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Review—Practical Issues and Future Perspective for Na-Ion Batteries – topic of research paper in Materials engineering. Download scholarly article PDF and read for free on CyberLeninka open science hub.
Review—Practical Issues and Future Perspective for Na-Ion Batteries Academic research paper on "Materials engineering"
2015 / Yunming Li, Zhenzhong Yang, Shuyin Xu, Linqin Mu, Lin Gu, et al.
Academic research paper on topic "Review—Practical Issues and Future Perspective for Na-Ion Batteries"
Research on electrochemical Na intercalation in battery system has been reported since the early 1980s but Na-ion batteries are not commercialized so far though studies on Li-ion batteries have been reported since the late 1970s and the practical batteries have been extensively utilized for portable device applications in the world since 1991. Now, targeted application of research and development for rechargeable batteries has changed toward realization of the sustainable energy society. With the change in social situation and development of the battery technology, studies on Na-ion batteries have been attracted significant interests since 2010. Although research interests of the electrode materials for Na-ion batteries are evoked in many researchers, advantages, disadvantages, and issues are not fully discussed for realizing the commercialization of Na-ion batteries. In this article, practical issues and perspective are reviewed on the basis of mainly our experimental experiences, know-how, and results, and the future direction is proposed to overcome the issues and to challenge the advanced performance.
© The Author(s) 2015. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. [DOI: 10.1149/2.0151514jes] All rights reserved.
Manuscript submitted July 14, 2015; revised manuscript received August 18, 2015. Published October 9, 2015. This paper is part of the JES Collection ofInvited Battery Review Papers.
Power storage technology has been dramatically developed since rechargeable lithium battery (LIB), which are often called a Li-ion battery as named by Sony Corp., was commercialized in 1991 and delivered great impact on economy with tapping into new markets. A high-energy powerful LIB for portable electronic devices such as lap top computers and mobile phones is one of the best examples, and indeed they become essential tools for our life. Thanks for the great research achievement, the price of the battery pack has been declining for more than 20 years, and LIBs are now able to be installed in power system for hybrid electric vehicles (HEV) and battery electric vehicles (BEV) with relatively affordable price. Continuous effort has been devoted on the development of LIBs toward higher-power/higher-energy performance, and they now become promising candidates for being a part of grid-scale energy storage incorporated with wind and solar power systems. When it comes to large-scale power system more than that for electric vehicles, the priority in research is shifted to production cost from performance and thus minor-metal free or low-cost materials that can be derived from more abundant resources have become increasingly desirable. Although LiMn2O4, LiFePO4, and LiNixMnyCozO2, which are utilized in HEV and BEV instead of costly LiCoO2, are recognized as low cost materials,1,2 lithium in the Earth's crust is unevenly distributed as minor-metal and consequently affecting to dependence on import of lithium resource and additionally to product costs. In contrast to lithium, sodium is unlimited in the Earth's crust and sea, and is one of the most abundant elements in the Earth's crust. Since the alternative to lithium is more desirable for realizing largescale power source and sodium is the second lightest alkali next to lithium, Na-ion batteries (NIBs) have attracted much attention as feasible technology for past 5 years.
much inexpensive aluminum because Na metal does not form alloy with Al, which is definitively advantageous of NIBs.
Although NIBs seem to bring numerous cost reduction, the atomic weight and standard potential of sodium are always placed on challenging issues to be considered. In general, potential and reversible capacity of electrode materials for use as practical batteries can play the first role in determining operating voltage and capacity of the cells, which affect the energy density. Table I compares the expected characteristics of Li, Na, Mg, and Al batteries studied currently. When transition metal oxides, ACoO2 (A = Li, Na, Mg and Al), are used as positive electrodes, LIBs with LiCoO2 show the highest operating voltage, leading to the highest gravimetric energy density if we assume the same intercalation reversibility and negative electrode of corresponding metals. NIBs are also able to achieve the second highest operating voltage more than 3 V, however, equilibrium potential of Na/Na+ in PC solution is 0.3 V higher than that of Li/Li+, leading to lower operating voltage of NIBs compared to that of LIBs with the same cutoff anodic potential for positive electrode. As regarding capacity, although atomic weight of Na is 3.3 times heavier than that of Li, the formula weight of NaCoO2 (114 g mol-1) is only 16% heavier than that of LiCoO2 (98 g mol-1). In the C6//LiCoO2 and C6//NaCoO2 cell configuration, the total weight gain from the substitution of sodium for lithium is only +9%, resulting in insignificant difference in the gravimetric capacities of the full cell configuration. As additional discussion on capacity, Mg and Al battery are studied as "beyond lithium"3,4 in recent years because divalent Mg2+ and trivalent Al3+ ions realize multi-electron reaction, and theoretically, they are believed to bring larger gravimetric capacity. However, as seen in Table I, their theoretical limit of capacity is even lower than lithium case, and unfortunately the operating voltages of Mg- and Al-ion batteries5,6 are much lower than 3 V. Further, it is general that Mg and Al electrodeposition is complex and lower reversible, and their larger Stoke's ionic size by strong sol-vation, results in lower transport number in electrolyte solution. As a result, it is difficult for us to find remarkable merits as a new battery system which overwhelms LIBs in performance so far. On contrary, NIB can be recognized as a primary candidate for an alternative to LIB in terms of cost reduction with minimum sacrifice on performance and risk avoidance from export restrictions for lithium resources.
Figure 1. (a) Schematic illustration of Na-ion batteries, and (b) a number of publications, related to the sodium for energy storage devices, published in the past three decades (reproduced from the database of Web of Science, Thomson Reuters). The number in 2015 is limited to the articles published from January to June.
on lithium insertion materials had been just started during the same period and we actually experienced big rush for development of LIBs after the late 1980s, very limited studies on sodium insertion materials were conducted, and only small number of papers and patents were published since 1980's. In addition, research condition and apparatuses including electrolyte solution, binders, separators, and glove box were insufficient for handling sodium metal at that time, which resulted in difficulty in fairly observing potential of the electrode performance as batteries. A few US and Japanese companies developed NIBs in full cell configurations where sodium-lead alloy composite and P2-type NaICoO2 were used respectively as a negative and a positive electrode in the 1980's.9,10 Surprisingly, these studies were published earlier than the commercialization of LIBs, and the sodium battery demonstrated excellent cyclability over 300 cycles. However, the average discharge voltage was lower than 3.0 V, which did not attract much attention against carbon//LiCoO2 cells on the front-line of the day.
Table I. Physical properties for Li and Na as charge carriers for rechargeable batteries compared to Mg and Al.
With growing global energy issues in the 21st-century, research interest in sodium insertion materials has now been completely renewed. The number of publications on NIBs has drastically increased in recent years since 2010 (Fig. 1b). Moreover, NIB session in international conferences has been established since 2012 at Pacific Rim Meeting on Electrochemical and Solid State Science (PRiME) and 1st International Conference on Sodium Batteries was held in 2013. Researchers have made best use of their abundant knowledge developed in LIBs to explore new materials and discussion for NIBs, leading excellent results of battery performance published in the literatures. Various positive electrode materials have been reported for NIBs such as layered and tunnel-type transition metal oxides,11-16 transition metal sulfides and fluorides,17-21 oxyanionic compounds,22-31 Prussian blue analogues32-34 and organic carboxylates and polymers.35,36 Sodium insertion materials show relatively higher rate performance than lithium materials due to the low Lewis acidity of Na+ ion and the estimated energy density of some positive electrode materials are comparable to those of positive electrode materials for LIBs. Electrochemical properties of negative electrode materials have been also investigated in Na cells and reported by many researchers. Although graphite often utilized in LIBs is electrochemically inactive in Na cells, hard carbon delivers more than 300 mAh g-1 of rechargeable capacity at low operation voltage as discussed in the later section. As investigated in LIBs, the electrode performances of sodium alloys,37-48 phosphides49-51 and organic carboxylates52-54 were studied. Although silicon regarded as a next generation material in LIBs is electrochemically inactive in Na cells, phosphorus delivers more than 1,500 mAh g-1 of rechargeable capacity.
As next step, we are now reaching an inflection point to consider issues for practical usage of NIBs. However, discussion on NIBs is more complicated than that on LIBs especially in measurement with half coin-type cells to test fundamental electrode performance, because Na metal used as a counter electrode is highly reactive compared to Li metal. In addition, formation of stable passivation film on Na metal and negative electrode materials in Na cells is more difficult,55 and experimental conditions including glove box, purity of Ar gas, and electrolyte quality rather influence the performance of Na battery cells. Hence reported results and data cannot be simply compared to reach unanimous conclusions.
In this paper, practical issues and material designs with future perspectives for NIBs with recent research progress are reviewed. Recently, battery performances with larger scale full cells than coin-and Swagelok-type cells have been reported by Sumitomo Chemical Co., Ltd., Sumitomo Electric Industries, Ltd., and Faradion Ltd. In the large scale cells, layered transition metal oxide and hard carbon are utilized as a positive and a negative electrode material, respectively. Now, these cells would most successfully simulate practical NIBs so far to the best of our knowledge. Therefore, the electrochemical properties are discussed mainly using layered transition metal oxides and hard carbon in this manuscript. To direct the research on NIBs and further understand the chemistry in NIBs, experimental and practical issues on electrode materials, binders, electrolyte salts, solvents, additives, and operating voltage are reviewed and future perspectives will be also added from our viewpoint.
Figure 3. Capacity retention for hard carbon electrodes in the coin-type cells with PC-based electrolyte solvent containing different Na salts; 1 mol dm-3 NaPF6, NaN(SO2CF3), and NaClO4 at a rate of 25 mA g-1. Reprinted with permission from Ref. 64. Copyright 2014 PCCP Owner Societies.
shown in Fig. 2b.64 Similar results of Na insertion properties for various hard carbons are reported in recent papers.65-87 Clear differences in irreversible capacity and cycle stability between the Dahn's pioneering results60 and ours originate from difference in the contamination, purity of electrolyte solution, and binder as described below.
Figure 2. (a) Charge/discharge curves of Na/1 mol dm-3 CF3SO3Na dissolved in diglyme/graphite cell at a current density of 37.2 mA g-1. Reprinted with permission from Ref. 59. Copyright 2011 WILEY-VCH Verbg GmbH&Co. KGaA, Weinheim. (b) Charge/discharge curves of hard carbon electrodes, derived from sucrose carbonized at 1300°C, at a rate of 25 mA g-1 in 1 mol dm-3 NaClO4 dissolved in PC:FEC (98:2 in vol %), and its capacity retention is also shown in the inset. Reprinted with permission from Ref. 64. Copyright 2014 PCCP Owner Societies.
though graphite can be used as a negative electrode material in Na cells with excellent cycle stability, reversible capacity is limited to less than 150 mAh g-1 and large irreversible capacity is observed at an initial cycle. Further investigation on Na+-solvent co-intercalation and optimization of electrodes and electrolyte solution is thought to be necessary for practical use.
Looking back on the history of LIBs, a 1 mol dm-3 LiBF4/ propylene carbonate (PC) solution was used for the first electrochemical study of LiCoO2 in Li cells by Mizushima, Goodenough, and coworkers.88 They reported only the first cycle of Li//LiCoO2 cycle due to the insufficient cyclability. Dr. Mizushima personally commented us in 2014 that he could not believe long cycle life of the Li//LiCoO2 cell because he observed anodic decomposition of electrolyte solution in the Li cells when they tested the cell in 1970s. As is known presently, the decomposition can be avoided by higher purity electrolyte solution as well as suitable selection of solvents, Li salts, and electrolyte additive etc., and these knowledge resulted in the practical Sony's Li-ion battery. For NIBs, cyclability is also achieved by designing electrolyte solutions with much higher purity.63 To utilize graphite as a negative electrode material in LIB, passivation surface layer, so-called solid electrolyte interphase (SEI), is required for good battery performance, which is adequately formed in high purity electrolyte consisting of Li salts, solvents, and additives.89 Nowadays, electrolyte solution for LIBs is developed and custom-designed for required performance, applications, and electrode materials, such as operation temperature, voltage limit, power capability, alloy electrode, LiMn2O4 and manganese dissolution, and so on. Consequently, the practical electrolyte in LIB is known to be a complex mixture containing multi additives.
Figure 4. Charge/discharge curves of hard carbon electrodes at a rate of 25 mA g 1 in 1 mol dm 3 (a) reagent grade and (b) battery grade NaPFg PC solution, (c) comparison of the curves and polarization at the end of sodiation and (d) their capacity retention. Photographs of the electrolyte solution use are inserted in (a) and (b).
1 mol dm-3 NaPF6/EC:PC.91 On the other hand, our group obtained opposite results that the coin-type cell with 1 mol dm-3 NaPF6/PC and NaN(SO2CF3)2/PC solutions exhibited larger reversible capacity and better cycle performance than those for 1 mol dm-3 NaClO4/PC solution.63,64 As mentioned above, the research groups tested using different-grade electrolyte solutions under different conditions including contamination level in glove box, therefore, the results should not be simply compared in our understanding. In general, purity of the electrolyte salts is known to significantly influence on the battery performances of LIBs. Water contamination in LiPF6 generates HF and worse the electrochemical performances in LIBs.89 Bhide and Adelhelm et al. proved the presence of NaF in NaPF6 (99.0%, Alfa Aesar) using X-ray diffraction and the observation of the insoluble fraction in NaPF6/EC:DMC solution by eyes.92 Detailed study on influence of impurities contained in NaPF6 salts on sodium insertion properties is required for further understanding. Therefore, influence of the NaPF6 salts with different purity on electrochemical properties has been investigated using the salts supplied different companies.
tion of 1 mol dm-3 NaPF6, and was used for Na//hard carbon cells. As anticipated from the coloration, the cell with the white-turbid solution by dissolving the reagent grade NaPF6 showed a smaller reversible capacity, a lower coulombic efficiency at the initial cycle, larger polarization and an insufficient cycle stability compared to those of the cell with a colorless and transparent solution by dissolving battery grade NaPF6 (Kishida Chemical Co. Ltd.), as shown in Fig. 4. In the both cells, sodium polyacrylate was used as a binder with hard carbon in the working electrodes.64 Surface of the hard carbon is covered with the polyacrylate binder, and surface passivation is highly improved in comparison to poly(vinylidene fluoride) (PVdF) binder74 as discussed latter. Of course, the electrolyte solution influences on electrochemical properties not only of negative electrode but also of positive electrode and Na metal counter electrode. From these results, high purity NaPF6 salt should be used for the research on aprotic NIBs instead of low purity NaPF6 and potentially explosive NaClO4 salt. It is also worth noting that more than 2 mol dm-3 of NaPF6 salt is dissolved in PC solvent at room temperature when we use the highly pure NaPF6. The electrochemical properties of Na//hard carbon cells with more than 2 mol dm-3 of NaPF6 electrolyte are under investigation. The results will be reported in the future elsewhere.
Figure 5. (a) Capacity retention for hard carbon electrodes in the beaker-type cells with 1 mol dm-3 NaClO4 dissolved in different solvent mixtures. Reprinted with permission from Ref. 64. Copyright 2014 Wiley Owner Societies. (b) Reversible capacity variation for hard carbon electrodes in 1 mol dm-3 NaClO4 PC solution in beaker-type or coin-type Na cells at a rate of 25 mA g-1. Reprinted from Ref. 96 with copyright permission from American Chemical Society. (c) Reversible capacity variation for hard carbon electrodes in 1 mol dm-3 NaClO4 PC solutions with and without additives at a rate of 25 mA g-1 in coin-type Na cells.
ionic conductivity for the solution and on the electrochemical properties in Na//hard carbon Swagelok cells.91,94,95 They concluded that the Na//hard carbon cells with 1 mol dm-3 NaClO4/EC:PC:DMC (45:45:10 wt%) solution exhibited the largest reversible capacity and the best rate performance among the cells with PC, EC0.5:PC0.5, EC0.5:DME0.5, EC0.5:DMC0.5, EC0.5:DEC0.5, EC0.4:PC0.4:DECa2, EC0.4:PC0. 4:DEC0 .2, EC0.4:PC04:DMC0.2 and EC0.45:PC0.45:DMC0.1 solvents with 1 mol dm-3 NaClO4 salt However, as described in the literatures, NaClO4-based electrolyte solution could not be used for commercial battery because of explosion hazards. Electrochemical properties of full cell, hard carbon//Na3V2(PO4)2F3 with 1 mol dm-3 NaPF6 (98%, Aldrich) EC0.45:PC0.45:DMC01 solution, was also investigated but the cell showed severe polarization compared to those of the cell with 1 mol dm-3 NaClO4 (98%, Aldrich) EC0.45:PC0.45:DMC01 solution. The electrochemical performances might be influenced by the impurity in lower purity NaPF6 salt as mentioned above. No report on systematic investigation of NaPF6-based electrolyte solution, its battery performances, and surface chemistry of electrode is found according to our knowledge. Higher purity NaPF6 salt and its lower contamination are certainly required to be commonly used for further investigation to understand NaPF6-based electrolyte solution for Na-ion research. Simultaneously, we have to note that a good glove box equipped with acceptable purification and circulation of inert atmosphere is also important to avoid contamination into Na cells.
In our investigation based upon the high purity electrolyte solution in Na cells, the different cycle retention was observed for beaker-type and coin-type Na/1 mol dm-3 NaClO4 PC/hard carbon cells (Fig. 5b).96 In the coin-type cell, thin glass separator soaked with the minimal amount of electrolyte solution is sandwiched between the Na and hard-carbon electrodes. In the beaker-type cell, sodium insertion electrodes are examined in flooded electrolyte solution. When electrolyte solution is gradually decomposed and consumed in Na cells during cycles, damage to electrolyte solution in coin-type cell is much significant due to its smaller quantity of electrolyte solution. Because the beaker-type cell contained ca. 10 ml of electrolyte solution while the coin-type cell had ca, 0.2 ml of the solution, capacity degradation in coin-type cell severely occurs than that in beaker-type cells. The results imply importance of the amount of electrolyte solution.
The other important component in the electrolyte effective to battery performances is electrolyte additive. In practical LIBs, less than 5 wt% of electrolyte additives play an important role to improve the battery performances.89 In Na cells, our group investigated the influence of additives, fluoroethylene carbonate (FEC), trans-difluoroetyhene carbonate (DFEC), and vinylene carbonate (VC) on the electrochemical properties of Na//hard carbon cells using coin-type cells.96 By the addition of ca. 2 vol% FEC in 1 mol dm-3 NaClO4/PC solution, the capacity retention was remarkably improved but the other additives did not show any beneficial effects in the NaClO4 solution (Fig. 5c). The effects of additives on the electrode performance might change in NaPF6 solution, which is under investigation by our group.
As recently reported, FEC addition in 1 mol dm-3 NaClO4 (Aldrich, > 98%) in EC : DEC (= 1:1 v/v, PANAX ETEC, Korea), 1 mol dm-3 NaPF6 in EC : DEC and 1 mol dm-3 NaClO4 in PC (Kishida Chemical) electrolyte solutions effectively improved cycle stability of alloy compounds, Sn4P3,46 Sb/C nanocomposite41 and phosphorus,51 respectively. Alloy compounds usually induce large volume expansion and shrinkage during Na insertion and extraction, respectively. Therefore, stable passivation surface is required and the influence of the electrolyte additive would be significant.
On the other hand, influences of the electrolyte additives in NaPF6 (99+%, Alfa Aesar)/PC on battery performances of positive electrode materials were recently reported by Delmas' group using Na//O3-Na0.82Mn1/3Fe2/3O2 cells and the cycle stability was significantly improved by adding 2 wt% FEC or VC.97 Although they showed clear influence of additives on the cycle performance, it is difficult to discuss based on only battery performance without considering additive effects on Na metal, and impurity of electrolyte salt, especially NaPF6, would be also another concern.
Figure 6. Charge/discharge curves of three electrode cells with NaTi2(PO4)3 as working electrode, Na metal as counter and reference electrodes at a rate of 5C in 1 mol dm-3 in NaClO4 in (a) EC:PC and (b) PC. Reprinted with permission from Ref. 98, Copyright 2014, with permission from Elsevier.
The influence of additives on electrochemical properties was reported for not only positive but also negative electrodes and metallic Na electrode. However, electrolyte salts used are different in the literatures and no description on Na metal as a counter electrode is seen. Therefore, overall studies on the influence of electrolyte salts, solvents, and additives on electrode performances of positive and negative electrodes as well as Na metal are necessary and would be reported elsewhere.
Figure 7. (a) Cycle performance of hard-carbon electrodes with CMC, PANa and PVdF binders in 1 mol dm-3 NaPF6 PC solution. (b) HAXPES spectra of F 1s for hard carbon electrode as prepared and after 1st cycle in NaClO4 or LiClO4 PC solution in Li- or Na-cell, respectively. Reprinted with permission from Ref. 74, Copyright 2014, with permission from Elsevier.
decomposition of PVdF requires both electron/ion connection from hard carbon/electrolyte respectively. This means that the three phase interface of hard carbon/PVdF/electrolyte influences the degree of electrochemical defluorination of PVdF, and that SEI formation on hard carbon should influence the connection between hard-carbon/PVdF interface.
The previous studies on electrolyte salts, solvents, additives and binders in Na cells are conducted mainly for hard carbon electrodes. The optimum combination of those components must depend on electrode materials and test conditions. For example, some transition metal oxides show electrocatalysis behavior and accelerate electrolyte decomposition on the surface. Therefore, suitable passivation on the electrode surface with effective binder and additive is very important to suppress the electrolyte decomposition. Controlling the surface reaction, electrolyte decomposition, and SEI formation is necessary to further improve the performance of NIBs.
Ionic liquid is also utilized as electrolyte solution in NIBs. Ionic liquid generally has negligibly low volatility, nonflammability, and high thermal and electrochemical stability. Recently, NIBs with ionic liquid can be operated at room temperature100 and Sumitomo Electric Industries Ltd. has studied to realize practical NIBs with ionic liquid. Although the NIBs exhibit sufficient cycle stability101 and are relatively safe, cost reduction of ionic liquid, increase in energy density, and further safety tests are required for practical use. LIBs with ionic liquid have been also studied broadly, therefore, we have to carefully consider merits and demerits of ionic liquids for the LIBs and NIB for practical applications.
In order to increase the operation voltage of NIBs, the materials operating at lower-potential for negative electrode materials are important which is essential to increase the energy density. Although hard carbon exhibits more than 550 mAh g-1 of reversible capacity by CCCV lithiation in Li cells,102 the redox potential in plateau region during insertion process into nanopores is almost 0 V vs. Li/Li+ and utilization of the plateau region at high current density has a high risk for the formation of metallic Li metal dendrite. Fig. 8a compares charge and discharge curves for Li//graphite, Li//hard carbon and Na//hard carbon cells in detail. Hard carbon electrodes in both Li and Na half cells show slope and plateau regions during (de)intercalation63 while graphite exhibited stepwise potential variation due to the formation of staging structure. Fig. 8b shows dQ/dV curves of the charge and discharge curves in the potential region between 0-0.3 V. The voltages of reduction and oxidation peaks are the lowest in Li//hard carbon cell and the highest in Li//graphite cell from Fig. 8b when optimized hard carbon for LIBs was used in both Li and Na cells. Interestingly, the voltages for Na//hard carbon was intermediate between Li//hard carbon and Li//graphite cells. A risk for the formation of dendrite metal in Na//hard carbon cell is, therefore, insignificant compared to that in Li//hard carbon cell. It is thought that both of the slope and plateau capacity of hard carbon can be utilized as a negative electrode material for Na-ion cell to deliver larger capacity with less risk of alkali metal deposition than those of Li-ion cells.
Figure 8. (a) Charge/discharge curves (corresponding to lithiation/ delithiation or sodiation/desodiation, respectively) at 2nd cycle for Li/1 mol dm-3 LiPF6 EC:DMC (= 50:50 vol%)/graphite, Li/1 mol dm-3 LiPF6 EC:DMC (= 50:50 vol%)/hard carbon, and Na/1 mol dm-3 NaPF6 PC/hard carbon cells tested at a current density of 25 mA g-1 in the voltage range of 0.0-2.0 V using coin-type cells. (b) Comparison of the dQ/dV curves between 0 and 0.3 V.
Figure 9. Average voltage (V) and energy density (Wh kg-1) versus gravimetric capacity (mAh g-1) for negative electrodes materials for Na-ion batteries: (black circles) carbonaceous materials, (red circles) oxides and phosphates as sodium insertion materials, (blue circles) alloy, (green) phosphide/phosphorus, and (gray circles) oxides and sulfides with conversion reaction. Energy density based on weight of active materials in positive and negative electrodes is calculated using their reversible discharge capacity. Positive electrode is assumed to be Na2/3 [Ni1/3Mn1/2Ti1/6]O2 for the calculation. Reprinted from Ref. 111 with copyright permission from American Chemical Society.
capacity positive electrode materials are more important to achieve higher energy battery.
Studies on Na batteries operable at room temperature had been started using layered TiS2 and NaICoO2 materials. Our group has also studied the electrode performance of the layered transition metal oxides as positive electrode materials for NIBs since 2004. One of the authors had a very good opportunity to study layered sodium oxides as a postdoctoral researcher in Dr. Delmas and Dr. Croguennec research group in 2003. In the next year, Okada's group also reported excellent and surprising data of 3.3 V operation of a-NaFeO2 in NaClO4 PC solution supplied by Tomiyama Pure Chemical Industries, Ltd.112 One of the authors previously examined sodium salt as an efficient electrolyte additive to improve graphite negative electrode for Li-ion cells in 2002.113 This is another reason why the author has been much interested in sodium insertion into carbon materials as a component of Na-ion system since 2003.
Figure 10. (a) Comparison of charge/discharge curves of Li//LiCoO2 and Na//NaCoO2 cells. (b) Schematic illustrations of crystal structures for O3 and P2 type NaxMeO2 (Me = transition metals). Reprinted from Ref. 111 with copyright permission from American Chemical Society.
MeO6 octahedra. Polymorphs are generated by stacking the sheets of edge-sharing MeO6 octahedra with different orientations along c-axis. Sodium-containing layered oxides can be categorized into two main groups using the classification proposed by Delmas et al.:115 O3-type or P2-type, in which the sodium ions are occupied at octahedral and prismatic sites, respectively, as shown in Fig. 10b. Although O3-type LiMeO2 is synthesized directly by solid state reaction or through Li+/Na+ ionic exchange process from NaMeO2, P2-type phases are not seen in Li-containing compounds because larger sodium ions can be located at trigonal prismatic sites where the smaller lithium ions cannot stabilize the P2 structure. From next section, experimental and practical issues on O3- and P2-type layered oxides in Na cells are reviewed.
O3-type sodium-containing layered transition metal oxides generally exhibit reversible Na intercalation/extraction into/from the structure even if O3-type lithium-containing layered oxides consisting of the same 3d transition metal oxides are electrochemically inactive in Li cells such as NaFeO2 and NaCrO2 except for NaScO2. In order to obtain large reversible capacity and high operating voltage for high energy density NIBs, reversibly available range of Na extraction in NaMeO2 (Me = transition metals) and adequately high voltage avoiding anodic decomposition of electrolyte solution are very important. However, the available reversible capacity is usually limited to the capacity corresponding to 0.5 moles of Na extraction from NaMeO2. By further Na extraction, O3-type oxides show large irreversible capacity and finally lose the reversibility of Na intercalation as shown for Na//O3-NaFeO2 cells in Fig. 11.116 The capacity decay is mainly due to irreversible structural changes accompanied by migration of transition metal ions, for example, iron, chromium, and titanium ions, from octahedral site in the slab to tetrahedral site and then to face-shared octahedral site in interslab space.11M19 Even though O3-type structure transforms into P3-type one by moderate Na extraction, having no tetrahedral sites in interslab space, another O3-type phase having tetrahedral sites appears again when the electrode is charged beyond 0.5 moles of Na extraction.118 Despite, NaFe1/2Co1/2O2,120 NaNi1/3Fe1/3Co1/3O2,121 NaNi1/3Fe1/3Mn1/3O2,122 and NaNi1/4Fe1/4Co1/4Mn1/4O2123 demonstrate larger reversible capacity corresponding to more than 0.6 moles of Na extraction. The metal doping in NaFeO2 effectively suppresses the irreversible migration of iron and extends the available range of Na extraction. Appropriate selection of transition metals and the composition to control the structural changes and to increase operating potential is important for O3-type layered oxides in Na system.
Me3+ is stable at octahedral sites in P3-type latt'ce.
A face-shared vacant tetrahedral site is formed in O3-type lartce by Na extraction.
Men+ migrates into the vacant tetrahedral site.
Men+ migrates into the vacant octahedralsite.
Figure 11. (a) Galvanostatic charge/discharge curves of Na//NaFeO2 cell. (b) Proposed mechanism for the migration process of transition metal ion on sodium extraction. (a) Reprinted from Ref. 116 with permission of The Electrochemical Society of Japan. Copyright 2012. (b) Reprinted from Ref. 118 with copyright permission from American Chemical Society.
NaOH, formed in Equation 1, is partially dissolved in NMP. Furthermore, Na2O, produced in Equations 2 and 3, will change into NaOH in atmosphere in Equation 4, and NaOH will be contained in NMR slurry.
To simulate the influence of the NaOH contamination from NaMeO2 on slurry condition, we made slurry with TiO2 and small portion of NaOH additive. The reason why we select TiO2 is that TiO2 is not hygroscopic, non-reactive with NaOH, water, and air, and white color which allows us to visually distinguish coloration of slurry. TiO2 white powder and PVdF were mixed with or without NaOH powder at a molar ratio of 1:1 (= TiO2 : NaOH) in NMP solvent by our assuming that NaOH formation in slurry mixture of NaTiO2 and PVdF by air-exposure, as shown in the above equations.
Figure 12. Photographs of the slurry just pasted on Al foil (without drying) in atmosphere for (a) LiCoO2 and (b) NaNi1/2Mn1/2O2 composites, powder mixtures of (c) TiO2 and PVdF and (d) TiO2, PVdF and NaOH at a molar ratio of TiO2 : NaOH = 1:1, and the slurry just pasted on Al foil (without drying) in inert atmosphere inside glove box for TiO2 and PVdF with NMP (e) without and (f) with NaOH.
the mixture of TiO2 and PVdF with NaOH powder and without NMP in Fig. 12d, supporting a slight reaction between PVdF and NaOH in power state in atmosphere. More obvious difference was observed by mixing with NMP under Ar-filled glove box. No coloration was observed for the sheet of TiO2 and PVdF slurry free from NaOH. However, black coloration and agglomeration were observed for TiO2 and PVdF slurry mixed with NaOH powder, indicating a chemical reaction between PVdF and NaOH in the slurry, because no significant coloration was seen for the powder mixture of TiO2 and NaOH. The coloration is due to defluorination for PVdF in NaOH solution.124,125 Clearly, the worse condition of the NaOH-added slurry is similar to the case of NaNi0.5Mn0.5O2 as seen in Figs. 12b and 12f.
If hygroscopic O3-NaMeO2 slurry is exposed to moist atmosphere, the extraction of Na+ and NaOH formation, as described in Eqs. 1, 2, 3 and 4, result in the increase in alkalinity of the slurry due to NaOH formation and its dissolution into NMP, leading to defluorination of PVdF binder in the NaOH-containing slurry, and then the agglomerated particles gradually appear. Furthermore, if we pasted the slurry on aluminum foil, the NaOH containing slurry should corrode aluminum foil, because aluminum is an amphoteric element. During handling O3-type NaMeO2 product, dry condition is required to avoid the damage to PVdF binder, Al foil, and also NaMeO2 product. This problem is similarly found in LiNiO2 and layered oxides containing Ni3+ in the Li system because of their hygroscopicity. The developed techniques for practical use for the hygroscopic Li-containing oxides would be applied to Na system.
expected to overcome the deterioration of slurry. Consequently, materials design considering control the hygroscopic character, phase transition, and operating potential is required for O3-type layered oxides.
In constant to O3-type layered oxides, P2-type oxides generally exhibit high operating voltage.15 The fact probably originates from the off-stoichiometry of sodium and the difference in oxygen stacking sequence in the structure: ABCABC in O3-type and ABBA in P2-type, resulting in suppression of irreversible structural change and almost all Na ions can be extracted from the structure without collapse of the crystal structure. As described above in Fig. 10a, lowering redox potential is significant in Na-rich region in Na cells. Utilizing the Na-poor region for x = 2/3 ~ 0 in NaxMeO2 leads to relatively high operating potential and P2-type layered oxides provide higher energy density of Na cells than that for O3-type layered oxides. Additionally, such higher potential in as-prepared materials is advantageous to suppression of hygroscopic damage.
Figure 13. (a) Charge curve of Na//P2-Na2/3Ni1/3Mn2/3O2 cells with indication of phase evolution region. (b) Schematic illustration for the reversible structural change from P2- to O2-type phase by the slab gliding.
Figure 14. Comparison of capacity retention rate of P2-Na2/3Ni1/3Mn2/3O2 electrodes with PVdF and CMC binder.
been developed for silicon negative electrode material in Li cells to keep the connection between active materials, carbon additive and current collector.99 P2-type Na2/3Ni1/3Mn2/3O2 is not hygroscopic and does not uptake water as crystal water in the structure.85,129 Therefore, no significant damage to the active materials during aqueous slurry process is expected and water-soluble CMC binder can be used for P2-type Na2/3Ni1/3Mn2/3O2, which differs from O3-type materials. CMC binder electrode exhibited remarkably improved capacity retention compared to that of PVdF electrode in the voltage range of 2.0-4.5 V at rate of 13 mA g-1 as shown in Fig. 14. Binder significantly influences on the electrode performance of not only negative electrode materials but also positive ones in Na batteries. Although stability of positive electrode materials against moisture and water is not often discussed by academic researchers, the stability is essential to use water dispersible/soluble binders for the materials, especially involving large volume change such as P2-type layered oxides.
As described above, most of Na containing layered transition metal oxides evidently react with moisture and water, resulting in H+/Na+ exchange and/or Na extraction form the structure on the basis of oxidation. Recently, Buchholz and Passerini et al. investigated water sensitivity of layered NaxNi0.22CoanMn0.66O2 and found that a hydrated phase, having long interslab distance, is formed at low sodium contents below 0.33 in the composition.130 Indeed, our group also observed the phases with long c lattice parameter after charge for x < 0.4 in NaxNi1/2Mn1/2O2.131 Even a laboratory made attachment of sample holder was used to avoid air exposure, extra peaks attributed to the hydrated phase was observed by ex-situ X-ray diffraction.131 The Na extracted phases should be highly reactive and promptly entrap water molecules through the tiny interstices of the holder. Ex-situ measurements such as X-ray and neutron diffraction after disassembling cells should be carefully conducted without air exposure otherwise in-situ measurements is required to obtain reliable data.
Figure 15. Average voltage (Vave) and energy density (Wh kg-1) versus gravimetric capacity (mAh g-1) for selected positive electrode materials for Na-ion batteries. Energy density was calculated by hypothesizing the hard carbon (reversible capacity of 300 mAh g-1 with Vave = 0.3 V vs Na/Na+, see Figure 2b) as negative electrode materials. Reprinted from Ref. 111 with copyright permission from American Chemical Society.
LiMn2O4 system. However, available voltage window without electrolyte decomposition at high voltage should be taken into account. Similar electrolyte solutions to those in practical LIBs are used for NIBs; therefore, anodic restriction of voltage to avoid the decomposition of electrolyte solution, leading to gas evolution and swelling of battery, could be identical in both battery system. As generally known among battery engineers, state-of-the-art LIB is charged up to 4.4 V vs. Li/Li+. Because the difference in standard electrode potentials between Li/Li+ and Na/Na+ is about 0.3 V, anodic cutoff voltage in Na cells should be limited to approximately 4.1 V vs. Na/Na+.
Figure 15b compares discharge curves of selected layered oxides. In the figure, charging beyond a red dotted line at 4.1 V will suffer from gas evolution in practical full cells of NIB. Our group recently reported that P2-type Na2/3Ni1/3Mn1/2Ti1/6O2 delivered 127 mAh g-1 of reversible capacity and the average voltage of 3.7 V at first discharge with good capacity retention, originating from successful suppression of the large volume change during charge and discharge.128 However, these performances are obtained by charge up to 4.5 V vs. Na/Na+. It is thought that the charge up to 4.5 V will lead to gradual decomposition of electrolyte solution, resulting in gas generation and short cycle life. To achieve the practical NIBs with high energy density and satisfactory cyclability, further developments of electrolyte or improving passivation for positive electrode are necessary. Recently, a computational chemistry has been applied to investigate the interphase between electrode/electrolyte with an additive in an atomic scale in the Li system.132 New findings from the calculations would be helpful to understand SEI in detail and further improve the electrochemical stability of the electrolytes.
On the basis of research and development of LIBs, NIBs have been rapidly developed since 2010. Simultaneously, we are facing with the drawbacks and issues: unstable SEI on the surface of negative electrode materials, anodic electrolyte decomposition at high charge voltage, degradation by contamination into battery and so on. Optimization of electrolyte solution is still required for NIBs especially for understanding dependency of the NaPF6 purity and suitable electrolyte additive(s) for NIBs. Contrary to the similar intercalation reaction in NIBs and LIBs, battery chemistry in NIB is totally different from that in LIB as observed for the differences in electrochemical activity of graphite, silicon and AMeO2 (A = Li and Na, Me = Fe, Cr, Co etc.), and the stability of crystal structure such as P2- and P3-type phase. Material design to exploit the advantages of NIBs consisting without any costly metals is further required to realize practical NIBs.
Recent progress, practical issues, and future perspective of Na-ion batteries are reviewed on the basis of recent literatures and our achievement. Theory, principle, material synthesis, and experimental methods for research and development of Na-ion batteries should be further established and understood with consideration of both similarity and differentia to Li-ion batteries. It is therefore no surprise that research on Na-ion batteries faces the same challenge as Li system, for example, electrolyte decomposition at high voltage and capacity fading upon cycling. However, as to further investigation, simultaneous developments of all materials for Na-ion batteries with those of Li-ion batteries are highly required, that is, electrode active materials, carbon additives, binders, electrolyte salts, solvents, current collectors, and so on. We believe that new finding and understanding in Na-ion chemistry, including materials science and surface chemistry, will synergistically affect acceleration of further developments of electrochemical energy devices, such as Li-ion batteries, Mg batteries, Al batteries, and redox capacitors.
The authors acknowledge the students, collaborators, and industrial partners who have contributed to this series of research over the past ten years. This work was partially granted by the Japan Society for the Promotion of Science (JSPS) through the "Funding for NEXT Program", initiated by the Council for Science and Technology Policy (CSTP), by MEXT program "Elements Strategy Initiative to Form Core Research Center" (since 2012), MEXT; Ministry of Education Culture, Sports, Science and Technology, Japan, and by Adaptable and Seamless Technology Transfer Program (A-STEP) through Target-driven R&D from Japan Science and Technology Agency, JST.
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