Toothpaste-like Electrode: A Novel Approach to Optimize the Interface

this novel solid-state battery can deliver a capacity of 80 mAh g–1 in a voltage range of 2.5–3.8 V at 0.1C rate using layered oxide Na0.66Ni0...
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Toothpaste-like Electrode: A Novel Approach to Optimize the Interface for Solid-State Sodium-Ion Batteries with Ultralong Cycle Life Lilu Liu,†,‡ Xingguo Qi,†,‡ Qiang Ma,†,§ Xiaohui Rong,†,‡ Yong-Sheng Hu,*,†,‡ Zhibin Zhou,§ Hong Li,†,‡ Xuejie Huang,†,‡ and Liquan Chen†,‡ †

Key Laboratory for Renewable Energy, Beijing Key Laboratory for New Energy Materials and Devices, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China ‡ School of Physical Sciences, University of Chinese Academy of Sciences, Beijing 100049, China § Key Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, 1037 Luoyu Road, Wuhan 430074, China S Supporting Information *

ABSTRACT: A non-sintered method with toothpaste electrode for improving electrode ionic conductivity and reducing interface impedance is introduced in solid-state rechargeable batteries. At 70 °C, this novel solid-state battery can deliver a capacity of 80 mAh g−1 in a voltage range of 2.5−3.8 V at 0.1C rate using layered oxide Na0.66Ni0.33Mn0.67O2, Na-β″-Al2O3 and sodium metal as cathode, electrolyte and anode, respectively. Moreover, the battery shows a superior stability and high reversibility, with a capacity retention of 90% after 10 000 cycles at 6C rate and a capacity of 79 mAh g−1 is recovered when the current rate is returned to 0.1C. Furthermore, a very thick electrode with active material mass loading of 6 mg cm−2 also presents a reasonable electrochemical performance. These results demonstrate that this is a promising approach to solve the interface problem and would open a new route in designing the next generation solid-state battery. KEYWORDS: toothpaste, ionic liquid, Na-β″-Al2O3, solid-state, sodium-ion batteries stability, flammability, and possible leakage of the organic liquid electrolytes hinder them to be applied in the large-scale energy storage systems because safety and cycling stability are their primary concerns. Inorganic solid electrolytes are therefore potential candidate to be developed in nextgeneration rechargeable batteries because of the special merits such as nonflammable components, easy handling, high thermal stability, and low self-discharge rates.12−14 A major challenge in the development of the next-generation solid-state battery technology is the poor performance resulted from the low mixed ionic and electronic conductivity in the electrodes and the large interface impedance between electrode and electrolyte because of the limited contact area between them.15−18 The poor interfacial contact inhibits the transport of sodium ions and also decreases the active sites for charge transfer reaction, thus increasing the polarization. Over the past decade, various attempts have been made to optimize the interfacial contact such as electrode particle size reducing,19 screen printing,20,21 sintering,13,22,23 pressing,24,25 molten salt,26

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nergy storage technology has been dramatically developed because of the tremendous development of renewable energies such as solar and wind power, which critically needs large-scale energy storage systems with long-life, high efficiency, and low cost. Electrochemical energy storage represents one of the most promising means to store electricity on a large scale because of its advantages, such as high energy conversion efficiency and simple maintenance, compared with other energy-storage technologies. Lithium-ion batteries (LIBs), the most successful electrochemical approach, have dominated the portable electronic device market since the commercialization in 1990s.1 However, the limited abundance and uneven distribution of lithium restrict the LIBs’ application in largescale energy storage systems such as smart grid, especially with the speed development of electric vehicles (EVs). Sodium-ion batteries (SIBs), potential alternatives of LIBs, have attracted great attention in recent years because of the lower cost (huge abundant and evenly distributed sodium resources) and similar working principle with LIBs.2−6 Generally, the rechargeable SIBs use organic liquid electrolytes to support the migration of sodium ions between cathode and anode,7−11 which possess some advantages such as maximizing the electrolyte-electrode contact area and minimizing the resistance between them. However, low thermal © XXXX American Chemical Society

Received: September 16, 2016 Accepted: November 17, 2016 Published: November 17, 2016 A

DOI: 10.1021/acsami.6b11773 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

Letter

ACS Applied Materials & Interfaces and lattice matching.27 Sintering is a traditional and popular approach to improve the interfacial contact. However, unwanted side reactions28−30 and elemental inter-diffusions31 often occur during the sintering process, thereby enlarging the interfacial resistance. In addition, the high cost due to the complicated preparation procedure limits the practical application of the solid-state sodium-ion batteries (SS-SIBs). Herein, we proposed a novel strategy to address the interfacial problem, wherein the contact area between electrodes and solid electrolyte was remarkably enlarged and the preparation technology of the single cell was simplified. To verify the strategy, we performed a series of electrochemical examination, with a traditional sodium ion conductor (Na-β″Al2O3 ceramic pellet) and layered oxide Na0.66Ni0.33Mn0.67O2 (NNM) as solid electrolyte and cathode material, at 70 °C and room temperature (RT) with different current rates. Superior performance with negligible capacity loss during 10 000 cycles was obtained through this design. The core idea of this strategy is to design a novel electrode that is soft and easy-to-handle and can be adhered onto the solid electrolyte pellet. Such an electrode is similar to a toothpaste. Moreover, the new designed toothpaste electrode can keep interface wet during the working process of the battery. To enlarge the contact area among solid particles and improve the battery performance, one feasible solution is to provide a mixed conducting network for the electrode.32,33 Meanwhile, the preparation procedure of the single cell could be simplified, which might be easier than that of liquid battery. In the traditional design (Figure 1a), electrons are conducted

conductive additive Super P (Figure 1b). A liquid thin layer is coated around the active material, changing the point contact among solid particles to area contact, which will enable Na+ ions transport along the surface of particles, increasing the speed of ion transport, thereby resulting in considerable improvement in ionic conductivity (among solid particles in electrode and electrolyte). The mass loading, as well as the percent of active material, can be increased owing to the optimization of solid interface and the remove of binder and electrolyte particles. Moreover, ionic liquid possesses some merits such as nonflammability, nonvolatility, high ionic conductivity and high viscosity, rendering it an appropriate candidate for our design. Actually, such quasi-solid or half-solid approaches with IL have also been reported in lithium−air and lithium-ion batteries.34,35 Zhou et al. reported that better performance was achieved with sustainable gel/solid interface in lithium−air battery. Junk el al also reported the same effect of adding liquid in the cathode, obtaining improved electrochemical performance. Recently, Zhang et al. added a drop of ionic liquid on the cathode side after co-sintering the cathode and ceramic electrolyte pellet, improving the cycling stability remarkably.36 However, these reports added ether lithium salt (LiTFSI) or solid electrolyte in the cathode, which lowered the proportion of active material and raised the cost. On the basis of these works, we propose this novel concept to solve the interfacial problem and simplify the preparation process of cathode, resulting in better performance, easier preparation, and lower cost. The cell preparation process was simplified to only one-step pasting before fabricating the battery (Supporting Information), meaning that the interfacial phase layer generated from the unwanted chemical reactions or elemental interdiffusions between electrode and electrolyte during the sintering process could be avoided and the cost shall be greatly reduced. On the basis of these analyses, the practical application of the SS-SIBs will be promoted with this designed new type electrode. For this novel-type electrode, a typical sodium ion conductor Na-β″-Al2O3 ceramic pellet, layered oxide Na0.66Ni0.33Mn0.67O2 (NNM, Figure S1) and ionic liquid PY14FSI (IL, Figure S2) were employed as solid electrolyte, active material and interfacial wetting agent to demonstrate its availability. Scanning electron microscopy (SEM) and Energy-dispersive spectroscopy (EDS) were carried out in order to have a deeper look at the cathode and interface (between cathode and electrolyte), as depicted in Figure 2 (40 wt % NNM) and Figure S3 (60 wt % NNM). The specific compositions are

Figure 1. Schematic diagrams of (a) a conventional sintering type and (b) the designed new type solid-state battery based on an inorganic ceramic electrolyte.

by carbon black, and ion migration among active material or through the interface of electrode and electrolyte is restricted because of the contact points between solid particles are limited. Solid electrolyte particles are usually added into the electrode and sintering process is always performed in order to optimize the interface between them. However, ion transport is still inhibited because the contact mode does not change, and the sintering process will result in other issues as discussed above. Here we adopted a functional ionic liquid acting as an ionic conductor, wetting agent as well as binder to construct the mixed ionic and electronic conducting network together with

Figure 2. SEM and the representative elemental mapping images of (a) the toothpaste cathode and (b) the cross section of the interface between cathode and electrolyte. The content of NNM is 40 wt %. B

DOI: 10.1021/acsami.6b11773 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

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Figure 3. Electrochemical performance of the “toothpaste”, 40 wt % at 70 °C. (a, b) Rate capability. (a) Discharge curves of the SS-SIB cycled at constant charge/discharge rates from 0.1C to 8C cycled between 2.5 and 3.8 V (one charge curve at 0.1C rate is also shown). (b) Specific Capacity and Coulombic efficiency versus cycle number at various current rates from 0.1C to 8C. (c) Long-term cycling performance. Specific capacity and Coulombic efficiency versus cycle number at 6C rate. (d) The 10 001st galvanostatic charge and discharge curve at 0.1C rate after a long cycle (10 000) at 6C rate.

3b compare the electrochemical performance at 70 °C with different current rates and it can deliver capacities of 80, 79, 77, 76, 73, 67, 58, and 51 mAh g−1 at constant rates of 0.1C, 0.2C, 0.4C, 1C, 2C, 4C, 6C, and 8C, respectively. A capacity of 80 mAh g−1 represents an equivalent of 91% of the NNMcathode’s theoretical capacity (88 mAh g−1) calculated from a single-electron process of Ni3+/Ni2+ redox couple. The higher charge capacity in the initial cycles may result from side reaction between ionic liquid and active material. In addition, the capacity retention at a high current rate of 8C is 64% of the initial capacity at 0.1C rate and no capacity loss is observed after 100 cycles. Benefiting from wetting effect of IL in this kind of battery design, the ionic conductivity can afford such a good rate capability which is much better than the performance with Na-β″-Al2O3 as electrolyte ever reported. In order to examine the long-term cycling stability, a large current rate of 6C was taken and excellent cycling perfromance was obtained with a high capacity retention of 90% after 10 000 cycles (Figure 3c), and the Coulombic efficiency remained nearly 100%. It should be noted that the capacity is recovered to 79 mAh g−1 when the current rate is returned to 0.1C rate after 10 000 cycles and no polarization is observed, demonstrating a high reversibility, which is the best result ever reported in SS-SIBs with normal active material mass loading (2 mg cm−2). The electrochemical performance of the battery with organic liquid electrolyte is tested for comparison (Figure S4). As to the long-term cycling performance, the discharge capacity decays slowly before 2800 cycles. Then an obvious fluctuation of Coulombic efficiency appears, which is caused by decomposition of the liquid

listed in Table S1. In the mapping images, C comes from Super P and part of IL; most of the Na comes from NNM and a small part from Na-β″-Al2O3; F, Ni/Mn and Al represent IL, NNM and electrolyte, respectively. It can be seen from Figure 2a that the active material particles disperse homogeneously in the ionic liquid and Super P slurry that compose the mixed ionic and electronic conducting network. Ion transport and electron conduction among the active material particles are facilitated by ionic liquid and Super P, respectively. In Figure 2b, the crosssection profile is depicted corresponding to what we designed in Figure 1b, from which we can see that the “toothpaste” adheres to the electrolyte closely, promoting ionic transport through the interface remarkably. The interfacial line is displayed clearly in the mapping images, and a small amount of F and Mn in the electrolyte area are attributed to the preparation process during which trace amounts of “toothpaste” were painted onto the electrolyte. The electrochemical performances of the solid-state batteries with this novel “toothpaste” cathode were evaluated at RT and 70 °C. (The Na+ ion conductivity of the Na-β″-Al2O3 solid electrolyte pellets are ∼1 × 10−3 S cm−1 at RT and reach to 1 × 10−2 S cm−1 at 70 °C37). When we prepare the toothpaste cathode, three factors (ionic conductivity, electronic conductivity, and cohesiveness) are taken into consideration, meaning the contents of active material, SP and IL should be balanced. The ratio of active material in previous reports is usually 40−50 wt % or even less than 40 wt % for SSSIBs14,38−40 and here we also choosed the proportion of 40 wt % (Table S1) to examine the effect of our design. Figure 3a and C

DOI: 10.1021/acsami.6b11773 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

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Figure 4. Electrochemical performance of the “toothpaste”, 40 wt % at 25 °C. (a) First, second, and tenth galvanostatic charge and discharge curves at a 0.1C rate cycled between 2.5 and 3.8 V. (b) Rate performance. Specific capacity and Coulombic efficiency versus cycle number at various current rates from 0.1C to 2C.

electrolyte. After 4100 cycles, the capacity declines rapidly, because the liquid electrolyte might run out, which will be avoided in solid-state batteries. Compared with liquid electrolytes, the Na+ ion conductivity of the solid electrolyte Na-β″-Al2O3 (∼1 × 10−3 S cm−1) is lower by an order of magnitude at RT, which is just enough for Na+ ion transport. It is possible for the battery to work at room temperature as the interface has been optimized with our design of the “toothpaste”. Therefore, the performance at room temperature was also tested with the results shown in Figure 4a, from which we can see that a 72 mAh g−1 reversible capacity is delivered at a current rate of 0.1C. The specific capacity is about 90% of the liquid one (80 mAh g−1, Figure S4a) and nearly no capacity loss is observed after 10 cycles, which manifests the good cycling stability. Moreover, the rate capability was also characterized, as depicted in Figure 4b. Though the battery works not as well as the one at 70 °C at 1C or larger rate, the rate and cycling performance at 0.1−0.5C rates are excellent, suggesting a good interface in our design and making it a promising way for the application of SS-SIBs. On the basis of the excellent electrochemical performance of 40 wt % active material, we further improved the active material content to 60 wt % (Table S1) in order to deeply explore the feasibility of this design. Furthermore, the active material mass loading is increased to about 6 mg cm−2, which is much larger than ever reported in solid-state lithium/sodium batteries. The specific capacity of the cell reached up to 83 mAh g−1 at a 0.1C rate (Figure 5a), which is comparable to the one using organic liquid electrolyte (80 mAh g−1, Figure S4a). The designed cathode with 60 wt % active material also demonstrates good rate capability, which is presented in Figure 5b. The capacity retention at a 2C rate is 78.3% of the initial capacity at 0.1C rate, and it exhibits a high reversibility. The most appealing property of this cathode is that the long-term cyclic stability with such a high active material mass loading (6 mg cm−2). As shown in Figure 5c, the cell exhibits capacity retention of 73.6% at a current rate of 2C rate over 650 cycles (a very small capacity decay of 0.04% per cycle). It should be noted that, the current density of 2C with an active material mass loading of 6 mg cm−2 equals to that of 6C with an active material mass loading of 2 mg cm−2. Compared to the electrochemical property of the battery with 40 wt % NNM (Figure 3a), the larger polarization reflected in the charge−discharge curves (Figure 5a) mainly results from the much thicker cathode with

Figure 5. Electrochemical performance of the “toothpaste”, 60 wt % at 70 °C. (a) First, second, and twentieth galvanostatic charge and discharge curves at a 0.1C rate cycled between 2.5 and 3.8 V. (b) Rate performance. Specific capacity and Coulombic efficiency versus cycle number at various current rates from 0.1C to 2C. (c) Long-term cycling performance. Specific capacity and Coulombic efficiency versus cycle number at 2C rate.

longer Na+ ion diffusion length. With the increase of NNM content (decrease of IL content), the diffusion kinetic of the Na+ ions becomes poor, which can be deduced from cyclic voltammograms for various scan rates (Figure S7). The novel toothpaste electrode exhibits the best cycling and rate performance demonstrated so far among all reported SS-SIBs based on Na-β″-Al2O3 solid electrolyte. When the NNM content is increased further, the shape of the cathode is no longer like a toothpaste, because little IL is difficult to wet the NNM and SP composite. Thus, ionic conducting network cannot be formed well. As a result, the SSSIB with this cathode shows a poor performance (Figure S5). Because of the designed ionic and electronic conducting network, the resistance of the battery with “toothpaste” cathode is decreased greatly. As shown in Figure S6, the resistances are about 80 Ω and 330 Ω for SS-SIBs with “toothpaste”, 40 wt % NNM cathode, and “toothpaste”, 60 wt % NNM cathode, D

DOI: 10.1021/acsami.6b11773 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

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(3) Pan, H.; Hu, Y.-S.; Chen, L. Room-Temperature Stationary Sodium-Ion Batteries for Large-Scale Electric Energy Storage. Energy Environ. Sci. 2013, 6, 2338−2360. (4) Hong, S. Y.; Kim, Y.; Park, Y.; Choi, A.; Choi, N.-S.; Lee, K. T. Charge Carriers in Rechargeable Batteries: Na Ions vs. Li Ions. Energy Environ. Sci. 2013, 6, 2067−2081. (5) Yabuuchi, N.; Kubota, K.; Dahbi, M.; Komaba, S. Research Development on Sodium-Ion Batteries. Chem. Rev. 2014, 114, 11636− 11682. (6) Islam, M. S.; Fisher, C. A. Lithium and Sodium Battery Cathode Materials: Computational Insights into Voltage, Diffusion and Nanostructural Properties. Chem. Soc. Rev. 2014, 43, 185−204. (7) Wang, Y.; Xiao, R.; Hu, Y. S.; Avdeev, M.; Chen, L. P2Na0.6[Cr0.6Ti0.4]O2 Cation-Disordered Electrode for High-Rate Symmetric Rechargeable Sodium-Ion Batteries. Nat. Commun. 2015, 6, 6954. (8) Xu, S.; Wang, Y.; Ben, L.; Lyu, Y.; Song, N.; Yang, Z.; Li, Y.; Mu, L.; Yang, H.-T.; Gu, L.; Hu, Y.-S.; Li, H.; Cheng, Z.-H.; Chen, L.; Huang, X. Fe-Based Tunnel-Type Na0.61[Mn0.27Fe0.34Ti0.39]O2 Designed by a New Strategy as a Cathode Material for Sodium-Ion Batteries. Adv. Energy Mater. 2015, 5, 1501156. (9) Mu, L.; Xu, S.; Li, Y.; Hu, Y. S.; Li, H.; Chen, L.; Huang, X. Prototype Sodium-Ion Batteries Using an Air-Stable and Co/Ni-Free O3-Layered Metal Oxide Cathode. Adv. Mater. 2015, 27, 6928−6933. (10) Qi, X.; Wang, Y.; Jiang, L.; Mu, L.; Zhao, C.; Liu, L.; Hu, Y.-S.; Chen, L.; Huang, X. Sodium-Deficient O3-Na0.9[Ni0.4MnxTi0.6−x]O2 Layered-Oxide Cathode Materials for Sodium-Ion Batteries. Part. Part. Syst. Charact. 2016, 33, 538−544. (11) Li, Y.; Hu, Y.-S.; Titirici, M.-M.; Chen, L.; Huang, X. Advanced Sodium-ion Batteries Using Superior Low Cost Pyrolyzed Anthracite Anode: Towards Practical Applications. Energy Storage Mater. 2016, 5, 191−197. (12) Hueso, K. B.; Armand, M.; Rojo, T. High Temperature Sodium Batteries: Status, Challenges and Future Trends. Energy Environ. Sci. 2013, 6, 734−749. (13) Wei, T.; Gong, Y.; Zhao, X.; Huang, K. An All-Ceramic SolidState Rechargeable Na+-Battery Operated at Intermediate Temperatures. Adv. Funct. Mater. 2014, 24, 5380−5384. (14) Hayashi, A.; Noi, K.; Sakuda, A.; Tatsumisago, M. Superionic Glass-Ceramic Electrolytes for Room-Temperature Rechargeable Sodium Batteries. Nat. Commun. 2012, 3, 856. (15) Ohta, N.; Takada, K.; Zhang, L.; Ma, R.; Osada, M.; Sasaki, T. Enhancement of the High-Rate Capability of Solid-State Lithium Batteries by Nanoscale Interfacial Modification. Adv. Mater. 2006, 18, 2226−2229. (16) Han, F.; Gao, T.; Zhu, Y.; Gaskell, K. J.; Wang, C. A Battery Made from a Single Material. Adv. Mater. 2015, 27, 3473−3483. (17) Xu, X.; Takada, K.; Watanabe, K.; Sakaguchi, I.; Akatsuka, K.; Hang, B. T.; Ohnishi, T.; Sasaki, T. Self-Organized Core−Shell Structure for High-Power Electrode in Solid-State Lithium Batteries. Chem. Mater. 2011, 23, 3798−3804. (18) Xu, X.; Takada, K.; Fukuda, K.; Ohnishi, T.; Akatsuka, K.; Osada, M.; Hang, B. T.; Kumagai, K.; Sekiguchi, T.; Sasaki, T. Tantalum Oxide Nanomesh as Self-Standing One Nanometre Thick Electrolyte. Energy Environ. Sci. 2011, 4, 3509−3512. (19) Nagao, M.; Hayashi, A.; Tatsumisago, M. High-capacity Li2SNanocarbon Composite Electrode for All-Solid-State Rechargeable Lithium Batteries. J. Mater. Chem. 2012, 22, 10015−10020. (20) Ohta, S.; Komagata, S.; Seki, J.; Saeki, T.; Morishita, S.; Asaoka, T. All-Solid-State Lithium Ion Battery Using Garnet-Type Oxide and Li3BO3 Solid Electrolytes Fabricated by Screen-Printing. J. Power Sources 2013, 238, 53−56. (21) Zhao, K.; Liu, Y.; Zhang, S.; He, S.; Zhang, N.; Yang, J.; Zhan, Z. A Room Temperature Solid-State Rechargeable Sodium Ion Cell Based on a Ceramic Na-β″-Al2O3 Electrolyte and NaTi2(PO4)3 Cathode. Electrochem. Commun. 2016, 69, 59−63. (22) Delaizir, G.; Viallet, V.; Aboulaich, A.; Bouchet, R.; Tortet, L.; Seznec, V.; Morcrette, M.; Tarascon, J.-M.; Rozier, P.; Dollé, M. The

respectively, which are much lower than SS-SIB with 70 wt % NNM cathode (2250 Ω). For comparison, the cathode without IL was also prepared, and the corresponding resistance is very large (1.5 × 106 Ω). The impedance results prove that our design dose play an important role in the ceramic-based electrolyte SS-SIBs. In conclusion, a new strategy is proposed to address the interfacial problem in solid-state batteries. The key point is to design a novel toothpaste-like electrode which could adhere onto the solid electrolyte pellet and keep interface wet during the working process of the battery. A mixed conducting network was introduced to change the contact mode and enlarge the contact area among solid particles, improving the battery performance greatly. The new designed SS-SIBs (40 wt % NNM cathode) shows an outstanding rate capability, superior stability and high reversibility at 70 °C. At a high current rate of 6C, an ultralong cycle of 10 000 times with a capacity retention of 90% was achieved. In addition, the battery presents a reasonable performance at room temperature. Furthermore, when the active material content was increased to 60 wt % in cathode, the battery (active material mass loading reached up to 6 mg cm−2) also delivered a good rate capability and cycle performance. All these results demonstrate that this new designed method is promising to be applied in solid-state Li/Na ion batteries.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications Web site at DOI: XXX. Experimental, table of cathode contents, XRD of NNM, structure of PY14FSI, SEM and mapping images, electrochemical performance, impedance spectra and Cyclic voltammograms. The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.6b11773.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Tel.: +86 10 82649808. Fax: +86 10 82649046. ORCID

Yong-Sheng Hu: 0000-0002-2992-7577 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the National Key Technologies R&D Program (Grant No. 2016YFB0901504), National Natural Science Foundation of China (Nos. 51222210 and 11234013) and One Hundred Talent Project of the Chinese Academy of Sciences.

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DOI: 10.1021/acsami.6b11773 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX