. Wang and co-workers[11d] synthesized a crystalline Sn/carbon composite by carbonization of tin oxide nanoparticles dispersed in resorcinol-formaldehyde gels in an argon atmosphere. Although the carbon-coated Sn composite showed promising electrochemical performance, its reversible capacity and rate performance for Na-ion batteries were unfortunately poorer than those for Li-ion batteries. Similar electrochemical behavior, revealing the poorer kinetics of Sn/carbon composites for Na-ion batteries, was also observed for Sn nanoparticles embedded in micron-sized disordered carbon.[11g] This is partly attributed to the larger charge-transfer resistance for Naion batteries, which is closely related to the formation of different SEI species. Therefore, optimized electrolytes and additives should be developed along with the Sn-based materials to decrease their charge transfer resistance. As another interesting approach to alleviating the volume changes of Sn-based electrodes, electrically conductive CNT-coated soft cellulose fibers were utilized as a buffer matrix (Figure 9). [11f] Because of their soft nature, the wood fibers released the mechanical stress caused by the volume change of Sn during sodiation and desodiation, resulting in improved cycle performance. The fibers can also absorb electrolytes because of their mesoporous structure, which improves the ionic conduction in the electrolyte. Moreover, various Sn-based binary alloy materials have been examined as anodes for Na-ion batteries. As an active-inactive

binary system, Sn0.9Cu0.1 nanoparticles (~ 100 nm) obtained by using a surfactant-assisted wet chemistry method showed excellent electrochemical performance including a reversible capacity of 420 mAhg1 at 0.2 C-rate and a capacity retention of 97% after 100 cycles, which is better than those of bare Sn nanoparticles with similar sizes.[13] The improved performance of Sn0.9Cu0.1 was suggested to be caused by the suppression of aggregation among nanoparticles owing to the presence of Cu. The addition of Cu in Sn was also effective in reducing the charge transfer resistance, resulting in the better rate performance for Sn0.9Cu0.1 than for bare Sn. As another example of Cu–Sn binary alloys, a series of amorphous (Cu6Sn5)1 x C x ( x = 0.15–0.52) nanocomposites were prepared by combinatorial sputtering.[14] As the amount of carbon increased, the reversible capacity decreased, but the cycle performance was improved. This indicates that the added carbon impedes Na ions from reaching the electrochemically active Cu6Sn5 region in the composite, resulting in a lower reversible capacity because of the lower utilization of Cu 6Sn5. However, the carbon matrix effectively inhibited the agglomeration of Sn and improved the cycle performance. Furthermore, Baggetto et al. recently showed both theoretically and experimentally that the kinetics of the conversion reaction of crystalline Cu6Sn5 into Cu and Na15Sn4 is very slow because of steric hindrance of Na ion diffusion.[15] Thus, they insisted that Cu6Sn5 should have a particle size less than 10 nm in order to utilize most of the reversible capacity provided by Sn. As an active–active binary system, SnSb showed more promising electrochemical performance than active–inactive binary alloys.[16] The sodiation mechanism of SnSb was suggested to be as given in Equations (1) and (2):[16a] +

SnSb þ 3Naþ þ 3e $ Na3 Sb þ Sn

ð1Þ

Na3 Sb þ Sn þ 3:75Naþ þ 3:75e $ Na3 Sb þ 0:25Na15 Sn4 ð2Þ SnSb is sodiated sequentially, where the initial conversion reaction forms Na3Sb and Sn, after which Sn is further sodiated to form Na15Sn4 at lower redox potential. Unlike active–inactive binary alloys, all components in SnSb are electrochemically active with Na, and thus SnSb can deliver a higher reversible capacity than Cu–Sb or Co–Sb alloys. In particular, bare SnSb[16b] and a SnSb/C [16a] composite obtained by high-energy milling of SnSb nanoparticles with carbon black at a 7:3 weight ratio were examined along with a SnSb/porous carbon nanofiber composite[16c] obtained by electrospinning using polyacrylonitrile (PAN)/poly(methyl methacrylate) (PMMA), Sn acetate, and Sb acetate precursors. These materials showed high reversible capacities of about 500 mAh g1 and stable cycle performance over 100 cycles. Figure 9.

a) Hierarchical structure of wood fiber. b) Soft wood fiber substrates effectively release sodiation generated stresses by structural wrinkling. The thickness of Sn is 50 nm and the fiber diameter is about 25 m m. c) Dual pathways for ion transport. The hierarchical and mesoporous structure of the fiber plays an important role as an electrolyte reservoir. Reproduced from ref. [11f] with permission. Chem. Eur. J. 2014, 20 , 11980 – 11992

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3. Ge- and In-Based Materials

Ceder and co-workers calculated that the theoretical maximum sodium concentration in Na–Si and Na–Ge systems is 50 at% representing the formation of NaSi and NaGe phases at < 0.1 V

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Minireview and about 0.4 V versus Na/Na , respectively.[12] However, there has been no reports of the observation of the electrochemically sodiated Na–Si phases, although a few Na–Si binary phases were chemically obtained. It is not still clear why Si does not electrochemically alloy with Na, but it seems that the electrochemical alloying reaction of Si with Na is kinetically inhibited because of the large polarization with a low redox potential close to 0 V versus Na/Na .[17] Unlike Si, Ge shows electrochemically reversible sodiation/desodiation with Na. Amorphous Ge nanocolumns with diameters of 20 nm delivered a reversible capacity of about 400 mAhg 1, which is higher than the theoretical capacity of 369 mAhg 1 assuming the formation of NaGe.[18] Ge nanocolumns also showed stable cycle performance over 100 cycles and exhibited good rate performance, delivering about 170 mAhg1 at 27 C-rate because of short diffusion length despite the slow diffusivity of Na in Ge (~ 1013 cm2 s1). Similar electrochemical behavior was independently observed in amorphous Ge thin films with thicknesses of hundreds of nm.[19] The reversible capacity was found to decrease, as the thickness increased. However, unlike Ge nanocolumns, Ge thin films delivered reversible capacities lower than the theoretical capacity. Ex situ XRD patterns of Ge film electrodes revealed that the fully sodiated phase was also amorphous. Therefore, it is not clear that the fully sodiated phase of Ge is NaGe as expected from the theoretical calculation. Recently, indium was also examined as an anode for Na-ion batteries.[20] However, the reversible capacity of In thin films is about 100 mAhg1 at approximately 0.4 V versus Na/Na , despite the theoretical specific capacity of In for Na-ion batteries of 467 mAh g1, assuming Na2In is formed during sodiation. An ex situ XRD pattern revealed that the sodiated phase was the mixture of NaIn and In even after being short-circuited for 40 h at 65 C. This indicates that In-based materials have poor sodiation kinetics and are not appropriate for Na-ion batteries. +

+

In 2013, Lee and co-workers reported for the first time that amorphous red phosphorus/carbon composites showed excellent electrochemical performance for Na-ion batteries. [22] The amorphous red phosphorus/carbon composite powders were obtained by mechanical ball milling using amorphous red phosphorus (P) and Super P carbon (C) with a 7:3 wt. ratio. The composite delivered the highest reversible capacity, 1890 mAhgP1, among any reported anode materials for Naion batteries. The high reversible capacity and low redox potential of phosphorus enable Na-ion batteries to have energy densities similar to those of Li-ion batteries, as shown in Figure 2. The P/C composite also showed good rate performance, delivering 1540 mA h g1 at a current density of 2.86 A g1 and stable cyclability over 30 cycles. The excellent electrochemical performance of the P/C composite is attributed to i) the improved electrical conductivity caused by the intimate nanoscale contact between phosphorus and carbon and ii) the use of the polyacrylic acid (PAA) binder, which is appropriate for electrode materials with large volume changes during charge and discharge. Ex situ XRD analysis of the P/C composite during sodiation and desodiation revealed that Na3P is formed after full sodiation (Figure 10). The volume change between phosphorus and Na3P is 491%, resulting in an increase in thickness of the P/C electrode by 187% after full sodiation. It is well known that PAA, carboxymethyl cellulose (CMC), and alginate binders are effective in accommodating the large volume change of high-capacity anode materials such as Si for Li-ion batteries.[23] Phosphorus is also an insulator

+

8

Phosphorus and Phosphides Recently, various groups have pioneered phosphorus-based materials showing promising electrochemical performance as an anode for Li-ion batteries.[21] In particular, crystalline black phosphorus,[21a,c] amorphous black phosphorus,[21d] and red phosphorus/mesoporous carbon composite materials[21e–g] have exhibited excellent performance including high reversible capacities of about 2000 mAh g1 and stable cycle performance for Li-ion batteries. However, the redox potential of phosphorus is about 0.8 V versus Li/Li , which is too high to be used as an anode, because the energy density of a full cell decreases as the redox potential of the anode increases. However, the redox potential of phosphorus for the insertion of Na ions is about 0.4 V versus Na/Na , which is appropriate for an anode in Na-ion batteries. Moreover, the theoretical specific capacity of phosphorus is 2596 mAhg 1, assuming Na3P is formed after full sodiation. Therefore, phosphorus-based materials are very promising as anodes for Na-ion batteries because of their high reversible capacities and appropriate redox potentials. +

+

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Figure 10. a) Voltage profiles of amorphous red P/C composites. b) Ex situ

XRD patterns of amorphous red P/C composite electrodes collected at various points as indicated in the inset. Reproduced from ref. [22] with permission.

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Minireview with very poor electrical conductivity (~ 1x1014 S cm1), and thus the addition of electrically conductive materials such as carbon to phosphorus is necessary to improve the electrochemical performance of phosphorus for Na-ion batteries. Independently and simultaneously, Qian et al.[24] reported that an amorphous red phosphorus and carbon composite obtained by ball-milling showed excellent electrochemical performance including, a high reversible capacity of 1750 mAh g1 and a stable cycle performance over 140 cycles. The improved cycle performance is ascribed to the formation of stable SEI layers because of the addition of the FEC additive. As demonstrated for alloy-based materials, the FEC additive was effective in enhancing the cycle performance of phosphorus. In addition, Li et al.,[25] demonstrated that a simple mixture of phosphorus and CNT obtained by hand-grinding showed good electrochemical performance, but its performance was worse than the phosphorus/carbon composites obtained by the mechanical ball-milling. Recently, Komaba and co-workers also examined the role of the FEC on the electrochemical performance of phosphorus.[26] Recently, Monconduit and co-workers examined NiP3 for the first time as an anode for Na-ion batteries, [27] although various transition metal phosphides have been introduced as anodes for Li-ion batteries.[28] NiP3 delivered a high reversible capacity of 1000 mAh g1 with a capacity loss of 11% after 15 cycles. The capacity fading was attributed to the agglomeration of active elements and the continuous SEI formation on the surface newly exposed to electrolytes in each cycle because of the volume changes during cycling. Furthermore, ex situ XRD analysis of NiP3 suggested that the sodiation/desodiation mechanism in the first cycle is as given in Equations (3) and (4):[27] Sodiation: NiP3 ðcrystallineÞ þ 9Naþ þ 9e ! 3Na3 P þ Ni

ð3Þ

Desodiation: 3Na3 P þ Ni ! NiP3 ðamorphousÞ þ 9Naþ þ 9e

ð4Þ

In addition, Lee and co-workers[4] recently reported that Sn4P3 showed excellent electrochemical performance for Naion batteries. Sn4P3 delivered a reversible capacity of about 700 mAh g1 and exhibited very stable cycle performance with a negligible capacity fading over 100 cycles. The cycle performance of Sn4P3 is better than those of previously reported Sn materials, because the phosphorus effectively inhibits the agglomeration of Sn during cycling. Moreover, the redox potential of Sn4P3 is lower than that of phosphorus, indicating that the energy density of full cells with Sn 4P3 can be higher than those of cells with phosphorus when the same reversible capacity is utilized. Ex situ XRD, TEM, and EXAFS analysis showed that Sn4P3 was converted into NaSn and Na x P upon sodiation, and after further full sodiation, Na15Sn4 and Na y P phases were observed. Then, upon desodiation, Sn4P3 was reversibly recovered. Qian et al. and Li et al. also have recently examined the electrochemical performance of Sn 4P3.[29] Chem. Eur. J. 2014, 20 , 11980 – 11992

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Metal Oxides and Sulfides Recently, many metal oxide materials have been examined as anodes for Na-ion batteries. Metal oxides can store Na ions by intercalation or conversion chemistries. Most Ti-based oxides[30] including TiO2(B),[30a] Na2Ti3O7,[30b–e] Na2Ti6O13,[30f] Na4Ti5O12,[30g] Li4Ti5O12,[30h–j] and P2-Na0.66[Li0.22Ti0.78]O2[30k] store of Na ions through intercalation chemistry and thus deliver relatively small reversible capacities of less than 300 mAhg 1 because of the limited number of storage sites in their crystalline structures. Therefore, these materials will not be discussed in this minireview, and instead, metal oxides storing Na ions via conversion reactions will be focused on in this chapter because of their high theoretical specific capacities (> 600 mAh g1). Metal oxides (MO x ) for the conversion reaction can be divided into two types based on the reaction mechanisms of sodiation/desodiation. In the first type of reaction, the M in MO x is an electrochemically inactive element such as Fe, [31] Cu,[32] Ni, or Co.[33] The sodiation/desodiation of these oxides proceeds via a conversion reaction, as given in Equation (5): +

+

+

MO x þ 2 x Naþ þ 2 x e $ x Na2 O þ M

ð5Þ

In the second type of reaction, the M in MO x is an electrochemically active elements such as Sn [34] or Sb.[35] The sodiation/desodiation of these oxides proceeds via a conversion reaction and a further alloying reaction, as given in Equations (6) and (7). MO x þ 2 x Naþ þ 2 x e $ x Na2 O þ M

ð6Þ

x Na2 O þ M þ y Naþ þ y e $ x Na2 O þ Na y M

ð7Þ

The reversibility of reaction (6) and the formation of intermediate phases such as Na z MO x during sodiation depend on the chosen active elements. Most metal oxides with inactive metal elements usually deliver relatively small reversible capacities less than 400 mAh g1, in spite of their high theoretical capacities (e.g., 1007, 674, 715, 1117, 890 mAhg1 for Fe2O3, CuO, CoO, MoO3, NiCo2O4, respectively). Nanostructured g-Fe2O3/a-Fe2O3 agglomerates made of nanoparticles with sizes of tens of nm delivered a reversible capacity of 300 mAhg 1 with stable cycle performance over 60 cycles, but showed a high polarization of > 1 V in the voltage profile. [31a] Nanosized hollow g-Fe2O3 obtained by using a method based on the Kirkendall effect was also examined for Na-ion batteries, and it delivered about 140 mAh g1 in the voltage range of 1–4 V versus Na/Na .[31b] The reversible capacity of Fe2O3 for Na-ion batteries was also compared with that of Fe 2O3 for Li-ion batteries. Fe3O4 delivered about 900 and 400 mAh g1 for Li-ion and Na-ion batteries, respectively.[31c] MoO3[36] and spinel NiCo2O4[33] also delivered smaller reversible capacities (410 and 200 mAh g1, respectively) than the theoretical values. However, recently, binder-free aligned porous CuO nanorod arrays grown on Cu foils showed promising electrochemical performance, including

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+


Minireview

Figure 12. The schematic illustration of the mechanism for the initial dis-

charge process of SnO2 nanocrystals as an anode in the Na-ion battery. At the high voltage plateau (from 3 V to ~ 0.8 V), Na ions insert into SnO2 nanocrystals. Subsequently, in the low voltage range (from ~ 0.8 V to 0.01 V), twostep reactions between SnO 2 and Na proceed not only from the surface, but also from the inside of SnO 2 nanocrystals. Reproduced from ref. [34a] with permission.

SnO2 þ Naþ þ e ! NaSnO2

ð8Þ

The reaction and failure mechanisms of SnO 2 were studied by in situ TEM analysis with density functional theory calculations, and the reaction mechanism was found to differ somewhat from the outlined above. [34b] Upon sodiation, SnO2 nanowires were changed into amorphous NaxSn nanoparticles dispersed in the Na2O matrix. Then, crystalline Na15Sn4 was formed accompanied by a large volume expansion ( > 100% increase in diameter) after full sodiation. Upon desodiation, Na15Sn4 was transformed to Sn nanoparticles confined in a hollow matrix of Na 2O, as shown in Figure 13. The formation of pores after desodiation increases the electrical impedance because of poor contact between the Sn and Na 2O, resulting in capacity fading. SnO2/reduced graphene oxide [34c] (rGO) and SnO2/graphene oxide[34d] (GO) composites also showed improved electrochemical performance, including a reversible capacity of 330 mAhg1 with a capacity retention of 81.3% after 150 cycles and 741 mAh g1 with a capacity retention of 86% after 100 cycles, respectively. In addition, hierarchical mesoporous SnO microspheres were examined as an anode material for Na-ion batteries. [34e] Unlike the reaction mechanism of SnO 2, the reaction mechanism of SnO was suggested by ex situ XRD analysis to be as given in Equations (12)–(14): Sodiation:

NaSnO2 þ 3Naþ þ 3e ! 2Na2 O þ Sn

ð9Þ

SnO ð tetragonalÞ þ 2Naþ þ 2e ! Na2 O þ Sn

Figure 11. a) Schematic diagram showing the strategy for binder-free CNA

electrode. b) Electrochemical performance of binder-free CNA electrode at a current density of 20 mAg1. Reproduced from ref. [32] with permission.

a high reversible capacity of about 600 mAh g1, although its cycle performance was not very stable (Figure 11). [32] Most metal oxides with active metal elements deliver high reversible capacities. For example, Wang and co-workers[34a] showed that octahedral SnO2 nanoparticles (~ 60 nm) obtained by using a hydrothermal method delivered a reversible capacity of about 500 mAhg1 with stable cycle performance. The improved cyclability is attributed to the retardation of the aggregation of Sn during cycling by the Na 2O matrix. Ex situ TEM analysis revealed that the sodiation/desodiation mechanism of SnO2 is as given in Equations (8)–(11) (Figure 12): Sodiation:

2Na2 O þ Sn þ ð9=4ÞNaþ þ ð9=4Þe ! 2Na2 O þ ð1=4ÞNa9 Sn4

ð10Þ

Na2 O þ Sn þ 0:5Naþ þ 0:5e ! Na2 O þ 0:5NaSn2 ð13Þ

Desodiation:

Desodiation: 2Na2 O þ ð1=4ÞNa9 Sn4 ! SnO2 þ ð25=4ÞNaþ þ ð25=4Þe ð11Þ Chem. Eur. J. 2014, 20 , 11980 – 11992

ð12Þ

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Na2 O þ 0:5NaSn2 ! x SnO ð orthorhombicÞ þ ð1 x ÞSn þ y Naþ þ y e

11989

ð14Þ


Minireview Summary and Outlook Na-ion batteries have been considered a promising candidate to replace Li-ion batteries, and recently, there have been exciting developments in this area. However, for the successful application of Na-ion batteries, the cost per energy unit of Na-ion batteries should be comparable to or even higher than that of the commercialized Li-ion batteries for the next-generation batteries, and thus anode materials with a high reversible capacity must be developed. Various anode materials such as alloys, phosphorus, metal phosphides, metal Figure 13. a) STEM Z-contrast image showing the reaction front of the SnO2 nanowire; and STEM-EELS showing: b) Sn M edge and c) Na K edges obtained with the electron beam positioned in the particle with a higher brightoxides, and metal sulfides have ness in the Z-contrast image; d) O K edge and e) Na K edge with the electron beam positioned in the Na2O been examined as anodes for matrix region close to the surface, which gives a low brightness in the Z-contrast image; f) schematic drawing Na-ion batteries, and have showing the morphology evolution of the SnO2 nanowire upon Na insertion and extraction. Reproduced from shown promising electrochemiref. [34b] with permission. cal performance, including high reversible capacity and stable After full desodiation, both SnO and Sn were observed, indicycle performance. However, large volume changes (more than cating that the formation of SnO was partially reversible. It is 50%) were observed during charging and discharging in most also notable that the initial SnO (tetragonal) and the desodiat- anode materials with high reversible capacities, which is a praced SnO (orthorhombic) have different crystal structures. SnO tical technical barrier because commercialized cells should delivered a reversible capacity of 525 mAh g1 at a current have volume changes less than 30%. Therefore, the tailored density of 40 mAg 1 with a capacity retention of 71% after design of anode materials with large volume changes and the 50 cycles. Sb2O4 thin films also delivered high reversible capaciimprovement of cell engineering are required to supplement 1 ty of about 800 and 600 mAhg at 1/70 and 1/10 C-rates, re- the shortcomings of those materials. Furthermore, many asspectively. [35] Based on ex situ XRD, TEM, and SAED results, the pects of the reaction and failure mechanisms in these materials reaction mechanism of Sb2O4 was suggested to be as given in are not fully understood, and therefore, in-depth studies on Equations (15) and (16): these issues are demanded to further improve their electrochemical performance. In particular, the interface chemistry beþ  ð15Þ Sb2 O4 þ 8Na þ 8e $ 4Na2 O þ 2Sb tween electrode materials and electrolytes is still not well char4Na2 O þ 2Sb þ 6Naþ þ 6e $ 4Na2 O þ 2Na3 Sb

ð16Þ

Recently, various transition metal sulfides such as FeS2[37] (pyrite), Ni3S2[38] (heazlewoodite), MoS2,[39] and Sb2S3[40] (stibnite) have shown promising electrochemical performance. FeS 2 and Ni3S2 delivered high reversible capacities of 630 mAh g1 at about 1.3 V and 420 mAhg 1 at about 0.9 V, respectively. The reversible capacity of MoS2 depended on the size of MoS 2 and the species of carbon in the composites. The MoS 2 embedded in carbon nanofibers obtained by electrospinning had lateral dimensions of 4 nm and a thickness of 0.4 nm (Figure 14) and delivered 1267 mAhg1 at a current density of 40 mAg1 with a capacity retention of 79% after 100 cycles.[39a] Meanwhile, MoS2/rGO only showed a reversible capacity of about 400 mAh g1.[39b] Sb2S3/rGO composites also exhibited excellent electrochemical performance including a reversible capacity of about 700 mA h g1 at a current density of 50 mAg1 with negligible capacity fading over 50 cycles (Figure 15 ).[40] Chem. Eur. J. 2014, 20 , 11980 – 11992

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Figure 14. a) TEM-BF micrograph. b) HRTEM image showing the ultrathin

MoS2 embedded in the carbon nanofiber. c), d) Corresponding HRTEM images from the marked region in (b) and (c), respectively, to show the detailed structure of single-layered ultrasmall MoS2 embedded in the amorphous carbon. Reproduced from ref. [39a] with permission.

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Minireview

Figure 15. a) First cycle charge and discharge profiles of bulk Sb 2S3, nano-

crystalline Sb2S3 and rGO/Sb2S3. b) Cycle performance of rGO/Sb 2S3 and commercial Sb2S3 in electrolyte with 0% and 5 % FEC. Reproduced from ref. [40] with permission.

acterized, although it is known that the electrochemical performance of anode materials is strongly dependent on the interface chemistry such as the SEI layer formation. Therefore, we need to focus more on the optimization of electrolytes through intensive studies on the interfacial behavior of electrode materials, which will provide an opportunity to improve the electrochemical performance of Na-ion batteries. Another concern for Na-ion batteries is their safety. Only a few reports have examined the thermal and electrochemical stability of electrode materials for Na-ion batteries, and it is not still clear whether Na-ion batteries are safe. Therefore, an in-depth understanding of the thermal and electrochemical safety of Na-ion batteries should be sought in future research.

Acknowledgements This research was supported by the MSIP (Ministry of Science, ICT&Future Planning), Korea, under the C-ITRC(Convergence Information Technology Research Center) support program (NIPA-2013-H0301-13-1009) supervised by the NIPA (National IT Industry Promotion Agency), and by the National Research Foundation of Korea (NRF) grant funded by the Korea Government (MSIP and MOE) (No. 2010-0019408 and No. NRF2013R1A1A2013446). Keywords: anode materials · batteries · energy storage

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